#------------------------------------------------------------------------------ #$Date: 2020-06-05 13:15:57 +0300 (Fri, 05 Jun 2020) $ #$Revision: 252726 $ #$URL: file:///home/coder/svn-repositories/cod/cif/1/55/77/1557765.cif $ #------------------------------------------------------------------------------ # # This file is available in the Crystallography Open Database (COD), # http://www.crystallography.net/ # # All data on this site have been placed in the public domain by the # contributors. # data_1557765 loop_ _publ_author_name 'Cliffe, Matthew J.' 'Keyzer, Evan N.' 'Bond, Andrew D.' 'Astle, Maxwell A.' 'Grey, Clare P.' _publ_section_title ; The structures of ordered defects in thiocyanate analogues of Prussian Blue ; _journal_issue 17 _journal_name_full 'Chemical Science' _journal_page_first 4430 _journal_paper_doi 10.1039/D0SC01246G _journal_volume 11 _journal_year 2020 _chemical_formula_moiety 'C12 Bi2 N12 S12 Zn3' _chemical_formula_sum 'C12 Bi2 N12 S12 Zn3' _chemical_formula_weight 1311.03 _chemical_name_systematic 'zinc(II) hexathiocyantosbismuthate(III)' _space_group_crystal_system monoclinic _space_group_IT_number 15 _space_group_name_Hall '-C 2yc' _space_group_name_H-M_alt 'C 1 2/c 1' _atom_sites_solution_primary dual _audit_creation_date 2018-04-20 _audit_creation_method ; Olex2 1.2 (compiled Mar 28 2017 19:26:29 for OlexSys, GUI svn.r5337) ; _audit_update_record ; 2020-02-27 deposited with the CCDC. 2020-04-09 downloaded from the CCDC. ; _cell_angle_alpha 90 _cell_angle_beta 93.6300(10) _cell_angle_gamma 90 _cell_formula_units_Z 4 _cell_length_a 26.3104(4) _cell_length_b 8.45870(10) _cell_length_c 15.7403(3) _cell_measurement_reflns_used 4170 _cell_measurement_temperature 109 _cell_measurement_theta_max 27.485 _cell_measurement_theta_min 0.998 _cell_volume 3496.00(9) _computing_molecular_graphics 'Olex2 (Dolomanov et al., 2009)' _computing_publication_material 'Olex2 (Dolomanov et al., 2009)' _computing_structure_refinement 'ShelXL (Sheldrick, 2015)' _computing_structure_solution 'ShelXT (Sheldrick, 2015)' _diffrn_ambient_temperature 109 _diffrn_detector 'CCD plate' _diffrn_detector_type 'CCD area detector' _diffrn_measured_fraction_theta_full 0.997 _diffrn_measured_fraction_theta_max 0.991 _diffrn_measurement_device Area _diffrn_measurement_device_type 'Nonius KappaCCD' _diffrn_measurement_method \w/2\q _diffrn_radiation_monochromator graphite _diffrn_radiation_probe x-ray _diffrn_radiation_type MoK\a _diffrn_radiation_wavelength 0.71073 _diffrn_reflns_av_R_equivalents 0.0288 _diffrn_reflns_av_unetI/netI 0.0346 _diffrn_reflns_Laue_measured_fraction_full 0.997 _diffrn_reflns_Laue_measured_fraction_max 0.991 _diffrn_reflns_limit_h_max 34 _diffrn_reflns_limit_h_min -33 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_l_max 20 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_number 7507 _diffrn_reflns_point_group_measured_fraction_full 0.997 _diffrn_reflns_point_group_measured_fraction_max 0.991 _diffrn_reflns_theta_full 25.242 _diffrn_reflns_theta_max 27.505 _diffrn_reflns_theta_min 3.538 _diffrn_source 'fine-focus sealed tube' _exptl_absorpt_coefficient_mu 12.807 _exptl_absorpt_correction_T_max 1.0 _exptl_absorpt_correction_T_min 0.55 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details 'DENZO/SCALEPACK (Otwinowski & Minor, 1997)' _exptl_crystal_colour orange _exptl_crystal_colour_primary orange _exptl_crystal_density_diffrn 2.491 _exptl_crystal_description block _exptl_crystal_F_000 2416 _exptl_crystal_preparation 'precipitated from solution' _exptl_crystal_size_max 0.12 _exptl_crystal_size_mid 0.1 _exptl_crystal_size_min 0.05 _refine_diff_density_max 1.161 _refine_diff_density_min -1.545 _refine_diff_density_rms 0.166 _refine_ls_extinction_method none _refine_ls_goodness_of_fit_ref 1.067 _refine_ls_hydrogen_treatment undef _refine_ls_matrix_type full _refine_ls_number_parameters 189 _refine_ls_number_reflns 3975 _refine_ls_number_restraints 0 _refine_ls_restrained_S_all 1.067 _refine_ls_R_factor_all 0.0336 _refine_ls_R_factor_gt 0.0259 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 _refine_ls_structure_factor_coef Fsqd _refine_ls_weighting_details 'w=1/[\s^2^(Fo^2^)+(0.0238P)^2^+15.7967P] where P=(Fo^2^+2Fc^2^)/3' _refine_ls_weighting_scheme calc _refine_ls_wR_factor_gt 0.0568 _refine_ls_wR_factor_ref 0.0596 _reflns_Friedel_coverage 0.000 _reflns_number_gt 3471 _reflns_number_total 3975 _reflns_threshold_expression 'I > 2\s(I)' _cod_data_source_file d0sc01246g3.cif _cod_data_source_block 5_al_Zn3Bi2SCN12_C2c _cod_depositor_comments 'Adding full bibliography for 1557765--1557770.cif.' _cod_database_code 1557765 _shelx_shelxl_version_number 2014/7 _shelx_space_group_comment ; The symmetry employed for this shelxl refinement is uniquely defined by the following loop, which should always be used as a source of symmetry information in preference to the above space-group names. They are only intended as comments. ; _olex2_refinement_description ; ; _shelx_res_file ; import.res created by SHELXL-2014/7 TITL import_a.res in C2/c REM Old TITL import in C2/n #15 REM SHELXT solution in C2/c REM R1 0.072, Rweak 0.003, Alpha 0.015, Orientation as input REM Formula found by SHELXT: Zn3 Bi2 S12 C12 N12 CELL 0.71073 26.3104 8.4587 15.7403 90 93.63 90 ZERR 4 0.0004 0.0001 0.0003 0 0.001 0 LATT 7 SYMM -X,+Y,0.5-Z SFAC Bi C N S Zn UNIT 8 48 48 48 12 L.S. 10 PLAN 20 TEMP -93.15 BOND $H LIST 6 fmap 2 acta OMIT 4 0 0 OMIT 0 0 2 OMIT 1 1 0 OMIT -2 0 2 OMIT 2 0 2 OMIT -1 1 1 OMIT 3 1 0 OMIT 1 1 1 OMIT 3 1 1 OMIT 2 0 0 REM REM REM WGHT 0.023800 15.796700 FVAR 0.07815 BI2 1 0.500000 0.500000 0.500000 10.50000 0.01379 0.01486 = 0.01768 0.00116 0.00218 0.00117 BI1 1 0.750000 -0.250000 0.500000 10.50000 0.02104 0.01685 = 0.01436 0.00246 0.00194 0.00289 ZN1 5 0.674312 0.258863 0.315172 11.00000 0.01800 0.01708 = 0.01411 -0.00003 0.00024 0.00105 ZN2 5 0.500000 1.015228 0.250000 10.50000 0.02727 0.01569 = 0.02209 0.00000 -0.00497 0.00000 S2 4 0.708948 0.803570 0.330352 11.00000 0.03072 0.01665 = 0.02154 0.00246 -0.00063 -0.00175 S1 4 0.814355 0.008712 0.467889 11.00000 0.01707 0.02797 = 0.02771 0.00565 -0.00469 0.00091 S3 4 0.540488 0.189471 0.501050 11.00000 0.02426 0.01865 = 0.02974 0.00251 0.01092 0.00225 S4 4 0.674170 0.029593 0.041831 11.00000 0.03416 0.03568 = 0.02074 -0.01195 0.00921 -0.01398 S6 4 0.562192 1.484826 0.153277 11.00000 0.03112 0.02935 = 0.02660 0.00408 -0.00316 -0.00844 S5 4 0.584285 0.624307 0.420734 11.00000 0.01767 0.04334 = 0.06330 0.03588 0.00945 0.00743 N2 3 0.687074 0.483733 0.298382 11.00000 0.02676 0.02117 = 0.01639 0.00002 -0.00133 0.00127 N1 3 0.734110 0.172032 0.381121 11.00000 0.02211 0.02066 = 0.02075 0.00160 0.00067 0.00301 N5 3 0.538441 0.873152 0.328723 11.00000 0.03241 0.02436 = 0.02812 0.00298 0.00091 -0.00011 N4 3 0.666933 0.148514 0.206185 11.00000 0.01914 0.02403 = 0.01878 -0.00194 0.00294 0.00026 N3 3 0.614297 0.227201 0.381740 11.00000 0.02075 0.02127 = 0.01972 -0.00125 0.00117 0.00221 N6 3 0.542059 1.167522 0.191165 11.00000 0.03038 0.03103 = 0.03138 0.00875 -0.00847 -0.00435 C1 2 0.767202 0.106940 0.416873 11.00000 0.01766 0.01893 = 0.02099 -0.00230 0.00229 -0.00320 C5 2 0.557096 0.769304 0.366760 11.00000 0.02115 0.01890 = 0.02467 0.00254 0.00461 0.00051 C6 2 0.550063 1.298079 0.175066 11.00000 0.02061 0.04013 = 0.02060 0.00515 0.00008 0.00007 C4 2 0.669746 0.099264 0.138749 11.00000 0.01363 0.02058 = 0.02448 -0.00259 -0.00002 0.00026 C2 2 0.696486 0.615356 0.311602 11.00000 0.01724 0.02311 = 0.01652 0.00087 0.00519 0.00283 C3 2 0.583953 0.213552 0.430759 11.00000 0.02499 0.01293 = 0.02004 -0.00444 -0.00425 -0.00093 HKLF 4 REM import_a.res in C2/c REM R1 = 0.0259 for 3471 Fo > 4sig(Fo) and 0.0336 for all 3975 data REM 189 parameters refined using 0 restraints END WGHT 0.0238 15.7915 REM Highest difference peak 1.161, deepest hole -1.545, 1-sigma level 0.166 Q1 1 0.7500 0.2500 0.5000 10.50000 0.05 1.16 Q2 1 0.4591 0.5986 0.4792 11.00000 0.05 1.03 Q3 1 0.5000 0.0000 0.5000 10.50000 0.05 1.00 Q4 1 0.5405 0.5926 0.5208 11.00000 0.05 0.92 Q5 1 0.7085 -0.3502 0.4793 11.00000 0.05 0.88 Q6 1 0.7902 -0.3421 0.5176 11.00000 0.05 0.86 Q7 1 0.7503 -0.3621 0.5002 11.00000 0.05 0.76 Q8 1 0.5000 0.6154 0.5007 11.00000 0.05 0.73 Q9 1 0.5763 0.9977 0.1825 11.00000 0.05 0.67 Q10 1 0.5850 0.6718 0.4619 11.00000 0.05 0.61 Q11 1 0.4530 0.5070 0.5340 11.00000 0.05 0.61 Q12 1 0.6931 0.0805 -0.0578 11.00000 0.05 0.58 Q13 1 0.5630 0.3772 0.4603 11.00000 0.05 0.57 Q14 1 0.7883 -0.0527 0.5604 11.00000 0.05 0.55 Q15 1 0.6993 -0.2427 0.5249 11.00000 0.05 0.51 Q16 1 0.5521 1.3465 0.0815 11.00000 0.05 0.51 Q17 1 0.7731 -0.2462 0.5174 11.00000 0.05 0.50 Q18 1 0.5689 0.6393 0.5211 11.00000 0.05 0.50 Q19 1 0.7292 0.7463 0.4043 11.00000 0.05 0.49 Q20 1 0.6799 0.1752 0.1437 11.00000 0.05 0.49 ; _shelx_res_checksum 38255 _olex2_submission_special_instructions 'No special instructions were received' loop_ _space_group_symop_operation_xyz 'x, y, z' '-x, y, -z+1/2' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y, z-1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z-1/2' loop_ _atom_site_label _atom_site_type_symbol _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 _atom_site_site_symmetry_order _atom_site_calc_flag _atom_site_refinement_flags_posn _atom_site_refinement_flags_adp _atom_site_refinement_flags_occupancy _atom_site_disorder_assembly _atom_site_disorder_group Bi2 Bi 0.5000 0.5000 0.5000 0.01540(7) Uani 1 2 d S T P . . Bi1 Bi 0.7500 -0.2500 0.5000 0.01738(7) Uani 1 2 d S T P . . Zn1 Zn 0.67431(2) 0.25886(6) 0.31517(3) 0.01643(11) Uani 1 1 d . . . . . Zn2 Zn 0.5000 1.01523(8) 0.2500 0.02196(16) Uani 1 2 d S T P . . S2 S 0.70895(5) 0.80357(13) 0.33035(7) 0.0231(2) Uani 1 1 d . . . . . S1 S 0.81435(4) 0.00871(14) 0.46789(7) 0.0245(2) Uani 1 1 d . . . . . S3 S 0.54049(4) 0.18947(13) 0.50105(7) 0.0238(2) Uani 1 1 d . . . . . S4 S 0.67417(5) 0.02959(15) 0.04183(7) 0.0299(3) Uani 1 1 d . . . . . S6 S 0.56219(5) 1.48483(15) 0.15328(8) 0.0292(3) Uani 1 1 d . . . . . S5 S 0.58429(5) 0.62431(17) 0.42073(10) 0.0411(4) Uani 1 1 d . . . . . N2 N 0.68707(15) 0.4837(4) 0.2984(2) 0.0216(8) Uani 1 1 d . . . . . N1 N 0.73411(14) 0.1720(4) 0.3811(2) 0.0212(8) Uani 1 1 d . . . . . N5 N 0.53844(16) 0.8732(5) 0.3287(2) 0.0283(9) Uani 1 1 d . . . . . N4 N 0.66693(14) 0.1485(4) 0.2062(2) 0.0206(8) Uani 1 1 d . . . . . N3 N 0.61430(14) 0.2272(4) 0.3817(2) 0.0206(8) Uani 1 1 d . . . . . N6 N 0.54206(16) 1.1675(5) 0.1912(3) 0.0314(10) Uani 1 1 d . . . . . C1 C 0.76720(17) 0.1069(5) 0.4169(3) 0.0191(9) Uani 1 1 d . . . . . C5 C 0.55710(17) 0.7693(5) 0.3668(3) 0.0214(9) Uani 1 1 d . . . . . C6 C 0.55006(18) 1.2981(6) 0.1751(3) 0.0272(11) Uani 1 1 d . . . . . C4 C 0.66975(16) 0.0993(5) 0.1387(3) 0.0196(9) Uani 1 1 d . . . . . C2 C 0.69649(16) 0.6154(5) 0.3116(3) 0.0188(9) Uani 1 1 d . . . . . C3 C 0.58395(18) 0.2136(5) 0.4308(3) 0.0196(9) Uani 1 1 d . . . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Bi2 0.01379(11) 0.01486(12) 0.01768(11) 0.00116(8) 0.00218(8) 0.00117(9) Bi1 0.02104(13) 0.01685(12) 0.01436(11) 0.00246(8) 0.00194(9) 0.00289(9) Zn1 0.0180(3) 0.0171(3) 0.0141(2) -0.00003(19) 0.00024(19) 0.0010(2) Zn2 0.0273(4) 0.0157(4) 0.0221(4) 0.000 -0.0050(3) 0.000 S2 0.0307(6) 0.0167(5) 0.0215(5) 0.0025(4) -0.0006(5) -0.0017(5) S1 0.0171(5) 0.0280(6) 0.0277(6) 0.0057(5) -0.0047(4) 0.0009(5) S3 0.0243(6) 0.0186(6) 0.0297(6) 0.0025(5) 0.0109(5) 0.0023(5) S4 0.0342(7) 0.0357(7) 0.0207(6) -0.0120(5) 0.0092(5) -0.0140(6) S6 0.0311(7) 0.0294(7) 0.0266(6) 0.0041(5) -0.0032(5) -0.0084(5) S5 0.0177(6) 0.0433(8) 0.0633(9) 0.0359(7) 0.0095(6) 0.0074(6) N2 0.027(2) 0.021(2) 0.0164(18) 0.0000(15) -0.0013(15) 0.0013(16) N1 0.022(2) 0.0207(19) 0.0208(19) 0.0016(15) 0.0007(16) 0.0030(16) N5 0.032(2) 0.024(2) 0.028(2) 0.0030(18) 0.0009(18) -0.0001(18) N4 0.0191(19) 0.024(2) 0.0188(18) -0.0019(15) 0.0029(15) 0.0003(16) N3 0.021(2) 0.0213(19) 0.0197(18) -0.0013(15) 0.0012(16) 0.0022(16) N6 0.030(2) 0.031(2) 0.031(2) 0.0088(19) -0.0085(18) -0.0043(19) C1 0.018(2) 0.019(2) 0.021(2) -0.0023(18) 0.0023(18) -0.0032(18) C5 0.021(2) 0.019(2) 0.025(2) 0.0025(19) 0.0046(19) 0.0005(19) C6 0.021(2) 0.040(3) 0.021(2) 0.005(2) 0.0001(19) 0.000(2) C4 0.014(2) 0.021(2) 0.024(2) -0.0026(18) 0.0000(17) 0.0003(17) C2 0.017(2) 0.023(2) 0.017(2) 0.0009(18) 0.0052(17) 0.0028(18) C3 0.025(2) 0.013(2) 0.020(2) -0.0044(17) -0.0043(19) -0.0009(18) loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source Bi Bi -4.1077 10.2566 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Zn Zn 0.2839 1.4301 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag S3 Bi2 S3 180.0 . 5_666 ? S6 Bi2 S3 80.81(3) 2_645 5_666 ? S6 Bi2 S3 80.81(3) 6_576 . ? S6 Bi2 S3 99.19(3) 6_576 5_666 ? S6 Bi2 S3 99.19(3) 2_645 . ? S6 Bi2 S6 180.0 6_576 2_645 ? S5 Bi2 S3 92.43(4) . . ? S5 Bi2 S3 92.43(4) 5_666 5_666 ? S5 Bi2 S3 87.57(4) 5_666 . ? S5 Bi2 S3 87.57(4) . 5_666 ? S5 Bi2 S6 93.91(4) . 2_645 ? S5 Bi2 S6 86.09(4) . 6_576 ? S5 Bi2 S6 93.91(4) 5_666 6_576 ? S5 Bi2 S6 86.09(4) 5_666 2_645 ? S5 Bi2 S5 180.00(6) 5_666 . ? S2 Bi1 S2 180.0 7_656 1_545 ? S1 Bi1 S2 95.43(3) 7_646 1_545 ? S1 Bi1 S2 84.57(3) 7_646 7_656 ? S1 Bi1 S2 84.57(3) . 1_545 ? S1 Bi1 S2 95.43(3) . 7_656 ? S1 Bi1 S1 180.0 . 7_646 ? S1 Bi1 S4 91.67(4) 7_646 6_556 ? S1 Bi1 S4 91.67(4) . 4_645 ? S1 Bi1 S4 88.33(4) 7_646 4_645 ? S1 Bi1 S4 88.33(4) . 6_556 ? S4 Bi1 S2 96.73(3) 4_645 1_545 ? S4 Bi1 S2 83.27(3) 4_645 7_656 ? S4 Bi1 S2 96.73(3) 6_556 7_656 ? S4 Bi1 S2 83.27(3) 6_556 1_545 ? S4 Bi1 S4 180.00(4) 6_556 4_645 ? N2 Zn1 N1 107.21(16) . . ? N2 Zn1 N3 110.81(15) . . ? N4 Zn1 N2 110.81(15) . . ? N4 Zn1 N1 108.44(15) . . ? N4 Zn1 N3 111.37(15) . . ? N3 Zn1 N1 108.03(15) . . ? N5 Zn2 N5 104.4(2) 2_655 . ? N5 Zn2 N6 112.76(17) . 2_655 ? N5 Zn2 N6 114.57(17) 2_655 2_655 ? N5 Zn2 N6 112.76(17) 2_655 . ? N5 Zn2 N6 114.57(17) . . ? N6 Zn2 N6 98.2(3) . 2_655 ? C2 S2 Bi1 94.21(15) . 1_565 ? C1 S1 Bi1 92.07(15) . . ? C3 S3 Bi2 99.07(16) . . ? C4 S4 Bi1 94.12(16) . 4_655 ? C6 S6 Bi2 96.40(17) . 2_665 ? C5 S5 Bi2 100.36(16) . . ? C2 N2 Zn1 161.8(3) . . ? C1 N1 Zn1 173.2(4) . . ? C5 N5 Zn2 168.3(4) . . ? C4 N4 Zn1 168.1(4) . . ? C3 N3 Zn1 170.0(4) . . ? C6 N6 Zn2 147.6(4) . . ? N1 C1 S1 178.6(4) . . ? N5 C5 S5 179.1(5) . . ? N6 C6 S6 179.1(5) . . ? N4 C4 S4 179.5(5) . . ? N2 C2 S2 179.1(4) . . ? N3 C3 S3 178.7(4) . . ? loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Bi2 S3 2.8341(11) . ? Bi2 S3 2.8341(11) 5_666 ? Bi2 S6 2.8310(12) 6_576 ? Bi2 S6 2.8310(12) 2_645 ? Bi2 S5 2.8161(12) . ? Bi2 S5 2.8161(12) 5_666 ? Bi1 S2 2.8525(11) 7_656 ? Bi1 S2 2.8525(11) 1_545 ? Bi1 S1 2.8320(12) 7_646 ? Bi1 S1 2.8319(12) . ? Bi1 S4 2.8383(12) 4_645 ? Bi1 S4 2.8383(12) 6_556 ? Zn1 N2 1.952(4) . ? Zn1 N1 1.971(4) . ? Zn1 N4 1.952(4) . ? Zn1 N3 1.968(4) . ? Zn2 N5 1.961(4) 2_655 ? Zn2 N5 1.961(4) . ? Zn2 N6 1.968(4) . ? Zn2 N6 1.968(4) 2_655 ? S2 Bi1 2.8526(11) 1_565 ? S2 C2 1.648(5) . ? S1 C1 1.658(5) . ? S3 C3 1.653(5) . ? S4 Bi1 2.8383(12) 4_655 ? S4 C4 1.646(4) . ? S6 Bi2 2.8310(12) 2_665 ? S6 C6 1.652(5) . ? S5 C5 1.631(5) . ? N2 C2 1.157(6) . ? N1 C1 1.147(6) . ? N5 C5 1.155(6) . ? N4 C4 1.147(5) . ? N3 C3 1.151(6) . ? N6 C6 1.155(7) . ?