Structural dynamics of a thermally silent triiron(II) spin crossover defect grid complex.
Velazquez-Garcia, Jose de Jesus; Basuroy, Krishnayan; Storozhuk, Darina; Wong, Joanne; Demeshko, Serhiy; Meyer, Franc; Henning, Robert; Techert, Simone; Dalton transactions (Cambridge, England : 2003)  (2023) –; doi:10.1039/d3dt02067c

data_7713865
_publ_section_title
;
 Structural dynamics of a thermally silent triiron(II) spin crossover
 defect grid complex.
;
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_paper_doi               10.1039/d3dt02067c
_journal_year                    2023
_chemical_formula_moiety         'C92 H62 Fe3 N24, 4(B F4), 4(C2 H3 N)'
_chemical_formula_sum            'C100 H74 B4 F16 Fe3 N28'
_chemical_formula_weight         2182.66
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-06-13
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-06-17 deposited with the CCDC.	2023-08-07 downloaded from the CCDC.
;
_cell_angle_alpha                91.34(3)
_cell_angle_beta                 95.92(3)
_cell_angle_gamma                107.86(3)
_cell_formula_units_Z            2
_cell_length_a                   14.030(3)
_cell_length_b                   14.500(3)
_cell_length_c                   24.380(5)
_cell_measurement_reflns_used    9430
_cell_measurement_temperature    130
_cell_measurement_theta_max      22.654
_cell_measurement_theta_min      1.289
_cell_volume                     4687.6(19)
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_diffrn_ambient_temperature      130
_diffrn_measured_fraction_theta_full 0.907
_diffrn_measured_fraction_theta_max 0.905
_diffrn_measurement_device_type
'High Precision 1-Axis Goniostat at P11 beamline(Petra III, DESY)'
_diffrn_measurement_method       '\f scan'
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.6199
_diffrn_reflns_av_R_equivalents  0.0141
_diffrn_reflns_av_unetI/netI     0.0116
_diffrn_reflns_Laue_measured_fraction_full 0.907
_diffrn_reflns_Laue_measured_fraction_max 0.905
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            63898
_diffrn_reflns_point_group_measured_fraction_full 0.907
_diffrn_reflns_point_group_measured_fraction_max 0.905
_diffrn_reflns_theta_full        21.835
_diffrn_reflns_theta_max         22.654
_diffrn_reflns_theta_min         1.289
_diffrn_source                   'undulator raditaion'
_exptl_absorpt_coefficient_mu    0.387
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            black
_exptl_crystal_density_diffrn    1.546
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             2224
_exptl_crystal_size_max          0.09
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.901
_refine_diff_density_min         -0.919
_refine_diff_density_rms         0.092
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.017
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1528
_refine_ls_number_reflns         17041
_refine_ls_number_restraints     266
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0543
_refine_ls_R_factor_gt           0.0531
_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^)+(0.0998P)^2^+2.9009P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1519
_refine_ls_wR_factor_ref         0.1532
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16245
_reflns_number_total             17041
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02067c16.cif
_cod_data_source_block           fe3_130k
_cod_original_cell_volume        4687.6(18)
_cod_database_code               7713865
_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
 N28A-C100
 1.14 with sigma of 0.02
 C98B-C97B
 1.456 with sigma of 0.01
 C100-N28A
 1.137 with sigma of 0.01
 C100-C99A
 1.456 with sigma of 0.01
 C97B-N27B
 2.593 with sigma of 0.02
 C99A-N28A
 2.593 with sigma of 0.02
 N27B-C98B
 1.14 with sigma of 0.02
 C98B-N27B
 1.137 with sigma of 0.01
 C97A-N27A
 2.593 with sigma of 0.02
 N27A-C98A
 1.14 with sigma of 0.02
 C98A-C97A
 1.456 with sigma of 0.01
 C98A-N27A
 1.137 with sigma of 0.01
 N28A-C99A
 2.59 with sigma of 0.04
 N27B-C97B
 2.59 with sigma of 0.04
 N27A-C97A
 2.59 with sigma of 0.04
 F16A-B4 \\sim F13B-B4
 with sigma of 0.02
 F11A-B3 \\sim F11B-B3
 with sigma of 0.02
 F10A-B3 \\sim F10B-B3
 with sigma of 0.02
 F12A-B3 \\sim F12B-B3
 with sigma of 0.02
 B3-F12A \\sim B3-F9 \\sim B3-F11A \\sim B3-F10A
 with sigma of 0.02
 F12A-F11A \\sim F12A-F10A \\sim F11A-F10A
 with sigma of 0.04
 F14A-F13B \\sim F14B-F13B
 with sigma of 0.02
 F13A-F13B \\sim F16B-F13B
 with sigma of 0.04
 F14B-F16B \\sim F14B-F13B \\sim F15B-F13B \\sim F16B-F13B
 with sigma of 0.04
 F15A-F13A \\sim F15B-F16B
 with sigma of 0.04
 F15A-F14A \\sim F15B-F14B
 with sigma of 0.04
 F14A-F16A \\sim F14B-F16A
 with sigma of 0.04
 F13A-F14A \\sim F16B-F14B
 with sigma of 0.04
 F13A-F16A \\sim F16B-F16A
 with sigma of 0.04
 F15A-F16A \\sim F15B-F16A
 with sigma of 0.04
 F15A-F13B \\sim F15B-F13B
 with sigma of 0.04
 N28A-C99A \\sim C99B-N28B
 with sigma of 0.04
 C100-C99A \\sim C1A-N28B
 with sigma of 0.02
 N28A-C100 \\sim C99B-C1A
 with sigma of 0.02
 F8A-F7A \\sim F8B-F7B
 with sigma of 0.04
 F5A-F8A \\sim F5B-F8B
 with sigma of 0.04
 F6A-F7A \\sim F6B-F7B
 with sigma of 0.04
 F5A-F6A \\sim F5B-F6B
 with sigma of 0.04
 F6A-B2A \\sim F6B-B2B
 with sigma of 0.02
 F5A-F7A \\sim F5B-F7B
 with sigma of 0.04
 F8A-B2A \\sim F8B-B2B
 with sigma of 0.02
 F6A-F8A \\sim F6B-F8B
 with sigma of 0.04
 F7A-B2A \\sim F7B-B2B
 with sigma of 0.02
 F5A-B2A \\sim F5B-B2B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
N27B \\sim C98B \\sim C97B: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
N27A \\sim C98A \\sim C97A: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
N28A \\sim C100 \\sim C99A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C99B \\sim C1A \\sim N28B: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
Uanis(C100) \\sim Ueq, Uanis(N28A) \\sim Ueq, Uanis(C99A) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(F11B) \\sim Ueq, Uanis(F12B) \\sim Ueq, Uanis(F10B) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C99B) \\sim Ueq, Uanis(C1A) \\sim Ueq, Uanis(N28B) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C98A) \\sim Ueq, Uanis(N27A) \\sim Ueq, Uanis(C97A) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(N28A) \\sim Ueq, Uanis(C100) \\sim Ueq, Uanis(C99A) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(F14B) \\sim Ueq, Uanis(F13B) \\sim Ueq, Uanis(F16B) \\sim Ueq,
Uanis(F15B) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(B2B) \\sim Ueq, Uanis(F7B) \\sim Ueq, Uanis(F5B) \\sim Ueq, Uanis(F6B)
\\sim Ueq, Uanis(F8B) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
4. Rigid body (RIGU) restrains
 N28A, C100, C99A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N27B, C98B, C97B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N27A, C98A, C97A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: F11A(0.9) F15A(0.8) F13A(0.8) F14A(0.8) F10A(0.9) F12A(0.9)
 F16A(0.8) N28A(0.78) C100(0.78) C99A(0.78) H99A(0.78) H99B(0.78) H99C(0.78)
 N27B(0.7) C98B(0.7) C97B(0.7) H97A(0.7) H97B(0.7) H97C(0.7) N27A(0.3)
 C98A(0.3) C97A(0.3) H97D(0.3) H97E(0.3) H97F(0.3) F13B(0.2) F11B(0.1)
 F10B(0.1) F12B(0.1) F15B(0.2) F16B(0.2) F14B(0.2) F5A(0.8) F6A(0.8) F8A(0.8)
 F7A(0.8) B2A(0.8) C99B(0.22) H99D(0.22) H99E(0.22) H99F(0.22) C1A(0.22)
 N28B(0.22) F7B(0.2) F5B(0.2) B2B(0.2) F6B(0.2) F8B(0.2)
6.a Aromatic/amide H refined with riding coordinates:
 N4(H4), N22(H22), C24(H24), C9(H9), C30(H30), C12(H12), C32(H32), C27(H27),
 C31(H31), C35(H35), C58(H58), C20(H20), C21(H21), C1(H1), C7(H7), C25(H25),
 C61(H61), C15(H15), C8(H8), C55(H55), C54(H54), C43(H43), C2(H2), C38(H38),
 C63(H63), C26(H26), C69(H69), C81(H81), C62(H62), C53(H53), C4(H4A), C17(H17),
 C3(H3), C44(H44), C40(H40), C70(H70), C50(H50), C16(H16), C39(H39), C84(H84),
 C49(H49), C22(H22A), C66(H66), C47(H47), C48(H48), C46(H46), C85(H85),
 C67(H67), C73(H73), C77(H77), C78(H78), C68(H68), C86(H86), C23(H23), C72(H72),
  C45(H45), C91(H91), C76(H76), C71(H71), C92(H92), C89(H89), C90(H90)
6.b Idealised Me refined as rotating group:
 C95(H95A,H95B,H95C), C93(H93A,H93B,H93C), C99A(H99A,H99B,H99C), C97B(H97A,
 H97B,H97C), C97A(H97D,H97E,H97F), C99B(H99D,H99E,H99F)
;
_olex2_submission_special_instructions 'No special instructions were received'