A Highly Water-Stable meta-Carborane-Based Copper Metal‒Organic Framework for Efficient High-Temperature Butanol Separation
Gan, Lei; Chidambaram, Arunraj; Fonquernie, Pol G.; Light, Mark E.; Choquesillo-Lazarte, Duane; Huang, Hongliang; Solano, Eduardo; Fraile, Julio; Viñas, Clara; Teixidor, Francesc; Navarro, Jorge A. R.; Stylianou, Kyriakos C.; Planas, José G.; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.0c01008

data_4134801
_publ_section_title
;
 A Highly Water-Stable meta-Carborane-Based Copper Metal--Organic
 Framework for Efficient High-Temperature Butanol Separation
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.0c01008
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         '0.5(C70 H88 B40 Cu4 N2 O18)'
_chemical_formula_sum            'C35 H44 B20 Cu2 N O9'
_chemical_formula_weight         965.99
_space_group_crystal_system      tetragonal
_space_group_IT_number           97
_space_group_name_Hall           'I 4 2'
_space_group_name_H-M_alt        'I 4 2 2'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2019-04-11
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   20.9233(5)
_cell_length_b                   20.9233(5)
_cell_length_c                   26.34200(10)
_cell_measurement_reflns_used    114985
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      34.2350
_cell_measurement_theta_min      1.6300
_cell_volume                     11532.1(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.18b (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.18b (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.18b (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.9424
_diffrn_measured_fraction_theta_max 0.9374
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \f      0.00 360.00   0.50    0.15   0.00   0.00  -0.00    --   720
  2  \f      0.00 360.00   0.50    0.15   0.00   0.00  45.00    --   720
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type  BL13_Xaloc_ALBA
_diffrn_measurement_method       '\f scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0115706000
_diffrn_orient_matrix_UB_12      0.0269214000
_diffrn_orient_matrix_UB_13      -0.0149997000
_diffrn_orient_matrix_UB_21      -0.0020809000
_diffrn_orient_matrix_UB_22      -0.0205655000
_diffrn_orient_matrix_UB_23      -0.0222748000
_diffrn_orient_matrix_UB_31      -0.0328108000
_diffrn_orient_matrix_UB_32      -0.0082445000
_diffrn_orient_matrix_UB_33      0.0067173000
_diffrn_radiation_monochromator  synchrotron
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.72932
_diffrn_reflns_av_R_equivalents  0.0727
_diffrn_reflns_av_unetI/netI     0.0247
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.944
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            224962
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.939
_diffrn_reflns_theta_full        25.950
_diffrn_reflns_theta_max         34.16
_diffrn_reflns_theta_min         1.62
_diffrn_source                   synchrotron
_exptl_absorpt_coefficient_mu    0.835
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.12269
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.18b (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.113
_exptl_crystal_description       plate
_exptl_crystal_F_000             3928
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.784
_refine_diff_density_min         -0.746
_refine_diff_density_rms         0.083
_refine_ls_abs_structure_details
;
 Flack x determined using 4065 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.031(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.066
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     305
_refine_ls_number_reflns         10372
_refine_ls_number_restraints     165
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0470
_refine_ls_R_factor_gt           0.0456
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1041P)^2^+1.3458P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1396
_refine_ls_wR_factor_ref         0.1413
_reflns_Friedel_coverage         0.814
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.934
_reflns_number_gt                9704
_reflns_number_total             10372
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c01008_si_002.cif
_cod_data_source_block           gl051607-re1
_cod_original_cell_volume        11532.1(6)
_cod_database_code               4134801
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.992
_shelx_estimated_absorpt_t_min   0.959
_reflns_odcompleteness_completeness 94.24
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     34.16
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All O(H,H) groups
2. Restrained distances
 N1-C19 \\sim N1-C17 \\sim N1-C21 \\sim N2-C20 \\sim N2-C18 \\sim N2-C22
 with sigma of 0.02
 C19-C20 \\sim C17-C18 \\sim C21-C22
 with sigma of 0.02
 C19-C17 \\sim C17-C21 \\sim C19-C21 \\sim C20-C18 \\sim C20-C22 \\sim C18-C22
 with sigma of 0.04
 C19-C18 \\sim C20-C17 \\sim C18-C21 \\sim C17-C22 \\sim C19-C22 \\sim C20-C21
 with sigma of 0.05
3. Uiso/Uaniso restraints and constraints
N1 \\sim N2 \\sim C17 \\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(C18) = Uanis(C17)
Uanis(C20) = Uanis(C19)
Uanis(C22) = Uanis(C21)
Uanis(N2) = Uanis(N1)
Uanis(C18) = Uanis(C17) = Uanis(C19) = Uanis(C20) = Uanis(C22) = Uanis(C21)
4. Rigid body (RIGU) restrains
 N1, N2, C17, C18, C19, C20, C21, C22
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: N1(0.25) N2(0.25) C17(0.25) H17A(0.25) H17B(0.25) C18(0.25)
 H18A(0.25) H18B(0.25) C19(0.25) H19A(0.25) H19B(0.25) C20(0.25) H20A(0.25)
 H20B(0.25) C21(0.25) H21A(0.25) H21B(0.25) C22(0.25) H22A(0.25) H22B(0.25)
 H5A(0.5) H5B(0.5)
6.a Free rotating group:
 N1(N2,C17,C18,C19,C20,C21,C22)
6.b Rotating group:
 O5(H5A,H5B)
6.c Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B), C20(H20A,H20B), C21(H21A,
 H21B), C22(H22A,H22B)
6.d Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C11(H11), C12(H12), C14(H14), C15(H15)
6.e Boron cage BH refined with riding coordinates:
 B1(H1), B2(H2), B3(H3A), B4(H4A), B5(H5), B6(H6A), B7(H7A), B8(H8), B9(H9),
 B10(H10)
;
_shelx_res_checksum              78835
_shelx_hkl_checksum              22319
_shelx_fab_checksum              99330
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a mylar loop oil'
_olex2_submission_original_sample_id GL051607_RE1
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 12.059
_oxdiff_exptl_absorpt_empirical_full_min 0.573