# Electronic Supplementary Material (ESI) for CrystEngComm # This journal is © The Royal Society of Chemistry 2011 data_global _journal_name_full CrystEngComm _journal_coden_Cambridge 1350 _journal_volume ? _journal_page_first ? _journal_year ? _publ_contact_author_name 'Prof. Zora Popovic' _publ_contact_author_email zpopovic@chem.pmf.hr _publ_section_title ; Coordination-driven self-assembly of thiocyanate complexes of Co(II), Ni(II) and Cu(II) with picolinamide: a structural and DFT study ; loop_ _publ_author_name M.Dakovic D.Vila-Vicosa M.Calhorda Z.Popovic # Attachment '- CIF files for compounds 1, 2 and 3.cif' #=============================================================================== data_[Co(NCS)2(pia)2] _database_code_depnum_ccdc_archive 'CCDC 784964' #=============================================================================== # 5. CHEMICAL DATA _chemical_name_systematic ; ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C14 H12 Co N6 O2 S2' _chemical_formula_structural ? _chemical_formula_sum 'C14 H12 Co N6 O2 S2' _chemical_formula_iupac ? _chemical_formula_weight 419.37 _chemical_compound_source 'see text' loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 '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' Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 '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' #=============================================================================== # 6. CRYSTAL DATA _symmetry_cell_setting Monoclinic _symmetry_space_group_name_Hall '-C 2yc' _symmetry_space_group_name_H-M 'C 2/c' _symmetry_Int_Tables_number 15 loop_ _symmetry_equiv_pos_site_id _symmetry_equiv_pos_as_xyz 1 x,y,z 2 -x,y,1/2-z 3 -x,-y,-z 4 x,-y,1/2+z 5 1/2+x,1/2+y,z 6 1/2-x,1/2+y,1/2-z 7 1/2-x,1/2-y,-z 8 1/2+x,1/2-y,1/2+z _cell_length_a 16.9550(10) _cell_length_b 8.2338(6) _cell_length_c 13.6300(10) _cell_angle_alpha 90 _cell_angle_beta 108.551(7) _cell_angle_gamma 90 _cell_volume 1803.9(2) _cell_formula_units_Z 4 _cell_measurement_temperature 296 _cell_measurement_reflns_used 7399 _cell_measurement_theta_min 3.7455 _cell_measurement_theta_max 36.5109 _cell_special_details ; ; _exptl_crystal_description plate _exptl_crystal_colour 'dark red' _exptl_crystal_size_max 0.352 _exptl_crystal_size_mid 0.259 _exptl_crystal_size_min 0.089 _exptl_crystal_size_rad ? _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.544 _exptl_crystal_density_method 'Not Measured' _exptl_crystal_F_000 852 _exptl_absorpt_coefficient_mu 1.203 _exptl_crystal_density_meas_temp ? # Permitted for _exptl_absorpt_correction_type : # analytical 'analytical from crystal shape' # Example: de Meulenaer&Tompa: ABST # cylinder 'cylindrical' # gaussian 'Gaussian from crystal shape' # Example: PLATON/ABSG # integration 'integration from crystal shape' # multi-scan 'symmetry-related measurements' # Example: SADABS, MULABS # none 'no absorption corr. applied' # numerical 'numerical from crystal shape' # psi-scan 'psi-scan corrections' # Example: PLATON/ABSP # refdelf 'refined from delta-F' # Example: SHELXA, DIFABS, DELABS # sphere 'spherical' # Example: PLATON/ABSS _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.31.5 (release 28-08-2006 CrysAlis171 .NET) (compiled Aug 28 2006,13:05:05) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. ; _exptl_absorpt_correction_T_min 0.692 _exptl_absorpt_correction_T_max 0.895 #=============================================================================== # 7. EXPERIMENTAL DATA _exptl_special_details ; ; _diffrn_ambient_temperature 296 _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_probe x-ray _diffrn_radiation_type MoK\a _diffrn_radiation_source 'Enhance (Mo) X-ray Source' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type ; Oxford Diffration Xcalibur diffractometer with Saphirre3 detector ; _diffrn_measurement_method CCD _diffrn_detector_area_resol_mean 16.3426 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? loop_ _diffrn_standard_refln_index_h _diffrn_standard_refln_index_k _diffrn_standard_refln_index_l ? ? ? # number of measured reflections (redundant set) _diffrn_reflns_number 18396 _diffrn_reflns_av_R_equivalents 0.0244 _diffrn_reflns_av_sigmaI/netI 0.0219 _diffrn_reflns_limit_h_min -23 _diffrn_reflns_limit_h_max 23 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 3.89 _diffrn_reflns_theta_max 30.00 _diffrn_reflns_theta_full 30.00 _diffrn_measured_fraction_theta_max 0.996 _diffrn_measured_fraction_theta_full 0.996 _diffrn_reflns_reduction_process ; ; # number of unique reflections _reflns_number_total 2624 # number of observed reflections (> n sig(I)) _reflns_number_gt 1781 _reflns_threshold_expression I>2\s(I) _computing_data_collection ; CrysAlis CCD, Oxford Diffraction Ltd., Version 1.171.31.5 (release 28-08-2006 CrysAlis171 .NET) (compiled Aug 28 2006,13:05:05) ; _computing_cell_refinement ; CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.31.5 (release 28-08-2006 CrysAlis171 .NET) (compiled Aug 28 2006,13:05:05) ; _computing_data_reduction ; CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.31.5 (release 28-08-2006 CrysAlis171 .NET) (compiled Aug 28 2006,13:05:05) ; _computing_structure_solution 'SHELXL-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material 'PLATON (Spek, 2003)' #=============================================================================== # 8. REFINEMENT DATA _refine_special_details ; Refinement on F^2^ for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating -R-factor-obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0483P)^2^] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom # Permitted for _refine_ls_hydrogen_treatment : # refall - refined all H parameters # refxyz - refined H coordinates only # refU - refined H U only # noref - no refinement of H parameters # constr - H parameters constrained # mixed - some constrained, some independent # undef - H-atom parameters not defined _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_abs_structure_details ? _refine_ls_abs_structure_Flack . _refine_ls_number_reflns 2614 _refine_ls_number_parameters 122 _refine_ls_number_restraints 0 _refine_ls_number_constraints ? _refine_ls_R_factor_all 0.0473 _refine_ls_R_factor_gt 0.0293 _refine_ls_wR_factor_ref 0.0856 _refine_ls_wR_factor_gt 0.0761 _refine_ls_goodness_of_fit_ref 1.041 _refine_ls_restrained_S_all 1.041 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 _refine_diff_density_max 0.330 _refine_diff_density_min -0.289 _refine_diff_density_rms 0.044 #=============================================================================== # 9. ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS loop_ _atom_site_label _atom_site_type_symbol _atom_site_thermal_displace_type _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_occupancy _atom_site_U_iso_or_equiv _atom_site_calc_flag _atom_site_refinement_flags Co1 Co Uani 0.50000 0.21816(4) 0.25000 1.000 0.0471(1) . . S1 S Uani 0.26709(3) -0.14946(7) 0.19783(4) 1.000 0.0726(2) . . O1 O Uani 0.40862(7) 0.40338(15) 0.19847(9) 1.000 0.0592(4) . . N1 N Uani 0.40389(9) 0.05144(18) 0.21935(11) 1.000 0.0591(5) . . N2 N Uani 0.49101(8) 0.25184(15) 0.09256(9) 1.000 0.0451(4) . . N3 N Uani 0.31424(11) 0.5094(3) 0.05935(17) 1.000 0.0794(7) . . C1 C Uani 0.34674(10) -0.0304(2) 0.20968(11) 1.000 0.0491(5) . . C2 C Uani 0.42669(9) 0.3443(2) 0.03715(11) 1.000 0.0462(4) . . C3 C Uani 0.40949(11) 0.3706(2) -0.06709(12) 1.000 0.0559(6) . . C4 C Uani 0.46072(13) 0.3023(2) -0.11663(13) 1.000 0.0614(6) . . C5 C Uani 0.52706(13) 0.2110(2) -0.06068(14) 1.000 0.0633(7) . . C6 C Uani 0.54020(11) 0.1872(2) 0.04437(13) 1.000 0.0542(6) . . C7 C Uani 0.38116(10) 0.4203(2) 0.10335(13) 1.000 0.0535(5) . . H3 H Uiso 0.36410 0.43340 -0.10360 1.000 0.0670 calc R H4 H Uiso 0.45020 0.31810 -0.18720 1.000 0.0740 calc R H5 H Uiso 0.56300 0.16540 -0.09240 1.000 0.0760 calc R H6 H Uiso 0.58500 0.12380 0.08210 1.000 0.0650 calc R H13N H Uiso 0.2970(16) 0.530(3) -0.006(2) 1.000 0.098(8) . . H23N H Uiso 0.2903(15) 0.561(3) 0.0950(18) 1.000 0.083(7) . . 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 Co1 0.0474(2) 0.0570(2) 0.0387(2) 0.0000 0.0162(1) 0.0000 S1 0.0482(3) 0.0740(3) 0.0884(4) 0.0142(3) 0.0115(2) -0.0050(2) O1 0.0598(7) 0.0714(8) 0.0471(6) -0.0045(5) 0.0180(5) 0.0134(6) N1 0.0574(8) 0.0684(10) 0.0538(8) -0.0044(7) 0.0211(7) -0.0068(7) N2 0.0487(7) 0.0485(7) 0.0403(6) -0.0025(5) 0.0171(5) -0.0015(5) N3 0.0624(10) 0.1078(15) 0.0642(11) 0.0029(10) 0.0147(9) 0.0312(10) C1 0.0472(9) 0.0583(10) 0.0412(7) -0.0004(7) 0.0132(6) 0.0080(7) C2 0.0463(8) 0.0469(8) 0.0424(7) -0.0047(6) 0.0101(6) -0.0063(7) C3 0.0605(10) 0.0585(11) 0.0420(8) -0.0022(7) 0.0070(7) -0.0053(8) C4 0.0807(12) 0.0621(11) 0.0413(8) -0.0037(8) 0.0194(8) -0.0131(9) C5 0.0886(13) 0.0586(11) 0.0569(10) -0.0096(8) 0.0431(10) -0.0057(9) C6 0.0615(10) 0.0538(10) 0.0534(9) -0.0012(7) 0.0269(8) 0.0024(7) C7 0.0475(9) 0.0607(10) 0.0503(9) -0.0027(7) 0.0128(7) 0.0004(7) #=============================================================================== # 10. MOLECULAR GEOMETRY _geom_special_details ; Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_1 _geom_bond_site_symmetry_2 _geom_bond_publ_flag Co1 O1 2.1277(13) . . yes Co1 N1 2.0691(16) . . yes Co1 N2 2.1206(12) . . yes Co1 O1 2.1277(13) . 2_655 yes Co1 N1 2.0691(16) . 2_655 yes Co1 N2 2.1206(12) . 2_655 yes S1 C1 1.6347(18) . . yes O1 C7 1.238(2) . . yes N1 C1 1.153(2) . . yes N2 C2 1.347(2) . . yes N2 C6 1.326(2) . . yes N3 C7 1.324(3) . . yes N3 H23N 0.84(3) . . no N3 H13N 0.86(3) . . no C2 C7 1.498(2) . . no C2 C3 1.374(2) . . no C3 C4 1.378(3) . . no C4 C5 1.366(3) . . no C5 C6 1.391(2) . . no C3 H3 0.9300 . . no C4 H4 0.9300 . . no C5 H5 0.9300 . . no C6 H6 0.9300 . . no 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_2 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O1 Co1 N1 87.99(5) . . . yes O1 Co1 N2 76.22(5) . . . yes O1 Co1 O1 88.43(5) . . 2_655 yes O1 Co1 N1 170.46(5) . . 2_655 yes O1 Co1 N2 92.90(5) . . 2_655 yes N1 Co1 N2 94.82(5) . . . yes O1 Co1 N1 170.46(5) 2_655 . . yes N1 Co1 N1 96.87(6) . . 2_655 yes N1 Co1 N2 95.14(5) . . 2_655 yes O1 Co1 N2 92.90(5) 2_655 . . yes N1 Co1 N2 95.14(5) 2_655 . . yes N2 Co1 N2 164.97(5) . . 2_655 yes O1 Co1 N1 87.99(5) 2_655 . 2_655 yes O1 Co1 N2 76.22(5) 2_655 . 2_655 yes N1 Co1 N2 94.82(5) 2_655 . 2_655 yes Co1 O1 C7 114.71(11) . . . yes Co1 N1 C1 171.96(14) . . . yes Co1 N2 C2 115.21(10) . . . yes Co1 N2 C6 126.49(11) . . . yes C2 N2 C6 118.27(13) . . . yes H13N N3 H23N 116(2) . . . no C7 N3 H13N 122.5(18) . . . no C7 N3 H23N 121.3(16) . . . no S1 C1 N1 178.67(15) . . . yes N2 C2 C3 122.45(15) . . . yes N2 C2 C7 112.25(13) . . . yes C3 C2 C7 125.21(15) . . . no C2 C3 C4 118.87(16) . . . no C3 C4 C5 119.10(16) . . . no C4 C5 C6 119.07(19) . . . no N2 C6 C5 122.22(17) . . . yes O1 C7 N3 121.29(17) . . . yes O1 C7 C2 119.31(15) . . . yes N3 C7 C2 119.36(16) . . . yes C2 C3 H3 121.00 . . . no C4 C3 H3 121.00 . . . no C3 C4 H4 120.00 . . . no C5 C4 H4 120.00 . . . no C4 C5 H5 120.00 . . . no C6 C5 H5 120.00 . . . no N2 C6 H6 119.00 . . . no C5 C6 H6 119.00 . . . no loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag N1 Co1 O1 C7 -81.66(12) . . . . no N2 Co1 O1 C7 13.80(12) . . . . no O1 Co1 O1 C7 107.18(12) 2_655 . . . no N2 Co1 O1 C7 -176.70(12) 2_655 . . . no O1 Co1 N2 C2 -10.80(11) . . . . no O1 Co1 N2 C6 171.54(14) . . . . no N1 Co1 N2 C2 75.94(12) . . . . no N1 Co1 N2 C6 -101.72(14) . . . . no O1 Co1 N2 C2 -98.46(11) 2_655 . . . no O1 Co1 N2 C6 83.88(14) 2_655 . . . no N1 Co1 N2 C2 173.30(11) 2_655 . . . no N1 Co1 N2 C6 -4.36(14) 2_655 . . . no Co1 O1 C7 N3 167.83(16) . . . . no Co1 O1 C7 C2 -14.83(19) . . . . no Co1 N2 C2 C3 -176.40(13) . . . . no Co1 N2 C2 C7 7.01(17) . . . . no C6 N2 C2 C3 1.5(2) . . . . no C6 N2 C2 C7 -175.13(14) . . . . no Co1 N2 C6 C5 177.15(13) . . . . no C2 N2 C6 C5 -0.5(2) . . . . no C7 C2 C3 C4 174.98(16) . . . . no N2 C2 C3 C4 -1.2(3) . . . . no C3 C2 C7 O1 -171.12(17) . . . . no N2 C2 C7 O1 5.4(2) . . . . no N2 C2 C7 N3 -177.25(17) . . . . no C3 C2 C7 N3 6.3(3) . . . . no C2 C3 C4 C5 -0.2(3) . . . . no C3 C4 C5 C6 1.1(3) . . . . no C4 C5 C6 N2 -0.8(3) . . . . no loop_ _geom_contact_atom_site_label_1 _geom_contact_atom_site_label_2 _geom_contact_distance _geom_contact_site_symmetry_1 _geom_contact_site_symmetry_2 _geom_contact_publ_flag S1 C4 3.671(2) . 4_555 no S1 N3 3.528(2) . 7_555 no S1 H23N 2.86(2) . 1_545 no S1 H3 2.8200 . 7_555 no S1 H13N 2.68(3) . 7_555 no O1 N1 2.9153(19) . . no O1 N2 2.6221(18) . . no O1 C2 2.3651(19) . . no O1 O1 2.9674(18) . 2_655 no O1 N2 3.0792(17) . 2_655 no O1 C4 3.404(2) . 4_565 no O1 H4 2.7400 . 4_565 no N1 O1 2.9153(19) . . no N1 N2 3.085(2) . . no N1 C7 3.389(2) . . no N1 N1 3.096(2) . 2_655 no N1 N2 3.0925(19) . 2_655 no N1 C6 3.252(2) . 2_655 no N2 N1 3.085(2) . . no N2 C7 2.364(2) . . no N2 O1 2.6221(18) . . no N2 N1 3.0925(19) . 2_655 no N2 O1 3.0792(17) . 2_655 no N3 S1 3.528(2) . 7_555 no N1 H6 2.7200 . 2_655 no N1 H5 2.6700 . 3_655 no N3 H3 2.6900 . . no C1 C4 3.382(2) . 4_555 no C2 C4 3.460(2) . 3_665 no C2 C3 3.560(2) . 3_665 no C3 C2 3.560(2) . 3_665 no C4 C7 3.483(3) . 3_665 no C4 S1 3.671(2) . 4_554 no C4 C2 3.460(2) . 3_665 no C4 C1 3.382(2) . 4_554 no C4 O1 3.404(2) . 4_564 no C5 C6 3.502(2) . 3_655 no C5 C7 3.543(2) . 3_665 no C6 C5 3.502(2) . 3_655 no C6 C6 3.432(2) . 3_655 no C7 C5 3.543(2) . 3_665 no C7 C4 3.483(3) . 3_665 no C1 H6 2.9900 . 2_655 no C1 H5 2.7700 . 3_655 no C1 H4 3.0200 . 4_555 no C1 H13N 3.06(3) . 7_555 no C3 H13N 2.66(3) . . no H3 N3 2.6900 . . no H3 H13N 2.1600 . . no H3 S1 2.8200 . 7_555 no H4 O1 2.7400 . 4_564 no H4 C1 3.0200 . 4_554 no H5 N1 2.6700 . 3_655 no H5 C1 2.7700 . 3_655 no H6 N1 2.7200 . 2_655 no H6 C1 2.9900 . 2_655 no H13N C3 2.66(3) . . no H13N H3 2.1600 . . no H13N S1 2.68(3) . 7_555 no H13N C1 3.06(3) . 7_555 no H23N S1 2.86(2) . 1_565 no loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A _geom_hbond_publ_flag # #D H A D - H H...A D...A D - H...A symm(A) # N3 H13N S1 0.86(3) 2.68(3) 3.528(2) 169(2) 7_555 yes N3 H23N S1 0.84(3) 2.86(2) 3.613(2) 151(2) 1_565 yes C3 H3 S1 0.9300 2.8200 3.7438(19) 174.00 7_555 yes # Loop Mechanism for Extra Tables(s) #loop_ #_publ_manuscript_incl_extra_item #'_geom_extra_tableA_col_1' #'_geom_extra_tableA_col_2' #'_geom_extra_tableA_col_3' #'_geom_extra_table_head_A' #'_geom_table_footnote_A' #'_geom_extra_tableB_col_1' #'_geom_extra_tableB_col_2' #'_geom_extra_tableB_col_3' #'_geom_extra_table_head_B' #'_geom_table_footnote_B' # #loop_ #_geom_extra_tableA_col_1 #_geom_extra_tableA_col_2 #_geom_extra_tableA_col_3 # ? ? ? # #loop_ #_geom_extra_tableB_col_1 #_geom_extra_tableB_col_2 #_geom_extra_tableB_col_3 # ? ? ? # #_geom_table_footnote_A #; # ? #; # #_geom_table_footnote_B #; # ? #; # #_geom_table_footnote_A #; # ? #; # #_geom_table_footnote_B #; # ? #; #===END #=============================================================================== data_[Cu(SCN)2(pia)2] _database_code_depnum_ccdc_archive 'CCDC 784965' #TrackingRef '- CIF files for compounds 1, 2 and 3.cif' #=============================================================================== # 5. CHEMICAL DATA _chemical_name_systematic ; ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C14 H12 Cu N6 O2 S2' _chemical_formula_structural ? _chemical_formula_sum 'C14 H12 Cu N6 O2 S2' _chemical_formula_iupac ? _chemical_formula_weight 423.99 _chemical_compound_source 'see text' loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 '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' Cu Cu 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 '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' #=============================================================================== # 6. CRYSTAL DATA _symmetry_cell_setting Triclinic _symmetry_space_group_name_Hall '-P 1' _symmetry_space_group_name_H-M 'P -1' _symmetry_Int_Tables_number 2 loop_ _symmetry_equiv_pos_site_id _symmetry_equiv_pos_as_xyz 1 x,y,z 2 -x,-y,-z _cell_length_a 6.5705(6) _cell_length_b 7.3530(7) _cell_length_c 9.6541(8) _cell_angle_alpha 96.773(7) _cell_angle_beta 92.797(7) _cell_angle_gamma 109.334(8) _cell_volume 435.12(7) _cell_formula_units_Z 1 _cell_measurement_temperature 296 _cell_measurement_reflns_used 10507 _cell_measurement_theta_min 3.7512 _cell_measurement_theta_max 37.0717 _cell_special_details ; ; _exptl_crystal_description block _exptl_crystal_colour 'dark green' _exptl_crystal_size_max 0.572 _exptl_crystal_size_mid 0.395 _exptl_crystal_size_min 0.113 _exptl_crystal_size_rad ? _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.618 _exptl_crystal_density_method 'Not Measured' _exptl_crystal_F_000 215 _exptl_absorpt_coefficient_mu 1.516 _exptl_crystal_density_meas_temp ? # Permitted for _exptl_absorpt_correction_type : # analytical 'analytical from crystal shape' # Example: de Meulenaer&Tompa: ABST # cylinder 'cylindrical' # gaussian 'Gaussian from crystal shape' # Example: PLATON/ABSG # integration 'integration from crystal shape' # multi-scan 'symmetry-related measurements' # Example: SADABS, MULABS # none 'no absorption corr. applied' # numerical 'numerical from crystal shape' # psi-scan 'psi-scan corrections' # Example: PLATON/ABSP # refdelf 'refined from delta-F' # Example: SHELXA, DIFABS, DELABS # sphere 'spherical' # Example: PLATON/ABSS _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.31.5 (release 28-08-2006 CrysAlis171 .NET) (compiled Aug 28 2006,13:05:05) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. ; _exptl_absorpt_correction_T_min 0.474 _exptl_absorpt_correction_T_max 0.845 #=============================================================================== # 7. EXPERIMENTAL DATA _exptl_special_details ; ; _diffrn_ambient_temperature 296 _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_probe x-ray _diffrn_radiation_type MoK\a _diffrn_radiation_source 'Enhance (Mo) X-ray Source' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type ; Oxford Diffraction Xcalibur diffractometer with Saphirre3 detector ; _diffrn_measurement_method CCD _diffrn_detector_area_resol_mean 16.3426 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? loop_ _diffrn_standard_refln_index_h _diffrn_standard_refln_index_k _diffrn_standard_refln_index_l ? ? ? # number of measured reflections (redundant set) _diffrn_reflns_number 12668 _diffrn_reflns_av_R_equivalents 0.0136 _diffrn_reflns_av_sigmaI/netI 0.0085 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 3.76 _diffrn_reflns_theta_max 29.98 _diffrn_reflns_theta_full 29.98 _diffrn_measured_fraction_theta_max 0.997 _diffrn_measured_fraction_theta_full 0.997 _diffrn_reflns_reduction_process ; ; # number of unique reflections _reflns_number_total 2534 # number of observed reflections (> n sig(I)) _reflns_number_gt 2278 _reflns_threshold_expression I>2\s(I) _computing_data_collection ; CrysAlis CCD, Oxford Diffraction Ltd., Version 1.171.31.5 (release 28-08-2006 CrysAlis171 .NET) (compiled Aug 28 2006,13:05:05) ; _computing_cell_refinement ; CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.31.5 (release 28-08-2006 CrysAlis171 .NET) (compiled Aug 28 2006,13:05:05) ; _computing_data_reduction ; CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.31.5 (release 28-08-2006 CrysAlis171 .NET) (compiled Aug 28 2006,13:05:05) ; _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material 'PLATON (Spek, 2003)' #=============================================================================== # 8. REFINEMENT DATA _refine_special_details ; Refinement on F^2^ for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating -R-factor-obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0448P)^2^+0.0926P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom # Permitted for _refine_ls_hydrogen_treatment : # refall - refined all H parameters # refxyz - refined H coordinates only # refU - refined H U only # noref - no refinement of H parameters # constr - H parameters constrained # mixed - some constrained, some independent # undef - H-atom parameters not defined _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method shelxl _refine_ls_extinction_coef 0.079(7) _refine_ls_extinction_expression FC^*^=KFC[1+0.001XFC^2^\L^3^/SIN(2\Q)]^-1/4^ _refine_ls_abs_structure_details ? _refine_ls_abs_structure_Flack . _refine_ls_number_reflns 2534 _refine_ls_number_parameters 124 _refine_ls_number_restraints 0 _refine_ls_number_constraints ? _refine_ls_R_factor_all 0.0287 _refine_ls_R_factor_gt 0.0252 _refine_ls_wR_factor_ref 0.0750 _refine_ls_wR_factor_gt 0.0710 _refine_ls_goodness_of_fit_ref 1.055 _refine_ls_restrained_S_all 1.055 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 _refine_diff_density_max 0.510 _refine_diff_density_min -0.339 _refine_diff_density_rms 0.079 #=============================================================================== # 9. ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS loop_ _atom_site_label _atom_site_type_symbol _atom_site_thermal_displace_type _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_occupancy _atom_site_U_iso_or_equiv _atom_site_calc_flag _atom_site_refinement_flags Cu1 Cu Uani 0.50000 0.50000 0.50000 1.000 0.0420(1) . . S1 S Uani 0.40207(6) 0.83596(5) 0.62436(4) 1.000 0.0435(1) . . O1 O Uani 0.27158(16) 0.45440(16) 0.34590(10) 1.000 0.0424(3) . . N1 N Uani 0.2701(3) 0.7132(2) 0.87899(15) 1.000 0.0549(5) . . N2 N Uani 0.68092(17) 0.65923(16) 0.37348(11) 1.000 0.0319(3) . . N3 N Uani 0.2079(2) 0.5270(2) 0.13335(12) 1.000 0.0450(4) . . C1 C Uani 0.3257(2) 0.7644(2) 0.77390(14) 1.000 0.0372(3) . . C2 C Uani 0.5726(2) 0.66292(17) 0.25281(12) 1.000 0.0308(3) . . C3 C Uani 0.6733(3) 0.7667(2) 0.15069(15) 1.000 0.0432(4) . . C4 C Uani 0.8929(3) 0.8687(3) 0.17591(18) 1.000 0.0543(5) . . C5 C Uani 1.0046(3) 0.8634(2) 0.29805(19) 1.000 0.0500(5) . . C6 C Uani 0.8932(2) 0.7562(2) 0.39593(15) 1.000 0.0409(4) . . C7 C Uani 0.3381(2) 0.54164(19) 0.24488(12) 1.000 0.0328(3) . . H3 H Uiso 0.59620 0.76810 0.06770 1.000 0.0520 calc R H4 H Uiso 0.96530 0.94150 0.10960 1.000 0.0650 calc R H5 H Uiso 1.15270 0.93060 0.31480 1.000 0.0600 calc R H6 H Uiso 0.96780 0.75170 0.47910 1.000 0.0490 calc R H13N H Uiso 0.248(4) 0.598(3) 0.067(3) 1.000 0.065(6) . . H23N H Uiso 0.071(4) 0.458(3) 0.133(2) 1.000 0.065(7) . . 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 Cu1 0.0295(1) 0.0622(2) 0.0261(1) 0.0219(1) -0.0035(1) 0.0004(1) S1 0.0453(2) 0.0466(2) 0.0398(2) 0.0150(1) 0.0104(1) 0.0134(2) O1 0.0322(4) 0.0610(6) 0.0282(4) 0.0173(4) -0.0032(3) 0.0054(4) N1 0.0640(9) 0.0633(8) 0.0387(7) 0.0195(6) 0.0032(6) 0.0195(7) N2 0.0310(5) 0.0382(5) 0.0248(4) 0.0089(4) 0.0018(4) 0.0080(4) N3 0.0413(6) 0.0658(8) 0.0276(5) 0.0165(5) -0.0037(5) 0.0154(6) C1 0.0366(6) 0.0391(6) 0.0354(6) 0.0091(5) -0.0017(5) 0.0116(5) C2 0.0357(6) 0.0352(5) 0.0235(5) 0.0076(4) 0.0036(4) 0.0135(5) C3 0.0513(8) 0.0515(8) 0.0317(6) 0.0190(6) 0.0098(6) 0.0186(6) C4 0.0534(9) 0.0597(9) 0.0495(9) 0.0263(7) 0.0201(7) 0.0104(7) C5 0.0375(7) 0.0529(8) 0.0540(9) 0.0135(7) 0.0125(6) 0.0049(6) C6 0.0330(6) 0.0474(7) 0.0378(6) 0.0089(5) 0.0009(5) 0.0069(5) C7 0.0345(6) 0.0421(6) 0.0234(5) 0.0068(4) -0.0002(4) 0.0147(5) #=============================================================================== # 10. MOLECULAR GEOMETRY _geom_special_details ; Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_1 _geom_bond_site_symmetry_2 _geom_bond_publ_flag Cu1 S1 2.8959(5) . . yes Cu1 O1 1.9772(10) . . yes Cu1 N2 1.9579(11) . . yes Cu1 S1 2.8959(5) . 2_666 yes Cu1 O1 1.9772(10) . 2_666 yes Cu1 N2 1.9579(11) . 2_666 yes S1 C1 1.6395(14) . . yes O1 C7 1.2479(16) . . yes N1 C1 1.158(2) . . yes N2 C2 1.3430(16) . . yes N2 C6 1.3328(18) . . yes N3 C7 1.3132(18) . . yes N3 H23N 0.87(3) . . no N3 H13N 0.87(3) . . no C2 C7 1.4959(19) . . no C2 C3 1.3780(19) . . no C3 C4 1.382(3) . . no C4 C5 1.370(3) . . no C5 C6 1.382(2) . . no C3 H3 0.9300 . . no C4 H4 0.9300 . . no C5 H5 0.9300 . . no C6 H6 0.9300 . . no 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_2 _geom_angle_site_symmetry_3 _geom_angle_publ_flag S1 Cu1 O1 89.71(3) . . . yes S1 Cu1 N2 89.80(3) . . . yes S1 Cu1 S1 180.00 . . 2_666 yes S1 Cu1 O1 90.30(3) . . 2_666 yes S1 Cu1 N2 90.21(3) . . 2_666 yes O1 Cu1 N2 82.46(5) . . . yes S1 Cu1 O1 90.30(3) 2_666 . . yes O1 Cu1 O1 180.00 . . 2_666 yes O1 Cu1 N2 97.54(5) . . 2_666 yes S1 Cu1 N2 90.21(3) 2_666 . . yes O1 Cu1 N2 97.54(5) 2_666 . . yes N2 Cu1 N2 180.00 . . 2_666 yes S1 Cu1 O1 89.71(3) 2_666 . 2_666 yes S1 Cu1 N2 89.80(3) 2_666 . 2_666 yes O1 Cu1 N2 82.46(5) 2_666 . 2_666 yes Cu1 S1 C1 99.50(5) . . . yes Cu1 O1 C7 113.44(9) . . . yes Cu1 N2 C2 113.86(9) . . . yes Cu1 N2 C6 126.45(9) . . . yes C2 N2 C6 119.68(12) . . . yes H13N N3 H23N 119(2) . . . no C7 N3 H13N 122.3(18) . . . no C7 N3 H23N 118.1(13) . . . no S1 C1 N1 179.45(15) . . . yes N2 C2 C3 122.10(13) . . . yes N2 C2 C7 112.01(10) . . . yes C3 C2 C7 125.89(12) . . . no C2 C3 C4 117.69(15) . . . no C3 C4 C5 120.42(17) . . . no C4 C5 C6 118.80(17) . . . no N2 C6 C5 121.30(14) . . . yes O1 C7 N3 121.48(13) . . . yes O1 C7 C2 118.23(11) . . . yes N3 C7 C2 120.29(12) . . . yes C2 C3 H3 121.00 . . . no C4 C3 H3 121.00 . . . no C3 C4 H4 120.00 . . . no C5 C4 H4 120.00 . . . no C4 C5 H5 121.00 . . . no C6 C5 H5 121.00 . . . no N2 C6 H6 119.00 . . . no C5 C6 H6 119.00 . . . no loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag O1 Cu1 S1 C1 118.06(6) . . . . no N2 Cu1 S1 C1 -159.48(6) . . . . no O1 Cu1 S1 C1 -61.94(6) 2_666 . . . no N2 Cu1 S1 C1 20.52(6) 2_666 . . . no S1 Cu1 O1 C7 89.28(10) . . . . no N2 Cu1 O1 C7 -0.55(10) . . . . no S1 Cu1 O1 C7 -90.72(10) 2_666 . . . no N2 Cu1 O1 C7 179.45(10) 2_666 . . . no S1 Cu1 N2 C2 -89.21(9) . . . . no S1 Cu1 N2 C6 92.07(11) . . . . no O1 Cu1 N2 C2 0.52(9) . . . . no O1 Cu1 N2 C6 -178.21(12) . . . . no S1 Cu1 N2 C2 90.79(9) 2_666 . . . no S1 Cu1 N2 C6 -87.93(11) 2_666 . . . no O1 Cu1 N2 C2 -179.48(9) 2_666 . . . no O1 Cu1 N2 C6 1.80(12) 2_666 . . . no Cu1 O1 C7 N3 179.79(11) . . . . no Cu1 O1 C7 C2 0.48(15) . . . . no Cu1 N2 C2 C3 -179.74(11) . . . . no Cu1 N2 C2 C7 -0.42(13) . . . . no C6 N2 C2 C3 -0.9(2) . . . . no C6 N2 C2 C7 178.41(12) . . . . no Cu1 N2 C6 C5 179.58(11) . . . . no C2 N2 C6 C5 0.9(2) . . . . no C7 C2 C3 C4 -179.14(15) . . . . no N2 C2 C3 C4 0.1(2) . . . . no C3 C2 C7 O1 179.25(14) . . . . no N2 C2 C7 O1 -0.05(18) . . . . no N2 C2 C7 N3 -179.36(12) . . . . no C3 C2 C7 N3 -0.1(2) . . . . no C2 C3 C4 C5 0.7(3) . . . . no C3 C4 C5 C6 -0.7(3) . . . . no C4 C5 C6 N2 -0.1(2) . . . . no loop_ _geom_contact_atom_site_label_1 _geom_contact_atom_site_label_2 _geom_contact_distance _geom_contact_site_symmetry_1 _geom_contact_site_symmetry_2 _geom_contact_publ_flag Cu1 N3 4.0009(13) . . no Cu1 N3 4.0009(13) . 2_666 no S1 O1 3.4981(11) . . no S1 N2 3.4898(12) . . no S1 N2 3.5014(12) . 2_666 no S1 S1 3.5852(6) . 2_676 no S1 O1 3.5149(12) . 2_666 no S1 C2 3.6817(13) . 2_676 no S1 C3 3.6144(16) . 2_676 no S1 H6 2.9500 . 1_455 no S1 H5 2.8500 . 2_776 no O1 S1 3.4981(11) . . no O1 N2 2.5935(16) . . no O1 C2 2.3582(17) . . no O1 S1 3.5149(12) . 2_666 no O1 N2 2.9596(15) . 2_666 no O1 C6 3.1378(18) . 2_666 no O1 H6 2.6300 . 2_666 no N1 N3 2.9312(19) . 1_556 no N1 C2 3.395(2) . 2_666 no N1 N3 3.040(2) . 2_566 no N2 S1 3.5014(12) . 2_666 no N2 C7 2.3552(18) . . no N2 C1 3.2539(18) . 2_666 no N2 S1 3.4898(12) . . no N2 O1 2.5935(16) . . no N2 O1 2.9596(15) . 2_666 no N3 Cu1 4.0009(13) . . no N3 N1 3.040(2) . 2_566 no N3 N1 2.9312(19) . 1_554 no N3 C5 3.449(2) . 1_455 no N1 H13N 2.08(3) . 1_556 no N1 H23N 2.17(3) . 2_566 no N1 H3 2.6400 . 1_556 no N3 H3 2.7400 . . no C1 C2 3.4061(19) . 2_666 no C1 C3 3.437(2) . 2_676 no C1 C4 3.450(3) . 2_676 no C2 C1 3.4061(19) . 2_666 no C2 S1 3.6817(13) . 2_676 no C2 N1 3.395(2) . 2_666 no C3 C1 3.437(2) . 2_676 no C3 S1 3.6144(16) . 2_676 no C4 C1 3.450(3) . 2_676 no C5 N3 3.449(2) . 1_655 no C1 H23N 2.83(2) . 2_566 no C3 H13N 2.69(3) . . no H3 N1 2.6400 . 1_554 no H3 N3 2.7400 . . no H3 H13N 2.2100 . . no H4 H4 2.3900 . 2_775 no H5 S1 2.8500 . 2_776 no H6 S1 2.9500 . 1_655 no H6 O1 2.6300 . 2_666 no H13N N1 2.08(3) . 1_554 no H13N C3 2.69(3) . . no H13N H3 2.2100 . . no H23N N1 2.17(3) . 2_566 no H23N C1 2.83(2) . 2_566 no loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A _geom_hbond_publ_flag # #D H A D - H H...A D...A D - H...A symm(A) # N3 H13N N1 0.87(3) 2.08(3) 2.9312(19) 165(3) 1_554 yes N3 H23N N1 0.87(3) 2.17(3) 3.040(2) 177.2(18) 2_566 yes C5 H5 S1 0.9300 2.8500 3.7768(19) 175.00 2_776 yes # Loop Mechanism for Extra Tables(s) #loop_ #_publ_manuscript_incl_extra_item #'_geom_extra_tableA_col_1' #'_geom_extra_tableA_col_2' #'_geom_extra_tableA_col_3' #'_geom_extra_table_head_A' #'_geom_table_footnote_A' #'_geom_extra_tableB_col_1' #'_geom_extra_tableB_col_2' #'_geom_extra_tableB_col_3' #'_geom_extra_table_head_B' #'_geom_table_footnote_B' # #loop_ #_geom_extra_tableA_col_1 #_geom_extra_tableA_col_2 #_geom_extra_tableA_col_3 # ? ? ? # #loop_ #_geom_extra_tableB_col_1 #_geom_extra_tableB_col_2 #_geom_extra_tableB_col_3 # ? ? ? # #_geom_table_footnote_A #; # ? #; # #_geom_table_footnote_B #; # ? #; # #_geom_table_footnote_A #; # ? #; # #_geom_table_footnote_B #; # ? #; #===END # Loop Mechanism for Extra Tables(s) #loop_ #_publ_manuscript_incl_extra_item #'_geom_extra_tableA_col_1' #'_geom_extra_tableA_col_2' #'_geom_extra_tableA_col_3' #'_geom_extra_table_head_A' #'_geom_table_footnote_A' #'_geom_extra_tableB_col_1' #'_geom_extra_tableB_col_2' #'_geom_extra_tableB_col_3' #'_geom_extra_table_head_B' #'_geom_table_footnote_B' # #loop_ #_geom_extra_tableA_col_1 #_geom_extra_tableA_col_2 #_geom_extra_tableA_col_3 # ? ? ? # #loop_ #_geom_extra_tableB_col_1 #_geom_extra_tableB_col_2 #_geom_extra_tableB_col_3 # ? ? ? # #_geom_table_footnote_A #; # ? #; # #_geom_table_footnote_B #; # ? #; # #_geom_table_footnote_A #; # ? #; # #_geom_table_footnote_B #; # ? #; #===END #=============================================================================== data_[Ni(NCS)2(pia)2] _database_code_depnum_ccdc_archive 'CCDC 784966' #TrackingRef '- CIF files for compounds 1, 2 and 3.cif' #=============================================================================== # 5. CHEMICAL DATA _chemical_name_systematic ; ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C14 H12 N6 Ni O2 S2' _chemical_formula_structural ? _chemical_formula_sum 'C14 H12 N6 Ni O2 S2' _chemical_formula_iupac ? _chemical_formula_weight 419.13 _chemical_compound_source 'see text' loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Ni Ni 0.3393 1.1124 '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' H H 0.0000 0.0000 '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' #=============================================================================== # 6. CRYSTAL DATA _symmetry_cell_setting Monoclinic _symmetry_space_group_name_Hall '-C 2yc' _symmetry_space_group_name_H-M 'C 2/c' _symmetry_Int_Tables_number 15 loop_ _symmetry_equiv_pos_site_id _symmetry_equiv_pos_as_xyz 1 x,y,z 2 -x,y,1/2-z 3 -x,-y,-z 4 x,-y,1/2+z 5 1/2+x,1/2+y,z 6 1/2-x,1/2+y,1/2-z 7 1/2-x,1/2-y,-z 8 1/2+x,1/2-y,1/2+z _cell_length_a 16.9021(3) _cell_length_b 8.2084(2) _cell_length_c 13.5353(3) _cell_angle_alpha 90 _cell_angle_beta 108.613(2) _cell_angle_gamma 90 _cell_volume 1779.66(7) _cell_formula_units_Z 4 _cell_measurement_temperature 296 _cell_measurement_reflns_used 7033 _cell_measurement_theta_min 3.8985 _cell_measurement_theta_max 37.2138 _cell_special_details ; ; _exptl_crystal_description plate _exptl_crystal_colour blue _exptl_crystal_size_max 0.333 _exptl_crystal_size_mid 0.248 _exptl_crystal_size_min 0.037 _exptl_crystal_size_rad ? _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.564 _exptl_crystal_density_method 'Not Measured' _exptl_crystal_F_000 856 _exptl_absorpt_coefficient_mu 1.345 _exptl_crystal_density_meas_temp ? # Permitted for _exptl_absorpt_correction_type : # analytical 'analytical from crystal shape' # Example: de Meulenaer&Tompa: ABST # cylinder 'cylindrical' # gaussian 'Gaussian from crystal shape' # Example: PLATON/ABSG # integration 'integration from crystal shape' # multi-scan 'symmetry-related measurements' # Example: SADABS, MULABS # none 'no absorption corr. applied' # numerical 'numerical from crystal shape' # psi-scan 'psi-scan corrections' # Example: PLATON/ABSP # refdelf 'refined from delta-F' # Example: SHELXA, DIFABS, DELABS # sphere 'spherical' # Example: PLATON/ABSS _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.31.5 (release 28-08-2006 CrysAlis171 .NET) (compiled Aug 28 2006,13:05:05) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. ; _exptl_absorpt_correction_T_min 0.721 _exptl_absorpt_correction_T_max 0.95100 #=============================================================================== # 7. EXPERIMENTAL DATA _exptl_special_details ; ; _diffrn_ambient_temperature 296 _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_probe x-ray _diffrn_radiation_type MoK\a _diffrn_radiation_source 'Enhance (Mo) X-ray Source' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type ; Oxford Diffraction Ycalibur diffractometer with Saphirre3 detector ; _diffrn_measurement_method CCD _diffrn_detector_area_resol_mean 16.3426 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? loop_ _diffrn_standard_refln_index_h _diffrn_standard_refln_index_k _diffrn_standard_refln_index_l ? ? ? # number of measured reflections (redundant set) _diffrn_reflns_number 17793 _diffrn_reflns_av_R_equivalents 0.0300 _diffrn_reflns_av_sigmaI/netI 0.0228 _diffrn_reflns_limit_h_min -23 _diffrn_reflns_limit_h_max 23 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 3.91 _diffrn_reflns_theta_max 29.98 _diffrn_reflns_theta_full 29.98 _diffrn_measured_fraction_theta_max 0.995 _diffrn_measured_fraction_theta_full 0.995 _diffrn_reflns_reduction_process ; ; # number of unique reflections _reflns_number_total 2581 # number of observed reflections (> n sig(I)) _reflns_number_gt 1940 _reflns_threshold_expression I>2\s(I) _computing_data_collection ; CrysAlis CCD, Oxford Diffraction Ltd., Version 1.171.31.5 (release 28-08-2006 CrysAlis171 .NET) (compiled Aug 28 2006,13:05:05) ; _computing_cell_refinement ; CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.31.5 (release 28-08-2006 CrysAlis171 .NET) (compiled Aug 28 2006,13:05:05) ; _computing_data_reduction ; CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.31.5 (release 28-08-2006 CrysAlis171 .NET) (compiled Aug 28 2006,13:05:05) ; _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ; ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Bruno et al., 2002) ; _computing_publication_material 'PLATON (Spek, 2003)' #=============================================================================== # 8. REFINEMENT DATA _refine_special_details ; Refinement on F^2^ for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating -R-factor-obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0282P)^2^+1.1366P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom # Permitted for _refine_ls_hydrogen_treatment : # refall - refined all H parameters # refxyz - refined H coordinates only # refU - refined H U only # noref - no refinement of H parameters # constr - H parameters constrained # mixed - some constrained, some independent # undef - H-atom parameters not defined _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_abs_structure_details ? _refine_ls_abs_structure_Flack . _refine_ls_number_reflns 2581 _refine_ls_number_parameters 122 _refine_ls_number_restraints 0 _refine_ls_number_constraints ? _refine_ls_R_factor_all 0.0554 _refine_ls_R_factor_gt 0.0340 _refine_ls_wR_factor_ref 0.0749 _refine_ls_wR_factor_gt 0.0648 _refine_ls_goodness_of_fit_ref 1.054 _refine_ls_restrained_S_all 1.054 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 _refine_diff_density_max 0.383 _refine_diff_density_min -0.291 _refine_diff_density_rms 0.052 #=============================================================================== # 9. ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS loop_ _atom_site_label _atom_site_type_symbol _atom_site_thermal_displace_type _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_occupancy _atom_site_U_iso_or_equiv _atom_site_calc_flag _atom_site_refinement_flags Ni1 Ni Uani 0.50000 0.22195(4) 0.25000 1.000 0.0393(1) . . S1 S Uani 0.26826(3) -0.14569(8) 0.19738(5) 1.000 0.0644(2) . . O1 O Uani 0.40859(8) 0.40188(18) 0.20164(10) 1.000 0.0497(5) . . N1 N Uani 0.40609(11) 0.0537(2) 0.21876(13) 1.000 0.0505(6) . . N2 N Uani 0.49144(9) 0.25129(18) 0.09541(11) 1.000 0.0388(5) . . N3 N Uani 0.31416(13) 0.5083(3) 0.0612(2) 1.000 0.0717(8) . . C1 C Uani 0.34839(12) -0.0277(2) 0.20869(14) 1.000 0.0424(6) . . C2 C Uani 0.42691(11) 0.3432(2) 0.03958(13) 1.000 0.0401(5) . . C3 C Uani 0.40958(13) 0.3687(3) -0.06567(15) 1.000 0.0498(6) . . C4 C Uani 0.46139(15) 0.3002(3) -0.11483(16) 1.000 0.0561(7) . . C5 C Uani 0.52810(15) 0.2097(3) -0.05811(16) 1.000 0.0560(7) . . C6 C Uani 0.54139(13) 0.1868(2) 0.04756(15) 1.000 0.0479(7) . . C7 C Uani 0.38105(12) 0.4195(2) 0.10608(15) 1.000 0.0453(6) . . H3 H Uiso 0.36380 0.43090 -0.10290 1.000 0.0600 calc R H4 H Uiso 0.45100 0.31550 -0.18590 1.000 0.0670 calc R H5 H Uiso 0.56420 0.16390 -0.08980 1.000 0.0670 calc R H6 H Uiso 0.58670 0.12440 0.08600 1.000 0.0570 calc R H13N H Uiso 0.2959(19) 0.524(3) -0.007(3) 1.000 0.090(10) . . H23N H Uiso 0.293(2) 0.558(4) 0.097(2) 1.000 0.089(10) . . 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 Ni1 0.0394(2) 0.0467(2) 0.0338(2) 0.0000 0.0143(1) 0.0000 S1 0.0414(3) 0.0659(4) 0.0793(4) 0.0120(3) 0.0102(3) -0.0057(2) O1 0.0493(8) 0.0599(9) 0.0408(7) -0.0027(6) 0.0155(6) 0.0112(6) N1 0.0495(9) 0.0565(11) 0.0488(9) -0.0055(8) 0.0203(8) -0.0067(8) N2 0.0425(8) 0.0408(9) 0.0350(7) -0.0019(6) 0.0150(6) -0.0018(6) N3 0.0566(12) 0.0978(18) 0.0580(13) 0.0041(12) 0.0144(10) 0.0288(12) C1 0.0433(10) 0.0472(11) 0.0369(9) 0.0003(8) 0.0133(8) 0.0072(8) C2 0.0408(9) 0.0408(10) 0.0368(9) -0.0032(8) 0.0096(7) -0.0054(7) C3 0.0530(11) 0.0525(12) 0.0385(10) 0.0001(9) 0.0071(8) -0.0046(9) C4 0.0761(14) 0.0570(13) 0.0363(10) -0.0032(9) 0.0196(10) -0.0106(11) C5 0.0791(15) 0.0508(12) 0.0507(11) -0.0079(10) 0.0383(11) -0.0043(11) C6 0.0567(11) 0.0447(12) 0.0488(11) -0.0012(9) 0.0260(9) 0.0030(9) C7 0.0410(10) 0.0494(12) 0.0443(10) -0.0022(9) 0.0118(8) 0.0009(8) #=============================================================================== # 10. MOLECULAR GEOMETRY _geom_special_details ; Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_1 _geom_bond_site_symmetry_2 _geom_bond_publ_flag Ni1 O1 2.0860(15) . . yes Ni1 N1 2.0438(18) . . yes Ni1 N2 2.0649(14) . . yes Ni1 O1 2.0860(15) . 2_655 yes Ni1 N1 2.0438(18) . 2_655 yes Ni1 N2 2.0649(14) . 2_655 yes S1 C1 1.632(2) . . yes O1 C7 1.235(2) . . yes N1 C1 1.154(3) . . yes N2 C2 1.343(2) . . yes N2 C6 1.327(3) . . yes N3 C7 1.319(3) . . yes N3 H23N 0.80(3) . . no N3 H13N 0.88(4) . . no C2 C7 1.500(3) . . no C2 C3 1.376(3) . . no C3 C4 1.378(3) . . no C4 C5 1.364(3) . . no C5 C6 1.388(3) . . no C3 H3 0.9300 . . no C4 H4 0.9300 . . no C5 H5 0.9300 . . no C6 H6 0.9300 . . no 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_2 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O1 Ni1 N1 87.99(6) . . . yes O1 Ni1 N2 78.12(6) . . . yes O1 Ni1 O1 89.85(6) . . 2_655 yes O1 Ni1 N1 172.70(6) . . 2_655 yes O1 Ni1 N2 92.33(6) . . 2_655 yes N1 Ni1 N2 94.05(6) . . . yes O1 Ni1 N1 172.70(6) 2_655 . . yes N1 Ni1 N1 94.98(7) . . 2_655 yes N1 Ni1 N2 95.00(6) . . 2_655 yes O1 Ni1 N2 92.33(6) 2_655 . . yes N1 Ni1 N2 95.00(6) 2_655 . . yes N2 Ni1 N2 166.61(6) . . 2_655 yes O1 Ni1 N1 87.99(6) 2_655 . 2_655 yes O1 Ni1 N2 78.12(6) 2_655 . 2_655 yes N1 Ni1 N2 94.05(6) 2_655 . 2_655 yes Ni1 O1 C7 113.91(12) . . . yes Ni1 N1 C1 170.79(16) . . . yes Ni1 N2 C2 114.67(12) . . . yes Ni1 N2 C6 126.74(13) . . . yes C2 N2 C6 118.58(15) . . . yes H13N N3 H23N 119(3) . . . no C7 N3 H13N 122(2) . . . no C7 N3 H23N 119(2) . . . no S1 C1 N1 178.38(17) . . . yes N2 C2 C3 122.30(18) . . . yes N2 C2 C7 112.30(15) . . . yes C3 C2 C7 125.31(18) . . . no C2 C3 C4 118.7(2) . . . no C3 C4 C5 119.3(2) . . . no C4 C5 C6 119.1(2) . . . no N2 C6 C5 122.00(19) . . . yes O1 C7 N3 121.9(2) . . . yes O1 C7 C2 119.03(17) . . . yes N3 C7 C2 119.05(19) . . . yes C2 C3 H3 121.00 . . . no C4 C3 H3 121.00 . . . no C3 C4 H4 120.00 . . . no C5 C4 H4 120.00 . . . no C4 C5 H5 120.00 . . . no C6 C5 H5 120.00 . . . no N2 C6 H6 119.00 . . . no C5 C6 H6 119.00 . . . no loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag N1 Ni1 O1 C7 -81.72(14) . . . . no N2 Ni1 O1 C7 12.84(14) . . . . no O1 Ni1 O1 C7 105.25(14) 2_655 . . . no N2 Ni1 O1 C7 -176.64(14) 2_655 . . . no O1 Ni1 N2 C2 -10.09(12) . . . . no O1 Ni1 N2 C6 171.34(16) . . . . no N1 Ni1 N2 C2 77.00(13) . . . . no N1 Ni1 N2 C6 -101.57(16) . . . . no O1 Ni1 N2 C2 -99.44(13) 2_655 . . . no O1 Ni1 N2 C6 81.99(16) 2_655 . . . no N1 Ni1 N2 C2 172.37(13) 2_655 . . . no N1 Ni1 N2 C6 -6.20(16) 2_655 . . . no Ni1 O1 C7 N3 168.90(17) . . . . no Ni1 O1 C7 C2 -13.6(2) . . . . no Ni1 N2 C2 C3 -176.79(16) . . . . no Ni1 N2 C2 C7 6.48(19) . . . . no C6 N2 C2 C3 1.9(3) . . . . no C6 N2 C2 C7 -174.82(16) . . . . no Ni1 N2 C6 C5 177.57(16) . . . . no C2 N2 C6 C5 -1.0(3) . . . . no C7 C2 C3 C4 174.9(2) . . . . no N2 C2 C3 C4 -1.4(3) . . . . no C3 C2 C7 O1 -171.7(2) . . . . no N2 C2 C7 O1 4.9(2) . . . . no N2 C2 C7 N3 -177.46(19) . . . . no C3 C2 C7 N3 5.9(3) . . . . no C2 C3 C4 C5 -0.1(4) . . . . no C3 C4 C5 C6 1.0(4) . . . . no C4 C5 C6 N2 -0.5(3) . . . . no loop_ _geom_contact_atom_site_label_1 _geom_contact_atom_site_label_2 _geom_contact_distance _geom_contact_site_symmetry_1 _geom_contact_site_symmetry_2 _geom_contact_publ_flag S1 C4 3.665(2) . 4_555 no S1 N3 3.514(3) . 7_555 no S1 H23N 2.88(3) . 1_545 no S1 H3 2.8100 . 7_555 no S1 H13N 2.65(4) . 7_555 no O1 N1 2.869(2) . . no O1 N2 2.616(2) . . no O1 C2 2.361(2) . . no O1 O1 2.946(2) . 2_655 no O1 N2 2.994(2) . 2_655 no O1 C4 3.396(3) . 4_565 no O1 H4 2.7400 . 4_565 no N1 O1 2.869(2) . . no N1 N2 3.006(2) . . no N1 C7 3.333(2) . . no N1 N1 3.013(3) . 2_655 no N1 N2 3.029(2) . 2_655 no N1 C6 3.193(3) . 2_655 no N2 N1 3.006(2) . . no N2 C7 2.362(3) . . no N2 O1 2.616(2) . . no N2 N1 3.029(2) . 2_655 no N2 O1 2.994(2) . 2_655 no N3 S1 3.514(3) . 7_555 no N1 H6 2.6700 . 2_655 no N1 H5 2.6500 . 3_655 no N3 H3 2.6900 . . no C1 C4 3.383(3) . 4_555 no C2 C4 3.456(3) . 3_665 no C2 C3 3.568(3) . 3_665 no C3 C2 3.568(3) . 3_665 no C4 C7 3.493(3) . 3_665 no C4 S1 3.665(2) . 4_554 no C4 C2 3.456(3) . 3_665 no C4 C1 3.383(3) . 4_554 no C4 O1 3.396(3) . 4_564 no C5 C6 3.478(3) . 3_655 no C5 C7 3.561(3) . 3_665 no C6 C5 3.478(3) . 3_655 no C6 C6 3.445(2) . 3_655 no C7 C5 3.561(3) . 3_665 no C7 C4 3.493(3) . 3_665 no C1 H6 2.9200 . 2_655 no C1 H5 2.7500 . 3_655 no C1 H4 3.0100 . 4_555 no C1 H13N 3.03(4) . 7_555 no C3 H13N 2.63(3) . . no H3 N3 2.6900 . . no H3 H13N 2.1300 . . no H3 S1 2.8100 . 7_555 no H4 O1 2.7400 . 4_564 no H4 C1 3.0100 . 4_554 no H5 N1 2.6500 . 3_655 no H5 C1 2.7500 . 3_655 no H6 N1 2.6700 . 2_655 no H6 C1 2.9200 . 2_655 no H13N C3 2.63(3) . . no H13N H3 2.1300 . . no H13N S1 2.65(4) . 7_555 no H13N C1 3.03(4) . 7_555 no H23N S1 2.88(3) . 1_565 no loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A _geom_hbond_publ_flag # #D H A D - H H...A D...A D - H...A symm(A) # N3 H13N S1 0.88(4) 2.65(4) 3.514(3) 165(2) 7_555 yes C3 H3 S1 0.9300 2.8100 3.737(2) 173.00 7_555 yes