A flexible iron(ii) complex in which zero-field splitting is resistant to structural variation
Zadrozny, Joseph M.; Greer, Samuel M.; Hill, Stephen; Freedman, Danna E.; Chem. Sci. 7 (2016) 416–; doi:10.1039/C5SC02477C

data_1540749
_publ_section_title
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 A flexible iron(ii) complex in which zero-field splitting is resistant to
 structural variation
;
_journal_issue                   1
_journal_name_full               'Chem. Sci.'
_journal_page_first              416
_journal_paper_doi               10.1039/C5SC02477C
_journal_volume                  7
_journal_year                    2016
_chemical_formula_moiety         'C6 Fe S10, 2(C24 H20 P), 1(C2 H3 N)'
_chemical_formula_sum            'C56 H43 Fe N P2 S10'
_chemical_formula_weight         1168.40
_chemical_name_common            (Ph4P)2[Fe(dmit)2](MeCN)
_chemical_properties_physical    'Air-sensitive, Oxygen-sensitive'
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-12-11
_audit_creation_method
;
Olex2 1.2
(compiled 2013.11.15 svn.r2839 for OlexSys, GUI svn.r4713)
;
_audit_update_record
;
2015-05-08 deposited with the CCDC.
2015-10-05 downloaded from the CCDC.
;
_cell_angle_alpha                64.7735(7)
_cell_angle_beta                 78.6184(8)
_cell_angle_gamma                78.0782(8)
_cell_formula_units_Z            2
_cell_length_a                   9.5532(3)
_cell_length_b                   16.9392(6)
_cell_length_c                   19.2199(7)
_cell_measurement_reflns_used    9937
_cell_measurement_temperature    100
_cell_measurement_theta_max      25.995
_cell_measurement_theta_min      2.361
_cell_volume                     2731.85(16)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0384
_diffrn_reflns_av_unetI/netI     0.0266
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            58746
_diffrn_reflns_theta_full        26.04
_diffrn_reflns_theta_max         26.04
_diffrn_reflns_theta_min         1.34
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.756
_exptl_absorpt_correction_T_max  0.801
_exptl_absorpt_correction_T_min  0.764
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0490 before and 0.0431 after correction.
The Ratio of minimum to maximum transmission is 0.8548.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'clear reddish red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.420
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1204.0
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.188
_refine_diff_density_max         0.483
_refine_diff_density_min         -0.273
_refine_diff_density_rms         0.049
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     646
_refine_ls_number_reflns         10673
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0330
_refine_ls_R_factor_gt           0.0252
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0230P)^2^+1.4716P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0574
_refine_ls_wR_factor_ref         0.0611
_reflns_number_gt                9165
_reflns_number_total             10782
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c5sc02477c2.cif
_cod_data_source_block           mo_jz20_0m
_cod_database_code               1540749
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C59-C60 \\sim C57-C58 \\sim C55-C56
 with sigma of 0.02
 N3-C60 \\sim C58-N2 \\sim N1-C56
 with sigma of 0.02
3. Others
 1*[Sof(C57)+Sof(H57A)+Sof(H57B)+Sof(H57C)+Sof(C58)+Sof(N2)]+1*[Sof(N1)+
 Sof(C56)+Sof(C55)+Sof(H55A)+Sof(H55B)+Sof(H55C)]+1*[Sof(C60)+Sof(N3)+Sof(C59)+
 Sof(H59A)+Sof(H59B)+Sof(H59C)]=1 with esd of 0.001
 Sof(C57)=Sof(H57A)=Sof(H57B)=Sof(H57C)=Sof(C58)=Sof(N2)=FVAR(1)
 Sof(N1)=Sof(C56)=Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(H55C)=FVAR(2)
 Sof(C60)=Sof(N3)=Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(H59C)=FVAR(3)
4.a Aromatic/amide H refined with riding coordinates:
 C32(H32), C54(H54), C44(H44), C50(H50), C36(H36), C46(H46), C48(H48),
 C38(H38), C33(H33), C51(H51), C35(H35), C40(H40), C39(H39), C42(H42), C53(H53),
  C52(H52), C41(H41), C45(H45), C47(H47), C34(H34), C19(H19), C23(H23),
 C18(H18), C29(H29), C22(H22), C26(H26), C30(H30), C21(H21), C20(H20), C8(H8),
 C16(H16), C14(H14), C12(H12), C27(H27), C11(H11), C28(H28), C9(H9), C10(H10),
 C15(H15), C17(H17)
4.b Idealised Me refined as rotating group:
 C57(H57A,H57B,H57C), C59(H59A,H59B,H59C), C55(H55A,H55B,H55C)
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