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_4129249
_publ_section_title
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 Isolation of bridging and terminal coinage metal-nitrene complexes.
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_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 Ag N14 P2, 2(C4 H8 O), C F3 O3 S'
_chemical_formula_sum            'C117 H168 Ag F3 N14 O5 P2 S'
_chemical_formula_weight         2109.52
_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             2013-07-12
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:54:37, GUI svn.r4466)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 113.346(2)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   20.956(2)
_cell_length_b                   25.095(3)
_cell_length_c                   24.505(3)
_cell_measurement_reflns_used    9875
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.42
_cell_measurement_theta_min      2.27
_cell_volume                     11832(2)
_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.
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_computing_publication_material
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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
;
XS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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  0.0712
_diffrn_reflns_av_unetI/netI     0.0759
_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       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            91060
_diffrn_reflns_theta_full        25.71
_diffrn_reflns_theta_max         25.71
_diffrn_reflns_theta_min         1.22
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.276
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.5844
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0485 before and 0.0431 after correction.
The Ratio of minimum to maximum transmission is 0.9462.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.184
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             4512
_exptl_crystal_size_max          0.123
_exptl_crystal_size_mid          0.119
_exptl_crystal_size_min          0.099
_platon_squeeze_details
;
The difference map peaklist indicates that there are three THF molecules in the
asymmetric unit. Only two could be refined from difference Fourier peaks. 
One of them is 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 and the contribution 
to the calculated structure factors of the disordered solvent is taken into account
by back-Fourier transformation with the program SQUEEZE (Sluis and Spek, 1990). 
Two voids were found in the unit cell with 114 electrons in each void. This 
electron number corresponds roughly to two THF molecules in each void.
;
_refine_diff_density_max         1.313
_refine_diff_density_min         -0.879
_refine_diff_density_rms         0.082
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1274
_refine_ls_number_reflns         22528
_refine_ls_number_restraints     42
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.1024
_refine_ls_R_factor_gt           0.0642
_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^)+(0.0979P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1610
_refine_ls_wR_factor_ref         0.1759
_reflns_number_gt                14851
_reflns_number_total             22528
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja5007355_si_001.cif
_cod_data_source_block           4b-DF498
_cod_database_code               4129249
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C25) \\sim Ueq, Uanis(F2) \\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(F1) \\sim Ueq, Uanis(O1) \\sim Ueq, Uanis(O2) \\sim Ueq, Uanis(O3) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
3. Others
 Fixed Sof: O03T(0.5) H03C(0.5) H03D(0.5) H03A(0.5) H03B(0.5) H03G(0.5)
 H03H(0.5) H03E(0.5) H03F(0.5) O1D(0.5)
4.a Ternary CH refined with riding coordinates:
 C19(H19), C22(H22), C31(H31), C34(H34), C43(H43), C46(H46), C55(H55),
 C58(H58), C67(H67), C70(H70), C79(H79), C82(H82), C91(H91), C94(H94),
 C103(H103), C106(H106)
4.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C03U(H03C,H03D), C03U(H03A,H03B), C03W(H03G,H03H),
 C03W(H03E,H03F), C03Y(H03I,H03J), C5(H5A,H5B), C6(H6A,H6B), C8(H8A,H8B),
 C9(H9A,H9B), C11(H11A,H11B), C12(H12A,H12B), C110(H11C,H11D), C111(H11E,H11F),
 C112(H11G,H11H), C113(H11I,H11J), C1F(H1FA,H1FB)
4.c Aromatic/amide H refined with riding coordinates:
 C15(H15), C16(H16), C17(H17), C27(H27), C28(H28), C29(H29), C39(H39),
 C40(H40), C41(H41), C51(H51), C52(H52), C53(H53), C63(H63), C64(H64), C65(H65),
  C75(H75), C76(H76), C77(H77), C87(H87), C88(H88), C89(H89), C99(H99),
 C100(H100), C101(H101)
4.d Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C23(H23A,H23B,H23C), C24(H24A,H24B,
 H24C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C35(H35A,H35B,H35C), C36(H36A,
 H36B,H36C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C47(H47A,H47B,H47C),
 C48(H48A,H48B,H48C), C56(H56A,H56B,H56C), C57(H57A,H57B,H57C), C59(H59A,H59B,
 H59C), C60(H60A,H60B,H60C), C68(H68A,H68B,H68C), C69(H69A,H69B,H69C), C71(H71A,
 H71B,H71C), C72(H72A,H72B,H72C), C80(H80A,H80B,H80C), C81(H81A,H81B,H81C),
 C83(H83A,H83B,H83C), C84(H84A,H84B,H84C), C92(H92A,H92B,H92C), C93(H93A,H93B,
 H93C), C95(H95A,H95B,H95C), C96(H96A,H96B,H96C), C104(H10A,H10B,H10C),
 C105(H10D,H10E,H10F), C107(H10G,H10H,H10I), C108(H10J,H10K,H10L)
;