#------------------------------------------------------------------------------
#$Date: 2025-06-15 12:58:01 +0100 (Sun, 15 Jun 2025) $
#$Revision: 300090 $
#$URL: svn://www.crystallography.net/cod/cif/2/02/35/2023519.cif $
#------------------------------------------------------------------------------
#
# This file is available in the Crystallography Open Database (COD),
# http://www.crystallography.net/. The original data for this entry
# were provided by IUCr Journals, http://journals.iucr.org/.
#
# The file may be used within the scientific community so long as
# proper attribution is given to the journal article from which the
# data were obtained.
#
data_2023519
loop_
_publ_author_name
'Armel Le Bail'
_publ_section_title
;
Ca(BF~4~)~2~.xH~2~O redefined from powder diffraction as
hydrogen-bonded Ca(H~2~O)~4~(BF~4~)~2~ ribbons
;
_journal_coeditor_code VX3013
_journal_issue 6
_journal_name_full 'Acta Crystallographica, Section C'
_journal_page_first 338
_journal_page_last 341
_journal_paper_doi 10.1107/S2053229625004395
_journal_volume 81
_journal_year 2025
_chemical_compound_source 'commercial, Alfa Aesar'
_chemical_formula_iupac 'Ca (B F4)2 .4H2 O'
_chemical_formula_moiety 'B F4, B F4, 4(H2 O), Ca'
_chemical_formula_structural Ca(H2O)4(BF4)2
_chemical_formula_sum 'B2 Ca F8 H8 O4'
_chemical_formula_weight 285.76
_chemical_name_common 'Calcium bi-tetrafluoroborate tetrahydrate'
_chemical_name_systematic
;
Calcium bis(tetrafluoroborate) tetrahydrate
Ca(BF~4~)~2~.xH~2~O
;
_space_group_IT_number 2
_space_group_name_Hall '-P 1'
_space_group_name_H-M_alt 'P -1'
_symmetry_cell_setting triclinic
_symmetry_space_group_name_Hall '-P 1'
_symmetry_space_group_name_H-M 'P -1'
_cell_angle_alpha 77.439(3)
_cell_angle_beta 89.579(3)
_cell_angle_gamma 88.625(2)
_cell_formula_units_Z 2
_cell_length_a 5.5192(3)
_cell_length_b 7.6756(3)
_cell_length_c 11.6518(5)
_cell_measurement_temperature 293
_cell_volume 481.65(4)
_computing_molecular_graphics
;
DIAMOND (Brandenburg, 1999)
;
_computing_publication_material
;
publCIF (Westrip, 2010)
;
_computing_structure_refinement
;
FULLPROF (Rodr\'iguez-Carvajal, 1993)
;
_computing_structure_solution
;
McMaille (Le Bail, 2004) and ESPOIR (Le Bail, 2001
;
_diffrn_ambient_temperature 293
_diffrn_measurement_device_type 'Siemens D501'
_diffrn_measurement_method diffractometer
_diffrn_radiation_monochromator graphite
_diffrn_radiation_probe x-ray
_diffrn_radiation_type CuK\a
_diffrn_radiation_wavelength 1.5418
_diffrn_source 'X-ray tube'
_exptl_absorpt_coefficient_mu 6.888
_exptl_crystal_density_diffrn 1.970
_exptl_crystal_density_method 'Not Measured'
_exptl_crystal_F_000 284
_pd_block_diffractogram_id Ca(BF4)2-xH2O
_pd_char_colour white
_pd_char_particle_morphology 'fine powder'
_pd_instr_location 'Le Mans, France'
_pd_meas_2theta_range_inc 0.020000
_pd_meas_2theta_range_max 110.00000
_pd_meas_2theta_range_min 5.00000
_pd_meas_number_of_points 5251
_pd_meas_scan_method step
_pd_prep_temperature 293
_pd_proc_2theta_range_inc 0.020000
_pd_proc_2theta_range_max 109.8169
_pd_proc_2theta_range_min 4.8169
_pd_proc_info_excluded_regions 'from 13.18 to 13.70 2-theta'
_pd_proc_ls_background_function manual
_pd_proc_ls_pref_orient_corr '(011) direction, p = 0.939(3)'
_pd_proc_ls_profile_function pseudo-Voigt
_pd_proc_ls_prof_R_factor 6.2134
_pd_proc_ls_prof_wR_expected 1.9733
_pd_proc_ls_prof_wR_factor 8.4193
_pd_proc_wavelength 1.540560
_pd_spec_mounting 'plate sample holder'
_pd_spec_mount_mode reflection
_pd_spec_shape flat_sheet
_pd_spec_size_axial 25
_pd_spec_size_equat 10
_pd_spec_size_thick 1
_refine_ls_goodness_of_fit_all 4.267
_refine_ls_number_parameters 115
_refine_ls_number_reflns 2831
_refine_ls_number_restraints 56
_iucr_refine_instructions_details
;
Fullprof .pcr file :
COMM Ca(BF4)2.5H2O P-1 Reduced cell B3+
! Current global Chi2 (Bragg contrib.) = 18.20
! Files => DAT-file: cell-reduced-b3+.dat, PCR-file: cell-reduced-b3+
!Job Npr Nph Nba Nex Nsc Nor Dum Iwg Ilo Ias Res Ste Nre Cry Uni Cor Opt Aut
0 5 2 26 3 1 1 1 1 0 1 0 0 0 0 0 0 0 0
!
!Ipr Ppl Ioc Mat Pcr Ls1 Ls2 Ls3 NLI Prf Ins Rpa Sym Hkl Fou Sho Ana
0 0 1 0 2 0 4 0 0 -3 0 -1 1 0 2 1 1
!
! Lambda1 Lambda2 Ratio Bkpos Wdt Cthm muR AsyLim Rpolarz 2nd-muR -> Patt# 1
1.540560 1.544330 0.50000 50.000 20.0000 0.7995 0.0000 90.00 0.0000 0.0000
!
!NCY Eps R_at R_an R_pr R_gl Thmin Step Thmax PSD Sent0
60 0.01 0.20 0.20 0.20 0.80 5.0000 0.020000 110.0000 0.000 0.000
!
!2Theta/TOF/E(Kev) Background for Pattern# 1
5.0400 5164.4971 0.00
5.6250 4331.5073 621.00
6.5620 3567.1917 631.00
7.6040 2983.8679 641.00
8.6460 2505.6533 651.00
10.6250 1610.5684 661.00
14.0620 1035.2476 671.00
16.9790 666.4976 681.00
18.9580 794.9919 691.00
21.7710 455.4686 701.00
25.1040 227.6074 711.00
27.6500 45.0386 721.00
32.3960 629.7895 731.00
37.6040 1100.9205 741.00
44.5830 1349.7579 751.00
49.4790 958.7382 761.00
54.1670 1025.3472 771.00
66.3540 809.1620 781.00
71.6670 742.4232 791.00
80.6250 766.8378 801.00
83.5420 923.9055 811.00
90.4170 955.9617 821.00
93.8540 952.0498 831.00
97.9170 815.8331 841.00
101.7710 909.4767 851.00
109.0620 804.5963 861.00
!
! Excluded regions (LowT HighT) for Pattern# 1
0.00 5.00
13.18 13.70
110.00 180.00
!
! Additional scattering factors for Pattern# 1
b+3 0.00800 0.00400 0
0.88550 1.01233 0.03653 4.18135 0.65726 0.34702 0.37565 2.16388 0.04506
!
115 !Number of refined parameters
!
! Zero Code SyCos Code SySin Code Lambda Code MORE ->Patt# 1
0.18306 511.0 0.00000 0.0 0.00000 0.0 0.000000 0.00 0
!-------------------------------------------------------------------------------
! Data for PHASE number: 1 ==> Current R_Bragg for Pattern# 1: 3.78
!-------------------------------------------------------------------------------
Ca(BF4)2.5H2O
!
!Nat Dis Ang Pr1 Pr2 Pr3 Jbt Irf Isy Str Furth ATZ Nvk Npr More
23 40 16 0.0 1.0 1.0 0 0 0 0 0 571.497 0 5 1
!
!Jvi Jdi Hel Sol Mom Ter Brind RMua RMub RMuc Jtyp Nsp_Ref Ph_Shift N_Domains
0 3 0 0 0 0 1.0000 0.0000 0.0000 0.0000 0 0 0 0
!
! Max_dst(dist) (angles) Bond-Valence Calc.
3.5000 3.0000 1
!
P -1 <--Space group symbol
!Atom Typ X Y Z Biso Occ In Fin N_t Spc /Codes
Ca Ca+2 0.50425 0.24507 0.25058 1.58311 1.00000 0 0 0 0
21.00 31.00 41.00 471.00 0.00
B1 B+3 0.69104 0.19105 0.56250 2.80185 1.00000 0 0 0 0
411.00 421.00 431.00 481.00 0.00
B2 B+3 0.24254 0.66071 0.05454 2.80185 1.00000 0 0 0 0
441.00 451.00 461.00 481.00 0.00
F1 F-1 0.50112 0.71099 0.41675 2.82743 1.00000 0 0 0 0
51.00 61.00 71.00 491.00 0.00
F2 F-1 0.09353 0.74731 0.40617 2.82743 1.00000 0 0 0 0
81.00 91.00 101.00 491.00 0.00
F3 F-1 0.33732 -0.02074 0.37373 2.82743 1.00000 0 0 0 0
111.00 121.00 131.00 491.00 0.00
F4 F-1 0.69160 0.18623 0.44738 2.82743 1.00000 0 0 0 0
141.00 151.00 161.00 491.00 0.00
F5 F-1 0.59515 0.23882 0.91279 2.82743 1.00000 0 0 0 0
171.00 181.00 191.00 491.00 0.00
F6 F-1 1.00869 0.71633 0.07529 2.82743 1.00000 0 0 0 0
201.00 211.00 221.00 491.00 0.00
F7 F-1 0.25093 0.67272 0.93338 2.82743 1.00000 0 0 0 0
231.00 241.00 251.00 491.00 0.00
F8 F-1 0.27061 0.48414 0.11228 2.82743 1.00000 0 0 0 0
261.00 271.00 281.00 491.00 0.00
O1 O-2 0.80422 0.02184 0.24884 3.86585 1.00000 0 0 0 0
291.00 301.00 311.00 501.00 0.00
O2 O-2 0.20025 0.35210 0.36824 3.86585 1.00000 0 0 0 0
321.00 331.00 341.00 501.00 0.00
O3 O-2 0.25273 0.10064 0.12626 3.86585 1.00000 0 0 0 0
351.00 361.00 371.00 501.00 0.00
O4 O-2 0.72631 0.51281 0.26349 3.86585 1.00000 0 0 0 0
381.00 391.00 401.00 501.00 0.00
H11 H 0.92910 0.08348 0.23737 4.00000 1.00000 0 0 0 0
911.00 921.00 931.00 0.00 0.00
H12 H 0.83644 -0.06624 0.30264 4.00000 1.00000 0 0 0 0
941.00 951.00 961.00 0.00 0.00
H21 H 0.07513 0.36983 0.32388 4.00000 1.00000 0 0 0 0
971.00 981.00 991.00 0.00 0.00
H22 H 0.13062 0.32709 0.43742 4.00000 1.00000 0 0 0 0
1001.00 1011.00 1021.00 0.00 0.00
H31 H 0.34402 0.04404 0.08966 4.00000 1.00000 0 0 0 0
1031.00 1041.00 1051.00 0.00 0.00
H32 H 0.18412 0.17947 0.07725 4.00000 1.00000 0 0 0 0
1061.00 1071.00 1081.00 0.00 0.00
H41 H 0.60912 0.57608 0.28022 4.00000 1.00000 0 0 0 0
1091.00 1101.00 1111.00 0.00 0.00
H42 H 0.80945 0.59276 0.21689 4.00000 1.00000 0 0 0 0
1121.00 1131.00 1141.00 0.00 0.00
!-------> Profile Parameters for Pattern # 1
! Scale Shape1 Bov Str1 Str2 Str3 Strain-Model
0.20397E-01 0.92824 0.00000 0.00000 0.00000 0.00000 0
11.00000 521.000 0.000 0.000 0.000 0.000
! U V W X Y GauSiz LorSiz Size-Model
0.075658 -0.103587 0.058281 0.000000 0.000000 0.000000 0.000000 0
0.000 871.000 531.000 0.000 0.000 0.000 0.000
! a b c alpha beta gamma #Cell Info
5.519200 7.675606 11.651834 77.438797 89.579201 88.624588
541.00000 551.00000 561.00000 571.00000 581.00000 591.00000
! Pref1 Pref2 Asy1 Asy2 Asy3 Asy4
0.93938 0.00000 0.03379 0.00611 0.00000 0.00000
1151.00 0.00 601.00 611.00 0.00 0.00
! Soft distance constraints:
B1 F1 -1 1.00000 1.00000 1.00000 1.38000 0.02000
B1 F2 -1 1.00000 1.00000 1.00000 1.38000 0.02000
B1 F3 -1 1.00000 0.00000 1.00000 1.38000 0.02000
B1 F4 1 0.00000 0.00000 0.00000 1.38000 0.02000
B2 F5 -1 1.00000 1.00000 1.00000 1.38000 0.02000
B2 F6 1 -1.00000 0.00000 0.00000 1.38000 0.02000
B2 F7 1 0.00000 0.00000 -1.00000 1.38000 0.02000
B2 F8 1 0.00000 0.00000 0.00000 1.38000 0.02000
F1 F2 1 0.00000 0.00000 0.00000 2.26000 0.02000
F1 F3 1 0.00000 1.00000 0.00000 2.26000 0.02000
F1 F4 -1 1.00000 1.00000 1.00000 2.26000 0.02000
F2 F3 1 0.00000 1.00000 0.00000 2.26000 0.02000
F2 F4 -1 1.00000 1.00000 1.00000 2.26000 0.02000
F3 F4 -1 1.00000 0.00000 1.00000 2.26000 0.02000
F5 F6 -1 2.00000 1.00000 1.00000 2.26000 0.02000
F5 F7 -1 1.00000 1.00000 2.00000 2.26000 0.02000
F5 F8 -1 1.00000 1.00000 1.00000 2.26000 0.02000
F6 F7 1 1.00000 0.00000 -1.00000 2.26000 0.02000
F6 F8 1 1.00000 0.00000 0.00000 2.26000 0.02000
F7 F8 1 0.00000 0.00000 1.00000 2.26000 0.02000
F1 H41 1 0.00000 0.00000 0.00000 2.05000 0.04000
F2 H12 1 -1.00000 1.00000 0.00000 2.05000 0.04000
F2 H22 -1 0.00000 1.00000 1.00000 2.05000 0.04000
F5 H31 -1 1.00000 0.00000 1.00000 2.05000 0.04000
F6 H32 -1 1.00000 1.00000 0.00000 2.05000 0.04000
F6 H42 1 0.00000 0.00000 0.00000 2.05000 0.04000
O3 H11 1 -1.00000 0.00000 0.00000 2.05000 0.04000
O4 H21 1 1.00000 0.00000 0.00000 2.05000 0.04000
O1 H11 1 0.00000 0.00000 0.00000 0.82000 0.02000
O1 H12 1 0.00000 0.00000 0.00000 0.82000 0.02000
O2 H21 1 0.00000 0.00000 0.00000 0.82000 0.02000
O2 H22 1 0.00000 0.00000 0.00000 0.82000 0.02000
O3 H31 1 0.00000 0.00000 0.00000 0.82000 0.02000
O3 H32 1 0.00000 0.00000 0.00000 0.82000 0.02000
O4 H41 1 0.00000 0.00000 0.00000 0.82000 0.02000
O4 H42 1 0.00000 0.00000 0.00000 0.82000 0.02000
H11 H12 1 0.00000 0.00000 0.00000 1.32000 0.02000
H21 H22 1 0.00000 0.00000 0.00000 1.32000 0.02000
H31 H32 1 0.00000 0.00000 0.00000 1.32000 0.02000
H41 H42 1 0.00000 0.00000 0.00000 1.32000 0.02000
! Soft angle constraints:
F1 B1 F2 -1 1 1.0000 1.0000 1.0000 0.0000 0.0000 0.0000 109.50 2.00
F1 B1 F3 -1 1 1.0000 1.0000 1.0000 0.0000 1.0000 0.0000 109.50 2.00
F2 B1 F3 -1 1 1.0000 1.0000 1.0000 0.0000 1.0000 0.0000 109.50 2.00
F4 B1 F1 1 -1 0.0000 0.0000 0.0000 1.0000 1.0000 1.0000 109.50 2.00
F4 B1 F2 1 -1 0.0000 0.0000 0.0000 1.0000 1.0000 1.0000 109.50 2.00
F4 B1 F3 1 -1 0.0000 0.0000 0.0000 1.0000 0.0000 1.0000 109.50 2.00
F8 B2 F5 1 -1 0.0000 0.0000 0.0000 1.0000 1.0000 1.0000 109.50 2.00
F8 B2 F6 1 1 0.0000 0.0000 0.0000 -1.0000 0.0000 0.0000 109.50 2.00
F8 B2 F7 1 1 0.0000 0.0000 0.0000 0.0000 0.0000-1.0000 109.50 2.00
F5 B2 F6 -1 -1 1.0000 1.0000 1.0000 2.0000 1.0000 1.0000 109.50 2.00
F5 B2 F7 -1 -1 1.0000 1.0000 1.0000 1.0000 1.0000 2.0000 109.50 2.00
F6 B2 F7 1 1 1.0000 0.0000 0.0000 1.0000 0.0000-1.0000 109.50 2.00
H11 O1 H12 1 1 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 104.50 2.00
H21 O2 H22 1 1 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 104.50 2.00
H31 O3 H32 1 1 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 104.50 2.00
H41 O4 H42 1 1 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 104.50 2.00
!-------------------------------------------------------------------------------
! Data for PHASE number: 2 ==> Current R_Bragg for Pattern# 1: 2.58
!-------------------------------------------------------------------------------
CaF2
!
!Nat Dis Ang Pr1 Pr2 Pr3 Jbt Irf Isy Str Furth ATZ Nvk Npr More
2 0 0 1.0 1.0 0.0 0 0 0 0 0 7195.558 0 5 1
!
!Jvi Jdi Hel Sol Mom Ter Brind RMua RMub RMuc Jtyp Nsp_Ref Ph_Shift N_Domains
0 3 0 0 0 0 1.0000 0.0000 0.0000 0.0000 0 0 0 0
!
! Max_dst(dist) (angles) Bond-Valence Calc.
3.5000 3.0000 1
!
F M -3 M <--Space group symbol
!Atom Typ X Y Z Biso Occ In Fin N_t Spc /Codes
Ca Ca+2 0.00000 0.00000 0.00000 1.50000 0.10000 0 0 0 0
0.00 0.00 0.00 0.00 0.00
F F-1 0.25000 0.25000 0.25000 1.50000 0.20000 0 0 0 0
0.00 0.00 0.00 0.00 0.00
!-------> Profile Parameters for Pattern # 1
! Scale Shape1 Bov Str1 Str2 Str3 Strain-Model
0.36710E-03 0.85536 0.00000 0.00000 0.00000 0.00000 0
881.00000 0.000 0.000 0.000 0.000 0.000
! U V W X Y GauSiz LorSiz Size-Model
0.075658 -0.122024 1.099675 0.000000 0.000000 0.000000 0.000000 0
0.000 0.000 891.000 0.000 0.000 0.000 0.000
! a b c alpha beta gamma #Cell Info
5.472317 5.472317 5.472317 90.000000 90.000000 90.000000
901.00000 901.00000 901.00000 0.00000 0.00000 0.00000
! Pref1 Pref2 Asy1 Asy2 Asy3 Asy4
1.00000 0.00000 0.03760 0.00756 0.00000 0.00000
0.00 0.00 0.00 0.00 0.00 0.00
! 2Th1/TOF1 2Th2/TOF2 Pattern to plot
5.000 110.000 1
Data file .dat
5.000 0.020 130.000 BF008
5205 5117 5071 4971 4954 5029 4956 5004
4775 4854 4912 4802 4889 4774 4756 4807
4656 4625 4751 4594 4520 4631 4589 4496
4430 4540 4542 4381 4541 4391 4523 4356
4351 4253 4186 4363 4343 4183 4315 4236
4213 4249 4140 4129 4272 4063 4039 4082
4111 3954 4000 4014 4056 3848 3918 3964
4031 3891 3914 3930 3918 3793 3737 3772
3890 3796 3735 3846 3743 3772 3629 3595
3691 3722 3708 3583 3577 3656 3626 3553
3513 3536 3551 3522 3440 3533 3436 3546
3448 3442 3485 3416 3400 3381 3368 3355
3445 3354 3410 3295 3302 3261 3325 3295
3195 3178 3252 3201 3134 3203 3187 3160
3129 3163 3192 3191 3043 3108 3144 3042
3091 3087 3085 3016 3080 2972 3038 2938
2958 3020 3055 3049 2939 3027 2948 2929
2962 3026 2909 3040 2894 2986 2985 2971
2992 2884 2911 2843 2864 2878 2710 2897
2799 2728 2723 2682 2738 2669 2811 2671
2618 2691 2658 2696 2638 2600 2682 2598
2658 2545 2572 2609 2662 2576 2617 2529
2495 2527 2560 2624 2548 2451 2567 2489
2396 2484 2496 2450 2452 2476 2471 2488
2346 2406 2531 2387 2367 2426 2422 2404
2367 2461 2395 2427 2482 2417 2431 2402
2419 2297 2303 2324 2207 2301 2176 2245
2195 2322 2258 2305 2234 2162 2255 2144
2182 2159 2136 2096 2089 2101 2135 2139
2035 2056 2039 1988 2063 2012 2045 1946
1966 2038 1995 1990 2069 2037 2016 1945
1964 2071 1867 1910 1946 1903 1905 1884
1881 1931 1908 1862 1928 1830 1770 1867
1788 1888 1836 1847 1811 1880 1769 1826
1829 1813 1878 1764 1808 1840 1845 1798
1759 1761 1697 1668 1775 1798 1765 1744
1745 1697 1720 1734 1777 1771 1744 1618
1706 1654 1660 1661 1686 1675 1693 1657
1659 1623 1720 1604 1645 1708 1648 1635
1617 1598 1655 1570 1651 1626 1626 1576
1633 1543 1625 1615 1543 1590 1556 1630
1540 1634 1618 1581 1637 1653 1613 1618
1703 1686 1697 1732 1699 1755 1795 1758
1859 1834 1975 1966 2095 2064 2046 2015
2024 2020 2111 1967 2108 2160 2102 2218
2197 2223 2328 2410 2456 2870 3094 3448
3930 4067 4196 4439 4970 5214 6076 6817
7752 8603 9850 10759 11547 12365 13241 14384
16236 19024 21774 24788 27092 29868 32616 33237
33341 31561 29611 28208 26200 23363 19994 16405
13071 10035 7965 6648 5594 5035 5029 4521
3994 3574 3065 2911 3631 5035 6042 6405
6234 5935 4658 3498 2895 2898 2936 3022
2800 2239 1783 1561 1444 1600 1649 1558
1467 1236 1203 1201 1181 1084 1120 1158
1189 1166 1149 1170 1147 1204 1102 1203
1144 1112 1090 1159 1163 1141 1127 1163
1118 1153 1133 1137 1197 1128 1118 1137
1124 1153 1136 1074 1150 1121 1122 1146
1178 1167 1167 1169 1261 1256 1235 1365
1337 1346 1346 1448 1434 1400 1498 1536
1517 1516 1509 1541 1597 1506 1445 1462
1395 1446 1451 1378 1365 1327 1376 1315
1345 1319 1359 1254 1351 1281 1272 1249
1231 1321 1280 1198 1198 1246 1226 1263
1228 1217 1184 1274 1204 1207 1215 1271
1247 1252 1256 1228 1329 1282 1348 1401
1361 1379 1408 1483 1496 1616 1742 1840
1945 2115 2388 2761 3001 3276 3655 3863
4496 4983 5583 6496 7299 8506 10246 11572
12900 13611 13553 12723 11178 10369 9059 7946
6654 5550 4677 3984 3237 2988 2743 2594
2469 2092 2019 1868 1636 1429 1370 1233
1051 1111 1023 974 938 964 967 932
963 923 964 994 969 1004 965 976
995 982 982 965 997 954 958 927
1035 995 1038 1036 1026 1073 1117 1005
1107 1129 1174 1189 1265 1259 1370 1449
1555 1669 1828 1948 2084 2020 2055 1999
1929 1860 1828 1697 1656 1660 1558 1567
1608 1772 1902 2148 2316 2527 2744 2985
3372 3728 4172 4655 4653 4561 4392 3999
3694 3342 2998 2469 2204 1927 1777 1565
1616 1485 1400 1489 1397 1347 1262 1298
1173 1120 1003 1013 998 964 925 922
948 983 964 937 980 932 953 931
876 902 950 980 923 876 910 922
850 961 892 890 936 909 913 944
918 942 958 914 902 925 926 897
893 935 927 959 1005 1038 1055 1170
1166 1133 1091 1036 1261 1463 1306 1081
1066 1146 1106 1243 1214 1303 1480 1537
1841 1882 2131 2300 2588 2898 3175 3662
3958 4333 4695 4935 4675 4415 4007 3675
3307 3100 3013 3008 2877 3019 3254 3646
3917 4352 4975 5887 6820 8024 9236 10608
11927 12616 13138 13206 11548 10159 8726 7375
6023 5049 4423 3726 3538 3229 3234 3293
3517 3596 3722 4099 4255 4451 5023 5604
6476 7108 7666 7889 7595 7080 6164 5079
4178 3341 2693 2313 2002 1922 1880 1838
1917 2027 2089 2003 1928 1732 1493 1459
1310 1189 1047 963 956 880 941 910
939 869 954 928 910 905 915 914
917 877 938 952 886 917 1012 901
954 916 909 962 928 918 838 882
903 913 923 898 925 990 969 1011
1037 1076 1105 1183 1278 1347 1465 1657
1802 2130 2512 2733 3086 3166 3283 3293
3030 3003 3178 3255 3651 4096 4556 4985
5471 5717 5870 6081 6055 5931 5836 5610
5345 4847 4349 3720 3025 2544 2301 2036
1895 1685 1660 1625 1592 1511 1474 1464
1424 1327 1246 1193 1189 1161 1072 1090
1008 984 1063 1095 1168 1153 1107 1223
1251 1367 1466 1480 1676 1829 1931 2397
2558 2939 3525 4171 4858 5634 6462 7133
7864 8315 8878 9339 9943 10722 12206 13821
15460 17218 18628 19641 20679 21650 21334 21086
21033 20133 19360 18856 17988 16459 14376 12465
10584 8943 7713 6344 5526 4917 4430 3938
3554 3130 2992 2804 2518 2315 2135 1944
1780 1661 1480 1288 1226 1153 1079 1008
1010 989 948 938 934 948 928 973
916 926 956 830 968 979 929 946
925 945 927 906 958 946 984 968
1014 1003 1003 1035 1065 1100 1135 1152
1285 1294 1485 1643 1766 2197 2385 2799
3473 4469 5565 7099 8792 10760 12609 13939
14578 14521 13485 12054 10308 8346 6789 5122
4249 3480 3068 2748 2547 2543 2392 2404
2467 2389 2294 2155 1896 1689 1537 1390
1305 1164 1080 1104 994 1075 997 986
1045 1038 1043 968 997 981 987 1002
1014 969 1023 1030 973 988 1085 1084
1132 1190 1120 1208 1315 1382 1406 1585
1621 1660 1674 1656 1637 1648 1548 1568
1587 1612 1678 1688 1760 1937 1896 1945
1925 1972 2017 2134 2234 2554 2936 3562
4330 5130 5599 6033 6374 6348 5877 5211
4461 3770 3303 2772 2615 2376 2164 2149
2198 2145 2145 2259 2146 2120 2185 2128
2147 2149 2173 2135 2249 2249 2369 2287
2471 2467 2621 2876 3029 3177 3425 3635
3935 4318 4829 5173 5769 6172 6636 7150
7511 7812 8285 8348 8279 8280 8076 7887
7554 7314 7164 6928 6981 7240 7374 7660
8420 9322 10383 12226 14340 17076 20280 24123
28237 31932 34982 37687 38510 37516 35398 32645
30005 26262 22705 19881 17538 15203 13653 12422
11242 10071 8977 8247 7553 6773 6652 6450
6211 6302 6202 6643 6598 6816 6714 6544
6179 5559 5104 4217 3626 3060 2723 2507
2215 2121 1929 1997 1891 1901 1929 1778
1755 1774 1732 1705 1685 1620 1625 1650
1671 1710 1816 1823 2029 2290 2574 3030
3781 4833 6085 7921 9609 11391 12729 13822
14281 13741 12961 11528 9754 8019 6686 5488
4457 3886 3461 3053 2791 2666 2558 2365
2288 2179 2104 1934 1858 1765 1765 1741
1809 1903 2120 2356 2710 3164 3428 3532
3510 3393 3155 2794 2502 2293 2186 2159
2205 2246 2515 2981 3437 4092 5012 6021
7033 7815 8331 8526 8360 7657 6797 5782
4856 4062 3410 2981 2760 2625 2564 2561
2685 2952 3204 3493 3848 3856 3926 4019
4136 4310 4710 5040 5702 6002 6193 6111
5842 5400 4917 4253 3711 3280 2614 2395
2088 1858 1890 1750 1666 1725 1682 1678
1549 1548 1528 1422 1388 1292 1258 1194
1212 1120 1161 987 1041 1089 1076 1105
1116 1113 1153 1225 1155 1308 1301 1478
1643 1838 2060 2345 2445 2568 2652 2587
2369 2262 2009 1801 1520 1457 1442 1343
1381 1351 1430 1395 1379 1561 1557 1636
1699 1842 1819 1763 1738 1717 1791 1743
1769 1877 1982 1981 2103 2041 2087 2079
1908 1812 1716 1594 1434 1366 1345 1374
1358 1371 1488 1591 1687 1746 1905 2185
2306 2528 3006 3361 3820 4123 4482 4563
4438 4209 3769 3285 2981 2606 2201 2093
1850 1776 1669 1638 1669 1586 1563 1510
1498 1606 1598 1444 1486 1438 1519 1499
1534 1638 1723 1828 1823 1868 1883 1823
1727 1722 1724 1665 1634 1613 1618 1549
1500 1534 1618 1635 1684 1782 1851 2035
2265 2851 3017 3299 3528 3553 3417 3320
2994 2684 2573 2321 2275 2259 2260 2300
2309 2383 2299 2381 2357 2257 2138 2166
2121 2131 2136 2234 2183 2099 2093 2180
2083 2023 1990 1955 1984 1983 1987 2086
2075 2268 2431 2562 2716 2833 2740 2783
2781 2628 2641 2480 2270 2234 2016 1997
1865 1847 1636 1556 1715 1616 1712 1852
1969 2026 2231 2345 2480 2552 2439 2354
2488 2379 2405 2461 2542 2890 3143 3631
3914 4060 4158 4046 3996 4110 4032 4047
4006 3798 3783 3632 3396 3264 2938 2725
2501 2265 2118 1974 1814 1720 1714 1707
1706 1690 1729 1776 1659 1776 1614 1684
1617 1595 1478 1407 1382 1394 1351 1383
1351 1325 1326 1312 1325 1370 1399 1346
1413 1422 1441 1538 1731 1831 1786 2017
2264 2264 2305 2184 2161 2143 2022 1844
1701 1664 1587 1517 1436 1471 1456 1488
1403 1422 1445 1444 1452 1421 1433 1453
1396 1393 1343 1353 1324 1354 1340 1382
1307 1413 1452 1396 1399 1371 1387 1464
1375 1396 1451 1489 1473 1437 1599 1600
1707 1800 1992 2267 2644 2850 2938 3142
3313 3374 3467 3583 3867 4116 4385 5019
5440 5732 5758 5864 5539 5308 4845 4448
4079 3657 3265 2937 2649 2611 2467 2302
2366 2294 2285 2134 2096 2178 2204 2188
2211 2297 2578 2982 3321 3826 4268 4672
5172 5213 5382 5319 5264 4932 4526 4203
3830 3665 3255 3082 3031 2990 2843 2937
2970 3071 3038 3133 3218 3176 3264 3202
3260 3108 3199 3074 3193 3094 3381 3634
4188 4790 5490 6087 6463 7070 7649 8066
8390 9096 9962 10497 11515 11472 10854 10550
9909 9449 8675 8157 7822 7806 7997 8506
9313 10166 10775 10909 10960 11000 10246 9481
8960 8104 7365 6577 5827 5236 4831 4619
4250 4161 4249 4397 4698 5119 5270 5655
6244 6904 8044 9528 11075 12852 14104 15045
15448 15662 15735 15345 14274 12967 11630 10332
9327 8344 7193 6366 5803 5313 4849 4459
4283 4093 3803 3454 3325 3036 2931 2784
2666 2670 2610 2682 2999 3089 3576 4082
4635 5148 5619 5831 5943 5794 5579 5351
5054 4576 4344 4025 3662 3444 3457 3392
3530 3799 4324 4771 5474 6031 6939 7794
8597 8912 9119 9167 9159 9085 8667 8049
7789 7666 7614 7479 7250 6867 6633 6350
6007 5691 5486 5076 4672 4371 4377 3909
3993 3747 3730 3548 3430 3419 3372 3230
3002 3045 2840 2960 3034 3331 3842 4366
4875 5604 6060 6308 6769 6835 6848 6492
6014 5736 5346 4789 4318 3790 3443 3356
3034 2891 2736 2655 2545 2451 2483 2303
2365 2288 2414 2415 2560 2782 3288 3759
4327 4772 5220 5055 5279 4987 4816 4636
4345 4170 3854 3561 3451 3553 3738 4148
4591 5527 6714 7212 7563 7759 7652 7197
6920 6598 6187 5516 4844 4218 4055 3705
3489 3187 2997 2925 2778 2689 2605 2566
2438 2320 2171 2167 2143 2108 2044 2041
2036 1944 1923 2083 2078 2117 2155 2363
2360 2582 2705 2734 2795 2767 2767 2684
2711 2618 2458 2629 2607 2493 2595 2782
2732 2714 2708 2722 2756 2778 2707 2946
3110 3599 3675 4130 4451 4572 4840 5164
5226 5282 5327 5547 5547 5867 6359 6871
7114 7106 7094 6923 6455 6246 5717 5512
5161 4958 4788 4694 4627 4585 4473 4406
4279 4281 4185 3874 3624 3525 3484 3394
3432 3449 3567 3592 3883 4173 4261 4465
4348 4240 4403 4163 4255 4103 4040 3739
3683 3611 3443 3320 3395 3394 3369 3410
3402 3405 3418 3425 3503 3493 3563 3697
3719 3814 3963 3961 4167 4221 4423 4630
4725 5011 5275 5650 5850 6315 6647 6654
6966 7028 7159 7344 7219 7297 7503 7383
7343 7241 7200 7032 7364 7282 7381 7397
7366 7342 6945 6654 6263 6125 5699 5533
5212 5077 4731 4638 4511 4285 4129 4102
4318 4560 5093 5707 6398 7618 8917 9959
10809 11482 11946 11938 11820 11657 11806 11929
12400 12554 12515 12819 12657 12276 11939 11229
10716 10137 9434 8740 7938 7354 6742 6098
5560 5067 4563 4217 4002 3776 3510 3222
3048 3040 2837 2825 2817 2889 3187 3439
3786 4158 4541 4986 5340 5419 5137 5085
4749 4540 4479 4397 4365 4327 4611 4677
5031 5411 5787 5739 5748 5149 4940 4468
4307 3986 3723 3296 2984 2740 2662 2439
2343 2364 2318 2315 2232 2136 2080 2055
2036 2120 1946 1964 1822 1776 1704 1809
1825 1739 1857 1793 2037 2090 2112 2171
2219 2272 2346 2274 2306 2270 2309 2343
2265 2253 2420 2467 2411 2388 2470 2569
2486 2532 2419 2343 2291 2141 2100 2191
2135 2229 2365 2397 2570 2747 2800 2748
2827 2758 2784 2800 2683 2743 2686 2724
2876 2899 2881 3105 3067 3389 3818 4072
4607 4972 5447 5635 5700 5702 5465 5372
5188 5053 4976 4816 4667 4558 4415 4457
4723 4879 5114 5528 5959 6097 6447 6800
6733 6903 6814 6702 6512 5935 5552 5043
4623 4212 3922 3584 3268 2989 2736 2615
2521 2377 2291 2256 2087 2139 2139 2007
2063 2128 2211 2266 2284 2429 2551 2741
2860 2952 3231 3393 3626 3822 4265 4511
4612 4886 5118 5282 5357 5516 5419 5241
4993 4762 4595 4383 4446 4482 4269 4117
4000 3953 3888 3769 3681 3510 3315 3290
3261 3168 3013 2903 2940 3026 3015 2814
2679 2637 2591 2611 2471 2445 2237 2152
2051 1941 1764 1744 1627 1615 1582 1468
1432 1370 1429 1288 1349 1377 1344 1306
1276 1195 1298 1216 1278 1294 1335 1333
1435 1482 1453 1434 1489 1559 1388 1459
1350 1427 1341 1355 1395 1404 1347 1326
1350 1343 1335 1310 1322 1299 1340 1326
1273 1274 1285 1272 1248 1210 1245 1231
1188 1198 1204 1219 1204 1181 1269 1245
1250 1272 1225 1274 1246 1283 1229 1282
1288 1236 1322 1314 1292 1305 1334 1313
1358 1342 1372 1342 1267 1390 1311 1252
1302 1336 1305 1226 1328 1294 1291 1297
1213 1326 1425 1333 1430 1422 1500 1516
1488 1514 1580 1611 1584 1662 1707 1784
1865 1906 2010 2110 2240 2242 2442 2588
2633 2658 2706 2671 2648 2588 2618 2473
2330 2439 2401 2416 2473 2413 2479 2344
2286 2375 2467 2439 2435 2442 2409 2402
2369 2414 2397 2433 2373 2405 2466 2541
2534 2544 2587 2559 2563 2447 2551 2554
2604 2604 2656 2700 2580 2720 2787 2710
2592 2501 2394 2437 2480 2289 2247 2156
2156 2140 1970 1916 1922 1865 1875 1833
1730 1774 1657 1681 1612 1565 1586 1570
1491 1456 1419 1411 1384 1450 1372 1371
1368 1379 1367 1388 1336 1288 1384 1305
1282 1224 1254 1314 1366 1382 1526 1572
1734 1842 1954 1956 2107 2096 2048 1923
1938 1804 1733 1829 1742 1694 1535 1535
1529 1341 1278 1374 1275 1307 1282 1246
1239 1292 1203 1239 1287 1392 1352 1377
1403 1310 1358 1368 1364 1431 1411 1409
1471 1570 1525 1613 1794 1698 1800 1796
1959 1968 1869 1812 1780 1806 1860 1976
2062 2182 2144 2316 2129 2081 2058 2155
2085 2135 2090 2063 2129 2119 2077 2039
1869 1827 1719 1740 1648 1646 1584 1476
1487 1357 1399 1326 1322 1258 1234 1214
1238 1281 1212 1341 1431 1372 1588 1653
1642 1691 1722 1640 1634 1701 1792 1721
1902 1950 1935 2010 2141 2181 2221 2362
2576 2553 2592 2641 2681 2709 2749 2652
2705 2820 2811 2801 2572 2591 2598 2524
2353 2283 2147 2112 2070 1956 1873 1862
1825 1852 1856 1905 1832 1802 1743 1748
1687 1716 1696 1648 1589 1524 1530 1433
1450 1351 1381 1316 1356 1322 1336 1340
1363 1442 1409 1564 1603 1605 1639 1688
1558 1627 1598 1657 1700 1691 1659 1737
1694 1624 1537 1488 1477 1470 1442 1441
1406 1355 1386 1357 1434 1524 1513 1560
1626 1597 1578 1625 1500 1510 1488 1474
1542 1465 1500 1437 1450 1422 1432 1378
1382 1365 1485 1456 1604 1790 1878 2004
2191 2465 2451 2373 2243 2291 2347 2572
2766 3008 3197 3084 3005 2900 2793 2602
2480 2361 2316 2337 2236 2243 2227 2120
2150 2223 2175 2168 2173 2185 2121 2076
1971 1985 1879 1839 1790 1779 1754 1756
1817 1746 1737 1663 1629 1526 1532 1462
1495 1494 1396 1506 1540 1610 1645 1712
1719 1802 1850 1873 1864 1822 1908 1938
1996 2002 2023 1940 1885 1844 1814 1639
1641 1614 1587 1455 1516 1436 1465 1457
1361 1373 1391 1385 1398 1428 1424 1410
1386 1305 1384 1348 1325 1305 1269 1310
1298 1388 1331 1352 1334 1332 1529 1569
1464 1589 1726 1739 1751 1722 1734 1740
1799 1840 1913 1943 1946 1977 1994 1978
1871 1858 1833 1881 1862 1802 1865 1805
1825 1890 1814 1916 2006 1994 2014 2095
1895 1878 1723 1664 1567 1708 1654 1657
1801 1886 1800 1924 1774 1778 1780 1733
1716 1742 1834 1863 1774 1727 1638 1616
1546 1456 1507 1398 1370 1384 1228 1220
1313 1230 1244 1242 1278 1255 1224 1167
1320 1244 1291 1260 1319 1356 1329 1374
1399 1421 1437 1493 1603 1702 1634 1758
1763 1797 1844 1813 1871 1922 1948 1978
1913 1814 1813 1658 1574 1591 1571 1538
1460 1447 1421 1319 1353 1346 1270 1248
1282 1221 1145 1145 1139 1091 1056 1063
1087 1009 1055 1003 1027 988 973 994
976 1020 987 987 966 998 1001 987
1036 1019 1042 1207 1111 1167 1241 1212
1166 1250 1245 1253 1332 1435 1557 1636
1729 1751 1765 1715 1827 1800 1678 1745
1647 1688 1685 1617 1598 1566 1460 1479
1353 1349 1298 1301 1250 1145 1157 1172
1180 1116 1152 1210 1176 1210 1249 1302
1303 1281 1328 1287 1289 1232 1336 1339
1443 1394 1357 1350 1352 1301 1340 1290
1265 1312 1375 1265 1263 1216 1194 1239
1217 1213 1104 1140 1126 1144 1127 1152
1164 1158 1186 1282 1253 1354 1440 1597
1604 1691 1771 1751 1846 1811 1861 1820
1892 1893 1900 1780 1813 1738 1726 1655
1617 1592 1637 1622 1562 1503 1531 1479
1473 1488 1525 1498 1522 1490 1544 1551
1625 1525 1594 1494 1507 1622 1574 1573
1683 1680 1647 1790 1866 1965 2054 2112
2198 2227 2253 2154 2087 2144 2204 2246
2300 2294 2422 2287 2257 2103 2014 1870
1816 1740 1799 1678 1791 1750 1748 1712
1744 1753 1714 1796 1840 1772 1760 1721
1664 1624 1568 1662 1611 1518 1569 1510
1405 1390 1351 1365 1341 1281 1284 1220
1198 1179 1240 1266 1227 1239 1245 1232
1274 1328 1359 1371 1528 1430 1555 1505
1495 1511 1466 1493 1470 1581 1590 1505
1610 1544 1523 1556 1448 1471 1563 1471
1513 1468 1527 1483 1558 1468 1565 1471
1458 1468 1382 1413 1416 1453 1386 1513
1566 1585 1568 1514 1513 1462 1380 1304
1380 1359 1323 1363 1397 1371 1439 1431
1343 1361 1263 1239 1198 1185 1184 1089
1145 1107 1156 1056 1114 1055 991 980
983 971 974 1024 947 979 985 1028
993 996 990 1002 961 1002 970 923
926 1002 977 957 1021 1001 1008 1059
1057 1099 1179 1261 1195 1132 1182 1178
1190 1164 1277 1298 1386 1378 1390 1285
1321 1333 1272 1290 1258 1190 1184 1174
1210 1182 1161 1134 1118 1098 1075 1034
994 1055 1100 1118 1158 1178 1155 1144
1167 1135 1080 1125 1075 1088 1087 1044
1018 1004 983 1032 961 982 983 1016
998 1035 1004 1033 1067 1104 1111 1124
1073 1072 1063 1018 1093 1029 1032 1126
1128 1091 1065 973 1051 998 992 939
986 980 957 954 968 950 928 976
990 883 918 972 977 1009 980 1039
989 1071 1095 1080 1138 1139 1104 1162
1311 1150 1238 1203 1241 1189 1206 1233
1135 1146 1169 1084 1043 1094 1081 1146
1082 1074 1087 1056 1081 1129 1094 1085
1181 1128 1148 1166 1141 1119 1175 1210
1234 1235 1341 1397 1508 1551 1624 1739
1770 1776 1624 1641 1452 1474 1393 1476
1483 1551 1560 1651 1549 1554 1541 1528
1358 1306 1332 1285 1375 1327 1281 1261
1263 1341 1251 1306 1347 1302 1362 1381
1341 1368 1478 1437 1530 1413 1469 1444
1451 1461 1422 1452 1440 1556 1392 1500
1422 1486 1422 1427 1483 1496 1471 1401
1411 1458 1409 1421 1381 1320 1388 1431
1455 1439 1438 1328 1385 1321 1301 1323
1306 1204 1216 1214 1254 1256 1254 1271
1245 1226 1209 1280 1340 1321 1329 1299
1423 1463 1360 1441 1392 1447 1390 1415
1477 1414 1368 1407 1441 1501 1461 1402
1409 1464 1427 1362 1326 1297 1430 1359
1433 1444 1516 1579 1472 1565 1516 1416
1367 1307 1301 1254 1283 1248 1250 1199
1211 1190 1111 1099 1056 1026 1032 1011
1015 1064 1094 1044 1072 1163 1106 1098
1088 1050 1059 1090 1052 1040 1076 1137
1138 1180 1184 1195 1141 1168 1222 1180
1221 1244 1242 1300 1214 1282 1261 1271
1184 1185 1246 1195 1200 1144 1139 1184
1097 1168 1079 1074 1039 1054 1043 958
998 983 963 967 1062 965 1066 1043
1063 1072 1110 1201 1124 1156 1108 1115
1086 1091 1088 1021 1041 1086 1085 1084
1162 1088 1165 1113 1069 1156 1151 1100
1087 1076 1007 1055 1095 1118 1104 1207
1255 1251 1231 1181 1100 1077 1057 1087
1095 1113 1111 1171 1268 1272 1423 1370
1394 1319 1324 1222 1168 1135 1099 1086
1091 1110 1115 1074 1070 1114 1074 1027
973 931 902 916 894 873 876 906
917 830 833 850 940 868 848 832
833 806 842 854 855 924 854 823
818 877 785 854 833 828 869 821
797 846 876 826 854 842 907 814
867 907 842 802 867 863 841 879
847 865 776 900 878 868 857 832
938 953 978 953 1012 922 1036 941
914 950 939 977 956 953 994 1065
1058 1115 1039 1052 1099 1158 1070 1066
1068 1113 1068 1049 1090 1127 1099 1118
1122 1143 1201 1156 1230 1193 1287 1306
1293 1398 1384 1378 1297 1381 1364 1290
1349 1399 1406 1435 1393 1385 1298 1279
1244 1196 1163 1169 1160 1133 1174 1145
1109 1107 1152 1084 1063 1031 1078 1084
1139 1117 1182 1201 1227 1180 1174 1208
1219 1224 1249 1137 1155 1247 1216 1123
1257 1136 1129 1154 1096 1173 1096 1162
1105 1095 1047 1074 1036 1007 1024 935
941 994 1009 1014 964 952 929 943
907 888 923 904 886 909 894 908
924 936 939 876 880 875 942 948
870 959 931 938 987 937 915 965
970 988 1007 991 1002 996 992 1021
939 973 956 956 993 1055 1045 1106
1022 1116 1038 1214 1145 1281 1351 1382
1520 1566 1663 1713 1871 1875 1889 1807
1816 1921 1766 1832 1710 1756 1797 1644
1721 1758 1649 1649 1627 1603 1578 1596
1508 1453 1497 1517 1503 1491 1382 1392
1409 1309 1306 1199 1279 1277 1359 1354
1491 1412 1523 1637 1633 1903 2100 2257
2289 2390 2269 2211 2155 1919 1868 1753
1722 1696 1757 1790 1863 1918 1966 1855
1735 1692 1550 1506 1361 1303 1232 1251
1252 1294 1196 1258 1219 1248 1345 1299
1302 1484 1483 1538 1580 1566 1654 1608
1599 1481 1452 1459 1522 1571 1570 1608
1756 1800 1878 2014 2132 2249 2201 2318
2409 2308 2335 2215 2222 2094 2092 2116
2055 2046 2135 2243 2237 2162 2110 2104
1939 1804 1794 1710 1680 1690 1675 1696
1665 1650 1764 1683 1662 1706 1768 1778
1850 1824 1796 1903 1834 1689 1747 1808
1808 1873 1839 1873 1875 1926 1978 2071
2083 2018 2018 2065 1987 1896 1895 2042
2057 2078 2032 2046 2010 2098 1970 2024
1834 1839 1786 1715 1793 1782 1833 1736
1751 1856 1676 1594 1502 1540 1501 1386
1431 1418 1461 1494 1427 1482 1448 1450
1445 1352 1394 1395 1376 1292 1426 1374
1423 1374 1404 1378 1440 1406 1370 1383
1422 1362 1359 1362 1332 1352 1440 1500
1527 1544 1581 1600 1530 1466 1444 1418
1444 1467 1441 1426 1337 1332 1342 1344
1295 1271 1245 1238 1232 1244 1295 1327
1291 1232 1202 1242 1210 1202 1129 1138
1106 1192 1119 1094 1128 1143 1135 1122
1107 1184 1164 1220 1245 1273 1236 1274
1274 1235 1156 1235 1144 1134 1155 1157
1090 1100 1104 1096 1201 1176 1111 1174
1115 1054 1113 1129 1105 1106 1084 1050
1070 1068 996 1060 1055 1022 1000 1015
1024 1064 1036 1067 997 1010 1062 999
1076 998 1084 1058 1053 1065 1025 986
1034 1067 1071 1093 1149 1131 1250 1274
1298 1361 1409 1407 1293 1316 1254 1252
1247 1110 1213 1197 1204 1255 1183 1265
1318 1381 1284 1164 1154 1184 1149 1134
1093 1111 1110 1061 1124 1112 1146 1097
1058 1080 1093 1132 1052 1072 1099 1142
1108 1137 1198 1253 1242 1196 1192 1173
1155 1150 1152 1205 1148 1213 1215 1246
1215 1249 1207 1181 1120 1234 1211 1212
1221 1288 1244 1258 1229 1241 1114 1119
1176 1148 1186 1177 1228 1160 1208 1206
1210 1253 1165 1182 1201 1237 1152 1195
1176 1240 1256 1287 1275 1298 1301 1377
1345 1303 1319 1231 1242 1236 1194 1193
1176 1151 1217 1269 1236 1308 1313 1252
1417 1318 1330 1306 1283 1275 1322 1230
1263 1265 1255 1292 1255 1230 1277 1247
1288 1366 1381 1346 1493 1422 1406 1360
1449 1383 1422 1460 1427 1342 1303 1330
1349 1347 1339 1317 1357 1429 1413 1359
1380 1449 1442 1351 1388 1415 1402 1449
1418 1462 1445 1474 1398 1353 1396 1482
1432 1385 1495 1508 1446 1498 1512 1480
1466 1461 1482 1491 1405 1434 1360 1413
1366 1332 1366 1332 1330 1292 1317 1277
1303 1243 1263 1230 1240 1221 1257 1261
1194 1230 1196 1279 1187 1241 1221 1253
1194 1207 1231 1198 1249 1227 1229 1269
1260 1293 1318 1242 1222 1255 1221 1299
1176 1170 1170 1148 1239 1164 1142 1239
1209 1234 1174 1220 1234 1142 1196 1208
1206 1228 1276 1281 1309 1259 1280 1240
1203 1272 1183 1293 1289 1306 1370 1369
1367 1329 1229 1253 1277 1317 1292 1241
1296 1299 1343 1327 1412 1388 1276 1317
1229 1324 1292 1200 1214 1210 1204 1193
1149 1192 1248 1113 1203 1142 1201 1108
1120 1105 1121 1090 1135 1126 1078 1078
1113 1115 1059 1057 1146 1107 1183 1143
1075 1147 1207 1201 1222 1220 1247 1183
1180 1115 1107 1072 1152 1153 1118 1164
1163 1200 1205 1193 1208 1137 1211 1194
1136 1212 1196 1188 1215 1195 1234 1234
1246 1195 1188 1153 1094 1148 1114 1140
1147 1122 1274 1204 1243 1341 1289 1368
1347 1364 1346 1254 1291 1260 1175 1212
1122 1162 1127 1145 1204 1244 1234 1237
1289 1277 1285 1367 1259 1258 1197 1233
1209 1264 1201 1245 1225 1148 1176 1153
1180 1119 1150 1129 1131 1110 1100 1036
1096 1103 1145 1165 1151 1045 1069 1092
1099 1113 1045 1059 1089 1035 1047 1084
1134 1186 1091 1178 1151 1093 1149 1163
1072 1058 1057 1110 1060 1088 1128 1146
1162 1070 1076 1109 1075 1119 1053 1020
1045 1092 1166 1115 1128 1096 1072 1136
1028 1072 1053 964 1033 1066 1007 981
1025 1058 1017 1057 1073 1098 1035 1103
1125 1077 1076 1043 1062 1060 1163 1125
1094 1078 1115 1073 1133 1056 1087 1078
1050 1097 1013 1029 1119 1007 1044 1113
1048 1090 1051 1032 994 1048 1070 988
1039 1008 1049 1038 1073 1041 962 1001
995 1022 1006 1039 997 1077 989 1048
1063 1043 1031 1022 1056 1020 1058 1010
1019 1053 1080 1005 1102 1017 1082 1002
1032 1051 991 992 1010 1022 1008 1042
1034 981 975 975 961 995 1012 1015
1060 1006 970 980 1058 1012 956 1043
1006 962 1002 1008 994 1013 1046 1025
987 1018 1042 1026 1064 1070 997 1030
949 964 1022 975 999 1034 988 986
1036 1035 990 961 1012 1082 1004 1027
1050 1013 1049 1017 1076 1125 1078 1039
987 1018 993 1074 1055 1019 977 1015
949 1009 997 1051 1001 1025 917 1021
999 1020 1020 1064 1011 988 936 1047
948 1000 1034 1069 1040 1055 1035 1039
1065 1039 1010 1054 1030 1032 1074 1025
979 1068 1025 1016 989 1021 955 1009
1104 1013 1047 1071 1026 1016 999 1062
969 1010 1015 969 1021 1014 1045 1081
1028 982 958 982 1001 1065 972 1030
998 1055 1021 1019 1032 1027 1061 960
1040 1039 1028 1044 1035 1062 1040 1044
1045 1086 1080 1055 1052 1023 1090 1053
1081 1033 1082 1085 1086 1092 1080 1147
1058 1101 1037 1135 1060 1119 1115 1104
1071 1050 1100 1143 1040 1129 1105 1156
1046 1056 1128 1146 1123 1102 1110 1199
1181 1215 1140 1175 1165 1164 1228 1175
1164 1235 1240 1127 1168 1213 1229 1268
1192 1161 1198 1157 1202 1179 1228 1292
1251 1264 1321 1308 1259 1269 1313 1336
1313 1280 1346 1328 1260 1287 1277 1288
1321 1237 1266 1264 1233 1205 1308 1242
1299 1298 1296 1294 1298 1220 1222 1275
1207 1283 1215 1216 1204 1181 1186 1174
1175 1169 1110 1092 1152 1067 1131 1115
1085 1109 1087 1172 1054 1137 1077 1092
1106 1028 1126 1012 1062 998 1048 1021
1068 1108 1022 1033 1019 1009 1002 1075
1016 1023 1045 1077 974 1033 1025 991
993 1085 999 1020 981 1012 958 1009
955 1022 974 1008 966 992 1037 994
1071 959 950 980 984 969 1039 975
1012 956 1007 1011 976 1006 966 949
1001 927 1019 1043 935 935 961 968
992 954 928 969 956 994 998 984
954 954 951 1008 964 968 961 968
958 906 992 967 976 952 902 905
940 988 912 990 979 923 898 942
964 933 947 920 941 932 949 924
980 983 957 968 930 984 927 954
961 937 968 1002 920 942 925 901
905 949 921 897 974 970 939 956
936 971 907 959 942 976 975 922
975 947 881 943 908 951 1001 909
947 914 990 920 954 905 985 936
960 931 927 911 994 923 944 987
962 977 979 965 980 953 898 927
969 940 964 939 915 920 941 948
966 990 947 936 957 898 885 936
897 938 964 913 987 975 947 972
941 995 972 980 961 960 932 944
950 983 981 951 976 957 957 886
993 956 976 929 944 977 940 971
1028 937 970 936 912 999 957 908
954 975 941 1005 1020 977 1008 984
999 983 964 1034 1043 1029 1055 1004
1001 1035 1000 1054 981 1006 996 995
1037 1047 1023 1004 1045 1078 1034 1080
1074 1116 1082 1061 1074 1107 1133 1066
1118 1043 1129 1153 1117 1107 1130 1139
1080 1099 1182 1153 1201 1136 1222 1171
1222 1198 1185 1198 1274 1204 1251 1204
1265 1279 1226 1323 1293 1175 1377 1314
1306 1318 1308 1301 1256 1288 1339 1347
1343 1397 1373 1355 1414 1391 1378 1416
1386 1418 1396 1438 1437 1409 1412 1464
1399 1455 1444 1424 1406 1441 1375 1407
1363 1308 1393 1377 1372 1394 1335 1357
1341 1272 1291 1317 1266 1257 1242 1287
1239 1281 1229 1228 1194 1160 1207 1233
1108 1254 1145 1151 1162 1089 1221 1169
1097 1096 1120 1131 1026 1038 1036 1161
1077 1100 1086 1031 1060 1010 1040 1081
1062 1045 1015 1012 973 981 1061 1015
1016 1055 1075 1118 1135 1133 1124 1083
1110 1082 1092 1081 1094 1112 1025 1022
1080 1035 929 979 961 1001 930 1064
964 1033 1025 944 1004 920 953 945
934 969 911 941 942 898 929 927
924 938 927 933 954 933 936 886
905 892 977 968 944 979 952 974
915 944 933 930 937 872 884 918
948 885 921 951 946 919 904 955
909 879 931 943 933 993 926 926
958 900 907 907 949 907 869 872
873 902 920 881 875 864 824 873
819 836 850 814 876 862 875 895
835 870 881 841 796 822 894 872
854 874 876 793 871 841 785 807
841 883 859 790 825 868 846 802
816 824 909 805 869 775 812 753
823 827 824 814 789 782 838 851
766 836 763 809 796 806 824 796
845 832 829 814 878 801 814 769
785 821 816 789 802 811 846 831
788 785 792 840 801 829 802 768
791 841 776 798 798 809 752 780
777 852 797 871 796 832 748 834
766 804 820 780 773 812 754 822
824 831 810 784 785 742 769 797
771 804 773 743 809 775 787 768
789 820 774 769 779 783 786 796
743 746 782 790 784 814 810 799
851 806 800 813 771 766 762 759
800 798 735 781 813 801 801 802
780 803 791 808 813 801 763 781
808 717 787 816 835 757 783 749
778 804 785 825 827 846 765 790
811 761 827 753 792 814 759 793
776 776 777 825 800 814 828 806
805 837 779 778 790 770 777 789
756 809 802 802 789 836 798 804
800 814 770 790 814 775 821 760
835 836 883 809 871 844 759 793
827 834 852 844 788 804 781 791
818 786 825 815 770 802 804 849
796 829 832 873 847 849 823 807
857 809 808 818 817 822 842 760
799 794 831 838 826 784 801 814
811 801 888 806 843 805 853 759
832 846 837 889 820 846 787 843
863 850 867 851 918 878 834 825
904 857 835 816 864 814 817 864
810 885 843 843 886 827 881 828
865 849 873 853 837 853 893 871
890 853 959 921 845 949 900 847
904 815 866 841 892 859 853 892
903 904 909 859 876 947 909 895
883 868 930 874 920 931 926 872
923 940 942 975 939 911 971 942
937 1006 926 931 954 1042 957 1072
1038 1024 1142 1155 1136 1115 1204 1124
1140 1173 1101 1101 1056 1006 1000 1043
1028 951 964 1070 996 1018 983 1090
1062 1069 1004 1116 1135 1141 1142 1149
1207 1204 1226 1258 1292 1255 1213 1229
1195 1160 1145 1120 1145 1073 979 1082
1058 1040 1023 1054 960 993 1099 996
1053 1093 1069 1054 1150 1118 1110 1089
1122 1141 1114 1104 1089 1121 1040 1123
1081 1112 1047 990 1060 1038 1058 1097
980 1063 1092 1086 1091 1068 1113 1072
1117 1111 1137 1138 1089 1083 1091 1097
1100 1098 1152 1131 1121 1169 1146 1153
1126 1228 1185 1172 1127 1157 1202 1151
1198 1186 1229 1211 1244 1218 1234 1180
1221 1231 1243 1303 1277 1288 1232 1297
1294 1293 1292 1304 1292 1316 1300 1305
1381 1317 1269 1262 1250 1266 1289 1238
1169 1178 1258 1164 1228 1230 1184 1193
1176 1180 1172 1169 1208 1221 1154 1173
1132 1201 1197 1101 1163 1148 1190 1120
1097 1138 1134 1189 1114 1173 1147 1205
1232 1242 1303 1369 1382 1409 1452 1413
1375 1375 1341 1311 1203 1192 1166 1119
1110 1039 1083 1007 1018 981 988 1021
1007 1017 998 973 1032 1056 1046 1091
1041 1057 1116 1084 1099 1018 1033 1044
1025 961 1013 986 950 984 907 969
935 933 902 924 977 911 947 903
956 965 858 897 949 911 950 911
877 897 868 868 857 849 912 833
874 886 886 854 904 921 869 887
844 889 819 918 892 888 850 851
859 855 854 885 854 854 832 785
837 860 802 885 795 870 828 825
829 832 809 816 857 895 803 876
797 829 857 800 813 841 815 820
759 819 808 855 846 824 846 834
788 794 833 805 794 816 837 811
839 830 833 840 806 834 770 830
805 786 764 863 839 862 772 764
828 821 851
;
_cod_data_source_file vx3013sup1.cif
_cod_data_source_block I
_cod_database_code 2023519
loop_
_symmetry_equiv_pos_as_xyz
x,y,z
-x,-y,-z
loop_
_atom_site_type_symbol
_atom_site_label
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
Ca Ca 0.5043(6) 0.2451(4) 0.2506(4) 0.0201(11) Uiso 1.00000
B B1 0.691(3) 0.191(2) 0.5625(13) 0.035(6) Uiso 1.00000
B B2 0.243(3) 0.6607(19) 0.0545(13) 0.035(6) Uiso 1.00000
F F1 0.5011(13) 0.7110(10) 0.4168(9) 0.0358(13) Uiso 1.00000
F F2 0.0935(10) 0.7473(10) 0.4062(8) 0.0358(13) Uiso 1.00000
F F3 0.3373(14) -0.0207(10) 0.3737(6) 0.0358(13) Uiso 1.00000
F F4 0.6916(14) 0.1862(10) 0.4474(6) 0.0358(13) Uiso 1.00000
F F5 0.5952(10) 0.2388(10) 0.9128(8) 0.0358(13) Uiso 1.00000
F F6 1.0087(12) 0.7163(10) 0.0753(8) 0.0358(13) Uiso 1.00000
F F7 0.2509(14) 0.6727(11) 0.9334(6) 0.0358(13) Uiso 1.00000
F F8 0.2706(13) 0.4841(10) 0.1123(7) 0.0358(13) Uiso 1.00000
O O1 0.8042(15) 0.0218(12) 0.2488(12) 0.0490(17) Uiso 1.00000
O O2 0.2003(15) 0.3521(17) 0.3682(8) 0.0490(17) Uiso 1.00000
O O3 0.2527(18) 0.1006(12) 0.1263(9) 0.0490(17) Uiso 1.00000
O O4 0.7263(16) 0.5128(12) 0.2635(10) 0.0490(17) Uiso 1.00000
H H11 0.929(6) 0.083(5) 0.237(4) 0.05066 Uiso 1.00000
H H12 0.836(8) -0.066(8) 0.303(7) 0.05066 Uiso 1.00000
H H21 0.075(6) 0.370(11) 0.324(2) 0.05066 Uiso 1.00000
H H22 0.131(7) 0.327(14) 0.4374(14) 0.05066 Uiso 1.00000
H H31 0.344(10) 0.044(5) 0.090(4) 0.05066 Uiso 1.00000
H H32 0.184(14) 0.179(8) 0.077(3) 0.05066 Uiso 1.00000
H H41 0.609(6) 0.576(5) 0.280(4) 0.05066 Uiso 1.00000
H H42 0.809(10) 0.593(5) 0.217(7) 0.05066 Uiso 1.00000
loop_
_atom_type_symbol
_atom_type_scat_Cromer_Mann_a1
_atom_type_scat_Cromer_Mann_a2
_atom_type_scat_Cromer_Mann_a3
_atom_type_scat_Cromer_Mann_a4
_atom_type_scat_Cromer_Mann_b1
_atom_type_scat_Cromer_Mann_b2
_atom_type_scat_Cromer_Mann_b3
_atom_type_scat_Cromer_Mann_b4
_atom_type_scat_Cromer_Mann_c
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Ca+2 15.63480 7.95180 8.43720 0.85370 -0.00740 0.60890 10.31160 25.99050
-14.87500 0.36410 1.28600
International_Tables_for_Crystallography_Vol.C(1991)_Tables_6.1.1.4_and_6.1.1.5
B+3 0.88550 0.03653 0.65726 0.37565 1.01233 4.18135 0.34702 2.16388 0.04506
0.00800 0.00400
International_Tables_for_Crystallography_Vol.C(1991)_Tables_6.1.1.4_and_6.1.1.5
F-1 3.63220 3.51057 1.26064 0.94071 5.27756 14.73530 0.44226 47.34370 0.65340
0.06900 0.05300
International_Tables_for_Crystallography_Vol.C(1991)_Tables_6.1.1.4_and_6.1.1.5
O-2 4.75800 3.63700 0.00000 0.00000 7.83100 30.05000 0.00000 0.00000 1.59400
0.04700 0.03200
International_Tables_for_Crystallography_Vol.C(1991)_Tables_6.1.1.4_and_6.1.1.5
H 0.49300 0.32291 0.14019 0.04081 10.51090 26.12570 3.14236 57.79970 0.00304
0.00000 0.00000
International_Tables_for_Crystallography_Vol.C(1991)_Tables_6.1.1.4_and_6.1.1.5
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle
F3 Ca F4 1_555 1_555 69.9(4)
F3 Ca F7 1_555 2_666 138.3(5)
F3 Ca F8 1_555 1_555 126.0(5)
F3 Ca O1 1_555 1_555 75.9(5)
F3 Ca O2 1_555 1_555 74.8(5)
F3 Ca O3 1_555 1_555 71.9(5)
F3 Ca O4 1_555 1_555 141.2(6)
F4 Ca F7 1_555 2_666 122.1(5)
F4 Ca F8 1_555 1_555 140.4(5)
F4 Ca O1 1_555 1_555 74.5(5)
F4 Ca O2 1_555 1_555 77.0(5)
F4 Ca O3 1_555 1_555 140.9(3)
F4 Ca O4 1_555 1_555 73.2(4)
F7 Ca F8 2_666 1_555 72.9(4)
F7 Ca O1 2_666 1_555 70.8(4)
F7 Ca O2 2_666 1_555 143.9(6)
F7 Ca O3 2_666 1_555 82.5(5)
F7 Ca O4 2_666 1_555 73.3(5)
F8 Ca O1 1_555 1_555 140.4(6)
F8 Ca O2 1_555 1_555 74.2(5)
F8 Ca O3 1_555 1_555 72.0(5)
F8 Ca O4 1_555 1_555 78.1(5)
O1 Ca O2 1_555 1_555 144.6(8)
O1 Ca O3 1_555 1_555 88.3(6)
O1 Ca O4 1_555 1_555 105.4(6)
O2 Ca O3 1_555 1_555 101.1(7)
O2 Ca O4 1_555 1_555 85.8(5)
O3 Ca O4 1_555 1_555 146.0(7)
F1 B1 F2 2_666 2_666 113.3(13)
F1 B1 F3 2_666 2_656 107.9(12)
F1 B1 F4 2_666 1_555 108.2(14)
F2 B1 F3 2_666 2_656 108.5(12)
F2 B1 F4 2_666 1_555 110.8(13)
F3 B1 F4 2_656 1_555 108.1(12)
F5 B2 F6 2_666 1_455 111.8(12)
F5 B2 F7 2_666 1_554 111.4(14)
F5 B2 F8 2_666 1_555 111.9(13)
F6 B2 F7 1_455 1_554 104.2(13)
F6 B2 F8 1_455 1_555 107.7(12)
F7 B2 F8 1_554 1_555 109.5(11)
H11 O1 H12 1_555 1_555 107(4)
H21 O2 H22 1_555 1_555 100(4)
H31 O3 H32 1_555 1_555 107(10)
H41 O4 H42 1_555 1_555 101(4)
O1 H11 O3 1_555 1_655 138(3)
F2 H12 O1 1_645 1_555 151(5)
O2 H21 O4 1_555 1_455 152(3)
F2 H22 O2 2_566 1_555 170(2)
F5 H31 O3 2_656 1_555 135(4)
F6 H32 O3 2_665 1_555 156(4)
F1 H41 O4 1_555 1_555 139(3)
F6 H42 O4 1_555 1_555 161(4)
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_site_symmetry_2
_geom_bond_distance
Ca F3 1_555 2.422(8)
Ca F4 1_555 2.468(8)
Ca F7 2_666 2.496(8)
Ca F8 1_555 2.501(8)
Ca O1 1_555 2.357(10)
Ca O2 1_555 2.399(11)
Ca O3 1_555 2.461(12)
Ca O4 1_555 2.450(10)
B1 F1 2_666 1.336(18)
B1 F2 2_666 1.371(18)
B1 F3 2_656 1.368(16)
B1 F4 1_555 1.350(17)
B2 F5 2_666 1.305(18)
B2 F6 1_455 1.388(18)
B2 F7 1_554 1.394(17)
B2 F8 1_555 1.382(15)
F1 F2 1_555 2.261(9)
F1 F3 1_565 2.186(10)
F1 F4 2_666 2.176(13)
F2 F3 1_565 2.222(10)
F2 F4 2_666 2.239(12)
F3 F4 2_656 2.199(9)
F5 F6 2_766 2.231(9)
F5 F7 2_667 2.230(12)
F5 F8 2_666 2.227(11)
F6 F7 1_654 2.195(11)
F6 F8 1_655 2.237(10)
F7 F8 1_556 2.266(10)
O1 H11 1_555 0.84(4)
O1 H12 1_555 0.83(6)
O2 H21 1_555 0.86(3)
O2 H22 1_555 0.87(2)
O3 H31 1_555 0.83(5)
O3 H32 1_555 0.82(5)
O4 H41 1_555 0.85(4)
O4 H42 1_555 0.86(5)
H11 H12 1_555 1.34(7)
H21 H22 1_555 1.33(3)
H31 H32 1_555 1.33(8)
H41 H42 1_555 1.31(7)
F1 H41 1_555 2.15(5)
F2 H12 1_465 2.17(6)
F2 H22 2_566 2.17(3)
F5 H31 2_656 2.20(4)
F6 H32 2_665 2.07(5)
F6 H42 1_555 2.04(7)
O3 H11 1_455 2.19(4)
O4 H21 1_655 2.23(5)
loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_site_symmetry_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_publ_flag
O1 H11 O3 1_655 0.84(4) 2.19(4) 2.859(14) 138(4) yes
O1 H12 F2 1_645 0.83(7) 2.17(6) 2.925(14) 151(5) yes
O2 H21 O4 1_455 0.86(3) 2.23(5) 3.015(13) 152(6) yes
O2 H22 F2 2_566 0.88(2) 2.18(3) 3.041(12) 170(7) yes
O3 H31 F5 2_656 0.83(5) 2.20(4) 2.847(12) 136(4) yes
O3 H32 F6 2_665 0.82(5) 2.07(5) 2.845(13) 156(6) yes
O4 H41 F1 . 0.85(4) 2.16(4) 2.848(13) 139(4) yes
O4 H42 F6 . 0.86(6) 2.05(7) 2.873(13) 161(6) yes
_cod_database_fobs_code 2023519