Chiral Cu(salen)-Based Metal-Organic Framework for Heterogeneously Catalyzed Aziridination and Amination of Olefins.
Liu, Yan; Li, Zijian; Yuan, Guozan; Xia, Qingchun; Yuan, Chen; Cui, Yong; Inorganic chemistry 55 (2016) 12500–12503; doi:10.1021/acs.inorgchem.6b02151

data_4349239
_publ_section_title
;
 Chiral Cu(salen)-Based Metal-Organic Framework for Heterogeneously
 Catalyzed Aziridination and Amination of Olefins.
;
_journal_issue                   24
_journal_name_full               'Inorganic chemistry'
_journal_page_first              12500
_journal_page_last               12503
_journal_paper_doi               10.1021/acs.inorgchem.6b02151
_journal_volume                  55
_journal_year                    2016
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C132 H164 Cd4 Cu4 N12 O28'
_chemical_formula_sum            'C132 H164 Cd4 Cu4 N12 O28'
_chemical_formula_weight         3070.50
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-10-19
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_cell_angle_alpha                90
_cell_angle_beta                 101.498(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.525(7)
_cell_length_b                   40.69(2)
_cell_length_c                   30.898(15)
_cell_measurement_reflns_used    3664
_cell_measurement_temperature    273(2)
_cell_measurement_theta_max      18.49
_cell_measurement_theta_min      2.25
_cell_volume                     17895(15)
_computing_cell_refinement       'SAINT v7.12A (Bruker, 2003)'
_computing_data_reduction        'SAINT v7.12A (Bruker, 2003)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      273.15
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0920
_diffrn_reflns_av_unetI/netI     0.2165
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       52
_diffrn_reflns_limit_k_min       -45
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            56316
_diffrn_reflns_point_group_measured_fraction_full 0.895
_diffrn_reflns_point_group_measured_fraction_max 0.869
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.612
_diffrn_reflns_theta_min         2.074
_exptl_absorpt_coefficient_mu    0.988
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            blue
_exptl_crystal_density_diffrn    1.140
_exptl_crystal_description       block
_exptl_crystal_F_000             6288
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.10
_refine_diff_density_max         0.817
_refine_diff_density_min         -0.664
_refine_diff_density_rms         0.096
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.16(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.897
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1425
_refine_ls_number_reflns         36141
_refine_ls_number_restraints     1812
_refine_ls_restrained_S_all      0.900
_refine_ls_R_factor_all          0.2018
_refine_ls_R_factor_gt           0.0794
_refine_ls_shift/su_max          0.009
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0804P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1636
_refine_ls_wR_factor_ref         0.2236
_reflns_Friedel_coverage         0.740
_reflns_Friedel_fraction_full    0.790
_reflns_Friedel_fraction_max     0.750
_reflns_number_gt                13338
_reflns_number_total             36141
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic6b02151_si_002.cif
_cod_data_source_block           1
_cod_original_cell_volume        17896(15)
_cod_database_code               4349239
_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
 C130-C132
 2.42 with sigma of 0.02
 N2-C19
 1.45 with sigma of 0.01
 N4-C49
 1.48 with sigma of 0.01
 N5-C72
 1.48 with sigma of 0.01
 C91-O20
 1.2 with sigma of 0.02
 C91-O19
 1.25 with sigma of 0.02
 N12-C132
 1.52 with sigma of 0.02
 N12-C130
 1.52 with sigma of 0.02
 O28-C130
 1.2 with sigma of 0.02
 N10-C126
 1.52 with sigma of 0.02
 N10-C125
 1.52 with sigma of 0.02
 N10-C124
 1.52 with sigma of 0.02
 O26-C124
 1.25 with sigma of 0.02
 N6-C79
 1.45 with sigma of 0.01
 O25-C121
 1.25 with sigma of 0.02
 C121-C123
 2.35 with sigma of 0.02
 C121-C122
 2.35 with sigma of 0.02
 C123-C122
 2.35 with sigma of 0.02
 C120-O24
 1.25 with sigma of 0.02
 C120-O23
 1.25 with sigma of 0.02
 C8-C9 = C8-C10 = C8-C11
 1.54 with sigma of 0.02
 C26-C27 = C26-C28 = C26-C29
 1.54 with sigma of 0.02
 C38-C39 = C38-C40 = C38-C41
 1.54 with sigma of 0.02
 C56-C57 = C56-C58 = C56-C59
 1.54 with sigma of 0.02
 C68-C69 = C68-C70 = C68-C71
 1.54 with sigma of 0.02
 C124-C126
 2.4 with sigma of 0.02
 O26-N10
 2.35 with sigma of 0.02
 C22-C26
 1.55 with sigma of 0.02
 C8-C9
 1.55 with sigma of 0.02
 C14-C15
 1.55 with sigma of 0.02
 C31-C32
 1.55 with sigma of 0.02
 C105-C104
 1.55 with sigma of 0.02
 C30-O6
 1.25 with sigma of 0.02
 C15-C16
 1.5 with sigma of 0.02
 C116-C117 = C116-C118 = C116-C119
 1.53 with sigma of 0.02
 N7-C102
 1.3 with sigma of 0.01
 C128-C129
 2.45 with sigma of 0.02
 C127-C128
 2.35 with sigma of 0.02
 O27-N11
 2.35 with sigma of 0.02
 N11-C129
 1.52 with sigma of 0.02
 N11-C128
 1.52 with sigma of 0.02
 N11-C127
 1.52 with sigma of 0.02
 O27-C127
 1.25 with sigma of 0.02
 C127-C129
 2.35 with sigma of 0.02
 N3-C42
 1.45 with sigma of 0.01
 C98-C96
 1.55 with sigma of 0.02
 C116-C112
 1.55 with sigma of 0.02
 C98-C99 = C98-C100 = C98-C101
 1.54 with sigma of 0.02
 C131-C132
 2.45 with sigma of 0.02
 N12-C131
 1.52 with sigma of 0.02
 C130-C131
 2.35 with sigma of 0.02
 N1-C12
 1.45 with sigma of 0.01
 C86-C87 = C86-C88 = C86-C89
 1.54 with sigma of 0.02
 C86-C88
 1.5 with sigma of 0.02
 N8-C109
 1.25 with sigma of 0.02
 C84-C90
 1.5 with sigma of 0.02
 N9-O25
 2.35 with sigma of 0.02
 N9-C123
 1.53 with sigma of 0.02
 N9-C122
 1.53 with sigma of 0.02
 N9-C121
 1.52 with sigma of 0.02
3. Restrained planarity
 C124, N10, C125, C126
 with sigma of 0.1
 C127, N11, C128, C129
 with sigma of 0.1
 C130, N12, C131, C132
 with sigma of 0.1
 C121, N9, C122, C123
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
N9 \\sim C123: within 1.7A with sigma of 0.02 and sigma for terminal atoms of
0.08
N9 \\sim C122: within 1.7A with sigma of 0.02 and sigma for terminal atoms of
0.08
N9 \\sim C121: within 1.7A with sigma of 0.02 and sigma for terminal atoms of
0.08
N10 \\sim C125: within 1.7A with sigma of 0.02 and sigma for terminal atoms of
0.08
N10 \\sim C126: within 1.7A with sigma of 0.02 and sigma for terminal atoms of
0.08
N10 \\sim C124: within 1.7A with sigma of 0.02 and sigma for terminal atoms of
0.08
N12 \\sim C132: within 1.7A with sigma of 0.02 and sigma for terminal atoms of
0.08
N12 \\sim C131: within 1.7A with sigma of 0.02 and sigma for terminal atoms of
0.08
C130 \\sim N12: within 1.7A with sigma of 0.02 and sigma for terminal atoms of
0.08
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6.a Fixed occupancy and ADP/Uiso:
 O15, O22, C1, C2, C3, C7, C9, C8, C11, C15, C30, C31, C48, C59, C60, C98,
 C102, C116, C121
6.b Ternary CH refined with riding coordinates:
 C13(H13), C18(H18), C43(H43), C48(H48), C73(H73), C78(H78), C103(H103),
 C108(H108)
6.c Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C15(H15A,H15B), C16(H16A,H16B), C17(H17A,H17B), C44(H44A,
 H44B), C45(H45A,H45B), C46(H46A,H46B), C47(H47A,H47B), C75(H75A,H75B),
 C74(H74A,H74B), C76(H76A,H76B), C77(H77A,H77B), C104(H10J,H10K), C106(H10L,
 H10M), C107(H10N,H10O), C105(H10P,H10Q)
6.d Me refined with riding coordinates:
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C27(H27A,H27B,
 H27C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C39(H39A,H39B,H39C), C40(H40A,
 H40B,H40C), C41(H41A,H41B,H41C), C57(H57A,H57B,H57C), C58(H58A,H58B,H58C),
 C59(H59A,H59B,H59C), C69(H69A,H69B,H69C), C70(H70A,H70B,H70C), C71(H71A,H71B,
 H71C), C87(H87A,H87B,H87C), C88(H88A,H88B,H88C), C89(H89A,H89B,H89C), C99(H99A,
 H99B,H99C), C100(H10D,H10E,H10F), C101(H10G,H10H,H10I), C117(H11D,H11E,H11F),
 C118(H11G,H11H,H11I), C119(H11J,H11K,H11L), C125(H12A,H12B,H12C), C126(H12D,
 H12E,H12F), C128(H12G,H12H,H12I), C129(H12J,H12K,H12L), C131(H13A,H13B,H13C),
 C132(H13D,H13E,H13F), C122(H12M,H12N,H12O), C123(H12P,H12Q,H12R)
6.e Aromatic/amide H refined with riding coordinates:
 C3(H3), C7(H7), C12(H12), C19(H19), C23(H23), C25(H25), C33(H33), C37(H37),
 C42(H42), C49(H49), C53(H53), C55(H55), C63(H63), C67(H67), C72(H72), C79(H79),
  C83(H83), C85(H85), C93(H93), C97(H97), C102(H102), C109(H109), C113(H113),
 C115(H115), C121(H121), C124(H124), C127(H127), C130(H130)
6.f Fitted hexagon refined as free rotating group:
 C20(C21,C22,C23,C24,C25), C32(C33,C34,C35,C36,C37), C50(C51,C52,C53,C54,C55),
 C62(C63,C64,C65,C66,C67), C80(C81,C82,C83,C84,C85), C92(C93,C94,C95,C96,C97),
 C110(C111,C112,C113,C114,C115)
;
_shelx_fab_checksum              49826
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'