Chiral porous metal-organic frameworks containing μ-oxo-bis[Ti(salan)] units for asymmetric cyanation of aldehydes.
Du, Xia; Li, Zijian; Liu, Yan; Yang, Shiping; Cui, Yong; Dalton transactions (Cambridge, England : 2003) 44 (2015) 12999–13002; doi:10.1039/c5dt01682g

data_7035521
_publ_section_title
;
 Chiral porous metal-organic frameworks containing \m-oxo-bis[Ti(salan)]
 units for asymmetric cyanation of aldehydes.
;
_journal_issue                   29
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              12999
_journal_page_last               13002
_journal_paper_doi               10.1039/c5dt01682g
_journal_volume                  44
_journal_year                    2015
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C41 H52 Br Cd N4 O5.5 Ti'
_chemical_formula_sum            'C41 H52 Br Cd N4 O5.5 Ti'
_chemical_formula_weight         929.07
_space_group_crystal_system      tetragonal
_space_group_IT_number           92
_space_group_name_Hall           'P 4abw 2nw'
_space_group_name_H-M_alt        'P 41 21 2'
_symmetry_space_group_name_Hall  'P 4abw 2nw'
_symmetry_space_group_name_H-M   'P 41 21 2'
_atom_sites_solution_hydrogens   geom
_audit_block_doi                 10.5517/cc14hywg
_audit_creation_date             2015-06-07
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2015-06-08 deposited with the CCDC.
2015-06-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   26.8901(2)
_cell_length_b                   26.8901(2)
_cell_length_c                   13.2591(3)
_cell_measurement_temperature    173(2)
_cell_volume                     9587.4(2)
_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      173.15
_diffrn_measured_fraction_theta_full 0.817
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker P4'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0486
_diffrn_reflns_av_unetI/netI     0.0592
_diffrn_reflns_Laue_measured_fraction_full 0.817
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            24662
_diffrn_reflns_point_group_measured_fraction_full 0.799
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         59.728
_diffrn_reflns_theta_min         3.287
_exptl_absorpt_coefficient_mu    6.282
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.287
_exptl_crystal_description       block
_exptl_crystal_F_000             3800
_exptl_crystal_size_max          0.07
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.521
_refine_diff_density_min         -1.063
_refine_diff_density_rms         0.109
_refine_ls_abs_structure_details
;
 Flack x determined using 2254 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.045(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     574
_refine_ls_number_reflns         6936
_refine_ls_number_restraints     157
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0775
_refine_ls_R_factor_gt           0.0672
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1500P)^2^+8.4316P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1965
_refine_ls_wR_factor_ref         0.2117
_reflns_Friedel_coverage         0.742
_reflns_Friedel_fraction_full    0.777
_reflns_Friedel_fraction_max     0.963
_reflns_number_gt                5995
_reflns_number_total             6936
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5dt01682g2.cif
_cod_data_source_block           mof2_sq
_cod_depositor_comments
'Adding full bibliography for 7035520--7035521.cif.'
_cod_original_cell_volume        9587.4(3)
_cod_original_formula_sum        'C41 H52 Br Cd N4 O5.50 Ti'
_cod_database_code               7035521
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.744
_shelx_estimated_absorpt_t_min   0.668
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C34-C28
 1.4 with sigma of 0.02
 O6A-C40A
 1.25 with sigma of 0.02
 O6-C40 = O5-C40
 1.22 with sigma of 0.02
 C40A-C41A
 1.51 with sigma of 0.02
 C41-C40 = C41A-C40A
 1.51 with sigma of 0.02
 O6A-C41A \\sim C41A-O5A
 with sigma of 0.02
3. Restrained planarity
 C22, N3, C19, C20, C18, C21
 with sigma of 0.1
4. Rigid bond restraints
 Cd1, C37
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C28, C34A
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
 C34, C35
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
 C34, C38
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
 N4, C37
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
 C37A, N4A
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
 C34A, C38A
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
 C40, O6
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C22A, C21A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C12, C18A
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C18A, C19A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C35A, C34A
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
 O5, N4
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
 O5, C40
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 O5, C40
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C40, C41
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C37A, N4A
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
 C38A, C34A
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
 C20A
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
 N3A, C21A
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
Cd1A \\sim O6: within 1.7A with sigma of 0.001 and sigma for terminal atoms of
0.08
C37 \\sim C38: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
Cd1 \\sim C37: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C35 \\sim C36: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C34 \\sim C35: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C34 \\sim C38: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C28 \\sim C34A: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C28 \\sim C34: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C34A \\sim C38A: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.08
C40 \\sim O6: within 1.7A with sigma of 0.001 and sigma for terminal atoms of
1.7
C40 \\sim O6: within 1.7A with sigma of 0.02 and sigma for terminal atoms of
0.08
O6A \\sim C40A: within 1.7A with sigma of 0.02 and sigma for terminal atoms of
0.08
C22A \\sim C21A: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C12 \\sim C18A: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C18A \\sim C19A: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C35A \\sim C34A: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C36A \\sim C35A: within 1.7A with sigma of 0.02 and sigma for terminal atoms of
0.08
O5 \\sim N4: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 0.08
O5 \\sim C40: within 1.7A with sigma of 0.02 and sigma for terminal atoms of
0.08
O5A \\sim C40A: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.08
C40 \\sim C41: within 1.7A with sigma of 0.02 and sigma for terminal atoms of
0.08
C41A \\sim C40A: within 1.7A with sigma of 0.005 and sigma for terminal atoms
of 0.08
Uanis(O5) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.2
Uanis(C37A) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.2
Uanis(C40A) = Uanis(C40)
Uanis(O6) = Uanis(O6A)
Uanis(C41A) = Uanis(C41)
Uanis(C41A) = Uanis(C41)
6. Rigid body (RIGU) restrains
 C18A, C12
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C22A, C21A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Others
 Sof(Cd1A)=Sof(Br1A)=Sof(O6A)=Sof(O5A)=Sof(C41A)=Sof(H41D)=Sof(H41E)=Sof(H41F)=
 Sof(C40A)=Sof(N4A)=Sof(C36A)=Sof(H36A)=Sof(C35A)=Sof(H35A)=Sof(C34A)=Sof(C38A)=
 Sof(H38A)=Sof(C37A)=Sof(H37A)=Sof(C22A)=Sof(H22A)=Sof(C18A)=Sof(C19A)=
 Sof(H19A)=Sof(C20A)=Sof(H20A)=Sof(N3A)=Sof(C21A)=Sof(H21A)=1-FVAR(1)
 Sof(Cd1)=Sof(C22)=Sof(H22)=Sof(Br1)=Sof(O5)=Sof(C40)=Sof(O6)=Sof(C41)=
 Sof(H41A)=Sof(H41B)=Sof(H41C)=Sof(C38)=Sof(H38)=Sof(C34)=Sof(C35)=Sof(H35)=
 Sof(C36)=Sof(H36)=Sof(N4)=Sof(C37)=Sof(H37)=Sof(N3)=Sof(C19)=Sof(H19)=Sof(C20)=
 Sof(H20)=Sof(C18)=Sof(C21)=Sof(H21)=FVAR(1)
8.a Ternary CH refined with riding coordinates:
 N0AA(H0AA), N2(H2), C3AA(H3AA), C2AA(H2AA)
8.b Secondary CH2 refined with riding coordinates:
 C23(H23A,H23B), C1AA(H1AA,H1AB), C7AA(H7AA,H7AB), C5(H5A,H5B), C8AA(H8AA,
 H8AB), C5AA(H5AA,H5AB)
8.c Me refined with riding coordinates:
 C39(H39A,H39B,H39C), C41(H41A,H41B,H41C), C41A(H41D,H41E,H41F)
8.d Aromatic/amide H refined with riding coordinates:
 C11(H11), C13(H13), C29(H29), C4AA(H4AA), C22(H22), C38(H38), C35(H35),
 C36(H36), C37(H37), C36A(H36A), C35A(H35A), C38A(H38A), C37A(H37A), C19(H19),
 C20(H20), C21(H21), C22A(H22A), C19A(H19A), C20A(H20A), C21A(H21A)
8.e Fitted hexagon refined as free rotating group:
 C11(C6AA,C9,C8,C13,C12), C29(C28,C4AA,C26,C24,C25), C38(C34,C35,C36,N4,C37),
 N4A(C36A,C35A,C34A,C38A,C37A), C22A(C18A,C19A,C20A,N3A,C21A)
8.f Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C32(H32A,H32B,H32C), C31(H31A,H31B,H31C), C33(H33A,H33B,
 H33C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C)
;
_shelx_res_checksum              87575
_shelx_fab_checksum              11622
_olex2_submission_special_instructions 'No special instructions were received'