# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2007 data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _publ_contact_author_name 'Mercouri G. Kanatzidis' _publ_contact_author_address ; Department of Chemistry Northwestern University Evanston Illinois 60091 UNITED STATES OF AMERICA ; _publ_contact_author_email M-KANATZIDIS@NORTHWESTERN.EDU _publ_section_title ; [Zn(H2O)4][Zn4Sn3Se9(MeNH2)]: A robust open framework chalcogenide with large nonlinear optical response ; loop_ _publ_author_name 'Mercouri G. Kanatzidis' 'Joon I. Jang' 'J. B. Ketterson' 'Manolis J. Manos' # Attachment 'CH3NH2Zn3Sn3Se8H4O8 corr.CIF' data_314441 _database_code_depnum_ccdc_archive 'CCDC 657916' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'N0.20 O0.80 Se1.80 Sn0.60 Zn0.60' _chemical_formula_weight 268.17 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source O O 0.0106 0.0060 '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' Se Se -0.0929 2.2259 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Sn Sn -0.6537 1.4246 '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' _symmetry_cell_setting Triclinic _symmetry_space_group_name_H-M P1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' _cell_length_a 7.8632(12) _cell_length_b 8.6162(13) _cell_length_c 10.2185(15) _cell_angle_alpha 105.735(2) _cell_angle_beta 110.632(2) _cell_angle_gamma 103.174(2) _cell_volume 582.04(15) _cell_formula_units_Z 5 _cell_measurement_temperature 273(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description needle _exptl_crystal_colour orange _exptl_crystal_size_max 0.17 _exptl_crystal_size_mid 0.06 _exptl_crystal_size_min 0.03 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 3.825 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 585 _exptl_absorpt_coefficient_mu 20.282 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.097 _exptl_absorpt_correction_T_max 0.2 _exptl_absorpt_process_details SADABS _exptl_special_details ; ? ; _diffrn_ambient_temperature 273(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker Smart platform CCD diffractometer' _diffrn_measurement_method 'profile data from \w scan and 4\f positions' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 5970 _diffrn_reflns_av_R_equivalents 0.0368 _diffrn_reflns_av_sigmaI/netI 0.0801 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 12 _diffrn_reflns_theta_min 2.31 _diffrn_reflns_theta_max 27.00 _reflns_number_total 4650 _reflns_number_gt 4209 _reflns_threshold_expression >2sigma(I) _computing_data_collection SMART _computing_cell_refinement SAINT _computing_data_reduction SAINT _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics Diamond _computing_publication_material ? _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness 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 threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) 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^)+(0.0000P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens ? _refine_ls_hydrogen_treatment ? _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0322(7) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.044(11) _refine_ls_number_reflns 4650 _refine_ls_number_parameters 183 _refine_ls_number_restraints 3 _refine_ls_R_factor_all 0.0421 _refine_ls_R_factor_gt 0.0372 _refine_ls_wR_factor_ref 0.0833 _refine_ls_wR_factor_gt 0.0812 _refine_ls_goodness_of_fit_ref 0.939 _refine_ls_restrained_S_all 0.939 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 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_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Sn1 Sn 0.61486(10) 0.53512(9) 0.53118(8) 0.01620(18) Uani 1 1 d . . . Sn2 Sn 0.32517(10) 0.22058(10) 0.09362(8) 0.01674(18) Uani 1 1 d . . . Sn3 Sn 0.75710(10) 0.65084(9) 0.22791(8) 0.01553(18) Uani 1 1 d . . . Zn1 Zn 1.28040(19) 0.65997(18) 0.24234(16) 0.0214(3) Uani 1 1 d . . . Zn2 Zn 0.91141(18) 0.79810(16) -0.05429(14) 0.0211(4) Uani 1 1 d . . . Zn3 Zn 1.0837(2) 0.2424(2) 0.59990(19) 0.0310(3) Uani 1 1 d . . . Se1 Se 1.05122(14) 0.82535(13) 0.21380(12) 0.0153(2) Uani 1 1 d . . . Se2 Se 0.46014(17) 0.21578(14) 0.35874(12) 0.0247(3) Uani 1 1 d . . . Se3 Se 0.73158(16) 0.49627(14) 0.77588(12) 0.0235(3) Uani 1 1 d . . . Se4 Se 0.17285(16) -0.07315(14) -0.10997(13) 0.0229(3) Uani 1 1 d . . . Se5 Se 0.91435(15) 0.66612(16) 0.49735(13) 0.0223(3) Uani 1 1 d . . . Se6 Se 0.39282(17) 0.70015(16) 0.51146(13) 0.0275(3) Uani 1 1 d . . . Se7 Se 0.61463(16) 0.33805(14) 0.04470(14) 0.0242(3) Uani 1 1 d . . . Se8 Se 0.08498(15) 0.36623(15) 0.05728(14) 0.0289(3) Uani 1 1 d . . . Se9 Se 0.53492(16) 0.81375(15) 0.18762(15) 0.0292(3) Uani 1 1 d . . . O1 O 1.2802(15) 0.1175(14) 0.6285(12) 0.051(3) Uani 1 1 d . . . O2 O 0.8585(16) 0.1133(14) 0.6331(14) 0.060(3) Uani 1 1 d . . . O3 O 0.9852(17) 0.2436(16) 0.3884(14) 0.064(3) Uani 1 1 d . . . O4 O 1.2233(17) 0.4840(15) 0.7611(13) 0.062(3) Uani 1 1 d . . . N N 0.7168(15) 0.9301(14) -0.0710(12) 0.030(2) 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 Sn1 0.0169(4) 0.0181(4) 0.0130(4) 0.0058(3) 0.0065(3) 0.0056(3) Sn2 0.0158(3) 0.0147(4) 0.0152(4) 0.0032(3) 0.0059(3) 0.0024(3) Sn3 0.0144(3) 0.0154(4) 0.0170(4) 0.0060(3) 0.0080(3) 0.0044(3) Zn1 0.0200(7) 0.0237(7) 0.0241(8) 0.0097(6) 0.0109(6) 0.0114(6) Zn2 0.0226(8) 0.0192(8) 0.0181(8) 0.0062(6) 0.0076(6) 0.0049(6) Zn3 0.0323(7) 0.0289(7) 0.0302(7) 0.0101(6) 0.0134(6) 0.0104(6) Se1 0.0136(5) 0.0170(5) 0.0155(5) 0.0068(4) 0.0068(4) 0.0047(4) Se2 0.0331(7) 0.0178(6) 0.0178(6) 0.0079(5) 0.0078(5) 0.0040(5) Se3 0.0307(6) 0.0175(6) 0.0145(6) 0.0064(5) 0.0053(5) 0.0026(5) Se4 0.0261(6) 0.0173(6) 0.0197(6) 0.0025(5) 0.0115(5) 0.0018(5) Se5 0.0155(5) 0.0300(7) 0.0180(6) 0.0099(5) 0.0058(4) 0.0040(5) Se6 0.0285(6) 0.0385(8) 0.0220(6) 0.0117(6) 0.0124(5) 0.0212(6) Se7 0.0239(6) 0.0192(6) 0.0262(7) 0.0011(5) 0.0164(5) 0.0026(5) Se8 0.0181(6) 0.0255(6) 0.0327(7) 0.0036(5) 0.0051(5) 0.0088(5) Se9 0.0244(6) 0.0309(7) 0.0480(8) 0.0237(7) 0.0224(6) 0.0163(5) O1 0.055(7) 0.055(7) 0.051(7) 0.025(6) 0.026(5) 0.026(5) O2 0.052(7) 0.051(7) 0.074(8) 0.025(6) 0.030(6) 0.008(5) O3 0.058(7) 0.088(9) 0.059(7) 0.047(7) 0.026(6) 0.027(6) O4 0.068(7) 0.050(7) 0.050(7) 0.012(5) 0.019(6) 0.010(6) N 0.030(5) 0.040(6) 0.027(6) 0.018(5) 0.010(5) 0.020(5) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; 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 Sn1 Se6 2.4799(13) . ? Sn1 Se3 2.4867(13) . ? Sn1 Se2 2.5474(14) . ? Sn1 Se5 2.5521(13) . ? Sn2 Se8 2.4736(13) . ? Sn2 Se4 2.4848(13) . ? Sn2 Se7 2.5458(13) . ? Sn2 Se2 2.5539(14) . ? Sn3 Se9 2.4731(13) . ? Sn3 Se1 2.5294(12) . ? Sn3 Se7 2.5363(14) . ? Sn3 Se5 2.5410(14) . ? Zn1 Se8 2.4345(18) 1_655 ? Zn1 Se9 2.4608(18) 1_655 ? Zn1 Se6 2.4687(19) 1_655 ? Zn1 Se1 2.5275(16) . ? Zn2 N 2.092(10) . ? Zn2 Se4 2.4305(18) 1_665 ? Zn2 Se3 2.4333(18) 1_554 ? Zn2 Se1 2.4859(17) . ? Zn3 O4 2.019(12) . ? Zn3 O3 2.027(11) . ? Zn3 O2 2.054(11) . ? Zn3 O1 2.060(10) . ? Se3 Zn2 2.4333(18) 1_556 ? Se4 Zn2 2.4305(18) 1_445 ? Se6 Zn1 2.4687(19) 1_455 ? Se8 Zn1 2.4345(18) 1_455 ? Se9 Zn1 2.4608(18) 1_455 ? 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 Se6 Sn1 Se3 112.82(5) . . ? Se6 Sn1 Se2 116.06(5) . . ? Se3 Sn1 Se2 96.99(4) . . ? Se6 Sn1 Se5 114.27(5) . . ? Se3 Sn1 Se5 107.39(4) . . ? Se2 Sn1 Se5 107.70(5) . . ? Se8 Sn2 Se4 108.75(5) . . ? Se8 Sn2 Se7 116.61(5) . . ? Se4 Sn2 Se7 98.85(4) . . ? Se8 Sn2 Se2 112.02(5) . . ? Se4 Sn2 Se2 112.66(5) . . ? Se7 Sn2 Se2 107.35(5) . . ? Se9 Sn3 Se1 104.27(4) . . ? Se9 Sn3 Se7 115.22(5) . . ? Se1 Sn3 Se7 112.37(5) . . ? Se9 Sn3 Se5 114.55(5) . . ? Se1 Sn3 Se5 100.14(4) . . ? Se7 Sn3 Se5 109.20(5) . . ? Se8 Zn1 Se9 113.89(7) 1_655 1_655 ? Se8 Zn1 Se6 116.28(7) 1_655 1_655 ? Se9 Zn1 Se6 113.63(6) 1_655 1_655 ? Se8 Zn1 Se1 105.60(6) 1_655 . ? Se9 Zn1 Se1 103.86(6) 1_655 . ? Se6 Zn1 Se1 101.51(6) 1_655 . ? N Zn2 Se4 111.8(3) . 1_665 ? N Zn2 Se3 108.8(3) . 1_554 ? Se4 Zn2 Se3 111.16(7) 1_665 1_554 ? N Zn2 Se1 105.4(3) . . ? Se4 Zn2 Se1 109.11(6) 1_665 . ? Se3 Zn2 Se1 110.44(6) 1_554 . ? O4 Zn3 O3 111.8(5) . . ? O4 Zn3 O2 109.5(5) . . ? O3 Zn3 O2 110.8(5) . . ? O4 Zn3 O1 107.1(5) . . ? O3 Zn3 O1 109.7(5) . . ? O2 Zn3 O1 107.9(4) . . ? Zn2 Se1 Zn1 107.54(6) . . ? Zn2 Se1 Sn3 101.79(5) . . ? Zn1 Se1 Sn3 106.31(5) . . ? Sn1 Se2 Sn2 103.10(5) . . ? Zn2 Se3 Sn1 98.72(5) 1_556 . ? Zn2 Se4 Sn2 100.45(6) 1_445 . ? Sn3 Se5 Sn1 101.06(4) . . ? Zn1 Se6 Sn1 99.79(5) 1_455 . ? Sn3 Se7 Sn2 101.00(5) . . ? Zn1 Se8 Sn2 102.40(5) 1_455 . ? Zn1 Se9 Sn3 101.49(5) 1_455 . ? _diffrn_measured_fraction_theta_max 0.978 _diffrn_reflns_theta_full 27.00 _diffrn_measured_fraction_theta_full 0.978 _refine_diff_density_max 1.481 _refine_diff_density_min -1.220 _refine_diff_density_rms 0.246