An expanded MIL-53-type coordination polymer with a reactive pendant ligand
Kunicki, Hannah; Chamberlain, Thomas W.; Clarkson, Guy J.; Kashtiban, Reza J.; Hooper, Joseph E.; Dawson, Daniel M.; Ashbrook, Sharon E.; Walton, Richard I.; CrystEngComm 20 (2018) 4355–; doi:10.1039/C8CE00891D

data_7231206
_publ_section_title
;
 An expanded MIL-53-type coordination polymer with a reactive pendant
 ligand
;
_journal_issue                   31
_journal_name_full               CrystEngComm
_journal_page_first              4355
_journal_paper_doi               10.1039/C8CE00891D
_journal_volume                  20
_journal_year                    2018
_chemical_formula_moiety         '0.25(C108 H76 Co4 N4 O20), 0.5(O)'
_chemical_formula_sum            'C27 H19 Co N O5.5'
_chemical_formula_weight         504.36
_space_group_crystal_system      orthorhombic
_space_group_IT_number           74
_space_group_name_Hall           '-I 2b 2'
_space_group_name_H-M_alt        'I m m a'
_symmetry_space_group_name_Hall  '-I 2b 2'
_symmetry_space_group_name_H-M   'I m m a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2018-03-01
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3461 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-05-08 deposited with the CCDC.
2018-06-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   25.1697(4)
_cell_length_b                   7.16550(10)
_cell_length_c                   16.6823(2)
_cell_measurement_reflns_used    4185
_cell_measurement_temperature    296(1)
_cell_measurement_theta_max      77.8070
_cell_measurement_theta_min      5.2910
_cell_volume                     3008.71(7)
_computing_cell_refinement
'CrysAlisPro, Agilent Technologies, Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET) (compiled Mar 27 2014,17:12:48)'
_computing_data_collection
'CrysAlisPro, Agilent Technologies, Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET) (compiled Mar 27 2014,17:12:48)'
_computing_data_reduction
'CrysAlisPro, Agilent Technologies, Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET) (compiled Mar 27 2014,17:12:48)'
_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      296(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1417
_diffrn_detector_type            Ruby
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.980
_diffrn_measurement_details
'#__ type_ start__ end____ width___ exp.time_ 1 omega -83.00 38.00 1.0000 20.5000 omega____ theta____ kappa____ phi______ frames - -41.7109 19.0000 -150.0000 121 #__ type_ start__ end____ width___ exp.time_ 2 omega -4.00 83.00 1.0000 20.5000 omega____ theta____ kappa____ phi______ frames - 41.7109 -99.0000 -30.0000 87 #__ type_ start__ end____ width___ exp.time_ 3 omega 41.00 98.00 1.0000 82.0000 omega____ theta____ kappa____ phi______ frames - 114.0000 -45.0000 30.0000 57 #__ type_ start__ end____ width___ exp.time_ 4 omega 38.00 91.00 1.0000 82.0000 omega____ theta____ kappa____ phi______ frames - 114.0000 -30.0000 -150.0000 53 #__ type_ start__ end____ width___ exp.time_ 5 omega 38.00 91.00 1.0000 82.0000 omega____ theta____ kappa____ phi______ frames - 114.0000 -30.0000 -60.0000 53 #__ type_ start__ end____ width___ exp.time_ 6 omega 38.00 91.00 1.0000 82.0000 omega____ theta____ kappa____ phi______ frames - 114.0000 -30.0000 -90.0000 53 #__ type_ start__ end____ width___ exp.time_ 7 omega 31.00 109.00 1.0000 82.0000 omega____ theta____ kappa____ phi______ frames - 114.0000 -94.0000 -180.0000 78 #__ type_ start__ end____ width___ exp.time_ 8 omega -118.00 -9.00 1.0000 20.5000 omega____ theta____ kappa____ phi______ frames - -41.7109 -77.0000 90.0000 109 #__ type_ start__ end____ width___ exp.time_ 9 omega -116.00 -17.00 1.0000 20.5000 omega____ theta____ kappa____ phi______ frames - -41.7109 -38.0000 -180.0000 99 #__ type_ start__ end____ width___ exp.time_ 10 omega 86.00 178.00 1.0000 82.0000 omega____ theta____ kappa____ phi______ frames - 114.0000 30.0000 30.0000 92 #__ type_ start__ end____ width___ exp.time_ 11 omega 31.00 77.00 1.0000 82.0000 omega____ theta____ kappa____ phi______ frames - 114.0000 -94.0000 -30.0000 46 #__ type_ start__ end____ width___ exp.time_ 12 omega 61.00 178.00 1.0000 82.0000 omega____ theta____ kappa____ phi______ frames - 114.0000 15.0000 -60.0000 117'
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Ruby, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0005481000
_diffrn_orient_matrix_UB_12      0.0919393000
_diffrn_orient_matrix_UB_13      -0.0057862000
_diffrn_orient_matrix_UB_21      -0.1616215000
_diffrn_orient_matrix_UB_22      0.0056082000
_diffrn_orient_matrix_UB_23      0.0401883000
_diffrn_orient_matrix_UB_31      0.1417618000
_diffrn_orient_matrix_UB_32      0.0067219000
_diffrn_orient_matrix_UB_33      0.0457986000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0353
_diffrn_reflns_av_unetI/netI     0.0251
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            8486
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.042
_diffrn_reflns_theta_min         5.303
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.744
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.57245
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'CrysAlisPro, Agilent Technologies, Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET) (compiled Mar 27 2014,17:12:48) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.113
_exptl_crystal_description       block
_exptl_crystal_F_000             1036
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.543
_refine_diff_density_min         -0.512
_refine_diff_density_rms         0.083
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     177
_refine_ls_number_reflns         1751
_refine_ls_number_restraints     159
_refine_ls_restrained_S_all      1.088
_refine_ls_R_factor_all          0.0591
_refine_ls_R_factor_gt           0.0535
_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^)+(0.1160P)^2^+3.4464P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1631
_refine_ls_wR_factor_ref         0.1712
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1541
_reflns_number_total             1751
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8ce00891d2.cif
_cod_data_source_block           hk3rt
_cod_depositor_comments
'Adding full bibliography for 7231205--7231207.cif.'
_cod_original_formula_sum        'C27 H19 Co N O5.50'
_cod_database_code               7231206
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C20 H20 N2 O2 Co'
_shelx_estimated_absorpt_t_max   0.764
_shelx_estimated_absorpt_t_min   0.330
_reflns_odcompleteness_completeness 99.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     69.95
_olex2_refinement_description
;
The asymmetric unit contains a cobalt with a biphenyl_4,4_dicarboxylate and a 4-styrylpyridine N-oxide ligand.
Additionally, there was a very small amount of electron density modeled as a partially occupied water molecule.
There is a lot of disorder and it is a relatively high symmetry space group.
The long axis of the diphenyl dicarboxylate sits on special position 4e with symmetry mm2 (two mirror planes and a 2 fold axis)
The carboxyl carbon (C17), the first carbon of the phenyl group (C18) and the carbon (C21) that links it to the symmetry
related phenyl of the biphenyl-4,4-dicarboxylate still sit on the mirror plane but the other carbons that make up the ring (C19 and C20) 
lie just off the mirror plane so were modeled over two positions either side of the mirror plane. Their occupancies were originally linked 
to a free variable but fixed at 50:50 for the final stages of the refinement.
The 4-styrylpyridine N-oxide also sits on special position 4e with symmetry mm2 (two mirror planes and a 2 fold axis).
Only the N-oxide oxygen (O1) still sits on the special position, the rest of the ligand lies just off the 2 fold axis and mirror planes.
The disorder was modeled by building the complete N-oxide ligand and refining behind a PART -1 instruction. Many DFIX and SIMU restraints
and AFIX 66 constraints were used to give these disordered components reasonable bonds lengths, angles and thermal parameters.
Additionally a small amount of electron density was modeled as a partially occupied water sitting on special position  8i on a mirror plane. 
It should have been refined at 0.5 occupancy to reflect its location on the special position but was refined at 0.125 occupancy 
(to reflect the amount of electron density).  No hydrogens were located for this solvent.

1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 C5-C8 = C9-C10
 1.4 with sigma of 0.0004
 C8-C9
 1.3 with sigma of 0.0004
3. Uiso/Uaniso restraints and constraints
N2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9: within 1.7A
with sigma of 0.002 and sigma for terminal atoms of 0.004
C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15: within 1.7A with sigma
of 0.001 and sigma for terminal atoms of 0.002
C18 \\sim C19A \\sim C20A \\sim C21 \\sim C19 \\sim C21: within 1.7A with sigma
of 0.004 and sigma for terminal atoms of 0.008
Uanis(C10) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C13)
\\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C15) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
4. Others
 Fixed Sof: N2(0.25) C3(0.25) H3(0.25) C4(0.25) H4(0.25) C5(0.25) C6(0.25)
 H6(0.25) C7(0.25) H7(0.25) C8(0.25) H8(0.25) C9(0.25) H9(0.25) C10(0.25)
 C11(0.25) H11(0.25) C12(0.25) H12(0.25) C13(0.25) H13(0.25) C14(0.25)
 H14(0.25) C15(0.25) H15(0.25) C19(0.5) H19(0.5) C20(0.5) H20(0.5) C19A(0.5)
 H19A(0.5) C20A(0.5) H20A(0.5) O100(0.125)
5.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C8(H8), C9(H9), C11(H11), C12(H12), C13(H13),
 C14(H14), C15(H15), C19(H19), C20(H20), C19A(H19A), C20A(H20A)
5.b Fitted hexagon refined as free rotating group:
 N2(C3,C4,C5,C6,C7), C10(C11,C12,C13,C14,C15)
;
_shelx_res_checksum              92879
_olex2_submission_special_instructions 'No special instructions were received'