Structures, Electronics, and Reactivity of Strained Phosphazane Cages: A Combined Experimental and Computational Study.
Roth, Torsten; Vasilenko, Vladislav; Wadepohl, Hubert; Wright, Dominic S.; Gade, Lutz H.; Inorganic chemistry 54 (2015) 7636–7644; doi:10.1021/acs.inorgchem.5b01292

data_4343969
_publ_section_title
;
 Structures, Electronics, and Reactivity of Strained Phosphazane Cages: A
 Combined Experimental and Computational Study.
;
_journal_issue                   15
_journal_name_full               'Inorganic chemistry'
_journal_page_first              7636
_journal_page_last               7644
_journal_paper_doi               10.1021/acs.inorgchem.5b01292
_journal_volume                  54
_journal_year                    2015
_chemical_formula_moiety         'C61 H69 Cl2 Ir2 N4 P2, C F3 O3 S, C H2 Cl2'
_chemical_formula_sum            'C63 H71 Cl4 F3 Ir2 N4 O3 P2 S'
_chemical_formula_weight         1609.43
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      14
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                ga_tro106
_audit_creation_date
;
'Thu Oct 23 15:58:21 2014'
;
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3151 for OlexSys, GUI svn.r4998)
;
_audit_update_record
'18.05.2015 18:27:41 CEST UTC+02:00  encif 1.32'
_cell_angle_alpha                90
_cell_angle_beta                 90.932(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.8852(3)
_cell_length_b                   21.8018(5)
_cell_length_c                   21.3323(5)
_cell_measurement_reflns_used    29220
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      28.5640
_cell_measurement_theta_min      3.6540
_cell_volume                     5991.9(2)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34k (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,16:31:05)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34k (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,16:31:05)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34k (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,16:31:05)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material
'encif (Wadepohl, 2009-14); encifer 1.5 (CCDC, 2014)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'SUPERFLIP (Palatinus, 2007-2009)'
_diffrn_ambient_environment      'perfluoro polyether oil / N~2~'
_diffrn_ambient_temperature      120(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 7.9621
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.944
_diffrn_measurement_details
;
  1 omega  -33.00   50.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380  -79.0000   65.0872 83

  2 omega   -7.00   89.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380   77.0000   30.0000 96

  3 omega   -1.00   73.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380   57.0000  -30.0000 74

  4 omega   -3.00   78.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380   57.0000  150.0000 81

  5 omega  -51.00   47.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380  -77.0000 -180.0000 98

  6 omega   -7.00   86.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380   77.0000 -150.0000 93

  7 omega  -42.00   49.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380  -77.0000  -90.0000 91

  8 omega  -45.00   50.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380  -79.0000   -0.9444 95

  9 omega  -12.00   89.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380   77.0000  -90.0000 101

 10 omega  -50.00   40.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380  -57.0000  150.0000 90

 11 omega  -12.00   89.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380   77.0000  150.0000 101

 12 omega  -50.00   20.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380  -57.0000 -120.0000 70

 13 omega  -50.00   40.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380  -57.0000  -60.0000 90

;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Agilent SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'polyimid foil'
_diffrn_orient_matrix_UB_11      0.0208422000
_diffrn_orient_matrix_UB_12      0.0090006000
_diffrn_orient_matrix_UB_13      -0.0291760000
_diffrn_orient_matrix_UB_21      -0.0501646000
_diffrn_orient_matrix_UB_22      -0.0018744000
_diffrn_orient_matrix_UB_23      -0.0140641000
_diffrn_orient_matrix_UB_31      -0.0089772000
_diffrn_orient_matrix_UB_32      0.0311961000
_diffrn_orient_matrix_UB_33      0.0075784000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0885
_diffrn_reflns_av_unetI/netI     0.0991
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.944
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            128457
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.944
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.897
_diffrn_reflns_theta_min         3.218
_diffrn_source                   'microfocus X-Ray tube'
_exptl_absorpt_coefficient_mu    4.764
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.82392
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34k (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,16:31:05)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.784
_exptl_crystal_description       needle
_exptl_crystal_F_000             3184
_exptl_crystal_size_max          0.258
_exptl_crystal_size_mid          0.191
_exptl_crystal_size_min          0.184
_refine_diff_density_max         1.705
_refine_diff_density_min         -1.145
_refine_diff_density_rms         0.143
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.898
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     801
_refine_ls_number_reflns         14900
_refine_ls_number_restraints     175
_refine_ls_restrained_S_all      0.912
_refine_ls_R_factor_all          0.0658
_refine_ls_R_factor_gt           0.0361
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0230P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0583
_refine_ls_wR_factor_ref         0.0608
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10012
_reflns_number_total             14900
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic5b01292_si_003.cif
_cod_data_source_block           ga_tro106_4
_cod_depositor_comments
'Adding full bibliography for 4343960--4343970.cif.'
_cod_original_sg_symbol_H-M      'P 21/c'
_cod_database_code               4343969
_audit_block_refno               2205
_audit_block_usercomment         'tr1479, needle, red'
_chemical_oxdiff_formula         'C62 H69 Cl2 F3 Ir2 N4 O3 P2 S'
_chemical_oxdiff_usercomment     'tr1479, needle, red'
_shelx_estimated_absorpt_t_max   0.647
_shelx_estimated_absorpt_t_min   0.647
_diffrn_oxdiff_twin_integration_method simultaneous
_shelxl_version_number           2014/7
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C91A-Cl3 \\sim C91B-Cl3 \\sim C91A-Cl4A \\sim C91B-Cl4B
 with sigma of 0.01
 Cl3-Cl4A \\sim Cl3-Cl4B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O1A \\sim O2A \\sim O3A \\sim O1B \\sim O2B \\sim O3B \\sim S1A \\sim S1B \\sim
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9
\\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17
\\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25
\\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim C30 \\sim C31 \\sim C32 \\sim C33
\\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim C38 \\sim C39 \\sim C40 \\sim C41
\\sim C42 \\sim C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim C48 \\sim C49
\\sim C50 \\sim C51 \\sim C52 \\sim C53 \\sim C54 \\sim C55 \\sim C56 \\sim C57
\\sim C58 \\sim C59 \\sim C60 \\sim C61 \\sim C81A \\sim C81B \\sim C91A \\sim
C91B: within 1.2A with sigma of 0.005 and sigma for terminal atoms of 0.005
4. Rigid body (RIGU) restrains
 S1A, C81A, F1A, F2A, F3A, O1A, O2A, O3A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S1B, C81B, F1B, F2B, F3B, O1B, O2B, O3B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C91A, C91B, Cl3, Cl4A, Cl4B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(S1B)=Sof(C81B)=Sof(F1B)=Sof(F2B)=Sof(F3B)=Sof(O1B)=Sof(O2B)=Sof(O3B)=1-
 FVAR(1)
 Sof(S1A)=Sof(C81A)=Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(O1A)=Sof(O2A)=Sof(O3A)=
 FVAR(1)
 Sof(C91B)=Sof(H91C)=Sof(H91D)=Sof(Cl4B)=1-FVAR(2)
 Sof(C91A)=Sof(H91A)=Sof(H91B)=Sof(Cl4A)=FVAR(2)
6.a Free rotating group:
 S1A(C81A,F1A,F2A,F3A,O1A,O2A,O3A), S1B(C81B,F1B,F2B,F3B,O1B,O2B,O3B)
6.b Ternary CH refined with riding coordinates:
 C14(H14), C27(H27), C28(H28), C31(H31), C32(H32), C35(H35), C54(H54),
 C55(H55), C58(H58), C59(H59)
6.c Secondary CH2 refined with riding coordinates:
 C29(H29A,H29B), C30(H30A,H30B), C33(H33A,H33B), C34(H34A,H34B), C56(H56A,
 H56B), C57(H57A,H57B), C60(H60A,H60B), C61(H61A,H61B), C91A(H91A,H91B),
 C91B(H91C,H91D)
6.d Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C9(H9), C10(H10), C11(H11),
 C12(H12), C13(H13), C16(H16), C17(H17), C18(H18), C19(H19), C20(H20), C22(H22),
  C23(H23), C24(H24), C25(H25), C26(H26), C38(H38), C40(H40), C47(H47), C49(H49)
6.e Idealised Me refined as rotating group:
 C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C51(H51A,H51B,
 H51C), C52(H52A,H52B,H52C), C53(H53A,H53B,H53C)
;
_shelx_res_checksum              32063
_olex2_submission_special_instructions 'No special instructions were received'
_cell_oxdiff_length_a            12.8843(3)
_cell_oxdiff_length_b            21.8094(5)
_cell_oxdiff_length_c            21.3263(5)
_cell_oxdiff_angle_alpha         90.008(2)
_cell_oxdiff_angle_beta          90.920(2)
_cell_oxdiff_angle_gamma         90.0501(19)
_cell_oxdiff_volume              5991.9(2)
_cell_oxdiff_measurement_reflns_used 29220
_cell_oxdiff_twin_number         2