Isolation of bridging and terminal coinage metal-nitrene complexes.
Dielmann, Fabian; Andrada, Diego M.; Frenking, Gernot; Bertrand, Guy; Journal of the American Chemical Society 136 (2014) 3800–3802; doi:10.1021/ja5007355

data_4129248
_publ_section_title
;
 Isolation of bridging and terminal coinage metal-nitrene complexes.
;
_journal_issue                   10
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              3800
_journal_page_last               3802
_journal_paper_doi               10.1021/ja5007355
_journal_volume                  136
_journal_year                    2014
_chemical_formula_moiety         'C108 H152 Cu N14 P2, C4 H8 O, C F3 O3 S'
_chemical_formula_sum            'C113 H160 Cu F3 N14 O4 P2 S'
_chemical_formula_weight         1993.09
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-07-15
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:54:37, GUI svn.r4466)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 112.552(2)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   20.6834(12)
_cell_length_b                   25.1597(16)
_cell_length_c                   24.6629(12)
_cell_measurement_reflns_used    3779
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      21.75
_cell_measurement_theta_min      2.34
_cell_volume                     11852.9(12)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_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
;
XL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0577
_diffrn_reflns_av_unetI/netI     0.0629
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            99674
_diffrn_reflns_theta_full        25.69
_diffrn_reflns_theta_max         25.69
_diffrn_reflns_theta_min         1.21
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.287
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6181
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.117
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             4280
_exptl_crystal_size_max          0.151
_exptl_crystal_size_mid          0.133
_exptl_crystal_size_min          0.119
_platon_squeeze_details
;
The difference map peaklist indicated that there are three THF molecules in the
asymmetric unit. Only one could be refined from difference Fourier peaks. 
Two of them were heavily disordered and it was impossible to refine any 
reasonable molecule from difference Fourier peaks. Therefore the midpoint, the 
size and the number of electrons in that void were refined with the program 
SQUEEZE (Sluis and Spek, 1990). Six voids were found in the unit cell with 
overall 364 electrons. This electron number corresponds roughly to eight THF
molecules in the unit cell.
;
_refine_diff_density_max         0.654
_refine_diff_density_min         -0.597
_refine_diff_density_rms         0.069
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1855
_refine_ls_number_reflns         22436
_refine_ls_number_restraints     372
_refine_ls_restrained_S_all      1.066
_refine_ls_R_factor_all          0.1197
_refine_ls_R_factor_gt           0.0763
_refine_ls_shift/su_max          0.088
_refine_ls_shift/su_mean         0.006
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1355P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2114
_refine_ls_wR_factor_ref         0.2316
_reflns_number_gt                13340
_reflns_number_total             22436
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja5007355_si_001.cif
_cod_data_source_block           4a-DF457b
_cod_database_code               4129248
_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-C86A = C91B-C86B
 1.52 with sigma of 0.02
3. Rigid bond restraints
 C71B, C71A, C72A, C72B, C70B, C70A, C65B, C65A, C64A, C64B, C63B, C63A, C8B,
 C9B, C81B, C69B, C69A, C80B, C80A, C79A, C79B, C68B, C68A, C67B, C67A, C74A,
 C73B, C73A, N9B, C77A, C77B, C7A, C82B, C82A, C83A, C83B, C1F, C1D, C1G, C1C,
 C1E, C1H, C92A, C92B, C91B, C91A, C93B, C93A, C86B, C87B, C86A, N13B, N13A,
 C12A, C12B, C11B, C11A, C10B, C8, C1I, C7, C1K, C99B, C95B, C99A, C98B, C97B,
 C9, C1J, C90A, C98A, C1L, C10, C12, C1M, C11, C96A, C96B, C76A, C76B, C88B,
 C87A, C88A, C89B, C89A, C90B, C85A, C85B, C94B, C94A, C81A, C74B, C75B, C75A,
 C84B, C78B, C78A, C62A, N14A, N14B, C97A, C1N, C66A, C66B, C61A, C61B, N10B,
 N10A, C8A, C9A, N11B, N11A, C95A, C7B, N9A, N12A, N12B, C10A, C62B, C84A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
4. Uiso/Uaniso restraints and constraints
C63A \\sim C63B: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 0.03
Uanis(C91A) \\sim Ueq, Uanis(C91B) \\sim Ueq: with sigma of 0.004 and sigma for terminal atoms of 0.004
Uanis(O2A) \\sim Ueq, Uanis(C1B) \\sim Ueq, Uanis(C1A) \\sim Ueq, Uanis(F2A) \\sim Ueq, Uanis(F1A) \\sim Ueq, Uanis(F1B) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C79A) = Uanis(C79B)
Uanis(C7B) = Uanis(C7A)
Uanis(C94A) = Uanis(C94B)
Uanis(C8B) = Uanis(C8A)
Uanis(C9B) = Uanis(C9A)
Uanis(C1G) = Uanis(C1C)
5. Others
 Fixed Sof: F1A(0.5) F2B(0.5) F3A(0.5) C95A(0.5) H95A(0.5) H95B(0.5) H95C(0.5)
 C1C(0.5) H1C(0.5) C96A(0.5) H96A(0.5) H96B(0.5) H96C(0.5) C94A(0.5) H94A(0.5)
 C1E(0.5) H1EA(0.5) H1EB(0.5) H1EC(0.5) C1D(0.5) H1DA(0.5) H1DB(0.5) H1DC(0.5)
 C1I(0.5) H1I(0.5) C1N(0.5) H1NA(0.5) H1NB(0.5) H1NC(0.5) C10A(0.5) C1J(0.5)
 C1L(0.5) H1L(0.5) C97A(0.5) C98A(0.5) C1M(0.5) H1MA(0.5) H1MB(0.5) H1MC(0.5)
 C1K(0.5) H1K(0.5) C99A(0.5) H99A(0.5) N13A(0.5) C85A(0.5) C90B(0.5) C89B(0.5)
 H89B(0.5) C88B(0.5) H88B(0.5) C87B(0.5) H87B(0.5) C86B(0.5) O1A(0.5) N14A(0.5)
 S1A(0.5) C11A(0.5) H11A(0.5) H11B(0.5) C12A(0.5) H12A(0.5) H12B(0.5) O2B(0.5)
 O3A(0.5) C69A(0.5) H69A(0.5) H69B(0.5) H69C(0.5) C79A(0.5) H79A(0.5) C81A(0.5)
 H81A(0.5) H81B(0.5) H81C(0.5) C72A(0.5) H72A(0.5) H72B(0.5) H72C(0.5)
 C71A(0.5) H71A(0.5) H71B(0.5) H71C(0.5) C68A(0.5) H68A(0.5) H68B(0.5)
 H68C(0.5) C67A(0.5) H67A(0.5) C73A(0.5) C74A(0.5) C75A(0.5) H75A(0.5)
 C78A(0.5) C77A(0.5) H77A(0.5) C1B(0.5) C76A(0.5) H76A(0.5) C82A(0.5) H82A(0.5)
 C80A(0.5) H80A(0.5) H80B(0.5) H80C(0.5) C84A(0.5) H84A(0.5) H84B(0.5)
 H84C(0.5) C83A(0.5) H83A(0.5) H83B(0.5) H83C(0.5) C93B(0.5) H93A(0.5)
 H93B(0.5) H93C(0.5) C92B(0.5) H92A(0.5) H92B(0.5) H92C(0.5) C9A(0.5) H9AA(0.5)
 H9AB(0.5) C91B(0.5) H91B(0.5) N9A(0.5) N12A(0.5) C7A(0.5) N11A(0.5) C63A(0.5)
 H63A(0.5) C62A(0.5) C61A(0.5) C66A(0.5) C64A(0.5) H64A(0.5) C70A(0.5)
 H70A(0.5) C8A(0.5) H8AA(0.5) H8AB(0.5) N10A(0.5) C65A(0.5) H65A(0.5) C87A(0.5)
 H87A(0.5) C89A(0.5) H89A(0.5) C90A(0.5) C88A(0.5) H88A(0.5) C86A(0.5)
 C93A(0.5) H93D(0.5) H93E(0.5) H93F(0.5) C91A(0.5) H91A(0.5) C92A(0.5)
 H92D(0.5) H92E(0.5) H92F(0.5) C73B(0.5) C76B(0.5) H76B(0.5) C75B(0.5)
 H75B(0.5) C74B(0.5) C71B(0.5) H71D(0.5) H71E(0.5) H71F(0.5) C70B(0.5)
 H70B(0.5) C72B(0.5) H72D(0.5) H72E(0.5) H72F(0.5) C81B(0.5) H81D(0.5)
 H81E(0.5) H81F(0.5) C82B(0.5) H82B(0.5) C78B(0.5) C77B(0.5) H77B(0.5)
 C80B(0.5) H80D(0.5) H80E(0.5) H80F(0.5) C79B(0.5) H79B(0.5) C11B(0.5)
 H11C(0.5) H11D(0.5) C10B(0.5) C61B(0.5) C12B(0.5) H12C(0.5) H12D(0.5) C8B(0.5)
 H8BA(0.5) H8BB(0.5) C7B(0.5) C1A(0.5) C9B(0.5) H9BA(0.5) H9BB(0.5) C68B(0.5)
 H68D(0.5) H68E(0.5) H68F(0.5) C67B(0.5) H67B(0.5) C69B(0.5) H69D(0.5)
 H69E(0.5) H69F(0.5) C64B(0.5) H64B(0.5) C63B(0.5) H63B(0.5) C62B(0.5)
 C66B(0.5) C65B(0.5) H65B(0.5) C83B(0.5) H83D(0.5) H83E(0.5) H83F(0.5)
 N11B(0.5) N10B(0.5) N9B(0.5) N14B(0.5) N13B(0.5) N12B(0.5) C12(0.5) H12E(0.5)
 H12F(0.5) H12G(0.5) F3B(0.5) F2A(0.5) F1B(0.5) C1G(0.5) H1G(0.5) C1H(0.5)
 H1HA(0.5) H1HB(0.5) H1HC(0.5) O2A(0.5) O1B(0.5) C1F(0.5) H1FA(0.5) H1FB(0.5)
 H1FC(0.5) S1B(0.5) O3B(0.5) C95B(0.5) H95D(0.5) H95E(0.5) H95F(0.5) C94B(0.5)
 H94B(0.5) C96B(0.5) H96D(0.5) H96E(0.5) H96F(0.5) C84B(0.5) H84D(0.5)
 H84E(0.5) H84F(0.5) C85B(0.5) C10(0.5) H10(0.5) C9(0.5) C8(0.5) H8(0.5)
 C11(0.5) H11E(0.5) H11F(0.5) H11G(0.5) C98B(0.5) C97B(0.5) C7(0.5) H7(0.5)
 C99B(0.5) H99B(0.5)
6.a Ternary CH refined with riding coordinates:
 C46(H46), C55(H55), C43(H43), C58(H58), C19(H19), C34(H34), C31(H31),
 C22(H22), C1C(H1C), C94A(H94A), C1L(H1L), C79A(H79A), C67A(H67A), C82A(H82A),
 C91B(H91B), C70A(H70A), C91A(H91A), C70B(H70B), C82B(H82B), C79B(H79B),
 C67B(H67B), C1G(H1G), C94B(H94B), C10(H10)
6.b Secondary CH2 refined with riding coordinates:
 C111(H11H,H11I), C110(H11J,H11K), C113(H11L,H11M), C112(H11N,H11O), C2(H2A,
 H2B), C6(H6A,H6B), C3(H3A,H3B), C5(H5A,H5B), C11A(H11A,H11B), C12A(H12A,H12B),
 C9A(H9AA,H9AB), C8A(H8AA,H8AB), C11B(H11C,H11D), C12B(H12C,H12D), C8B(H8BA,
 H8BB), C9B(H9BA,H9BB)
6.c Aromatic/amide H refined with riding coordinates:
 C53(H53), C51(H51), C52(H52), C39(H39), C40(H40), C41(H41), C15(H15),
 C16(H16), C17(H17), C27(H27), C29(H29), C28(H28), C1I(H1I), C1K(H1K),
 C99A(H99A), C89B(H89B), C88B(H88B), C87B(H87B), C75A(H75A), C77A(H77A),
 C76A(H76A), C63A(H63A), C64A(H64A), C65A(H65A), C87A(H87A), C89A(H89A),
 C88A(H88A), C76B(H76B), C75B(H75B), C77B(H77B), C64B(H64B), C63B(H63B),
 C65B(H65B), C8(H8), C7(H7), C99B(H99B)
6.d Fitted hexagon refined as free rotating group:
 C85A(C90B,C89B,C88B,C87B,C86B)
6.e Idealised Me refined as rotating group:
 C48(H48A,H48B,H48C), C47(H47A,H47B,H47C), C45(H45A,H45B,H45C), C44(H44A,H44B,
 H44C), C56(H56A,H56B,H56C), C57(H57A,H57B,H57C), C59(H59A,H59B,H59C), C60(H60A,
 H60B,H60C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C33(H33A,H33B,H33C),
 C32(H32A,H32B,H32C), C35(H35A,H35B,H35C), C24(H24A,H24B,H24C), C23(H23A,H23B,
 H23C), C36(H36A,H36B,H36C), C95A(H95A,H95B,H95C), C96A(H96A,H96B,H96C),
 C1E(H1EA,H1EB,H1EC), C1D(H1DA,H1DB,H1DC), C1N(H1NA,H1NB,H1NC), C1M(H1MA,H1MB,
 H1MC), C69A(H69A,H69B,H69C), C81A(H81A,H81B,H81C), C72A(H72A,H72B,H72C),
 C71A(H71A,H71B,H71C), C68A(H68A,H68B,H68C), C80A(H80A,H80B,H80C), C84A(H84A,
 H84B,H84C), C83A(H83A,H83B,H83C), C93B(H93A,H93B,H93C), C92B(H92A,H92B,H92C),
 C93A(H93D,H93E,H93F), C92A(H92D,H92E,H92F), C71B(H71D,H71E,H71F), C72B(H72D,
 H72E,H72F), C81B(H81D,H81E,H81F), C80B(H80D,H80E,H80F), C68B(H68D,H68E,H68F),
 C69B(H69D,H69E,H69F), C83B(H83D,H83E,H83F), C12(H12E,H12F,H12G), C1H(H1HA,H1HB,
 H1HC), C1F(H1FA,H1FB,H1FC), C95B(H95D,H95E,H95F), C96B(H96D,H96E,H96F),
 C84B(H84D,H84E,H84F), C11(H11E,H11F,H11G)
;