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_7117406
_publ_section_title
;
 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 Br11.98 N24 Zn5.99, 1.71(C12 H22 O2), 0.62(C H Cl3)'
_chemical_formula_sum
'C93.14 H86.24 Br11.98 Cl1.87 N24 O3.42 Zn5.99'
_chemical_formula_weight         3012.07
_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                 104.9361(14)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   33.964(3)
_cell_length_b                   14.5897(14)
_cell_length_c                   33.787(3)
_cell_measurement_reflns_used    9112
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      12.673
_cell_measurement_theta_min      2.220
_cell_volume                     16177(3)
_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     0.40651
_diffrn_reflns_av_R_equivalents  0.1001
_diffrn_reflns_av_unetI/netI     0.0783
_diffrn_reflns_laue_measured_fraction_full 0.999
_diffrn_reflns_laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       40
_diffrn_reflns_limit_h_min       -40
_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            163312
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        14.020
_diffrn_reflns_theta_max         14.020
_diffrn_reflns_theta_min         0.707
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.083
_exptl_absorpt_correction_T_max  0.9075
_exptl_absorpt_correction_T_min  0.7156
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014/4) was used for absorption correction.
wR2(int) was 0.1490 before and 0.0816 after correction.
The Ratio of minimum to maximum transmission is 0.7885.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.237
_exptl_crystal_description       prism
_exptl_crystal_F_000             5886
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.601
_refine_diff_density_min         -0.955
_refine_diff_density_rms         0.236
_refine_ls_abs_structure_details
;
 Flack x determined using 7739 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.054(19)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1432
_refine_ls_number_reflns         28563
_refine_ls_number_restraints     95
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.0997
_refine_ls_R_factor_gt           0.0710
_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^)+(0.1378P)^2^+29.0441P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2044
_refine_ls_wR_factor_ref         0.2298
_reflns_Friedel_coverage         0.915
_reflns_friedel_fraction_full    0.997
_reflns_friedel_fraction_max     0.996
_reflns_number_gt                20713
_reflns_number_total             28563
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5cc03840e2.cif
_cod_data_source_block           znbr2menthylacetate-chiralfrc_b
_cod_original_cell_volume        16176(3)
_cod_database_code               7117406
_shelxl_version_number           2014-7
_shelx_estimated_absorpt_t_max   0.940
_shelx_estimated_absorpt_t_min   0.681
_refine_ls_abs_structure_hooft   0.026(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. Shared sites
{Zn1, Zn1A}
3. Restrained distances
 Zn1-Br1 \\sim Zn1A-Br1A
 with sigma of 0.02
 Zn1-Br2 \\sim Zn1A-Br2A
 with sigma of 0.02
 Zn2-Br4 \\sim Zn2A-Br4A \\sim Zn2B-Br4B
 with sigma of 0.02
 Zn2-N2 \\sim Zn2A-N2 \\sim Zn2B-N2
 with sigma of 0.02
 Zn2-N7 \\sim Zn2A-N7 \\sim Zn2B-N7
 with sigma of 0.02
 Zn3-Br5 \\sim Zn3A-Br5A
 with sigma of 0.02
 Zn3-Br6 \\sim Zn3A-Br6A
 with sigma of 0.02
 Zn3-N9 \\sim Zn3A-N9
 with sigma of 0.02
 Zn3-N13 \\sim Zn3A-N13
 with sigma of 0.02
 Zn4-Br8 \\sim Zn4A-Br8A \\sim Zn4B-Br8B
 with sigma of 0.02
 Zn4-N15 \\sim Zn4A-N15 \\sim Zn4B-N15
 with sigma of 0.02
 Zn4-N19 \\sim Zn4A-N19 \\sim Zn4B-N19
 with sigma of 0.02
 Zn5-Br10 \\sim Zn5A-Br1N
 with sigma of 0.02
 Zn5-N20 \\sim Zn5A-N20
 with sigma of 0.02
 C74-C82 \\sim C86-C94
 with sigma of 0.02
 C77-C84 \\sim C89-C96
 with sigma of 0.02
 C83-C82 \\sim C82-C81
 with sigma of 0.02
 C97-Cl1 \\sim C97-Cl2 \\sim C97-Cl3
 with sigma of 0.02
4. Rigid bond restraints
 C82, C74, C73, C75, C76, C77, C78
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
C93 \\sim C94: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C98 \\sim Cl4 \\sim Cl5 \\sim Cl6: within 1.7A with sigma of 0.04 and sigma for
terminal atoms of 0.08
Uanis(Zn1) = Uanis(Zn1A)
Uanis(Br1) = Uanis(Br1A)
Uanis(Br2) = Uanis(Br2A)
Uanis(Zn2) = Uanis(Zn2A) = Uanis(Zn2B)
Uanis(Br3) = Uanis(Br3A) = Uanis(Br3B)
Uanis(Br4) = Uanis(Br4A) = Uanis(Br4B)
Uanis(Zn3) = Uanis(Zn3A)
Uanis(Br5) = Uanis(Br5A)
Uanis(Br6) = Uanis(Br6A)
Uanis(Zn4) = Uanis(Zn4A) = Uanis(Zn4B)
Uanis(Br7) = Uanis(Br7A) = Uanis(Br7B)
Uanis(Br8) = Uanis(Br8A) = Uanis(Br8B)
Uanis(Zn5) = Uanis(Zn5A)
Uanis(Br9) = Uanis(Br9A)
Uanis(Br10) = Uanis(Br1N)
6. Rigid body (RIGU) restrains
 C82, C83
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C93, C94
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C98, Cl4, Cl5, Cl6
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Same fragment restrains
{C98, Cl4, Cl5, Cl6} sigma for 1-2: 0.02, 1-3: 0.04
as
{C97, Cl1, Cl2, Cl3}
8. Others
 1*[Sof(Zn2)+Sof(Br3)+Sof(Br4)]+1*[Sof(Zn2A)+Sof(Br3A)+Sof(Br4A)]+1*[Sof(Zn2B)+
 Sof(Br3B)+Sof(Br4B)]=1 with esd of 0.1
 1*[Sof(Zn4)+Sof(Br7)+Sof(Br8)]+1*[Sof(Zn4A)+Sof(Br7A)+Sof(Br8A)]+1*[Sof(Zn4B)+
 Sof(Br7B)+Sof(Br8B)]=1 with esd of 0.1
 Sof(Zn2)=Sof(Br3)=Sof(Br4)=FVAR(1)
 Sof(Zn3A)=Sof(Br5A)=Sof(Br6A)=1-FVAR(2)
 Sof(Zn3)=Sof(Br5)=Sof(Br6)=FVAR(2)
 Sof(Zn1A)=Sof(Br1A)=Sof(Br2A)=1-FVAR(3)
 Sof(Zn1)=Sof(Br1)=Sof(Br2)=FVAR(3)
 Sof(Zn2A)=Sof(Br3A)=Sof(Br4A)=FVAR(4)
 Sof(Zn2B)=Sof(Br3B)=Sof(Br4B)=FVAR(5)
 Sof(Zn5A)=Sof(Br9A)=Sof(Br1N)=1-FVAR(6)
 Sof(Zn5)=Sof(Br9)=Sof(Br10)=FVAR(6)
 Sof(Zn4)=Sof(Br7)=Sof(Br8)=FVAR(7)
 Sof(Zn4A)=Sof(Br7A)=Sof(Br8A)=FVAR(8)
 Sof(Zn4B)=Sof(Br7B)=Sof(Br8B)=FVAR(9)
 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(10)
 Sof(C85)=Sof(H85)=Sof(C86)=Sof(H86)=Sof(C87)=Sof(H87A)=Sof(H87B)=Sof(C88)=
 Sof(H88A)=Sof(H88B)=Sof(C89)=Sof(H89)=Sof(C90)=Sof(H90A)=Sof(H90B)=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(11)
 Sof(C97)=Sof(H97)=Sof(Cl1)=Sof(Cl2)=Sof(Cl3)=FVAR(12)
 Sof(C98)=Sof(H98)=Sof(Cl4)=Sof(Cl5)=Sof(Cl6)=0.5*FVAR(14)
9.a Ternary CH refined with riding coordinates:
 C73(H73), C74(H74), C77(H77), C82(H82), C85(H85), C86(H86), C89(H89),
 C94(H94), C97(H97), C98(H98)
9.b Secondary CH2 refined with riding coordinates:
 C75(H75A,H75B), C76(H76A,H76B), C78(H78A,H78B), C87(H87A,H87B), C88(H88A,
 H88B), C90(H90A,H90B)
9.c 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),
  C69(H69), C25(H25), C27(H27), C28(H28), C29(H29), C30(H30), C32(H32),
 C33(H33), C37(H37), C38(H38), C40(H40), C41(H41), C46(H46), C45(H45), C43(H43),
  C42(H42), C47(H47), C48(H48), C50(H50), C51(H51), C55(H55), C56(H56),
 C58(H58), C59(H59), C64(H64), C63(H63), C61(H61), C60(H60), C65(H65), C66(H66),
  C68(H68)
9.d Idealised Me refined as rotating group:
 C80(H80A,H80B,H80C), C81(H81A,H81B,H81C), C83(H83A,H83B,H83C), C84(H84A,H84B,
 H84C), C92(H92A,H92B,H92C), C93(H93A,H93B,H93C), C95(H95A,H95B,H95C), C96(H96A,
 H96B,H96C)
;
_shelx_res_checksum              94311
_shelx_hkl_checksum              74234
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'