A post-synthetically reduced borane-functionalised metal-organic framework with oxidation-inhibiting reactivity
Ablott, Timothy Andrew; Telfer, Shane; Richardson, Christopher; CrystEngComm  (2020) –; doi:10.1039/D0CE00930J

data_7240931
_publ_section_title
;
 A post-synthetically reduced borane-functionalised metal-organic
 framework with oxidation-inhibiting reactivity
;
_journal_name_full               CrystEngComm
_journal_paper_doi               10.1039/D0CE00930J
_journal_year                    2020
_chemical_absolute_configuration n/a
_chemical_formula_moiety         'C48 H30 O16 Zn4'
_chemical_formula_sum            'C48 H30 O16 Zn4'
_chemical_formula_weight         1124.20
_chemical_name_common            wuf-30
_chemical_properties_physical    Air-sensitive
_space_group_crystal_system      tetragonal
_space_group_IT_number           113
_space_group_name_Hall           'P -4 2ab'
_space_group_name_H-M_alt        'P -4 21 m'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-06-27
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-06-28 deposited with the CCDC.	2020-07-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   17.212(3)
_cell_length_b                   17.212(3)
_cell_length_c                   17.1680(18)
_cell_measurement_reflns_used    3273
_cell_measurement_temperature    293
_cell_measurement_theta_max      65.2
_cell_measurement_theta_min      7.3
_cell_volume                     5086.1(14)
_computing_cell_refinement
'CrystalClear-SM Expert 2.0 rc14 (Rigaku, 2009)'
_computing_data_collection
'CrystalClear-SM Expert 2.0 rc14 (Rigaku, 2009)'
_computing_data_reduction
'CrystalClear-SM Expert 2.0 rc14 (Rigaku, 2009)'
_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 (Sheldrick, 2015)'
_diffrn_ambient_temperature      293
_diffrn_detector                 RX
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'Rigaku IP'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_details
;
scan:
	Number of images: 72
	           Slice: 20.0000 - 200.0000
	     Image width: 2.5000
	        Exp time: 90.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	             Chi: 0.0000
	             Phi: 0.0000
	             XTD: 127.4000
	          2theta: -0.0315
scan:
	Number of images: 66
	           Slice: 20.0000 - 185.0000
	     Image width: 2.5000
	        Exp time: 90.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	             Chi: 15.0000
	             Phi: 0.0000
	             XTD: 127.4000
	          2theta: -0.0315
scan:
	Number of images: 66
	           Slice: 20.0000 - 185.0000
	     Image width: 2.5000
	        Exp time: 90.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	             Chi: 15.0000
	             Phi: 90.0000
	             XTD: 127.4000
	          2theta: -0.0315
;
_diffrn_measurement_device       'Crystal Goniometer'
_diffrn_measurement_device_type  'Rigaku RAXIS conversion'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support Fiber
_diffrn_orient_matrix_type       FS_PROCESS
_diffrn_orient_matrix_UB_11      -0.052949
_diffrn_orient_matrix_UB_12      -0.021544
_diffrn_orient_matrix_UB_13      -0.010408
_diffrn_orient_matrix_UB_21      0.017082
_diffrn_orient_matrix_UB_22      -0.016421
_diffrn_orient_matrix_UB_23      -0.053184
_diffrn_orient_matrix_UB_31      0.016737
_diffrn_orient_matrix_UB_32      -0.051397
_diffrn_orient_matrix_UB_33      0.021354
_diffrn_radiation_monochromator  Confocal
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.1042
_diffrn_reflns_av_unetI/netI     0.0568
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            31615
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        65.079
_diffrn_reflns_theta_max         65.079
_diffrn_reflns_theta_min         7.278
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           40.0
_diffrn_source_power             2.0
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    1.351
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.34
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   '(ABSCOR; Higashi, 1995)'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    0.734
_exptl_crystal_description       prism
_exptl_crystal_F_000             1132
_exptl_crystal_size_max          0.69
_exptl_crystal_size_mid          0.6
_exptl_crystal_size_min          0.3
_refine_diff_density_max         1.340
_refine_diff_density_min         -0.817
_refine_diff_density_rms         0.181
_refine_ls_abs_structure_details
;
 Flack x determined using 1031 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.02(3)
_refine_ls_extinction_coef       0.14(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2017/1 (Sheldrick 2017)'
_refine_ls_goodness_of_fit_ref   1.925
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     113
_refine_ls_number_reflns         4529
_refine_ls_number_restraints     143
_refine_ls_restrained_S_all      1.904
_refine_ls_R_factor_all          0.1844
_refine_ls_R_factor_gt           0.1781
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.4773
_refine_ls_wR_factor_ref         0.4859
_reflns_Friedel_coverage         0.808
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                3334
_reflns_number_total             4529
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0ce00930j3.cif
_cod_data_source_block           WUF-30
_cod_original_cell_volume        5086.1(16)
_cod_database_code               7240931
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.687
_shelx_estimated_absorpt_t_min   0.456
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.5(3)
 0.5(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 O1-C1
 1.3 with sigma of 0.01
 O2-C1
 1.3 with sigma of 0.01
 C21-C20
 1.45 with sigma of 0.02
 C6-C8
 1.5 with sigma of 0.02
 C32-C31 = C33-C32 = C34-C33 = C24-C23 = C23-C22 = C22-C21
 1.39 with sigma of 0.02
 C35-C33
 1.5 with sigma of 0.02
 C22-C22_$1
 2.41 with sigma of 0.04
 C23-C23_$1
 2.41 with sigma of 0.04
 C32_$1-C32
 2.41 with sigma of 0.04
 C33_$1-C33
 2.41 with sigma of 0.04
4. Restrained planarity
 C1, O1, C2, O2, C3, C4, C5, C6, C7
 with sigma of 0.1
 C6, C8, O8, C9
 with sigma of 0.1
 C33, C35, O35, C36
 with sigma of 0.1
5. Rigid bond restraints
 C2, C3, C4
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
6. Uiso/Uaniso restraints and constraints
Uanis(O20) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C24) = Uanis(C23)
Uanis(C21) = Uanis(C22)
Uanis(C23) = Uanis(C22)
Uanis(C24) = Uanis(C21)
Uanis(C2) = Uanis(C3)
Uanis(C2) = Uanis(C4)
Uanis(C31) = Uanis(C32) = Uanis(C33) = Uanis(C34)
7. Rigid body (RIGU) restrains
 C1, O1, C2, O2, C3, C4, C5, C6, C7
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C21, C22, C23, H23, C24, C30, O30, C31, C32, H32, C33, C34
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
8. Others
 Fixed Sof: H6(0.5) C8(0.5) O8(0.5) C9(0.5) H9A(0.5) H9B(0.5) H9C(0.5)
 H33(0.25) C35(0.25) O35(0.25) C36(0.25) H36A(0.25) H36B(0.25) H36C(0.25)
 Fixed Uiso: C8(0.25) O8(0.25) C9(0.25) C35(0.25) O35(0.25) C36(0.25)
 Fixed X: C8(0.9625) O8(0.953381) C9(1.021261) C20(0.5) C35(0.60271)
 O35(0.591161) C36(0.668851)
 Fixed Y: C8(0.123951) O8(0.1435) C9(0.16644) C20(0) C35(0.109261)
 O35(0.123211) C36(0.14901)
 Fixed Z: C8(0.46173) O8(0.53174) C9(0.41306) C20(1.167381) C35(0.8384)
 O35(0.909389) C36(0.79756)
9.a Me refined with everything fixed:
 C9(H9A,H9B,H9C), C36(H36A,H36B,H36C)
9.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C22(H22), C23(H23), C32(H32), C33(H33)
9.c Fitted hexagon refined as free rotating group:
 C2(C3,C4,C5,C6,C7)
;
_shelx_res_checksum              77910
_olex2_exptl_crystal_mounting_method 'Mounted in a polymer sleeve'
_olex2_submission_special_instructions 'No special instructions were received'