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_7114589
_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 S3'
_chemical_formula_sum            'C64 H82 N4 Ni2 S3'
_chemical_formula_weight         1120.93
_chemical_name_systematic
;
 ?
;
_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     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-11-11
_audit_creation_method
;
Olex2 1.2
(compiled 2013.09.17 svn.r2790 for OlexSys, GUI svn.r4601)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 96.027(2)
_cell_angle_gamma                90.00
_cell_formula_units_Z            8
_cell_length_a                   16.6760(4)
_cell_length_b                   18.4118(5)
_cell_length_c                   38.8467(10)
_cell_measurement_reflns_used    18037
_cell_measurement_temperature    123.00(10)
_cell_measurement_theta_max      73.4800
_cell_measurement_theta_min      3.2610
_cell_volume                     11861.4(5)
_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
;
SHELX, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
SHELX, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      123.00(10)
_diffrn_detector_area_resol_mean 10.3546
_diffrn_measured_fraction_theta_full 0.9870
_diffrn_measured_fraction_theta_max 0.9517
_diffrn_measurement_device_type  'SuperNova, Single source at offset), Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0003307000
_diffrn_orient_matrix_UB_12      0.0658794000
_diffrn_orient_matrix_UB_13      -0.0244127000
_diffrn_orient_matrix_UB_21      0.0037180000
_diffrn_orient_matrix_UB_22      -0.0515834000
_diffrn_orient_matrix_UB_23      -0.0310309000
_diffrn_orient_matrix_UB_31      -0.0928244000
_diffrn_orient_matrix_UB_32      -0.0018963000
_diffrn_orient_matrix_UB_33      -0.0055073000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0291
_diffrn_reflns_av_unetI/netI     0.0386
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       47
_diffrn_reflns_limit_l_min       -47
_diffrn_reflns_number            47574
_diffrn_reflns_theta_full        66.97
_diffrn_reflns_theta_max         73.76
_diffrn_reflns_theta_min         3.32
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.086
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80603
_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_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    purple
_exptl_crystal_density_diffrn    1.255
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             4784
_exptl_crystal_size_max          0.0873
_exptl_crystal_size_mid          0.0823
_exptl_crystal_size_min          0.0742
_refine_diff_density_max         0.717
_refine_diff_density_min         -0.425
_refine_diff_density_rms         0.051
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.010
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1315
_refine_ls_number_reflns         22844
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.010
_refine_ls_R_factor_all          0.0475
_refine_ls_R_factor_gt           0.0367
_refine_ls_shift/su_max          0.014
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0467P)^2^+3.8796P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0903
_refine_ls_wR_factor_ref         0.0961
_reflns_number_gt                19041
_reflns_number_total             22844
_reflns_threshold_expression     >2\s(I)
_cod_data_source_file            c4cc02601b2.cif
_cod_data_source_block           7-S
_cod_database_code               7114589
_chemical_oxdiff_formula         'C64 H82 N4 Ni S2'
_reflns_odcompleteness_completeness 98.70
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Others
 Fixed Uiso: H2(0.032) H3(0.033) H4(0.038) H5(0.038) H6(0.037) H7(0.039)
 H8(0.04) H11(0.042) H12(0.042) H13(0.034) H15(0.041) H16A(0.068) H16B(0.068)
 H16C(0.068) H17A(0.073) H17B(0.073) H17C(0.073) H18(0.032) H19A(0.05)
 H19B(0.05) H19C(0.05) H20A(0.058) H20B(0.058) H20C(0.058) H23(0.049) H24(0.05)
 H25(0.043) H27(0.052) H28A(0.09) H28B(0.09) H28C(0.09) H29A(0.088) H29B(0.088)
 H29C(0.088) H30(0.034) H31A(0.053) H31B(0.053) H31C(0.053) H32A(0.057)
 H32B(0.057) H32C(0.057) H34(0.031) H35(0.03) H36(0.042) H37(0.042) H38(0.039)
 H39(0.039) H40(0.04) H43(0.052) H44(0.059) H45(0.052) H47(0.047) H48A(0.094)
 H48B(0.094) H48C(0.094) H49A(0.069) H49B(0.069) H49C(0.069) H50(0.042)
 H51A(0.071) H51B(0.071) H51C(0.071) H52A(0.066) H52B(0.066) H52C(0.066)
 H55(0.039) H56(0.043) H57(0.041) H59(0.037) H60A(0.093) H60B(0.093)
 H60C(0.093) H61A(0.09) H61B(0.09) H61C(0.09) H62(0.04) H63A(0.072) H63B(0.072)
 H63C(0.072) H64A(0.066) H64B(0.066) H64C(0.066) H66(0.034) H67(0.037)
 H68(0.046) H69(0.049) H70(0.047) H71(0.041) H72(0.043) H75(0.043) H76(0.047)
 H77(0.041) H79(0.039) H80A(0.076) H80B(0.076) H80C(0.076) H81A(0.069)
 H81B(0.069) H81C(0.069) H82(0.038) H83A(0.059) H83B(0.059) H83C(0.059)
 H84A(0.065) H84B(0.065) H84C(0.065) H87(0.055) H88(0.061) H89(0.054)
 H91(0.043) H92A(0.07) H92B(0.07) H92C(0.07) H93A(0.067) H93B(0.067)
 H93C(0.067) H94(0.048) H95A(0.09) H95B(0.09) H95C(0.09) H96A(0.089)
 H96B(0.089) H96C(0.089) H98(0.031) H99(0.031) H100(0.044) H101(0.043)
 H102(0.038) H103(0.036) H104(0.041) H107(0.041) H108(0.045) H109(0.04)
 H111(0.039) H11A(0.068) H11B(0.068) H11C(0.068) H11D(0.064) H11E(0.064)
 H11F(0.064) H114(0.034) H11G(0.058) H11H(0.058) H11I(0.058) H11J(0.057)
 H11K(0.057) H11L(0.057) H119(0.042) H120(0.046) H121(0.041) H123(0.037)
 H12A(0.07) H12B(0.07) H12C(0.07) H12D(0.062) H12E(0.062) H12F(0.062)
 H126(0.039) H12G(0.062) H12H(0.062) H12I(0.062) H12J(0.072) H12K(0.072)
 H12L(0.072)
 Fixed X: H2(-0.0726) H3(-0.1177) H4(-0.0874) H5(0.0351) H6(0.1459) H7(0.0868)
 H8(-0.0589) H11(-0.0113) H12(0.1115) H13(0.1804) H15(-0.1079) H16A(-0.1685)
 H16B(-0.1091) H16C(-0.0763) H17A(-0.2197) H17B(-0.1621) H17C(-0.1619)
 H18(0.1275) H19A(0.2595) H19B(0.2514) H19C(0.2522) H20A(0.1453) H20B(0.1295)
 H20C(0.0601) H23(-0.2169) H24(-0.1268) H25(-0.0018) H27(-0.1811) H28A(-0.2823)
 H28B(-0.2014) H28C(-0.27) H29A(-0.3149) H29B(-0.3033) H29C(-0.2545)
 H30(0.0846) H31A(0.1045) H31B(0.0169) H31C(0.0316) H32A(0.1781) H32B(0.1108)
 H32C(0.1387) H34(0.4227) H35(0.4276) H36(0.4842) H37(0.3749) H38(0.4027)
 H39(0.5346) H40(0.5763) H43(0.5573) H44(0.4449) H45(0.3239) H47(0.5622)
 H48A(0.6891) H48B(0.6229) H48C(0.6604) H49A(0.6608) H49B(0.6283) H49C(0.5743)
 H50(0.2815) H51A(0.1595) H51B(0.2059) H51C(0.2133) H52A(0.2209) H52B(0.3148)
 H52C(0.2729) H55(0.3594) H56(0.4893) H57(0.591) H59(0.2958) H60A(0.1945)
 H60B(0.275) H60C(0.2465) H61A(0.2774) H61B(0.1959) H61C(0.2435) H62(0.5734)
 H63A(0.7095) H63B(0.6869) H63C(0.6581) H64A(0.6513) H64B(0.5608) H64C(0.6242)
 H66(0.5142) H67(0.4726) H68(0.4374) H69(0.4854) H70(0.6298) H71(0.6694)
 H72(0.5463) H75(0.4998) H76(0.6137) H77(0.6989) H79(0.4436) H80A(0.3563)
 H80B(0.3982) H80C(0.446) H81A(0.3202) H81B(0.3861) H81C(0.3624) H82(0.6787)
 H83A(0.8158) H83B(0.7867) H83C(0.7973) H84A(0.7213) H84B(0.6983) H84C(0.6308)
 H87(0.5372) H88(0.4072) H89(0.3213) H91(0.6345) H92A(0.731) H92B(0.663)
 H92C(0.6815) H93A(0.6693) H93B(0.5803) H93C(0.5972) H94(0.3766) H95A(0.2525)
 H95B(0.3178) H95C(0.2544) H96A(0.2589) H96B(0.2633) H96C(0.3304) H98(0.9883)
 H99(1.0143) H100(1.09) H101(0.9669) H102(0.8801) H103(0.9551) H104(1.0909)
 H107(0.78) H108(0.8737) H109(1.0072) H111(0.8134) H11A(0.6748) H11B(0.7172)
 H11C(0.6907) H11D(0.7426) H11E(0.7645) H11F(0.8326) H114(1.0957) H11G(1.1971)
 H11H(1.1331) H11I(1.1329) H11J(1.1584) H11K(1.0695) H11L(1.0908) H119(0.917)
 H120(1.0448) H121(1.1476) H123(0.8462) H12A(0.8032) H12B(0.8954) H12C(0.8674)
 H12D(0.7378) H12E(0.7974) H12F(0.7881) H126(1.1283) H12G(1.2468) H12H(1.1726)
 H12I(1.2269) H12J(1.245) H12K(1.2212) H12L(1.1677)
 Fixed Y: H2(1.006) H3(1.0132) H4(0.7249) H5(0.6794) H6(0.6704) H7(0.6915)
 H8(0.7206) H11(0.7995) H12(0.8465) H13(0.9224) H15(0.8194) H16A(0.7237)
 H16B(0.7354) H16C(0.7081) H17A(0.8468) H17B(0.9141) H17C(0.8657) H18(0.9629)
 H19A(1.0026) H19B(0.92) H19C(0.9783) H20A(1.0849) H20B(1.0647) H20C(1.0571)
 H23(0.8407) H24(0.8646) H25(0.9123) H27(0.8663) H28A(0.7788) H28B(0.7497)
 H28C(0.7777) H29A(0.908) H29B(0.9141) H29C(0.9651) H30(0.9337) H31A(1.0579)
 H31B(1.0437) H31C(1.0577) H32A(0.9654) H32B(0.9605) H32C(0.8903) H34(0.464)
 H35(0.5074) H36(0.8077) H37(0.8692) H38(0.8523) H39(0.7884) H40(0.7485)
 H43(0.5783) H44(0.5523) H45(0.5318) H47(0.624) H48A(0.6429) H48B(0.681)
 H48C(0.6071) H49A(0.5341) H49B(0.4919) H49C(0.4997) H50(0.5458) H51A(0.5503)
 H51B(0.5496) H51C(0.6167) H52A(0.4334) H52B(0.4251) H52C(0.4291) H55(0.759)
 H56(0.7656) H57(0.7017) H59(0.6801) H60A(0.7534) H60B(0.7976) H60C(0.7688)
 H61A(0.5828) H61B(0.6236) H61C(0.6365) H62(0.5981) H63A(0.6285) H63B(0.6741)
 H63C(0.6995) H64A(0.5187) H64B(0.5163) H64C(0.5598) H66(0.019) H67(-0.0197)
 H68(0.2844) H69(0.2398) H70(0.2752) H71(0.3464) H72(0.3635) H75(0.2892)
 H76(0.2622) H77(0.1717) H79(0.2198) H80A(0.3141) H80B(0.32) H80C(0.3404)
 H81A(0.1877) H81B(0.1286) H81C(0.1843) H82(0.0645) H83A(0.0675) H83B(0.1456)
 H83C(0.1251) H84A(-0.02) H84B(0.0346) H84C(0.0008) H87(0.0709) H88(0.1097)
 H89(0.1306) H91(0.0578) H92A(0.0502) H92B(0.0561) H92C(0.1223) H93A(-0.0591)
 H93B(-0.058) H93C(-0.0576) H94(0.1338) H95A(0.1924) H95B(0.2299) H95C(0.1773)
 H96A(0.0637) H96B(0.0403) H96C(0.0151) H98(0.5096) H99(0.5422) H100(0.2579)
 H101(0.21) H102(0.1515) H103(0.1529) H104(0.207) H107(0.2981) H108(0.256)
 H109(0.2886) H111(0.375) H11A(0.3666) H11B(0.2944) H11C(0.3515) H11D(0.4821)
 H11E(0.4729) H11F(0.4886) H114(0.3853) H11G(0.3194) H11H(0.2843) H11I(0.2651)
 H11J(0.4398) H11K(0.4679) H11L(0.409) H119(0.4502) H120(0.4247) H121(0.4058)
 H123(0.4493) H12A(0.5685) H12B(0.5676) H12C(0.5747) H12D(0.4627) H12E(0.4657)
 H12F(0.3938) H126(0.4037) H12G(0.3413) H12H(0.2997) H12I(0.3479) H12J(0.4746)
 H12K(0.4852) H12L(0.5191)
 Fixed Z: H2(0.183) H3(0.1209) H4(0.1458) H5(0.1825) H6(0.1444) H7(0.0827)
 H8(0.0831) H11(0.2717) H12(0.2927) H13(0.259) H15(0.1863) H16A(0.2135)
 H16B(0.2471) H16C(0.213) H17A(0.2161) H17B(0.2161) H17C(0.2493) H18(0.1705)
 H19A(0.187) H19B(0.1958) H19C(0.2253) H20A(0.187) H20B(0.2249) H20C(0.1946)
 H23(0.0276) H24(-0.0117) H25(0.0061) H27(0.1195) H28A(0.1095) H28B(0.0975)
 H28C(0.07) H29A(0.1077) H29B(0.0682) H29C(0.0952) H30(0.0914) H31A(0.0817)
 H31B(0.0913) H31C(0.0527) H32A(0.0532) H32B(0.022) H32C(0.0427) H34(0.1454)
 H35(0.2051) H36(0.1954) H37(0.1578) H38(0.0956) H39(0.0953) H40(0.1562)
 H43(0.0382) H44(0.0013) H45(0.022) H47(0.1264) H48A(0.1079) H48B(0.0825)
 H48C(0.0721) H49A(0.139) H49B(0.1053) H49C(0.1358) H50(0.1094) H51A(0.0738)
 H51B(0.0408) H51C(0.0657) H52A(0.0929) H52B(0.0996) H52C(0.0616) H55(0.2671)
 H56(0.2936) H57(0.2716) H59(0.1863) H60A(0.2037) H60B(0.2043) H60C(0.239)
 H61A(0.2235) H61B(0.2132) H61C(0.2497) H62(0.1937) H63A(0.208) H63B(0.2397)
 H63C(0.2019) H64A(0.2308) H64B(0.2384) H64C(0.263) H66(0.0384) H67(0.094)
 H68(0.1127) H69(0.1727) H70(0.1852) H71(0.1342) H72(0.0923) H75(-0.0173) H76(-
 0.0434) H77(-0.0216) H79(0.0606) H80A(0.0411) H80B(0.0069) H80C(0.0425)
 H81A(0.0295) H81B(0.0251) H81C(-0.0047) H82(0.0533) H83A(0.0442) H83B(0.0532)
 H83C(0.0148) H84A(0.0137) H84B(-0.0167) H84C(0.0035) H87(0.2272) H88(0.2308)
 H89(0.1815) H91(0.1502) H92A(0.1984) H92B(0.2232) H92C(0.1999) H93A(0.1709)
 H93B(0.1533) H93C(0.1937) H94(0.0958) H95A(0.0967) H95B(0.1228) H95C(0.1365)
 H96A(0.0835) H96B(0.1224) H96C(0.0997) H98(0.0619) H99(0.1234) H100(0.0952)
 H101(0.0589) H102(0.099) H103(0.1591) H104(0.1552) H107(0.0052) H108(-0.0293)
 H109(-0.0178) H111(0.086) H11A(0.0696) H11B(0.0601) H11C(0.0312) H11D(0.0697)
 H11E(0.0317) H11F(0.0617) H114(0.056) H11G(0.0325) H11H(0.0049) H11I(0.0442)
 H11J(0.0108) H11K(0.0104) H11L(-0.0163) H119(0.2405) H120(0.2652) H121(0.2311)
 H123(0.1518) H12A(0.1615) H12B(0.1567) H12C(0.1938) H12D(0.185) H12E(0.219)
 H12F(0.1973) H126(0.1384) H12G(0.1577) H12H(0.1698) H12I(0.1961) H12J(0.1524)
 H12K(0.1901) H12L(0.1586)
;