High temperature anionic Fe(III) spin crossover behavior in a mixed-valence Fe(II)/Fe(III) complex.
Ouyang, Zhi-Jian; Mo, Xiao-Ying; Ye, Jia-Qi; Yu, Xiao-Xuan; Huang, Shu-Yuan; Liu, Xiao-Ling; Chen, Wen-Bin; Gao, Song; Dong, Wen; Dalton transactions (Cambridge, England : 2003) 50 (2021) 5960–5967; doi:10.1039/d1dt00111f

data_7707048
_publ_section_title
;
 High temperature anionic Fe(III) spin crossover behavior in a
 mixed-valence Fe(II)/Fe(III) complex.
;
_journal_issue                   17
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              5960
_journal_page_last               5967
_journal_paper_doi               10.1039/d1dt00111f
_journal_volume                  50
_journal_year                    2021
_chemical_formula_moiety
'4(C22 H12 Fe N12 O4), 2(C36 H24 Fe N6), 6(C4 H9 N O), 7(H2 O)'
_chemical_formula_sum            'C184 H164 Fe6 N66 O29'
_chemical_formula_weight         4098.90
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-04-27
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-04-28 deposited with the CCDC.	2021-03-31 downloaded from the CCDC.
;
_cell_angle_alpha                82.518(2)
_cell_angle_beta                 74.902(2)
_cell_angle_gamma                84.267(2)
_cell_formula_units_Z            1
_cell_length_a                   16.2038(4)
_cell_length_b                   16.8009(3)
_cell_length_c                   17.1213(3)
_cell_measurement_reflns_used    23880
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.4440
_cell_measurement_theta_min      2.6600
_cell_volume                     4451.26(16)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.963
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -28.00  50.00   0.50    0.50    --   46.37 -25.00  57.00  156
  2  \w     -5.00  62.00   0.50    0.50    --   46.37 -57.00   0.00  134
  3  \w     33.00 118.00   0.50    0.50    --   46.37  25.00-139.00  170
  4  \w    134.00 178.00   0.50    3.00    --  107.00  25.00-139.00   88
  5  \w    133.00 178.00   0.50    3.00    --  107.00  15.00   0.00   90
  6  \w     96.00 130.00   0.50    3.00    --  107.00  25.00-139.00   68
  7  \w     89.00 129.00   0.50    3.00    --  107.00  15.00   0.00   80
  8  \w     49.00  75.00   0.50    3.00    --  107.00 -45.00  90.00   52
  9  \w    101.00 127.00   0.50    3.00    --  107.00 -77.00 150.00   52
 10  \w     76.00 122.00   0.50    3.00    --  107.00-134.00  68.08   92
 11  \w     82.00 117.00   0.50    3.00    --  107.00-125.00  30.00   70
 12  \w     58.00 115.00   0.50    3.00    --  107.00-125.00  90.00  114
 13  \w     51.00  77.00   0.50    3.00    --  107.00-125.00  30.00   52
 14  \w     34.00  96.00   0.50    3.00    --  107.00 -94.00  90.00  124
 15  \w     42.00 105.00   0.50    3.00    --  107.00 -94.00 120.00  126
 16  \w     36.00  77.00   0.50    3.00    --  107.00 -45.00   0.00   82
 17  \w     46.00  79.00   0.50    3.00    --  107.00 -45.00 -60.00   66
 18  \w     36.00 127.00   0.50    3.00    --  107.00 -77.00-120.00  182
 19  \w     73.00 116.00   0.50    3.00    --  107.00-125.00-150.00   86
 20  \w     67.00 103.00   0.50    3.00    --  107.00 -94.00-180.00   72
 21  \w     36.00  69.00   0.50    3.00    --  107.00 -30.00-150.00   66
 22  \w     44.00  70.00   0.50    3.00    --  107.00 -45.00-180.00   52
 23  \w     35.00  62.00   0.50    3.00    --  107.00 -30.00-120.00   54
 24  \w     34.00 108.00   0.50    3.00    --  107.00 -94.00  30.00  148
 25  \w     31.00  72.00   0.50    3.00    --  107.00 -25.00  57.00   82
 26  \w     35.00  79.00   0.50    3.00    --  107.00 -45.00 120.00   88
 27  \w     38.00  68.00   0.50    3.00    --  107.00 -30.00 150.00   60
 28  \w     34.00  75.00   0.50    3.00    --  107.00 -77.00 150.00   82
 29  \w     32.00  71.00   0.50    3.00    --  107.00 -30.00  30.00   78
 30  \w    -25.00  68.00   0.50    0.50    --   46.37 -77.00 150.00  186
 31  \w    -15.00  22.00   0.50    0.50    --  -46.37  25.00-139.00   74
 32  \w    -68.00 -35.00   0.50    3.00    -- -102.00  25.00-139.00   66
 33  \w    -70.00 -29.00   0.50    3.00    -- -102.00  61.00 -60.00   82
 34  \w    -94.00 -22.00   0.50    0.50    --  -46.37 125.00 -60.00  144
 35  \w   -117.00 -32.00   0.50    0.50    --  -46.37 -25.00  57.00  170
 36  \w   -107.00 -77.00   0.50    0.50    --  -46.37-125.00  30.00   60
 37  \w   -142.00-116.00   0.50    3.00    -- -102.00 -94.00 -60.00   52
 38  \w   -177.00-123.00   0.50    3.00    -- -102.00 -25.00  57.00  108
 39  \w   -169.00-144.00   0.50    3.00    -- -102.00 -94.00 -60.00   50
 40  \w   -116.00 -26.00   0.50    3.00    -- -102.00  15.00-120.00  180
 41  \w   -116.00 -90.00   0.50    3.00    -- -102.00 125.00-180.00   52
 42  \w   -116.00 -55.00   0.50    3.00    -- -102.00 125.00 -90.00  122
 43  \w   -116.00 -78.00   0.50    3.00    -- -102.00  61.00 -60.00   76
 44  \w   -117.00 -67.00   0.50    3.00    -- -102.00  61.00  30.00  100
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0597501000
_diffrn_orient_matrix_UB_12      -0.0229884000
_diffrn_orient_matrix_UB_13      -0.0809551000
_diffrn_orient_matrix_UB_21      0.0780454000
_diffrn_orient_matrix_UB_22      0.0196930000
_diffrn_orient_matrix_UB_23      0.0277952000
_diffrn_orient_matrix_UB_31      0.0090622000
_diffrn_orient_matrix_UB_32      -0.0876219000
_diffrn_orient_matrix_UB_33      0.0382445000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0428
_diffrn_reflns_av_unetI/netI     0.0437
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.963
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            60753
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.963
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.089
_diffrn_reflns_theta_min         2.659
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.603
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.74022
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.529
_exptl_crystal_description       block
_exptl_crystal_F_000             2118
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.994
_refine_diff_density_min         -0.614
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.102
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1367
_refine_ls_number_reflns         18150
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.104
_refine_ls_R_factor_all          0.0596
_refine_ls_R_factor_gt           0.0498
_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^)+(0.0726P)^2^+2.4528P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1355
_refine_ls_wR_factor_ref         0.1412
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15067
_reflns_number_total             18150
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt00111f2.cif
_cod_data_source_block           18-11-26-40_oy-5
_cod_depositor_comments
'Adding full bibliography for 7707047--7707048.cif.'
_cod_database_code               7707048
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C H O N Fe'
_shelx_estimated_absorpt_t_max   0.803
_shelx_estimated_absorpt_t_min   0.656
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Others
 Fixed Sof: O15(0.5) H15A(0.5) H15B(0.5) H96A(0.5) H96B(0.5) H96C(0.5)
 H96D(0.5) H96E(0.5) H96F(0.5) H97A(0.5) H97B(0.5) H97C(0.5) H97D(0.5)
 H97E(0.5) H97F(0.5) H99A(0.5) H99B(0.5) H99C(0.5) H99D(0.5) H99E(0.5)
 H99F(0.5) O18(0.5) N34(0.5) C95(0.5) O17(0.5) N33(0.5) C98(0.5) O13(0.4)
 H13A(0.4) H13B(0.4) O14(0.6) H14A(0.6) H14B(0.6)
 Fixed Uiso: H2(0.053) H4(0.053) H3(0.039) H4A(0.041) H5(0.041) H6(0.041)
 H8(0.035) H14(0.038) H15(0.04) H16(0.04) H17(0.036) H19(0.033) H6A(0.08)
 H8A(0.059) H25(0.048) H26(0.05) H27(0.054) H28(0.058) H30(0.05) H36(0.039)
 H37(0.041) H38(0.044) H39(0.043) H41(0.038) H45(0.037) H46(0.042) H47(0.04)
 H49(0.039) H50(0.041) H52(0.041) H53(0.041) H54(0.035) H57(0.047) H58(0.052)
 H59(0.051) H61(0.049) H62(0.048) H64(0.045) H65(0.043) H66(0.037) H69(0.038)
 H70(0.044) H71(0.045) H73(0.044) H74(0.046) H76(0.045) H77(0.043) H78(0.038)
 H81A(0.078) H81B(0.078) H81C(0.078) H82A(0.074) H82B(0.074) H82C(0.074)
 H84A(0.07) H84B(0.07) H84C(0.07) H90A(0.155) H90B(0.155) H90C(0.155)
 H91A(0.14) H91B(0.14) H91C(0.14) H94A(0.1) H94B(0.1) H94C(0.1) H12A(0.074)
 H12B(0.074) H15A(0.08) H15B(0.08) H16A(0.075) H16B(0.075) H96A(0.142)
 H96B(0.142) H96C(0.142) H96D(0.142) H96E(0.142) H96F(0.142) H97A(0.097)
 H97B(0.097) H97C(0.097) H97D(0.097) H97E(0.097) H97F(0.097) H99A(0.067)
 H99B(0.067) H99C(0.067) H99D(0.067) H99E(0.067) H99F(0.067) H13A(0.164)
 H13B(0.164) H14A(0.157) H14B(0.157)
 Fixed X: H2(0.0954) H4(0.5559) H3(0.1368) H4A(0.0633) H5(0.0216) H6(0.0313)
 H8(0.1746) H14(0.5272) H15(0.619) H16(0.6707) H17(0.6513) H19(0.4207)
 H6A(0.1548) H8A(0.5755) H25(0.3852) H26(0.3528) H27(0.2896) H28(0.216)
 H30(0.1946) H36(0.5709) H37(0.6675) H38(0.7112) H39(0.6798) H41(0.4328)
 H45(0.1799) H46(0.1754) H47(0.2922) H49(0.4477) H50(0.5673) H52(0.6446)
 H53(0.6364) H54(0.5089) H57(0.1713) H58(0.0308) H59(-0.0319) H61(-0.0144)
 H62(0.072) H64(0.2204) H65(0.3618) H66(0.4074) H69(0.3439) H70(0.3937)
 H71(0.4362) H73(0.453) H74(0.4285) H76(0.3586) H77(0.2999) H78(0.2871)
 H81A(0.0601) H81B(0.0663) H81C(-0.0236) H82A(-0.0669) H82B(0.0171) H82C(-
 0.0316) H84A(0.0946) H84B(0.1726) H84C(0.1572) H90A(0.9267) H90B(0.91)
 H90C(0.8411) H91A(0.7673) H91B(0.8113) H91C(0.8646) H94A(0.8203) H94B(0.8185)
 H94C(0.9038) H12A(0.1342) H12B(0.1543) H15A(0.8614) H15B(0.8163) H16A(0.6983)
 H16B(0.7095) H96A(0.0372) H96B(-0.0319) H96C(0.0657) H97A(0.0127) H97B(-
 0.0111) H97C(-0.0812) H99A(-0.0476) H99B(0.0211) H99C(0.0501) H13A(0.0672)
 H13B(0.1505) H14A(0.0563) H14B(0.0105)
 Fixed Y: H2(1.0313) H4(0.4664) H3(0.9171) H4A(1.0153) H5(1.0807) H6(1.0889)
 H8(0.8789) H14(0.8393) H15(0.7891) H16(0.6812) H17(0.5629) H19(0.5513)
 H6A(0.3143) H8A(-0.1853) H25(-0.0794) H26(-0.0417) H27(0.0543) H28(0.1741)
 H30(0.2282) H36(0.1655) H37(0.1074) H38(0.0017) H39(-0.1024) H41(-0.0782)
 H45(0.6874) H46(0.7841) H47(0.858) H49(0.8851) H50(0.8476) H52(0.7457)
 H53(0.63) H54(0.5694) H57(0.5062) H58(0.4996) H59(0.594) H61(0.722)
 H62(0.8154) H64(0.8739) H65(0.8594) H66(0.7547) H69(0.5953) H70(0.4902)
 H71(0.3669) H73(0.2787) H74(0.2659) H76(0.3264) H77(0.4396) H78(0.5616)
 H81A(1.2598) H81B(1.1663) H81C(1.2137) H82A(1.2365) H82B(1.2756) H82C(1.3053)
 H84A(1.0513) H84B(1.1048) H84C(1.038) H90A(-0.569) H90B(-0.5531) H90C(-0.5929)
 H91A(-0.4797) H91B(-0.3982) H91C(-0.4764) H94A(-0.3973) H94B(-0.4899) H94C(-
 0.4471) H12A(0.3975) H12B(0.434) H15A(-0.2112) H15B(-0.2788) H16A(-0.2271)
 H16B(-0.2736) H96A(0.6462) H96B(0.7189) H96C(0.7345) H97A(0.8871) H97B(0.8296)
 H97C(0.8604) H99A(0.8) H99B(0.7269) H99C(0.8147) H13A(0.3795) H13B(0.3797)
 H14A(0.5161) H14B(0.4524)
 Fixed Z: H2(0.9915) H4(0.3148) H3(0.5583) H4A(0.6337) H5(0.7597) H6(0.8899)
 H8(0.8867) H14(0.5465) H15(0.4359) H16(0.3487) H17(0.3035) H19(0.4637)
 H6A(0.6699) H8A(-0.0032) H25(0.5407) H26(0.6688) H27(0.7678) H28(0.8008)
 H30(0.5699) H36(0.2505) H37(0.1482) H38(0.0569) H39(-0.0024) H41(0.1232)
 H45(0.3724) H46(0.4579) H47(0.4418) H49(0.3613) H50(0.2662) H52(0.1651)
 H53(0.1082) H54(0.1384) H57(0.321) H58(0.3179) H59(0.2376) H61(0.1331)
 H62(0.0561) H64(0.0124) H65(0.0185) H66(0.1028) H69(0.0457) H70(-0.033)
 H71(0.0254) H73(0.1578) H74(0.2948) H76(0.4303) H77(0.4928) H78(0.4152)
 H81A(1.2202) H81B(1.2424) H81C(1.2529) H82A(1.0928) H82B(1.0419) H82C(1.1259)
 H84A(1.1892) H84B(1.1541) H84C(1.1044) H90A(0.0483) H90B(-0.0387) H90C(0.0341)
 H91A(0.1569) H91B(0.1294) H91C(0.1533) H94A(-0.1328) H94B(-0.1046) H94C(-0.12)
 H12A(0.5423) H12B(0.602) H15A(0.0506) H15B(0.0606) H16A(-0.106) H16B(-0.0389)
 H96A(0.6088) H96B(0.6163) H96C(0.5876) H97A(0.4796) H97B(0.5607) H97C(0.5136)
 H99A(0.3626) H99B(0.3522) H99C(0.3434) H13A(0.4504) H13B(0.4132) H14A(0.4868)
 H14B(0.4917)
;
_shelx_res_checksum              86848
_shelx_hkl_checksum              74323
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.781
_oxdiff_exptl_absorpt_empirical_full_min 0.742