The Thermally Induced Decarboxylation Mechanism of a Mixed-Oxidation State Carboxylate-Based Iron Metal-Organic Framework
Drake, Hannah; Day, Gregory S.; Vali, Shaik Waseem; Xiao, Zhifeng; Banerjee, Sayan; Li, Jialuo; Joseph, Elizabeth; Kuszynski, Jason E.; Perry, Zachary; Kirchon, Angelo; Ozdemir, Osman; Lindahl, Paul; Zhou, Hong-Cai; Chemical Communications  (2019) –; doi:10.1039/C9CC04555D

data_7124224
_publ_section_title
;
 The Thermally Induced Decarboxylation Mechanism of a Mixed-Oxidation
 State Carboxylate-Based Iron Metal-Organic Framework
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C9CC04555D
_journal_year                    2019
_chemical_formula_moiety         'C48 H30 Fe6 N6 O32'
_chemical_formula_sum            'C48 H30 Fe6 N6 O32'
_chemical_formula_weight         1537.88
_chemical_name_common            PCN-250
_chemical_name_systematic
'catena-[hexakis(m-5,5'-((E)-diazenediyl)bis(benzene-1,3-dicarboxylato))-tetrakis(m-oxo)-dodeca-aqua-dodeca-iron unknown solvate]'
_space_group_crystal_system      cubic
_space_group_IT_number           218
_space_group_name_Hall           'P -4n 2 3'
_space_group_name_H-M_alt        'P -4 3 n'
_symmetry_space_group_name_Hall  'P -4n 2 3'
_symmetry_space_group_name_H-M   'P -4 3 n'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2019-09-09
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2019.08.16 svn.r3652 for OlexSys, GUI svn.r5895)
;
_audit_update_record
;
2019-09-12 deposited with the CCDC.    2019-09-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.9834(5)
_cell_length_b                   21.9834(5)
_cell_length_c                   21.9834(5)
_cell_measurement_reflns_used    9876
_cell_measurement_temperature    200.0
_cell_measurement_theta_max      28
_cell_measurement_theta_min      0.5
_cell_volume                     10623.9(4)
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL 2018/3 (Sheldrick, 2015)'
_diffrn_ambient_temperature      200.0
_diffrn_measured_fraction_theta_full 0.964
_diffrn_measured_fraction_theta_max 0.971
_diffrn_measurement_device_type  'Bruker P4'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           Synchrotron
_diffrn_radiation_wavelength     0.7288
_diffrn_reflns_av_R_equivalents  0.2412
_diffrn_reflns_av_unetI/netI     0.0753
_diffrn_reflns_Laue_measured_fraction_full 0.964
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            67255
_diffrn_reflns_point_group_measured_fraction_full 0.966
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        25.930
_diffrn_reflns_theta_max         29.029
_diffrn_reflns_theta_min         1.343
_diffrn_source                   'Advanced Light Source, Beamline 12.2.1'
_exptl_absorpt_coefficient_mu    0.907
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            'clear dark red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    0.961
_exptl_crystal_description       block
_exptl_crystal_F_000             3088
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_platon_squeeze_details          )
_refine_diff_density_max         0.426
_refine_diff_density_min         -0.544
_refine_diff_density_rms         0.083
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.09(3)
_refine_ls_extinction_coef       0.118(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.102
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     142
_refine_ls_number_reflns         4288
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.102
_refine_ls_R_factor_all          0.0468
_refine_ls_R_factor_gt           0.0414
_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^)+(0.0786P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1160
_refine_ls_wR_factor_ref         0.1273
_reflns_Friedel_coverage         0.855
_reflns_Friedel_fraction_full    0.968
_reflns_Friedel_fraction_max     0.973
_reflns_number_gt                3835
_reflns_number_total             4288
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc04555d2.cif
_cod_data_source_block           pcn-250_afteractivation
_cod_original_cell_volume        10623.9(7)
_cod_database_code               7124224
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.956
_shelx_estimated_absorpt_t_min   0.915
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.91(3)
 0.09(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All O(H,H) groups
3.a Rotating group:
 O6(H6A,H6B)
3.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C6(H6), C4(H4)
;
_platon_squeeze_special_details
;
A solvent mask was calculated and 3939 electrons were
found in a volume of 6109\%A^3 in 1 void per unit cell.
This is consistent with the presence of 
24[C3H7NO] per Formula Unit 
which account for 3840 electrons 
per unit cell.
;
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'