Enhancing catalytic alkane hydroxylation by tuning the outer coordination sphere in a heme-containing metal-organic framework.
Zee, David Z.; Harris, T. David; Chemical science 11 (2020) 5447–5452; doi:10.1039/d0sc01796e

data_1558028
_publ_section_title
;
 Enhancing catalytic alkane hydroxylation by tuning the outer coordination
 sphere in a heme-containing metal-organic framework.
;
_journal_issue                   21
_journal_name_full               'Chemical science'
_journal_page_first              5447
_journal_page_last               5452
_journal_paper_doi               10.1039/d0sc01796e
_journal_volume                  11
_journal_year                    2020
_chemical_formula_moiety         'C168 H114 N12 O64 Zr12'
_chemical_formula_sum            'C168 H114 N12 O64 Zr12'
_chemical_formula_weight         4419.35
_chemical_melting_point          ?
_chemical_name_common            PCN-224'
_chemical_name_systematic        '[H2TCPP]3[Zr6O4(OH)4(CH3CO2)6]2'
_space_group_crystal_system      cubic
_space_group_IT_number           229
_space_group_name_Hall           '-I 4 2 3'
_space_group_name_H-M_alt        'I m -3 m'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2020-02-24
_audit_creation_method
;
Olex2 1.3
(compiled 2019.11.21 svn.r41b79517 for OlexSys, GUI svn.r6003)
;
_audit_update_record
;
2020-03-26 deposited with the CCDC.	2020-05-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   38.649(4)
_cell_length_b                   38.649(4)
_cell_length_c                   38.649(4)
_cell_measurement_reflns_used    9717
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      68.11
_cell_measurement_theta_min      3.62
_cell_volume                     57732(10)
_computing_cell_refinement       'SAINT V8.34A (Bruker, 2017)'
_computing_data_collection       'APEX2 V2017.3 (Bruker, 2017)'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker Kappa APEX CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'Quazar optics'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0364
_diffrn_reflns_av_unetI/netI     0.0106
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       45
_diffrn_reflns_limit_h_min       -46
_diffrn_reflns_limit_k_max       43
_diffrn_reflns_limit_k_min       -45
_diffrn_reflns_limit_l_max       45
_diffrn_reflns_limit_l_min       -46
_diffrn_reflns_number            240641
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        66.566
_diffrn_reflns_theta_max         66.566
_diffrn_reflns_theta_min         1.616
_diffrn_source                   microsource
_diffrn_source_current           0.64
_diffrn_source_power             0.0286272
_diffrn_source_voltage           44.73
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.942
_exptl_absorpt_correction_T_max  0.7530
_exptl_absorpt_correction_T_min  0.6926
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016) was used for absorption correction.
wR2(int) was 0.0528 before and 0.0466 after correction.
The Ratio of minimum to maximum transmission is 0.9198.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear dark violet'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    0.508
_exptl_crystal_description       cuboctahedral
_exptl_crystal_F_000             8792
_exptl_crystal_preparation
;
Single crystals were directly synthesized via solvothermal methods from ZrCl4,
DMF, benzoic acid, acetic acid, and tetrakis(carboxyphenyl)porphyrin.
;
_exptl_crystal_recrystallization_method 'See preparation details.'
_exptl_crystal_size_max          0.344
_exptl_crystal_size_mid          0.303
_exptl_crystal_size_min          0.264
_refine_diff_density_max         1.248
_refine_diff_density_min         -0.574
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.132
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     139
_refine_ls_number_reflns         4767
_refine_ls_number_restraints     217
_refine_ls_restrained_S_all      1.115
_refine_ls_R_factor_all          0.0610
_refine_ls_R_factor_gt           0.0563
_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^)+(0.0616P)^2^+175.0492P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1399
_refine_ls_wR_factor_ref         0.1450
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4422
_reflns_number_total             4767
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc01796e2.cif
_cod_data_source_block           PCN-224'
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_chemical_melting_point' value 'not measured' was changed
to '?' -- the value is undefined or not given.

Automatic conversion script
Id: cif_fix_values 7556 2019-12-06 15:28:31Z antanas 

 Adding full bibliography for 1558028--1558030.cif.

 Adding full bibliography for 1558028--1558030.cif.
;
_cod_original_cell_volume        57731(19)
_cod_database_code               1558028
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O4-C9 \\sim O4A-C9A
 with sigma of 0.02
 C9-C10 \\sim C9A-C10A
 with sigma of 0.02
 O4-C10 \\sim O4A-C10A
 with sigma of 0.04
3. Restrained planarity
 O4, O4_$2, C9, C10
 with sigma of 0.1
 O4A_$2, O4A_$8, C9A_$8, C10A_$8
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
5. Rigid body (RIGU) restrains
 O3, N1, C1, C2, C3, C4, C5, C6, C7, C8
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Zr1, O1, O3, O2, O4, C9, C10, O4A, C9A, C10A, O2A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(O4A)=1-FVAR(1)
 Sof(C9A)=Sof(C10A)=Sof(H10D)=Sof(H10E)=Sof(H10F)=0.5*(1-FVAR(2))
 Sof(C9)=Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=0.5*FVAR(2)
 Sof(O4)=FVAR(1)
 Sof(O2A)=0.5*(1-FVAR(3))
 Sof(O2)=0.5*FVAR(3)
 Fixed Sof: H1(0.25)
7.a Aromatic/amide H refined with riding coordinates:
 N1(H1), C3(H3), C4(H4), C8(H8)
7.b Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C10A(H10D,H10E,H10F)
;
_shelx_res_checksum              37770
_olex2_exptl_crystal_mounting_method
;
In a solvent-free, dinitrogen-filled glovebox, activated crystals were coated 
with Paratone-N oil. The crystals were removed from the glovebox. A suitable 
single crystal was mounted on a MiTeGen loop, and cooled under a stream of N2 
at 100 K for collection.
;
_olex2_submission_original_sample_id PCN-224'
_olex2_submission_special_instructions 'No special instructions were received'