The crystalline sponge method: MOF terminal ligand effects
Timothy R. Ramadhar; Shao-Liang Zheng; Yu-Sheng Chen; Jon Clardy; Chem.Commun. 51 (2015) 11252–; doi:10.1039/c5cc03840E

data_7117407
_publ_section_title
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 The crystalline sponge method: MOF terminal ligand effects
;
_journal_name_full               Chem.Commun.
_journal_page_first              11252
_journal_paper_doi               10.1039/c5cc03840E
_journal_volume                  51
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety
'C72 H48 Cl12 N24 Zn6, 1.89(C12 H22 O2), 0.44(C H Cl3)'
_chemical_formula_sum            'C95.1 H90 Cl13.31 N24 O3.78 Zn6'
_chemical_formula_weight         2493.49
_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'
_symmetry_space_group_name_Hall  'C 2y'
_symmetry_space_group_name_H-M   'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2015-05-26
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2015-05-27 deposited with the CCDC.
2015-06-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.2725(12)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   33.391(2)
_cell_length_b                   14.3975(10)
_cell_length_c                   33.897(2)
_cell_measurement_reflns_used    9874
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      13.431
_cell_measurement_theta_min      2.224
_cell_volume                     15720.4(17)
_computing_cell_refinement       'SAINT v8.34A (Bruker-AXS, 2013)'
_computing_data_collection       'APEX2 v2014.9 (Bruker-AXS, 2014)'
_computing_data_reduction        'SAINT v8.34A (Bruker-AXS, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2014 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXTL XT-2014 (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'three-circle goniometer with fixed chi'
_diffrn_measurement_device_type  'Bruker D8 goniometer'
_diffrn_measurement_method       'omega and phi scans'
_diffrn_radiation_monochromator  'Si 1 1 1'
_diffrn_radiation_source         synchrotron
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.40656
_diffrn_reflns_av_R_equivalents  0.0981
_diffrn_reflns_av_unetI/netI     0.0791
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       39
_diffrn_reflns_limit_h_min       -39
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            158634
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        14.015
_diffrn_reflns_theta_max         14.015
_diffrn_reflns_theta_min         0.712
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.612
_exptl_absorpt_correction_T_max  0.9802
_exptl_absorpt_correction_T_min  0.8703
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014/4) was used for absorption correction.
wR2(int) was 0.1134 before and 0.0812 after correction.
The Ratio of minimum to maximum transmission is 0.8879.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.054
_exptl_crystal_description       prism
_exptl_crystal_F_000             5060
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.744
_refine_diff_density_min         -0.877
_refine_diff_density_rms         0.284
_refine_ls_abs_structure_details
;
 Flack x determined using 6818 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.05(2)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1373
_refine_ls_number_reflns         27736
_refine_ls_number_restraints     80
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.1178
_refine_ls_R_factor_gt           0.0847
_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^)+(0.1777P)^2^+14.8349P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2399
_refine_ls_wR_factor_ref         0.2730
_reflns_Friedel_coverage         0.909
_reflns_Friedel_fraction_full    0.991
_reflns_Friedel_fraction_max     0.991
_reflns_number_gt                19831
_reflns_number_total             27736
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5cc03840e2.cif
_cod_data_source_block           zncl2menthylacetate_a
_cod_original_cell_volume        15720.2(19)
_cod_original_formula_sum        'C95.10 H90 Cl13.31 N24 O3.78 Zn6'
_cod_database_code               7117407
_shelxl_version_number           2014-7
_shelx_estimated_absorpt_t_max   0.982
_shelx_estimated_absorpt_t_min   0.914
_refine_ls_abs_structure_hooft   0.031(19)
_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
 Zn1-Cl1 \\sim Zn1A-Cl1A
 with sigma of 0.02
 Zn1-Cl2 \\sim Zn1A-Cl2A
 with sigma of 0.02
 Zn2-Cl3 \\sim Zn2A-Cl3A
 with sigma of 0.02
 Zn2-Cl4 \\sim Zn2A-Cl4A
 with sigma of 0.02
 Zn2-N7 \\sim Zn2A-N7
 with sigma of 0.02
 Zn4-Cl7 \\sim Zn4A-Cl7A
 with sigma of 0.02
 Zn4-Cl8 \\sim Zn4A-Cl8A
 with sigma of 0.02
 Zn4-N8 \\sim Zn4A-N8
 with sigma of 0.02
 Zn4-N13 \\sim Zn4A-N13
 with sigma of 0.02
 Zn6-Cl12 \\sim Zn6A-Cl1P
 with sigma of 0.02
 Zn6-N20 \\sim Zn6A-N20
 with sigma of 0.02
 C81-C82 \\sim C82-C83
 with sigma of 0.02
 C93-C94 \\sim C94-C95
 with sigma of 0.02
 C109-Cl13 \\sim C109-Cl14 \\sim C109-Cl15
 with sigma of 0.02
 Cl13-Cl14 \\sim Cl13-Cl15 \\sim Cl14-Cl15
 with sigma of 0.02
3. Rigid bond restraints
 C8, C9, C10
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C74, C75, C76, C77
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C81, C82, C83
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C86, C87, C88, C89, C90
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C109, Cl15, Cl13, Cl14
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C60 \\sim C61 \\sim C62: within 1.7A with sigma of 0.04 and sigma for terminal
atoms of 0.08
C81 \\sim C82 \\sim C83: within 1.7A with sigma of 0.04 and sigma for terminal
atoms of 0.08
C93 \\sim C94 \\sim C95: within 1.7A with sigma of 0.04 and sigma for terminal
atoms of 0.08
Cl15 \\sim Cl13 \\sim C109 \\sim Cl14: within 1.7A with sigma of 0.04 and sigma
for terminal atoms of 0.08
Uanis(Zn1) = Uanis(Zn1A)
Uanis(Cl1) = Uanis(Cl1A)
Uanis(Cl2) = Uanis(Cl2A)
Uanis(Zn2) = Uanis(Zn2A)
Uanis(Cl3) = Uanis(Cl3A)
Uanis(Cl4) = Uanis(Cl4A)
Uanis(Zn3) = Uanis(Zn3A)
Uanis(Cl5) = Uanis(Cl5A)
Uanis(Cl6) = Uanis(Cl6A)
Uanis(Zn4) = Uanis(Zn4A)
Uanis(Cl7) = Uanis(Cl7A)
Uanis(Cl8) = Uanis(Cl8A)
Uanis(Zn6) = Uanis(Zn6A)
Uanis(Cl12) = Uanis(Cl1P)
Uanis(Cl1Q) = Uanis(Cl11)
5. Others
 Sof(Zn1A)=Sof(Cl1A)=Sof(Cl2A)=1-FVAR(1)
 Sof(Zn1)=Sof(Cl1)=Sof(Cl2)=FVAR(1)
 Sof(Zn6A)=Sof(Cl1P)=Sof(Cl1Q)=1-FVAR(2)
 Sof(Zn6)=Sof(Cl11)=Sof(Cl12)=FVAR(2)
 Sof(Zn2A)=Sof(Cl3A)=Sof(Cl4A)=1-FVAR(3)
 Sof(Zn2)=Sof(Cl3)=Sof(Cl4)=FVAR(3)
 Sof(Zn4A)=Sof(Cl7A)=Sof(Cl8A)=1-FVAR(4)
 Sof(Zn4)=Sof(Cl7)=Sof(Cl8)=FVAR(4)
 Sof(Zn3A)=Sof(Cl5A)=Sof(Cl6A)=1-FVAR(5)
 Sof(Zn3)=Sof(Cl5)=Sof(Cl6)=FVAR(5)
 Sof(C73)=Sof(H73)=Sof(C74)=Sof(H74)=Sof(C75)=Sof(H75A)=Sof(H75B)=Sof(C76)=
 Sof(H76A)=Sof(H76B)=Sof(C77)=Sof(H77)=Sof(C78)=Sof(H78A)=Sof(H78B)=Sof(O1)=
 Sof(C79)=Sof(C80)=Sof(H80A)=Sof(H80B)=Sof(H80C)=Sof(O2)=Sof(C81)=Sof(H81A)=
 Sof(H81B)=Sof(H81C)=Sof(C82)=Sof(H82)=Sof(C83)=Sof(H83A)=Sof(H83B)=Sof(H83C)=
 Sof(C84)=Sof(H84A)=Sof(H84B)=Sof(H84C)=FVAR(6)
 Sof(C90)=Sof(H90A)=Sof(H90B)=Sof(C89)=Sof(H89)=Sof(C88)=Sof(H88A)=Sof(H88B)=
 Sof(C87)=Sof(H87A)=Sof(H87B)=Sof(C86)=Sof(H86)=Sof(C85)=Sof(H85)=Sof(O3)=
 Sof(C91)=Sof(C92)=Sof(H92A)=Sof(H92B)=Sof(H92C)=Sof(O4)=Sof(C93)=Sof(H93A)=
 Sof(H93B)=Sof(H93C)=Sof(C94)=Sof(H94)=Sof(C95)=Sof(H95A)=Sof(H95B)=Sof(H95C)=
 Sof(C96)=Sof(H96A)=Sof(H96B)=Sof(H96C)=FVAR(7)
 Sof(C109)=Sof(H109)=Sof(Cl13)=Sof(Cl14)=Sof(Cl15)=FVAR(8)
6.a Ternary CH refined with riding coordinates:
 C73(H73), C74(H74), C77(H77), C82(H82), C89(H89), C86(H86), C85(H85),
 C94(H94), C109(H109)
6.b Secondary CH2 refined with riding coordinates:
 C75(H75A,H75B), C76(H76A,H76B), C78(H78A,H78B), C90(H90A,H90B), C88(H88A,
 H88B), C87(H87A,H87B)
6.c Me refined with riding coordinates:
 C81(H81A,H81B,H81C), C93(H93A,H93B,H93C), C96(H96A,H96B,H96C)
6.d Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4), C5(H5), C6(H6), C7(H7), C9(H9), C10(H10), C11(H11),
 C12(H12), C14(H14), C15(H15), C19(H19), C20(H20), C22(H22), C23(H23), C24(H24),
  C25(H25), C27(H27), C28(H28), C29(H29), C30(H30), C32(H32), C33(H33),
 C37(H37), C38(H38), C40(H40), C41(H41), C42(H42), C43(H43), C45(H45), C46(H46),
  C47(H47), C48(H48), C50(H50), C51(H51), C55(H55), C56(H56), C58(H58),
 C59(H59), C60(H60), C61(H61), C63(H63), C64(H64), C65(H65), C66(H66), C68(H68),
  C69(H69)
6.e Idealised Me refined as rotating group:
 C80(H80A,H80B,H80C), C83(H83A,H83B,H83C), C84(H84A,H84B,H84C), C92(H92A,H92B,
 H92C), C95(H95A,H95B,H95C)
;
_shelx_res_checksum              92996
_shelx_hkl_checksum              71484
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'