# Supplementary Material (ESI) for Journal of Materials Chemistry # This journal is (C) The Royal Society of Chemistry 2006 data_global _journal_coden_Cambridge 1145 _publ_contact_author_name 'Isabelle Gautier-Luneau' _publ_contact_author_email isabelle.gautier-luneau@grenoble.cnrs.fr _publ_contact_author_address 'Laboratoire de Cristallographie-CNRS BP 166. 38042 Grenoble France' _publ_requested_journal 'J. Mat. Chem.' _publ_section_title ; New materials for infrared non linear optic. Syntheses, structural characterisations, second harmonic generation and optical transparency of M(IO3)3 metallic iodates. ; loop_ _publ_author_name _publ_author_address 'Phanon, Delphine' ; CNRS Laboratoire de Cristallographie BP 166. Grenoble 38042 France ; 'Mosset, Alain' ; CNRS Laboratoire de Cristallographie BP 166. Grenoble 38042 France ; 'Gautier-Luneau, Isabelle' ; CNRS Laboratoire de Cristallographie BP 166. Grenoble 38042 France ; data_compound_1 _database_code_depnum_ccdc_archive 'CCDC 620320' #----------------------------------------------------------------------------# # CHEMICAL INFORMATION # #----------------------------------------------------------------------------# _chemical_name_systematic ; ? ; _chemical_name_common 'alpha indium iodate' _chemical_formula_moiety 'I3 In1 O9' _chemical_formula_sum 'I3 In O9' _chemical_formula_weight 639.52 _chemical_compound_source 'synthesis as described' _chemical_absolute_configuration ad #----------------------------------------------------------------------------# # UNIT CELL INFORMATION # #----------------------------------------------------------------------------# _symmetry_cell_setting hexagonal _symmetry_space_group_name_H-M 'P 63' _symmetry_space_group_name_Hall 'P 6c' _symmetry_Int_Tables_number 173 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z+1/2' '-y, x-y, z' '-x+y, -x, z' 'x-y, x, z+1/2' 'y, -x+y, z+1/2' _cell_length_a 9.5410(10) _cell_length_b 9.5410(10) _cell_length_c 5.2660(10) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 120 _cell_volume 415.14(10) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) #----------------------------------------------------------------------------# # CRYSTAL INFORMATION # #----------------------------------------------------------------------------# _exptl_crystal_description needle _exptl_crystal_colour colourless _exptl_crystal_size_max 0.3 _exptl_crystal_size_mid 0.05 _exptl_crystal_size_min 0.03 _exptl_crystal_density_diffrn 5.116 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 560 loop_ _exptl_crystal_face_index_h _exptl_crystal_face_index_k _exptl_crystal_face_index_l _exptl_crystal_face_perp_dist -1 2 0 0.015000 1 -2 0 0.015000 0 0 1 0.140000 0 0 -1 0.140000 -2 0 0 0.017000 2 0 0 0.017000 0 1 0 0.015000 0 -1 0 0.015000 #----------------------------------------------------------------------------# # ABSORPTION CORRECTION # #----------------------------------------------------------------------------# _exptl_absorpt_coefficient_mu 7.421 _exptl_absorpt_correction_type integration _exptl_absorpt_correction_T_min 0.675 _exptl_absorpt_correction_T_max 0.826 _exptl_absorpt_process_details 'Coppens, 1970' #----------------------------------------------------------------------------# # DATA COLLECTION # #----------------------------------------------------------------------------# _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.56085 _diffrn_radiation_type AgKa _diffrn_radiation_monochromator graphite _diffrn_orient_matrix_type X=UH _diffrn_orient_matrix_UB_11 0.01 _diffrn_orient_matrix_UB_12 0 _diffrn_orient_matrix_UB_13 0 _diffrn_orient_matrix_UB_21 0 _diffrn_orient_matrix_UB_22 0.01 _diffrn_orient_matrix_UB_23 0 _diffrn_orient_matrix_UB_31 0 _diffrn_orient_matrix_UB_32 0 _diffrn_orient_matrix_UB_33 0.01 _diffrn_measurement_device '95mm CCD camera on \k-goniostat' _diffrn_measurement_device_type KappaCCD _diffrn_measurement_method CCD _diffrn_radiation_probe x-ray _diffrn_reflns_av_R_equivalents 0.0624 _diffrn_reflns_av_unetI/netI 0.0254 _diffrn_reflns_number 5342 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -6 _diffrn_reflns_limit_l_max 6 _diffrn_reflns_theta_min 3.37 _diffrn_reflns_theta_max 21.38 _diffrn_reflns_theta_full 21.38 _diffrn_measured_fraction_theta_full 0.989 _diffrn_measured_fraction_theta_max 0.989 _reflns_number_total 642 _reflns_number_gt 594 _reflns_threshold_expression >2sigma(I) #----------------------------------------------------------------------------# # COMPUTER PROGRAMS USED # #----------------------------------------------------------------------------# _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material 'WinGX publication routines (Farrugia, 1999)' #----------------------------------------------------------------------------# # REFINEMENT INFORMATION # #----------------------------------------------------------------------------# _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^)+(0.0131P)^2^+1.2490P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens none _refine_ls_hydrogen_treatment none _refine_ls_extinction_method none _refine_ls_number_reflns 642 _refine_ls_number_parameters 40 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0275 _refine_ls_R_factor_gt 0.0226 _refine_ls_wR_factor_ref 0.0391 _refine_ls_wR_factor_gt 0.038 _refine_ls_goodness_of_fit_ref 1.129 _refine_ls_restrained_S_all 1.128 _refine_ls_shift/su_max 0 _refine_ls_shift/su_mean 0 _refine_ls_abs_structure_details 'Flack H D (1983), 288 Friedel pairs' _refine_ls_abs_structure_Flack -0.08(10) _refine_diff_density_max 0.793 _refine_diff_density_min -1.082 _refine_diff_density_rms 0.191 #----------------------------------------------------------------------------# # ATOMIC TYPES, COORDINATES AND THERMAL PARAMETERS # #----------------------------------------------------------------------------# loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source In In -1.2843 0.8542 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' I I -0.8919 1.1868 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0056 0.0036 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 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 In In 0.6667 0.3333 0.89998(13) 0.01007(17) Uani 1 3 d S . . I I 0.31528(4) 0.33584(5) 0.76468(16) 0.01242(11) Uani 1 1 d . . . O1 O 0.4664(5) 0.2840(6) 0.6606(9) 0.0134(9) Uani 1 1 d . . . O2 O 0.1681(6) 0.2294(6) 0.5256(10) 0.0278(12) Uani 1 1 d . . . O3 O 0.4194(6) 0.5402(5) 0.6291(10) 0.0164(10) 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 In 0.0098(2) 0.0098(2) 0.0105(4) 0 0 0.00492(12) I 0.01304(18) 0.01424(18) 0.01257(17) 0.0035(2) 0.0013(3) 0.00878(14) O1 0.012(2) 0.019(2) 0.015(2) -0.0010(18) 0.0019(17) 0.013(2) O2 0.023(3) 0.026(3) 0.030(3) 0.001(2) -0.012(2) 0.009(2) O3 0.014(2) 0.010(2) 0.022(3) 0.0038(18) -0.002(2) 0.004(2) #----------------------------------------------------------------------------# # MOLECULAR GEOMETRY # #----------------------------------------------------------------------------# _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 In O1 2.136(4) 3_655 ? In O1 2.136(4) 4_665 ? In O1 2.136(4) . ? In O3 2.139(5) 5_655 ? In O3 2.139(5) 6 ? In O3 2.139(5) 2_665 ? I O1 1.827(4) . ? I O2 1.778(5) . ? I O3 1.833(5) . ? 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 O1 In O1 88.70(17) 3_655 4_665 ? O1 In O1 88.70(17) 3_655 . ? O1 In O1 88.70(17) 4_665 . ? O1 In O3 96.05(17) 3_655 5_655 ? O1 In O3 84.48(18) 4_665 5_655 ? O1 In O3 171.59(17) . 5_655 ? O1 In O3 84.48(18) 3_655 6 ? O1 In O3 171.59(17) 4_665 6 ? O1 In O3 96.05(17) . 6 ? O3 In O3 91.3(2) 5_655 6 ? O1 In O3 171.59(18) 3_655 2_665 ? O1 In O3 96.05(17) 4_665 2_665 ? O1 In O3 84.48(18) . 2_665 ? O3 In O3 91.3(2) 5_655 2_665 ? O3 In O3 91.3(2) 6 2_665 ? O2 I O1 97.9(2) . . ? O2 I O3 100.6(2) . . ? O1 I O3 95.1(2) . . ? #===END data_compound_2 _database_code_depnum_ccdc_archive 'CCDC 620321' #----------------------------------------------------------------------------# # CHEMICAL INFORMATION # #----------------------------------------------------------------------------# _chemical_name_systematic ; ? ; _chemical_name_common 'beta indium iodate' _chemical_formula_moiety 'I3 In1 O9' _chemical_formula_sum 'I3 In O9' _chemical_formula_weight 639.52 _chemical_compound_source 'synthesis as described' #----------------------------------------------------------------------------# # UNIT CELL INFORMATION # #----------------------------------------------------------------------------# _symmetry_cell_setting trigonal _symmetry_space_group_name_H-M 'R -3' _symmetry_space_group_name_Hall '-R 3' _symmetry_Int_Tables_number 148 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' 'x+2/3, y+1/3, z+1/3' '-y+2/3, x-y+1/3, z+1/3' '-x+y+2/3, -x+1/3, z+1/3' 'x+1/3, y+2/3, z+2/3' '-y+1/3, x-y+2/3, z+2/3' '-x+y+1/3, -x+2/3, z+2/3' '-x, -y, -z' 'y, -x+y, -z' 'x-y, x, -z' '-x+2/3, -y+1/3, -z+1/3' 'y+2/3, -x+y+1/3, -z+1/3' 'x-y+2/3, x+1/3, -z+1/3' '-x+1/3, -y+2/3, -z+2/3' 'y+1/3, -x+y+2/3, -z+2/3' 'x-y+1/3, x+2/3, -z+2/3' _cell_length_a 9.7530(10) _cell_length_b 9.7530(10) _cell_length_c 14.1740(10) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 120 _cell_volume 1167.61(19) _cell_formula_units_Z 6 _cell_measurement_temperature 293(2) #----------------------------------------------------------------------------# # CRYSTAL INFORMATION # #----------------------------------------------------------------------------# _exptl_crystal_description block _exptl_crystal_colour colourless _exptl_crystal_size_max 0.2 _exptl_crystal_size_mid 0.12 _exptl_crystal_size_min 0.05 _exptl_crystal_density_diffrn 5.457 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1680 loop_ _exptl_crystal_face_index_h _exptl_crystal_face_index_k _exptl_crystal_face_index_l _exptl_crystal_face_perp_dist 0 0 1 0.027000 0 0 -1 0.027000 1 -2 0 0.040000 -1 2 0 0.060000 -1 -2 0 0.032000 -3 1 0 0.049000 1 1 0 0.086000 3 -2 0 0.072000 1 -1 0 0.049000 -1 1 0 0.063000 #----------------------------------------------------------------------------# # ABSORPTION CORRECTION # #----------------------------------------------------------------------------# _exptl_absorpt_coefficient_mu 7.916 _exptl_absorpt_correction_type integration _exptl_absorpt_correction_T_min 0.43 _exptl_absorpt_correction_T_max 0.664 _exptl_absorpt_process_details 'Coppens, 1970' #----------------------------------------------------------------------------# # DATA COLLECTION # #----------------------------------------------------------------------------# _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.56085 _diffrn_radiation_type AgKa _diffrn_radiation_monochromator graphite _diffrn_radiation_probe x-ray _diffrn_orient_matrix_type X=UH _diffrn_orient_matrix_UB_11 0.01 _diffrn_orient_matrix_UB_12 0 _diffrn_orient_matrix_UB_13 0 _diffrn_orient_matrix_UB_21 0 _diffrn_orient_matrix_UB_22 0.01 _diffrn_orient_matrix_UB_23 0 _diffrn_orient_matrix_UB_31 0 _diffrn_orient_matrix_UB_32 0 _diffrn_orient_matrix_UB_33 0.01 _diffrn_measurement_device '95mm CCD camera on \k-goniostat' _diffrn_measurement_device_type KappaCCD _diffrn_measurement_method CCD _diffrn_reflns_av_R_equivalents 0.0415 _diffrn_reflns_av_unetI/netI 0.0271 _diffrn_reflns_number 2257 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 3.3 _diffrn_reflns_theta_max 21.4 _diffrn_reflns_theta_full 21.4 _diffrn_measured_fraction_theta_full 0.988 _diffrn_measured_fraction_theta_max 0.988 _reflns_number_total 598 _reflns_number_gt 553 _reflns_threshold_expression >2sigma(I) #----------------------------------------------------------------------------# # COMPUTER PROGRAMS USED # #----------------------------------------------------------------------------# _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material 'WinGX publication routines (Farrugia, 1999)' #----------------------------------------------------------------------------# # REFINEMENT INFORMATION # #----------------------------------------------------------------------------# _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^)+(0.0164P)^2^+7.4827P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens none _refine_ls_hydrogen_treatment none _refine_ls_extinction_method none _refine_ls_number_reflns 598 _refine_ls_number_parameters 40 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0271 _refine_ls_R_factor_gt 0.0229 _refine_ls_wR_factor_ref 0.0468 _refine_ls_wR_factor_gt 0.0455 _refine_ls_goodness_of_fit_ref 1.216 _refine_ls_restrained_S_all 1.216 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0 _refine_diff_density_max 0.878 _refine_diff_density_min -1.102 _refine_diff_density_rms 0.221 #----------------------------------------------------------------------------# # ATOMIC TYPES, COORDINATES AND THERMAL PARAMETERS # #----------------------------------------------------------------------------# loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source In In -1.2843 0.8542 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' I I -0.8919 1.1868 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0056 0.0036 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 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 In In 0 0 0.82309(4) 0.00909(15) Uani 1 3 d S . . I I 0.37133(4) 0.33736(3) 0.75258(2) 0.01106(12) Uani 1 1 d . . . O1 O 0.1842(4) 0.1574(4) 0.7278(2) 0.0116(7) Uani 1 1 d . . . O2 O 0.3919(5) 0.3068(4) 0.8761(3) 0.0202(8) Uani 1 1 d . . . O3 O 0.2918(4) 0.4684(4) 0.7582(2) 0.0147(7) 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 In 0.00836(19) 0.00836(19) 0.0106(3) 0 0 0.00418(9) I 0.00853(18) 0.00974(18) 0.01423(18) -0.00304(11) 0.00038(12) 0.00406(13) O1 0.0100(17) 0.0091(17) 0.0118(16) -0.0016(13) 0.0003(13) 0.0018(14) O2 0.030(2) 0.0146(18) 0.0179(18) -0.0025(15) -0.0119(16) 0.0123(17) O3 0.0190(18) 0.0125(18) 0.0168(18) -0.0043(14) -0.0020(14) 0.0109(15) #----------------------------------------------------------------------------# # MOLECULAR GEOMETRY # #----------------------------------------------------------------------------# _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 In O3 2.141(3) 16_556 ? In O3 2.141(3) 17_446 ? In O3 2.141(3) 18_546 ? In O1 2.156(3) 3 ? In O1 2.156(3) 2 ? In O1 2.156(3) . ? I O3 1.798(3) . ? I O2 1.803(4) . ? I O1 1.825(3) . ? 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 O3 In O3 91.18(13) 16_556 17_446 ? O3 In O3 91.18(13) 16_556 18_546 ? O3 In O3 91.18(13) 17_446 18_546 ? O3 In O1 174.72(13) 16_556 3 ? O3 In O1 93.97(13) 17_446 3 ? O3 In O1 89.82(13) 18_546 3 ? O3 In O1 93.97(13) 16_556 2 ? O3 In O1 89.82(13) 17_446 2 ? O3 In O1 174.72(13) 18_546 2 ? O1 In O1 84.94(13) 3 2 ? O3 In O1 89.82(13) 16_556 . ? O3 In O1 174.72(13) 17_446 . ? O3 In O1 93.97(13) 18_546 . ? O1 In O1 84.94(13) 3 . ? O1 In O1 84.94(13) 2 . ? O3 I O2 101.41(16) . . ? O3 I O1 96.46(16) . . ? O2 I O1 99.66(16) . . ?