Synthesis of a NbO Type Homochiral Cu(II) Metal-Organic Framework: Ferroelectric Behavior and Heterogeneous Catalysis of Three-Component Coupling and Pechmann Reactions.
Gupta, Anoop K.; De, Dinesh; Katoch, Rajesh; Garg, Ashish; Bharadwaj, Parimal K.; Inorganic chemistry 56 (2017) 4698–4706; doi:10.1021/acs.inorgchem.7b00342

data_4349425
_publ_section_title
;
 Synthesis of a NbO Type Homochiral Cu(II) Metal-Organic Framework:
 Ferroelectric Behavior and Heterogeneous Catalysis of Three-Component
 Coupling and Pechmann Reactions.
;
_journal_issue                   8
_journal_name_full               'Inorganic chemistry'
_journal_page_first              4698
_journal_page_last               4706
_journal_paper_doi               10.1021/acs.inorgchem.7b00342
_journal_volume                  56
_journal_year                    2017
_chemical_absolute_configuration S
_chemical_formula_moiety         'C21 H16 Cu2 N2 O10'
_chemical_formula_sum            'C21 H16 Cu2 N2 O10'
_chemical_formula_weight         583.44
_space_group_crystal_system      trigonal
_space_group_IT_number           146
_space_group_name_Hall           'R 3'
_space_group_name_H-M_alt        'R 3 :H'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2017-02-06
_audit_creation_method
;
Olex2 1.2
(compiled 2017.01.04 svn.r3372 for OlexSys, GUI svn.r5292)
;
_cell_angle_alpha                90.000(5)
_cell_angle_beta                 90.000(5)
_cell_angle_gamma                120.000(5)
_cell_formula_units_Z            9
_cell_length_a                   18.616(5)
_cell_length_b                   18.616(5)
_cell_length_c                   37.566(5)
_cell_measurement_reflns_used    999
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.490
_cell_measurement_theta_min      2.188
_cell_volume                     11275(5)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker SMART APEX'
_diffrn_measurement_method       /w-scans
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71069
_diffrn_reflns_av_R_equivalents  0.1366
_diffrn_reflns_av_unetI/netI     0.0896
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       44
_diffrn_reflns_limit_l_min       -45
_diffrn_reflns_number            43985
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.240
_diffrn_reflns_theta_max         25.490
_diffrn_reflns_theta_min         2.188
_exptl_absorpt_coefficient_mu    0.876
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6386
_exptl_absorpt_correction_type   empirical
_exptl_crystal_density_diffrn    0.773
_exptl_crystal_description       Block
_exptl_crystal_F_000             2646
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.17
_platon_squeeze_details
;
TITL r-3_b in R 3
CELL   18.6160   18.6160   37.5660     90.00     90.00    120.00
SPGR R3
C101 1.000 1.001 0.024 !       4.89 eA-3
C102 0.999 1.001 0.281 !       4.10 eA-3
C103 0.751 0.377 0.515 !       4.06 eA-3
C104 0.188 0.810 0.110 !       3.85 eA-3
Q105 0.717 0.438 0.421 !       3.77 eA-3
C106 0.999 1.010 0.407 !       3.52 eA-3
C107 0.665 0.331 0.222 !       3.36 eA-3
C108 1.001 0.988 0.922 !       3.25 eA-3
C109 1.000 0.998 0.140 !       3.24 eA-3
C110 1.000 1.009 0.226 !       3.03 eA-3
C111 0.502 0.017 0.367 !       2.98 eA-3
C112 1.001 1.004 0.336 !       2.58 eA-3
C113 0.626 0.307 0.376 !       2.57 eA-3
C114 0.701 0.361 0.209 !       2.56 eA-3
C115 0.421 0.700 0.440 !       2.55 eA-3
C116 0.843 0.421 0.757 !       2.46 eA-3
C117 1.000 0.999 0.438 !       2.40 eA-3
C118 0.314 0.640 0.042 !       2.37 eA-3
C119 0.387 0.592 0.527 !       2.29 eA-3
C120 0.204 0.338 0.258 !       2.29 eA-3
C121 0.922 0.061 0.447 !       2.23 eA-3
C122 0.343 0.235 0.032 !       2.19 eA-3
C123 0.392 0.957 0.344 !       2.16 eA-3
C124 0.888 0.623 0.016 !       2.15 eA-3
Q125 0.424 0.143 0.437 !       2.07 eA-3
C126 0.988 0.489 0.891 !       2.07 eA-3
C127 0.593 0.864 0.252 !       2.04 eA-3
C128 0.609 0.373 0.401 !       2.01 eA-3
C129 0.546 0.089 0.829 !       1.98 eA-3
C130 0.981 0.456 0.914 !       1.96 eA-3
C131 0.886 0.224 0.030 !       1.95 eA-3
C132 0.919 0.439 0.385 !       1.93 eA-3
C133 0.955 0.029 0.405 !       1.90 eA-3
C134 0.176 0.385 0.728 !       1.90 eA-3
C135 0.970 0.019 0.209 !       1.87 eA-3
C136 0.278 0.722 0.100 !       1.83 eA-3
C137 0.437 0.548 0.485 !       1.82 eA-3
C138 0.659 0.336 0.524 !       1.81 eA-3
C139 0.328 0.630 0.875 !       1.80 eA-3
C140 0.985 0.565 0.913 !       1.79 eA-3
C141 0.699 0.767 0.712 !       1.77 eA-3
C142 0.465 0.970 0.919 !       1.74 eA-3
C143 0.841 0.669 0.172 !       1.71 eA-3
C144 0.375 0.735 0.059 !       1.71 eA-3
C145 0.469 0.422 0.384 !       1.71 eA-3
C146 0.329 0.626 0.400 !       1.70 eA-3
Q147 0.175 0.345 0.833 !       1.69 eA-3
C148 0.246 0.640 0.524 !       1.69 eA-3
C149 1.002 0.971 0.731 !       1.68 eA-3
C150 0.468 0.593 0.889 !       1.67 eA-3
C151 0.062 0.116 0.241 !       1.66 eA-3
C152 0.284 0.625 0.929 !       1.64 eA-3
C153 0.519 0.732 0.330 !       1.63 eA-3
C154 0.098 0.327 0.218 !       1.62 eA-3
C155 0.097 0.767 0.228 !       1.61 eA-3
C156 0.534 0.770 0.360 !       1.60 eA-3
C157 0.530 0.348 0.883 !       1.60 eA-3
Q158 0.941 0.888 0.251 !       1.59 eA-3
C159 0.359 0.661 0.407 !       1.58 eA-3
C160 0.892 0.776 0.431 !       1.58 eA-3
Q161 0.129 0.315 0.836 !       1.56 eA-3
C162 0.168 0.783 0.830 !       1.56 eA-3
C163 0.873 0.200 0.444 !       1.53 eA-3
Q164 0.749 0.957 0.102 !       1.53 eA-3
Q165 0.188 0.308 0.111 !       1.52 eA-3
C166 0.142 0.091 0.530 !       1.51 eA-3
C167 0.813 0.905 0.798 !       1.51 eA-3
C168 0.594 0.816 0.148 !       1.50 eA-3
Q169 0.282 0.825 0.838 !       1.50 eA-3
Q170 0.517 0.981 0.772 !       1.50 eA-3
C171 0.955 0.908 0.366 !       1.50 eA-3
C172 0.671 0.328 0.838 !       1.48 eA-3
Q173 0.468 0.640 0.516 !       1.48 eA-3
C174 0.188 0.266 0.710 !       1.48 eA-3
C175 0.998 0.504 0.813 !       1.47 eA-3
C176 0.440 0.814 0.203 !       1.46 eA-3
Q177 0.160 0.845 0.811 !       1.46 eA-3
C178 0.422 0.840 0.275 !       1.45 eA-3
Q179 0.252 0.659 0.924 !       1.44 eA-3
C180 0.766 0.156 0.013 !       1.44 eA-3
C181 1.000 1.002 0.695 !       1.44 eA-3
Q182 0.528 0.902 0.777 !       1.43 eA-3
C183 0.282 0.233 0.615 !       1.42 eA-3
C184 0.515 0.611 0.314 !       1.42 eA-3
C185 0.052 0.031 0.616 !       1.41 eA-3
C186 0.624 0.375 0.367 !       1.41 eA-3
C187 0.051 0.862 0.585 !       1.41 eA-3
Q188 0.952 0.348 0.758 !       1.41 eA-3
C189 1.002 1.003 0.975 !       1.40 eA-3
C190 0.828 0.014 0.678 !       1.39 eA-3
C191 0.249 0.624 0.555 !       1.39 eA-3
C192 0.747 0.937 0.651 !       1.36 eA-3
C193 0.970 0.947 0.510 !       1.36 eA-3
C194 0.440 0.488 0.502 !       1.36 eA-3
C195 0.812 0.412 0.728 !       1.36 eA-3
C196 0.860 0.504 0.461 !       1.35 eA-3
C197 0.752 0.527 0.945 !       1.34 eA-3
Q198 0.052 0.672 0.094 !       1.34 eA-3
C199 1.003 0.815 0.623 !       1.34 eA-3
;
_refine_diff_density_max         1.123
_refine_diff_density_min         -0.598
_refine_diff_density_rms         0.098
_refine_ls_abs_structure_details
;
 Flack x determined using 2749 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.499(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     256
_refine_ls_number_reflns         9276
_refine_ls_number_restraints     29
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0916
_refine_ls_R_factor_gt           0.0674
_refine_ls_shift/su_max          0.046
_refine_ls_shift/su_mean         0.006
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1132P)^2^+23.1681P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1691
_refine_ls_wR_factor_ref         0.1944
_reflns_Friedel_coverage         0.992
_reflns_Friedel_fraction_full    0.992
_reflns_Friedel_fraction_max     0.992
_reflns_number_gt                7137
_reflns_number_total             9276
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic7b00342_si_001.cif
_cod_data_source_block           LCu
_cod_original_cell_volume        11275(6)
_cod_original_sg_symbol_H-M      'R 3'
_cod_database_code               4349425
_shelx_shelxl_version_number     2016/4
_shelx_estimated_absorpt_t_max   0.865
_shelx_estimated_absorpt_t_min   0.844
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C4-C3
 1.4 with sigma of 0.02
 C2-C3
 1.4 with sigma of 0.02
 C2-C8
 1.4 with sigma of 0.02
 C8-C7
 1.4 with sigma of 0.02
 C7-C6
 1.4 with sigma of 0.02
 C6-C4
 1.4 with sigma of 0.02
 N1-C18
 1.45 with sigma of 0.02
 N1-C19
 1.45 with sigma of 0.02
 C20-N2
 1.45 with sigma of 0.02
 N2-C17
 1.45 with sigma of 0.02
 C20-C19
 1.5 with sigma of 0.02
 C17-C18
 1.5 with sigma of 0.02
 C17-C21
 1.5 with sigma of 0.02
 C17-C20
 2.3 with sigma of 0.04
 C19-C17
 2.75 with sigma of 0.04
 C19-C18
 2.4 with sigma of 0.04
3. Restrained planarity
 C7, C2, C4, C8, C6, C3
 with sigma of 0.1
 C7, C2, C4, C8, C6, C3, N2
 with sigma of 0.1
 C1, C7, C2, C4, C8, C6, C3, C5, N2
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(C4) = Uanis(C5)
Uanis(C10) = Uanis(C11)
Uanis(C14) = Uanis(C16)
Uanis(C7) = Uanis(N1)
Uanis(Cu1) = Uanis(OW1)
Uanis(N2) = Uanis(C20)
Uanis(C12) = Uanis(O7)
5. Others
 Fixed X: C21(1.003409)
 Fixed Y: C21(0.287)
 Fixed Z: C21(0.8155)
6.a Ternary CH refined with riding coordinates:
 C17(H17)
6.b Secondary CH2 refined with riding coordinates:
 C19(H19A,H19B), C20(H20A,H20B), C18(H18A,H18B)
6.c Me refined with riding coordinates:
 C21(H21A,H21B,H21C)
6.d Aromatic/amide H refined with riding coordinates:
 C8(H8), C6(H6), C3(H3), C13(H13), C16(H16), C10(H10)
;
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'