Diphosphene radical cations and dications with a π-conjugated C2P2C2-framework
Ghadwal, Rajendra S.; Sharma, Mahendra Kumar; Rottschäfer, Dennis; Blomeyer, Sebastian; Neumann, Beate; Stammler, Georg; Hinz, Alexander; van Gastel, Maurice; Chemical Communications  (2019) –; doi:10.1039/C9CC04701H

data_7123947
_publ_section_title
;
 Diphosphene radical cations and dications with a \p-conjugated
 C2P2C2-framework
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C9CC04701H
_journal_year                    2019
_chemical_formula_moiety         'C68 H82 N4 P2, 2(Cl4 Ga), 6(C H2 Cl2)'
_chemical_formula_sum            'C74 H94 Cl20 Ga2 N4 P2'
_chemical_formula_weight         1949.91
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-01-29
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-04-09 deposited with the CCDC.    2019-08-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.5820(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   14.5173(2)
_cell_length_b                   15.6525(2)
_cell_length_c                   19.9706(2)
_cell_measurement_reflns_used    35248
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      76.2240
_cell_measurement_theta_min      3.5460
_cell_volume                     4537.73(10)
_computing_cell_refinement       'CrysAlisPro 1.171.40.35a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.35a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.35a (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      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3114
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.991
_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    -64.00  30.00   1.00    3.46    --  -38.50  57.00  30.00   94
  2  \w   -116.00  -5.00   1.00    3.46    --  -38.50 -19.00   0.00  111
  3  \w    -64.00  30.00   1.00    3.46    --  -38.50  57.00 150.00   94
  4  \w   -110.00  -8.00   1.00    3.46    --  -38.50 -77.00-120.00  102
  5  \w     12.00 114.00   1.00    3.46    --   42.45  77.00 120.00  102
  6  \w     17.00 111.00   1.00    3.46    --   42.45  57.00-120.00   94
  7  \w     12.00 114.00   1.00    3.46    --   42.45  77.00  60.00  102
  8  \w     20.00  94.00   1.00    3.46    --   42.45-121.00-128.00   74
  9  \w      1.00  81.00   1.00    3.46    --   42.45 -99.00 -60.00   80
 10  \w     23.00  96.00   1.00    3.46    --   42.45-125.00  60.00   73
 11  \w     12.00 114.00   1.00    3.46    --   42.45  77.00 -30.00  102
 12  \w     17.00 111.00   1.00    3.46    --   42.45  57.00  60.00   94
 13  \w     12.00 114.00   1.00    3.46    --   42.45  77.00-120.00  102
 14  \w      9.00  35.00   1.00    3.46    --   42.45  86.00 163.87   26
 15  \w     22.00 113.00   1.00    3.46    --   42.45  38.00-120.00   91
 16  \w     81.00 178.00   1.00   13.82    --  111.00  76.00-169.71   97
 17  \w     81.00 178.00   1.00   13.82    --  111.00  75.00  50.25   97
 18  \w     83.00 178.00   1.00   13.82    --  111.00  67.00-142.61   95
 19  \w     31.00 110.00   1.00   13.82    --  111.00 -94.00  30.00   79
 20  \w     84.00 178.00   1.00   13.82    --  111.00  63.00 162.29   94
 21  \w     84.00 178.00   1.00   13.82    --  111.00  66.00-136.65   94
 22  \w     81.00 178.00   1.00   13.82    --  111.00  77.00  60.00   97
 23  \w     31.00 110.00   1.00   13.82    --  111.00 -94.00-120.00   79
 24  \w     85.00 178.00   1.00   13.82    --  111.00  61.00-150.00   93
 25  \w     85.00 178.00   1.00   13.82    --  111.00  61.00-120.00   93
 26  \w     85.00 178.00   1.00   13.82    --  111.00  61.00  90.00   93
 27  \w     85.00 178.00   1.00   13.82    --  111.00  61.00 -60.00   93
 28  \w     81.00 178.00   1.00   13.82    --  111.00  77.00-180.00   97
 29  \w     87.00 178.00   1.00   13.82    --  111.00  50.00  66.82   91
 30  \w     41.00 118.00   1.00   13.82    --  111.00-125.00  30.00   77
 31  \w     31.00 110.00   1.00   13.82    --  111.00 -94.00 150.00   79
 32  \w     81.00 178.00   1.00   13.82    --  111.00  77.00 -30.00   97
 33  \w     81.00 173.00   1.00   13.82    --  111.00  77.00   0.00   92
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0617718000
_diffrn_orient_matrix_UB_12      -0.0799238000
_diffrn_orient_matrix_UB_13      0.0038684000
_diffrn_orient_matrix_UB_21      -0.0077207000
_diffrn_orient_matrix_UB_22      -0.0104961000
_diffrn_orient_matrix_UB_23      -0.0765662000
_diffrn_orient_matrix_UB_31      0.0859418000
_diffrn_orient_matrix_UB_32      0.0564612000
_diffrn_orient_matrix_UB_33      -0.0086808000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0332
_diffrn_reflns_av_unetI/netI     0.0167
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            80119
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.492
_diffrn_reflns_theta_min         3.588
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.803
_exptl_absorpt_correction_T_max  0.679
_exptl_absorpt_correction_T_min  0.429
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.35a (Rigaku Oxford Diffraction, 2018)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.427
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1996
_exptl_crystal_size_max          0.147
_exptl_crystal_size_mid          0.095
_exptl_crystal_size_min          0.088
_refine_diff_density_max         1.322
_refine_diff_density_min         -1.142
_refine_diff_density_rms         0.080
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     485
_refine_ls_number_reflns         9445
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0526
_refine_ls_R_factor_gt           0.0478
_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^)+(0.0635P)^2^+8.2774P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1288
_refine_ls_wR_factor_ref         0.1326
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8498
_reflns_number_total             9445
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc04701h2.cif
_cod_data_source_block           compound3a
_cod_database_code               7123947
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C74 H94 Cl20 Ga2 N4 P2'
_diffrn_oxdiff_digest_frames
;
014e9cd53f574c3d4b95f5dc96a3b6f253000278c3d
;
_diffrn_oxdiff_digest_hkl
;
017478698c30385d2118462c2071e4c80a97d2
;
_reflns_odcompleteness_completeness 99.91
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_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. Uiso/Uaniso restraints and constraints
Uanis(Cl9B) = Uanis(Cl9)
Uanis(C37) = Uanis(C37B)
Uanis(Cl10) = Uanis(Cl11)
Uanis(Cl3B) = Uanis(Cl3)
Uanis(Cl4B) = Uanis(Cl4)
3. Others
 Sof(Cl3B)=Sof(Cl4B)=1-FVAR(1)
 Sof(Cl3)=Sof(Cl4)=FVAR(1)
 Sof(C37B)=Sof(H37C)=Sof(H37D)=Sof(Cl9B)=Sof(Cl11)=1-FVAR(2)
 Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(Cl9)=Sof(Cl10)=FVAR(2)
4.a Ternary CH refined with riding coordinates:
 C10(H10), C13(H13), C22(H22), C25(H25)
4.b Secondary CH2 refined with riding coordinates:
 C35(H35A,H35B), C36(H36A,H36B), C37(H37A,H37B), C37B(H37C,H37D)
4.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C6(H6), C7(H7), C8(H8), C18(H18), C19(H19), C20(H20),
 C30(H30), C31(H31), C32(H32), C33(H33), C34(H34)
4.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C15(H15A,H15B,
 H15C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C26(H26A,H26B,H26C), C27(H27A,
 H27B,H27C)
;
_shelx_res_checksum              82007
_olex2_date_sample_data_collection 2019-01-08
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.257
_oxdiff_exptl_absorpt_empirical_full_min 0.757