Synthesis and reactivity of cyclo-tetra(stibinophosphonium) tetracations: redox and coordination chemistry of phosphine‒antimony complexes
Chitnis, Saurabh S.; Robertson, Alasdair P. M.; Burford, Neil; Weigand, Jan J.; Fischer, Roland; Chem. Sci. 6 (2015) 2559–; doi:10.1039/C4SC03939D

data_1518667
_publ_section_title
;
 Synthesis and reactivity of cyclo-tetra(stibinophosphonium) tetracations:
 redox and coordination chemistry of phosphine--antimony complexes
;
_journal_issue                   4
_journal_name_full               'Chem. Sci.'
_journal_page_first              2559
_journal_paper_doi               10.1039/C4SC03939D
_journal_volume                  6
_journal_year                    2015
_chemical_formula_moiety         'C38 H68 N2 P3 Sb4, 3(C F3 O3 S), C2 H3 N'
_chemical_formula_sum            'C43 H71 F9 N3 O9 P3 S3 Sb4'
_chemical_formula_weight         1621.12
_chemical_name_systematic        '[(Me3P)3(nacnac)Sb4][OTf]3'
_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             2014-12-08
_audit_creation_method
;
Olex2 1.2
(compiled 2014.11.28 svn.r3106 for OlexSys, GUI svn.r4959)
;
_audit_update_record
;
2014-12-18 deposited with the CCDC.
2015-02-03 downloaded from the CCDC.
;
_cell_angle_alpha                91.8200(10)
_cell_angle_beta                 97.5640(10)
_cell_angle_gamma                112.0740(10)
_cell_formula_units_Z            2
_cell_length_a                   11.4789(3)
_cell_length_b                   11.9874(3)
_cell_length_c                   26.0864(7)
_cell_measurement_reflns_used    9989
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30.00
_cell_measurement_theta_min      2.20
_cell_volume                     3284.57(15)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XH (Sheldrick, 2008)'
_computing_structure_solution    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_temperature      99.99
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0334
_diffrn_reflns_av_unetI/netI     0.0335
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            64496
_diffrn_reflns_theta_full        27.00
_diffrn_reflns_theta_max         27.00
_diffrn_reflns_theta_min         0.79
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.867
_exptl_absorpt_correction_T_max  0.742
_exptl_absorpt_correction_T_min  0.660
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            'pale yellow'
_exptl_crystal_density_diffrn    1.639
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       Block
_exptl_crystal_F_000             1600
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.16
_refine_diff_density_max         1.664
_refine_diff_density_min         -1.163
_refine_diff_density_rms         0.153
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.173
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     825
_refine_ls_number_reflns         14357
_refine_ls_number_restraints     84
_refine_ls_restrained_S_all      1.176
_refine_ls_R_factor_all          0.0565
_refine_ls_R_factor_gt           0.0405
_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^)+(0.0427P)^2^+15.7976P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1047
_refine_ls_wR_factor_ref         0.1174
_reflns_number_gt                11697
_reflns_number_total             14357
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c4sc03939d2.cif
_cod_data_source_block           rf555_0m
_cod_depositor_comments
'Adding full bibliography for 1518666--1518671.cif.'
_cod_database_code               1518667
_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
 P2A-C32A \\sim P2B-C32B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
F5A \\sim F5B: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C31A \\sim C31B: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C32A \\sim C32B: within 1.7A with sigma of 0.02 and sigma for terminal atoms of
0.04
C30A \\sim C30B: within 1.7A with sigma of 0.02 and sigma for terminal atoms of
0.04
Uanis(O4B) \\sim Ueq, Uanis(C42) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(F4A) \\sim Ueq, Uanis(F4B) \\sim Ueq: with sigma of 0.03 and sigma for
terminal atoms of 0.06
Uanis(F5A) \\sim Ueq, Uanis(F5B) \\sim Ueq: with sigma of 0.03 and sigma for
terminal atoms of 0.06
Uanis(O6A) = Uanis(O6B)
Uanis(C40A) = Uanis(C40B)
4. Same fragment restrains
{C40B, F4B, F5B, F6B, S3B, O4B, O5B, O6B} sigma for 1-2: 0.02, 1-3: 0.04
as
{C40A, F4A, F5A, F6A, S3A, O4A, O5A, O6A}
5. Others
 Sof(P2B)=Sof(C30B)=Sof(H30D)=Sof(H30E)=Sof(H30F)=Sof(C31B)=Sof(H31D)=
 Sof(H31E)=Sof(H31F)=Sof(C32B)=Sof(H32D)=Sof(H32E)=Sof(H32F)=1-FVAR(1)
 Sof(P2A)=Sof(C30A)=Sof(H30A)=Sof(H30B)=Sof(H30C)=Sof(C31A)=Sof(H31A)=
 Sof(H31B)=Sof(H31C)=Sof(C32A)=Sof(H32A)=Sof(H32B)=Sof(H32C)=FVAR(1)
 Sof(C41B)=Sof(F7B)=Sof(F8B)=Sof(F9B)=1-FVAR(2)
 Sof(C41A)=Sof(F7A)=Sof(F8A)=Sof(F9A)=FVAR(2)
 Sof(C40B)=Sof(F4B)=Sof(F5B)=Sof(F6B)=Sof(S3B)=Sof(O4B)=Sof(O5B)=Sof(O6B)=1-
 FVAR(3)
 Sof(C40A)=Sof(F4A)=Sof(F5A)=Sof(F6A)=Sof(S3A)=Sof(O4A)=Sof(O5A)=Sof(O6A)=
 FVAR(3)
6.a Ternary CH refined with riding coordinates:
 C1(H1), C12(H12), C15(H15), C24(H24), C27(H27)
6.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C20(H20), C21(H21), C22(H22)
6.c Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C5(H5A,H5B,H5C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C),
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C25(H25A,H25B,H25C), C26(H26A,H26B,
 H26C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C33(H33A,H33B,H33C), C34(H34A,
 H34B,H34C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C),
 C38(H38A,H38B,H38C), C30A(H30A,H30B,H30C), C31A(H31A,H31B,H31C), C32A(H32A,
 H32B,H32C), C30B(H30D,H30E,H30F), C31B(H31D,H31E,H31F), C32B(H32D,H32E,H32F),
 C42(H42A,H42B,H42C)
;
_olex2_submission_special_instructions 'No special instructions were received'