Selective P4 activation by an organometallic nickel(I) radical: formation of a dinuclear nickel(II) tetraphosphide and related di- and trichalcogenides
Stefan Pelties; Dirk Herrmann; Bas de Bruin; Frantisek Hartl; Robert Wolf; Chem.Commun. 50 (2014) 7014–; doi:10.1039/C4CC02601B

data_7114591
_publ_section_title
;
 Selective P4 activation by an organometallic nickel(I) radical: formation
 of a dinuclear nickel(II) tetraphosphide and related di- and
 trichalcogenides
;
_journal_name_full               Chem.Commun.
_journal_page_first              7014
_journal_paper_doi               10.1039/C4CC02601B
_journal_volume                  50
_journal_year                    2014
_chemical_formula_moiety         'C64 H82 N4 Ni2 P4, 0.5(C4 H8 O)'
_chemical_formula_sum            'C66 H86 N4 Ni2 O0.5 P4'
_chemical_formula_weight         1184.69
_chemical_name_systematic
;
 ?
;
_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_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     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-08-20
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:59:47, GUI svn.r4466)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 91.093(2)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   13.7371(2)
_cell_length_b                   23.6940(5)
_cell_length_c                   19.4754(3)
_cell_measurement_reflns_used    11884
_cell_measurement_temperature    123.01(10)
_cell_measurement_theta_max      73.5770
_cell_measurement_theta_min      3.7170
_cell_volume                     6337.83(19)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
;
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
SHELXS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      123.01(10)
_diffrn_detector_area_resol_mean 10.3546
_diffrn_measured_fraction_theta_full 0.9893
_diffrn_measured_fraction_theta_max 0.9553
_diffrn_measurement_details
;
  1 omega  -59.00   35.00   0.5000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.2064   37.0000  -90.0000 188

  2 omega  -97.00   -2.00   0.5000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.2064  125.0000   90.0000 190

  3 omega   31.00   69.00   0.5000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      106.9800  -30.0000   30.0000 76

  4 omega   47.00  156.00   0.5000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      106.9800   15.0000  -30.0000 218

  5 omega   32.00   77.00   0.5000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      106.9800  -45.0000   60.0000 90

  6 omega   84.00  158.00   0.5000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      106.9800   30.0000 -150.0000 148

  7 omega   29.00   63.00   0.5000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      106.9800  -30.0000   90.0000 68

  8 omega   23.00  109.00   0.5000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      106.9800  -94.0000 -120.0000 172

  9 omega   29.00   69.00   0.5000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      106.9800  -30.0000    0.0000 80

 10 omega -115.00  -12.00   0.5000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.2064  -57.0000  -90.0000 206

 11 omega -120.00  -61.00   0.5000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.2064  -77.0000  150.0000 118
;
_diffrn_measurement_device_type  'SuperNova, Single source at offset), Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0960033000
_diffrn_orient_matrix_UB_12      0.0113910000
_diffrn_orient_matrix_UB_13      -0.0398166000
_diffrn_orient_matrix_UB_21      -0.0541870000
_diffrn_orient_matrix_UB_22      -0.0395506000
_diffrn_orient_matrix_UB_23      0.0490049000
_diffrn_orient_matrix_UB_31      -0.0208814000
_diffrn_orient_matrix_UB_32      0.0503099000
_diffrn_orient_matrix_UB_33      0.0476717000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0367
_diffrn_reflns_av_unetI/netI     0.0402
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            27288
_diffrn_reflns_theta_full        66.97
_diffrn_reflns_theta_max         73.59
_diffrn_reflns_theta_min         3.22
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.012
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80032
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.242
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             2520
_exptl_crystal_size_max          0.2598
_exptl_crystal_size_mid          0.074
_exptl_crystal_size_min          0.0434
_refine_diff_density_max         0.356
_refine_diff_density_min         -0.438
_refine_diff_density_rms         0.053
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.017
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     712
_refine_ls_number_reflns         12211
_refine_ls_number_restraints     23
_refine_ls_restrained_S_all      1.020
_refine_ls_R_factor_all          0.0465
_refine_ls_R_factor_gt           0.0366
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0511P)^2^+1.5462P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0925
_refine_ls_wR_factor_ref         0.0995
_reflns_number_gt                10235
_reflns_number_total             12211
_reflns_threshold_expression     >2\s(I)
_cod_data_source_file            c4cc02601b2.cif
_cod_data_source_block           mp21c
_cod_original_formula_sum        'C66 H86 N4 Ni2 O0.50 P4'
_cod_database_code               7114591
_chemical_oxdiff_formula         'C64 H84 N4 Ni2 P4'
_reflns_odcompleteness_completeness 98.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Others
 Fixed Sof: O1(0.5) C101(0.5) H10A(0.5) H10B(0.5) C102(0.5) H10C(0.5)
 H10D(0.5) C103(0.5) H10E(0.5) H10F(0.5) C104(0.5) H10G(0.5) H10H(0.5)
 Fixed Uiso: H2(0.029) H3(0.029) H4(0.038) H5(0.04) H6(0.043) H7(0.043)
 H8(0.039) H11(0.029) H12(0.033) H13(0.033) H15(0.028) H16A(0.056) H16B(0.056)
 H16C(0.056) H17A(0.049) H17B(0.049) H17C(0.049) H18(0.034) H19A(0.065)
 H19B(0.065) H19C(0.065) H20A(0.062) H20B(0.062) H20C(0.062) H23(0.045)
 H24(0.05) H25(0.041) H27(0.037) H28A(0.06) H28B(0.06) H28C(0.06) H29A(0.061)
 H29B(0.061) H29C(0.061) H30(0.032) H31A(0.056) H31B(0.056) H31C(0.056)
 H32A(0.053) H32B(0.053) H32C(0.053) H34(0.034) H35(0.033) H36(0.053)
 H37(0.049) H38(0.046) H39(0.049) H40(0.055) H43(0.038) H44(0.04) H45(0.035)
 H47(0.036) H48A(0.069) H48B(0.069) H48C(0.069) H49A(0.078) H49B(0.078)
 H49C(0.078) H50(0.037) H51A(0.072) H51B(0.072) H51C(0.072) H52A(0.073)
 H52B(0.073) H52C(0.073) H55(0.035) H56(0.039) H57(0.038) H59(0.031)
 H60A(0.049) H60B(0.049) H60C(0.049) H61A(0.051) H61B(0.051) H61C(0.051)
 H62(0.041) H63A(0.078) H63B(0.078) H63C(0.078) H64A(0.093) H64B(0.093)
 H64C(0.093) H10A(0.105) H10B(0.105) H10C(0.156) H10D(0.156) H10E(0.14)
 H10F(0.14) H10G(0.105) H10H(0.105)
 Fixed X: H2(-0.0287) H3(-0.0591) H4(0.1136) H5(0.1053) H6(0.1985) H7(0.2632)
 H8(0.2243) H11(0.0359) H12(0.1907) H13(0.2669) H15(-0.1003) H16A(-0.2207)
 H16B(-0.1397) H16C(-0.1463) H17A(-0.1693) H17B(-0.0608) H17C(-0.0881)
 H18(0.1795) H19A(0.3471) H19B(0.352) H19C(0.3283) H20A(0.2289) H20B(0.1293)
 H20C(0.226) H23(-0.1372) H24(0.0114) H25(0.1531) H27(-0.1798) H28A(-0.3221)
 H28B(-0.2691) H28C(-0.2375) H29A(-0.2882) H29B(-0.1812) H29C(-0.2311)
 H30(0.1812) H31A(0.2493) H31B(0.1909) H31C(0.1353) H32A(0.3334) H32B(0.2773)
 H32C(0.2834) H34(-0.6336) H35(-0.6112) H36(-0.1281) H37(-0.1879) H38(-0.3538)
 H39(-0.396) H40(-0.2521) H43(-0.4) H44(-0.4953) H45(-0.5893) H47(-0.3692)
 H48A(-0.2402) H48B(-0.2403) H48C(-0.2804) H49A(-0.3921) H49B(-0.4415) H49C(-
 0.4919) H50(-0.5879) H51A(-0.635) H51B(-0.6171) H51C(-0.5293) H52A(-0.7546)
 H52B(-0.7288) H52C(-0.744) H55(-0.3518) H56(-0.3555) H57(-0.4192) H59(-0.4098)
 H60A(-0.32) H60B(-0.3126) H60C(-0.2598) H61A(-0.4974) H61B(-0.5558) H61C(-
 0.4986) H62(-0.4916) H63A(-0.3893) H63B(-0.468) H63C(-0.4894) H64A(-0.6411)
 H64B(-0.6207) H64C(-0.6359) H10A(-0.0619) H10B(0.0503) H10C(-0.0191)
 H10D(0.0816) H10E(-0.0019) H10F(-0.1022) H10G(-0.0882) H10H(0.0128)
 Fixed Y: H2(0.2623) H3(0.3337) H4(0.1215) H5(0.0544) H6(0.0964) H7(0.1901)
 H8(0.2011) H11(0.0343) H12(0.0445) H13(0.1313) H15(0.1397) H16A(0.1085)
 H16B(0.0828) H16C(0.1483) H17A(0.0516) H17B(0.0528) H17C(0.022) H18(0.2546)
 H19A(0.2651) H19B(0.2049) H19C(0.2115) H20A(0.2962) H20B(0.2648) H20C(0.237)
 H23(0.3582) H24(0.3817) H25(0.3634) H27(0.2796) H28A(0.2802) H28B(0.3148)
 H28C(0.2525) H29A(0.3555) H29B(0.3747) H29C(0.3915) H30(0.2788) H31A(0.3549)
 H31B(0.3974) H31C(0.3566) H32A(0.3128) H32B(0.2888) H32C(0.3542) H34(0.1566)
 H35(0.1112) H36(0.0274) H37(0.0875) H38(0.0548) H39(-0.0266) H40(-0.0477)
 H43(0.2163) H44(0.1629) H45(0.09) H47(0.1936) H48A(0.2499) H48B(0.192)
 H48C(0.2463) H49A(0.2917) H49B(0.289) H49C(0.2604) H50(0.0417) H51A(-0.0336)
 H51B(0.0035) H51C(-0.014) H52A(0.0318) H52B(0.0954) H52C(0.0733) H55(0.0593)
 H56(-0.0375) H57(-0.0803) H59(0.1573) H60A(0.2036) H60B(0.1474) H60C(0.1527)
 H61A(0.2011) H61B(0.1493) H61C(0.1442) H62(-0.0126) H63A(-0.0914) H63B(-
 0.1208) H63C(-0.1095) H64A(-0.0589) H64B(-0.0638) H64C(-0.0043) H10A(0.5381)
 H10B(0.5393) H10C(0.4459) H10D(0.4625) H10E(0.4517) H10F(0.4656) H10G(0.5528)
 H10H(0.5393)
 Fixed Z: H2(-0.1127) H3(-0.0251) H4(0.2272) H5(0.127) H6(0.0317) H7(0.0721)
 H8(0.1965) H11(-0.1057) H12(-0.1468) H13(-0.1433) H15(-0.0181) H16A(-0.0972)
 H16B(-0.1434) H16C(-0.1332) H17A(0.0042) H17B(0.0306) H17C(-0.0383) H18(-
 0.0588) H19A(-0.0753) H19B(-0.1084) H19C(-0.0304) H20A(-0.1623) H20B(-0.1734)
 H20C(-0.1983) H23(0.2259) H24(0.2743) H25(0.2167) H27(0.0728) H28A(0.1374)
 H28B(0.1956) H28C(0.1807) H29A(0.0539) H29B(0.0401) H29C(0.1088) H30(0.0723)
 H31A(0.0122) H31B(0.0574) H31C(0.0068) H32A(0.1088) H32B(0.1717) H32C(0.1602)
 H34(0.2655) H35(0.1536) H36(0.3044) H37(0.4018) H38(0.4309) H39(0.353)
 H40(0.2812) H43(0.4792) H44(0.5504) H45(0.5065) H47(0.2995) H48A(0.3403)
 H48B(0.3793) H48C(0.415) H49A(0.2969) H49B(0.3687) H49C(0.3047) H50(0.3324)
 H51A(0.4019) H51B(0.4677) H51C(0.422) H52A(0.3545) H52B(0.3419) H52C(0.4169)
 H55(-0.0131) H56(-0.0045) H57(0.0909) H59(0.1189) H60A(0.0348) H60B(-0.0073)
 H60C(0.0645) H61A(0.0282) H61B(0.0557) H61C(-0.0129) H62(0.2436) H63A(0.232)
 H63B(0.1849) H63C(0.2624) H64A(0.2268) H64B(0.148) H64C(0.1815) H10A(-0.0746)
 H10B(-0.0911) H10C(-0.0587) H10D(-0.0236) H10E(0.0722) H10F(0.035)
 H10G(0.0674) H10H(0.1028)
;