A homochiral vanadium-salen based cadmium bpdc MOF with permanent porosity as an asymmetric catalyst in solvent-free cyanosilylation.
Bhunia, Asamanjoy; Dey, Subarna; Moreno, José María; Diaz, Urbano; Concepcion, Patricia; Van Hecke, Kristof; Janiak, Christoph; Van Der Voort, Pascal; Chemical communications (Cambridge, England) 52 (2016) 1401–1404; doi:10.1039/c5cc09459c

data_7118465
_publ_section_title
;
 A homochiral vanadium-salen based cadmium bpdc MOF with permanent
 porosity as an asymmetric catalyst in solvent-free cyanosilylation.
;
_journal_issue                   7
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              1401
_journal_page_last               1404
_journal_paper_doi               10.1039/c5cc09459c
_journal_volume                  52
_journal_year                    2016
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C104 H100 Cd2 N8 O13.63 V2'
_chemical_formula_sum            'C104 H100 Cd2 N8 O13.63 V2'
_chemical_formula_weight         2006.69
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      orthorhombic
_space_group_IT_number           17
_space_group_name_Hall           'P 2c 2'
_space_group_name_H-M_alt        'P 2 2 21'
_symmetry_space_group_name_Hall  'P 2c 2'
_symmetry_space_group_name_H-M   'P 2 2 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-04-06
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3151 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2015-09-02 deposited with the CCDC.
2015-11-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.0460(5)
_cell_length_b                   24.0462(6)
_cell_length_c                   28.8442(6)
_cell_measurement_reflns_used    13815
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      75.7310
_cell_measurement_theta_min      3.0180
_cell_volume                     11823.0(5)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4839
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measurement_details
;
  1 omega   -2.00   23.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       41.6798  -19.0000 -138.0000 25

  2 omega  149.00  175.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  108.0000 -161.0000 26

  3 omega   59.00   85.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000 -121.0000   17.0000 26

  4 omega  109.00  143.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  108.0000 -161.0000 34

  5 omega   49.00   77.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       41.6798 -125.0000 -150.0000 28

  6 omega  -43.00   13.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.5000   30.0000 -150.0000 56

  7 omega -122.00  -83.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.5000  -94.0000  -60.0000 39

  8 omega -123.00  -81.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.5000  -94.0000  150.0000 42

  9 omega   33.00   73.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -94.0000  150.0000 40

 10 omega   83.00  108.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -94.0000  150.0000 25

 11 omega   43.00  121.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000 -125.0000   90.0000 78

 12 omega   50.00   98.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -45.0000 -120.0000 48

 13 omega   40.00   86.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -30.0000   30.0000 46

 14 omega   83.00  176.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   19.0000   28.0000 93

 15 omega -118.00   -9.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.6798  -77.0000 -150.0000 109

 16 omega   35.00   91.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -30.0000 -180.0000 56

 17 omega   58.00  111.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   15.0000  -60.0000 53

 18 omega   58.00  178.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   15.0000 -180.0000 120
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0762871000
_diffrn_orient_matrix_UB_12      0.0330311000
_diffrn_orient_matrix_UB_13      -0.0078762000
_diffrn_orient_matrix_UB_21      -0.0436341000
_diffrn_orient_matrix_UB_22      0.0544626000
_diffrn_orient_matrix_UB_23      0.0110872000
_diffrn_orient_matrix_UB_31      0.0209486000
_diffrn_orient_matrix_UB_32      -0.0069140000
_diffrn_orient_matrix_UB_33      0.0516651000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0926
_diffrn_reflns_av_unetI/netI     0.1091
_diffrn_reflns_laue_measured_fraction_full 0.999
_diffrn_reflns_laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            68492
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.966
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.620
_diffrn_reflns_theta_min         3.178
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.565
_exptl_absorpt_correction_T_max  0.946
_exptl_absorpt_correction_T_min  0.889
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.127
_exptl_crystal_description       plate
_exptl_crystal_F_000             4124.1
_exptl_crystal_size_max          0.1328
_exptl_crystal_size_mid          0.1279
_exptl_crystal_size_min          0.0661
_refine_diff_density_max         1.382
_refine_diff_density_min         -0.799
_refine_diff_density_rms         0.079
_refine_ls_abs_structure_details
;
 Flack x determined using 6032 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.003(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.957
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1193
_refine_ls_number_reflns         24063
_refine_ls_number_restraints     42
_refine_ls_restrained_S_all      0.959
_refine_ls_R_factor_all          0.0767
_refine_ls_R_factor_gt           0.0564
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0431P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1276
_refine_ls_wR_factor_ref         0.1393
_reflns_Friedel_coverage         0.814
_reflns_friedel_fraction_full    0.989
_reflns_friedel_fraction_max     0.942
_reflns_number_gt                17587
_reflns_number_total             24063
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5cc09459c2.cif
_cod_data_source_block           ab-212-f
_cod_database_code               7118465
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C104 H100 Cd2 N8 O13.63 V2'
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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. Uiso/Uaniso restraints and constraints
C12 \\sim C13 \\sim C37 \\sim C38: within 1.7A with sigma of 0.01 and sigma for
terminal atoms of 0.02
C60 \\sim C61 \\sim C62 \\sim C63 \\sim C64 \\sim C65: within 1.7A with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C13) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(V1A) = Uanis(V1B)
Uanis(O13A) = Uanis(O13B)
Uanis(V2A) = Uanis(V2B)
Uanis(O14A) = Uanis(O14B)
3. Others
 Sof(V1B)=1-FVAR(1)
 Sof(O13B)=0.5*(1-FVAR(2))
 Sof(V1A)=Sof(O13A)=FVAR(1)
 Sof(V2B)=1-FVAR(2)
 Sof(O14B)=0.5*(1-FVAR(3))
 Sof(V2A)=Sof(O14A)=FVAR(2)
4.a Ternary CH refined with riding coordinates:
 C15(H15), C20(H20), C88(H88), C93(H93)
4.b Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B), C89(H89A,
 H89B), C90(H90A,H90B), C91(H91A,H91B), C92(H92A,H92B)
4.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C12(H12), C13(H13), C14(H14), C21(H21), C23(H23), C25(H25),
 C33(H33), C34(H34), C35(H35), C36(H36), C37(H37), C38(H38), C41(H41), C42(H42),
  C44(H44), C45(H45), C47(H47), C48(H48), C50(H50), C51(H51), C55(H55),
 C56(H56), C58(H58), C59(H59), C61(H61), C62(H62), C64(H64), C65(H65), C68(H68),
  C69(H69), C70(H70), C71(H71), C72(H72), C73(H73), C75(H75), C76(H76),
 C78(H78), C82(H82), C87(H87), C94(H94), C96(H96), C97(H97)
4.d Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C29(H29A,H29B,H29C),
 C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C84(H84A,H84B,H84C), C85(H85A,H85B,
 H85C), C86(H86A,H86B,H86C), C101(H10D,H10E,H10F), C102(H10G,H10H,H10I),
 C103(H10J,H10K,H10L)
;
_shelx_res_checksum              99912
_olex2_exptl_crystal_mounting_method 'mounted on a nylon loop'
_olex2_submission_special_instructions 'No special instructions were received'