Structural Dynamics of Spin Crossover in Iron(II) Complexes with Extended-Tripod Ligands
Stock, P.; Wiedemann, D.; Petzold, H.; Horner, G.; Inorganics 5 (2017) 60–; doi:10.3390/inorganics5030060

data_1556528
_publ_section_title
;
 Structural Dynamics of Spin Crossover in Iron(II) Complexes with
 Extended-Tripod Ligands
;
_journal_name_full               Inorganics
_journal_page_first              60
_journal_paper_doi               10.3390/inorganics5030060
_journal_volume                  5
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_iupac          '[Fe (C21 H24 N9 P S)](B F4)2.1.5C H3 C N'
_chemical_formula_moiety
'(C21 H24 Fe N9 P S 2+), 2(B F4 1-), 1.5(C2 H3 N)'
_chemical_formula_sum            'C24 H28.5 B2 F8 Fe N10.5 P S'
_chemical_formula_weight         756.57
_chemical_name_systematic
; {tris[1-methyl-2-(pyridin-2-ylmethylene-\kN)hydrazinyl-\kN^2^]phosphane
 sulfide}iron(II) tetrafluoroborate--acetonitrile(2/3)
;
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   .
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   11.3421(5)
_cell_length_b                   15.3291(7)
_cell_length_c                   36.7355(18)
_cell_measurement_reflns_used    5458
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      26.2660
_cell_measurement_theta_min      3.5410
_cell_volume                     6387.0(5)
_computing_cell_refinement
'CrysAlisPro 1.171.37 (Agilent Technologies, 2014)'
_computing_data_collection
'CrysAlisPro 1.171.37 (Agilent Technologies, 2014)'
_computing_data_reduction
'CrysAlisPro 1.171.37 (Agilent Technologies, 2014)'
_computing_molecular_graphics    'MERCURY (Macrae et al., 2008)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2017 (Sheldrick, 2015b)'
_computing_structure_solution    'SHELXT-2014 (Sheldrick, 2015a)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.3031
_diffrn_detector_type            'Agilent Sapphire3'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Agilent Xcalibur'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'glass capillary'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0582
_diffrn_reflns_av_unetI/netI     0.0910
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       45
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            27331
_diffrn_reflns_point_group_measured_fraction_full 0.984
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.999
_diffrn_reflns_theta_min         3.583
_diffrn_source                   'fine-focus sealed tube'
_diffrn_source_type              'Agilent Enhance'
_diffrn_standards_interval_count .
_diffrn_standards_interval_time  .
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.671
_exptl_absorpt_correction_T_max  0.921
_exptl_absorpt_correction_T_min  0.819
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.37 (Agilent Technologies, 2014)

Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by Clark and Reid (Clark & Reid, 1995).

Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            black
_exptl_crystal_density_diffrn    1.574
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             3080
_exptl_crystal_size_max          0.4152
_exptl_crystal_size_mid          0.3068
_exptl_crystal_size_min          0.1624
_refine_diff_density_max         0.504
_refine_diff_density_min         -0.533
_refine_diff_density_rms         0.068
_refine_ls_abs_structure_details
;
 Flack x determined using 3083 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.012(12)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.018
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     932
_refine_ls_number_reflns         12295
_refine_ls_number_restraints     253
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0810
_refine_ls_R_factor_gt           0.0578
_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^)+(0.0427P)^2^+1.3949P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1078
_refine_ls_wR_factor_ref         0.1180
_reflns_Friedel_coverage         0.780
_reflns_Friedel_fraction_full    0.970
_reflns_Friedel_fraction_max     0.961
_reflns_number_gt                9499
_reflns_number_total             12295
_reflns_threshold_expression     I>2\s(I)
_cod_data_source_file            stock13_final.cif
_cod_data_source_block           stock13
_cod_original_formula_sum        'C24 H28.50 B2 F8 Fe N10.50 P S'
_cod_database_code               1556528
_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
 B40A-F41A = B40A-F42A = B40A-F43A = B40A-F44A
 1.35467 with sigma of 0.01
 F41A-F42A = F41A-F43A = F41A-F44A = F42A-F43A = F42A-F44A = F43A-F44A
 2.212176 with sigma of 0.02
 B40B-F41B = B40B-F42B = B40B-F43B = B40B-F44B
 1.35467 with sigma of 0.01
 F41B-F42B = F41B-F43B = F41B-F44B = F42B-F43B = F42B-F44B = F43B-F44B
 2.212176 with sigma of 0.02
3. Rigid bond restraints
 N90, C91A, C92A, C91B, C92B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 B40A, F41A, F42A, F43A, F44A, B40B, F41B, F42B, F43B, F44B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
N90 \\sim C91A \\sim C92A \\sim C91B \\sim C92B: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02
B40A \\sim F41A \\sim F42A \\sim F43A \\sim F44A \\sim B40B \\sim F41B \\sim
F42B \\sim F43B \\sim F44B: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
5. Same fragment restrains
{N90, C91B, C92B} sigma for 1-2: 0.01, 1-3: 0.02
as
{N90, C91A, C92A}
6. Others
 Sof(C91B)=Sof(C92B)=Sof(H92D)=Sof(H92E)=Sof(H92F)=1-FVAR(1)
 Sof(C91A)=Sof(C92A)=Sof(H92A)=Sof(H92B)=Sof(H92C)=FVAR(1)
 Sof(B40B)=Sof(F41B)=Sof(F42B)=Sof(F43B)=Sof(F44B)=1-FVAR(2)
 Sof(B40A)=Sof(F41A)=Sof(F42A)=Sof(F43A)=Sof(F44A)=FVAR(2)
 1(DFIX)=1(DFIX)=FVAR(3)
 1(DFIX)=1(DFIX)=1.633*FVAR(4)
7.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C5(H5), C6(H6), C7(H7), C9(H9), C11(H11), C12(H12), C13(H13),
 C14(H14), C16(H16), C18(H18), C19(H19), C20(H20), C21(H21), C23(H23), C25(H25),
  C26(H26), C27(H27), C28(H28), C30(H30), C32(H32), C33(H33), C34(H34),
 C35(H35), C37(H37), C39(H39), C40(H40), C41(H41), C42(H42)
7.b Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C8(H8A,H8B,H8C), C15(H15A,H15B,H15C), C22(H22A,H22B,H22C),
 C29(H29A,H29B,H29C), C36(H36A,H36B,H36C), C72(H72A,H72B,H72C), C82(H82A,H82B,
 H82C), C92A(H92A,H92B,H92C), C92B(H92D,H92E,H92F)
;
_olex2_submission_special_instructions 'No special instructions were received'