Double Hangman Iron Porphyrin and the Effect of Electrostatic Nonbonding Interactions on Carbon Dioxide Reduction.
Margarit, Charles G.; Asimow, Naomi G.; Gonzalez, Miguel I.; Nocera, Daniel G.; The journal of physical chemistry letters  (2020) 1890–1895; doi:10.1021/acs.jpclett.9b03897

data_8000421
_publ_section_title
;
 Double Hangman Iron Porphyrin and the Effect of Electrostatic Nonbonding
 Interactions on Carbon Dioxide Reduction.
;
_journal_name_full               'The journal of physical chemistry letters'
_journal_page_first              1890
_journal_page_last               1895
_journal_paper_doi               10.1021/acs.jpclett.9b03897
_journal_year                    2020
_chemical_absolute_configuration unk
_chemical_formula_moiety
'0.5(C66.76 H51.03 N4 O12.76 Zn), 0.5(C66.59 H49.86 N4 O12.59 Zn), 0.6(C H2 Cl2)'
_chemical_formula_sum            'C67.28 H51.67 Cl1.19 N4 O12.68 Zn'
_chemical_formula_weight         1226.60
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-06-18
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3510 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 97.376(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.6905(9)
_cell_length_b                   19.3639(13)
_cell_length_c                   28.2678(19)
_cell_measurement_reflns_used    9690
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.02
_cell_measurement_theta_min      2.46
_cell_volume                     7431.8(9)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_collection       'Bruker APEX3'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_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, 2018)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type
'Bruker D8 Venture equipped with a Bruker Photon-100 CMOS Detector'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0645
_diffrn_reflns_av_unetI/netI     0.0453
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            96059
_diffrn_reflns_point_group_measured_fraction_full 0.977
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        23.290
_diffrn_reflns_theta_max         23.290
_diffrn_reflns_theta_min         2.179
_diffrn_source
'High Brilliance I\mS Microfocus X-ray Source'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.429
_exptl_absorpt_correction_T_max  0.938
_exptl_absorpt_correction_T_min  0.783
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016) was used for absorption correction.
wR2(int) was 0.1372 before and 0.0751 after correction.
The Ratio of minimum to maximum transmission is 0.8348.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'dark red'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.096
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             2540
_exptl_crystal_size_max          0.589
_exptl_crystal_size_mid          0.227
_exptl_crystal_size_min          0.152
_refine_diff_density_max         0.756
_refine_diff_density_min         -0.577
_refine_diff_density_rms         0.076
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.422(19)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1709
_refine_ls_number_reflns         20995
_refine_ls_number_restraints     2177
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0905
_refine_ls_R_factor_gt           0.0755
_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^)+(0.1515P)^2^+3.9808P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2128
_refine_ls_wR_factor_ref         0.2286
_reflns_Friedel_coverage         0.896
_reflns_Friedel_fraction_full    0.957
_reflns_Friedel_fraction_max     0.957
_reflns_number_gt                17096
_reflns_number_total             20995
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jz9b03897_si_002.cif
_cod_data_source_block           cm005_sq
_cod_depositor_comments          'Adding full bibliography for 8000421.cif.'
_cod_database_code               8000421
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.938
_shelx_estimated_absorpt_t_min   0.786
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.578(19)
 0.422(19)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
3. Restrained distances
 O13-H13
 0.87 with sigma of 0.01
 C111-C82 = C1H-C82 = C88-C72
 1.49 with sigma of 0.02
 O26-H26
 0.87 with sigma of 0.01
 O26-C134
 1.43 with sigma of 0.02
 C115-C117 = C1L-C1A = C92-C94
 1.46 with sigma of 0.02
 O20B-C122 = O20A-C1F = O20B-C116 = O20A-C1G = O14-C93 = O14-C99
 1.38 with sigma of 0.02
 C100-C98 = C123-C121 = C1N-C1E
 1.46 with sigma of 0.02
 O21B-C124 = O21A-C1M = C101-O15
 1.45 with sigma of 0.02
 O21B-C123 = O21A-C1N = O15-C100
 1.32 with sigma of 0.02
 O22B-C123 = O22A-C1N = O16-C100
 1.21 with sigma of 0.02
 C101-C100
 2.36 with sigma of 0.03
 C98-O16
 2.38 with sigma of 0.02
 O15-C98
 2.34 with sigma of 0.02
 C100-C98
 1.49 with sigma of 0.02
 C67-H13
 1.937898 with sigma of 0.02
 Zn1A-H13
 2.721619 with sigma of 0.02
 C134-H26
 2.012032 with sigma of 0.02
 Zn2A-H26
 2.75682 with sigma of 0.02
 O20B-C116 \\sim O20B-C122
 with sigma of 0.02
 O21A-O22A \\sim O21B-O22B
 with sigma of 0.02
4. Restrained planarity
 O15, C100, O16, C98, C97, C96, C95, C94, C99
 with sigma of 0.1
 O16, O15, C100, C99, C94, C95, C96, C97, C98, O14, C89, C90, C91, C92, C93,
 C88, C101
 with sigma of 0.1
5. Uiso/Uaniso restraints and constraints
Cl1 \\sim C135 \\sim Cl2: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
Cl4 \\sim C136 \\sim Cl3: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
O13 \\sim C67: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
Zn1A \\sim Zn1B: within 2A with sigma of 0.02 and sigma for terminal atoms of
0.04
C134 \\sim O26: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
C97 \\sim H70 \\sim C98 \\sim C96 \\sim C95 \\sim C94 \\sim C99 \\sim C93 \\sim
C92 \\sim C91 \\sim C90 \\sim C89 \\sim C88 \\sim O16 \\sim O15 \\sim C100
\\sim O14 \\sim O20B \\sim C117 \\sim C118 \\sim C119 \\sim C120 \\sim C121
\\sim C122 \\sim C114 \\sim C115 \\sim C116 \\sim O22B \\sim C124 \\sim O21B
\\sim C123 \\sim O20A \\sim C1A \\sim C1B \\sim C1C \\sim C1D \\sim C1E \\sim
C1F \\sim C1K \\sim C1L \\sim C1G \\sim O21A \\sim C1M \\sim C1N \\sim O22A
\\sim C112 \\sim C113 \\sim C111 \\sim C1J \\sim C1H \\sim C1I: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
O16 \\sim O15 \\sim C100 \\sim C99 \\sim C97 \\sim C98 \\sim O14 \\sim C101
\\sim C94 \\sim C89 \\sim C90 \\sim C91 \\sim C92 \\sim C93 \\sim C88 \\sim C95
\\sim C96: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04
C80 \\sim C79 \\sim C78 \\sim N7 \\sim C81 \\sim C82 \\sim C83 \\sim N8 \\sim
C84 \\sim C85 \\sim C86 \\sim C87 \\sim C68 \\sim N5 \\sim Zn2A \\sim Zn2B
\\sim C71 \\sim C70 \\sim C69 \\sim C72 \\sim C73 \\sim N6 \\sim C76 \\sim C75
\\sim C74 \\sim C77: within 2A with sigma of 0.04 and sigma for terminal atoms
of 0.08
6. Rigid body (RIGU) restrains
 C57, O8, C56, O9, C54, C53, C52, C51, C50, C55, O7, C44, C49, C48, C47, C46,
 C45
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C34, O2, C33, O3, C31, C30, C29, C28, O1, C26, C25, C32, C27, C24, C23, C22,
 C21
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C67, O13
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C109, Zn2A, N8, N5, N6, N7, O26, C86, C83, Zn2B, C71, C68, C76, C73, C78, C81,
  C134, C87, C85, C84, C82, C72, C70, C69, C77, C75, C74, C79, C80, C125, C111,
 C1H, C88, C102, C130, C126, C116, C112, C1G, C1I, C89, C93, C107, C103, C129,
 C127, O20B, C115, C113, O20A, C1L, C1J, C90, O14, C92, C106, C104, O25, C128,
 O23, C122, C117, C114, C1F, C1A, C1K, C91, C99, C94, C105, O19, O17, C133, O24,
  C131, C121, C118, C1E, C1B, C98, C95, O18, C110, C108, C132, C120, C123, C119,
  C1D, C1N, C1C, C100, C97, C96, O22B, O21B, O21A, O22A, O16, O15, C124, C1M,
 C101
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Others
 Sof(Zn1B)=1-FVAR(1)
 Sof(H67A)=Sof(H67B)=Sof(H67C)=Sof(H67D)=Sof(H67E)=Sof(H67F)=0.5*FVAR(2)
 Sof(Zn1A)=Sof(O13)=Sof(H13)=Sof(C67)=FVAR(1)
 Sof(Zn2B)=1-FVAR(2)
 Sof(H13J)=Sof(H13K)=Sof(H13L)=Sof(H13M)=Sof(H13N)=Sof(H13O)=0.5*FVAR(3)
 Sof(Zn2A)=Sof(O26)=Sof(H26)=Sof(C134)=FVAR(2)
 Sof(Cl2)=Sof(Cl1)=Sof(C135)=Sof(H13Q)=Sof(H13R)=FVAR(3)
 Sof(Cl4)=Sof(Cl3)=Sof(C136)=Sof(H13S)=Sof(H13T)=FVAR(4)
 Sof(O20B)=Sof(C118)=Sof(H118)=Sof(C119)=Sof(H119)=Sof(C120)=Sof(H120)=
 Sof(C121)=Sof(C122)=Sof(C117)=Sof(C115)=Sof(C116)=Sof(C111)=Sof(C112)=
 Sof(H112)=Sof(C113)=Sof(H113)=Sof(C114)=Sof(H114)=Sof(O22B)=Sof(C124)=
 Sof(O21B)=Sof(C123)=1-FVAR(5)
 Sof(H12A)=Sof(H12B)=Sof(H12C)=Sof(H12D)=Sof(H12E)=Sof(H12F)=0.5*(1-FVAR(6))
 Sof(O20A)=Sof(C1A)=Sof(C1B)=Sof(H1B)=Sof(C1C)=Sof(H1C)=Sof(C1D)=Sof(H1D)=
 Sof(C1E)=Sof(C1F)=Sof(C1G)=Sof(C1H)=Sof(C1I)=Sof(H1I)=Sof(C1J)=Sof(H1J)=
 Sof(C1K)=Sof(H1K)=Sof(C1L)=Sof(O21A)=Sof(C1M)=Sof(H1MA)=Sof(H1MB)=Sof(H1MC)=
 Sof(C1N)=Sof(O22A)=FVAR(5)
 Fixed Sof: H70(0.5) H57A(0.5) H57B(0.5) H57C(0.5) H57D(0.5) H57E(0.5)
 H57F(0.5) H34A(0.5) H34B(0.5) H34C(0.5) H34D(0.5) H34E(0.5) H34F(0.5)
 H10G(0.5) H10H(0.5) H10I(0.5) H10J(0.5) H10K(0.5) H10L(0.5)
8.a Secondary CH2 refined with riding coordinates:
 C135(H13Q,H13R), C136(H13S,H13T)
8.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C130(H130), C59(H59), C36(H36), C12(H12), C7(H7), C52(H52), C3(H3),
 C47(H47), C63(H63), C46(H46), C79(H79), C118(H118), C119(H119), C120(H120),
 C107(H107), C2(H2), C84(H84), C17(H17), C103(H103), C24(H24), C18(H18),
 C112(H112), C113(H113), C114(H114), C13(H13P), C53(H53), C22(H22), C51(H51),
 C23(H23), C75(H75), C74(H74), C45(H45), C80(H80), C126(H126), C70(H70),
 C40(H40), C69(H69), C85(H85), C29(H29), C28(H28), C30(H30), C95(H95), C96(H96),
  C97(H97), C89(H89), C90(H90), C91(H91), C1B(H1B), C1C(H1C), C1D(H1D),
 C1I(H1I), C1J(H1J), C1K(H1K)
8.c Fitted hexagon refined as free rotating group:
 C118(C119,C120,C121,C122,C117), C115(C116,C111,C112,C113,C114), C99(C94,C95,
 C96,C97,C98), C89(C90,C91,C92,C93,C88), C1A(C1B,C1C,C1D,C1E,C1F), C1G(C1H,C1I,
 C1J,C1K,C1L)
8.d Disordered Me refined with riding coordinates:
 C57(H57A,H57B,H57C,H57D,H57E,H57F), C124(H12A,H12B,H12C,H12D,H12E,H12F),
 C67(H67A,H67B,H67C,H67D,H67E,H67F), C34(H34A,H34B,H34C,H34D,H34E,H34F),
 C134(H13J,H13K,H13L,H13M,H13N,H13O), C101(H10G,H10H,H10I,H10J,H10K,H10L)
8.e Idealised Me refined as rotating group:
 C132(H13A,H13B,H13C), C64(H64A,H64B,H64C), C65(H65A,H65B,H65C), C133(H13D,
 H13E,H13F), C43(H43A,H43B,H43C), C109(H10A,H10B,H10C), C110(H11A,H11B,H11C),
 C108(H10D,H10E,H10F), C42(H42A,H42B,H42C), C131(H13G,H13H,H13I), C41(H41A,H41B,
 H41C), C66(H66A,H66B,H66C), C1M(H1MA,H1MB,H1MC)
;
_shelx_res_checksum              95831
_shelx_hkl_checksum              95070
_shelx_fab_checksum              83211
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'