Bespoke photoreductants: tungsten arylisocyanides.
Sattler, Wesley; Henling, Lawrence M.; Winkler, Jay R.; Gray, Harry B.; Journal of the American Chemical Society 137 (2015) 1198–1205; doi:10.1021/ja510973h

data_4123298
_publ_section_title
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 Bespoke photoreductants: tungsten arylisocyanides.
;
_journal_issue                   3
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              1198
_journal_page_last               1205
_journal_paper_doi               10.1021/ja510973h
_journal_volume                  137
_journal_year                    2015
_chemical_formula_moiety         'C150 H150 N6 W, C6 H6, C5 H12'
_chemical_formula_sum            'C161 H168 N6 W'
_chemical_formula_weight         2370.85
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2014-05-28
_audit_creation_method
;
Olex2 1.2
(compiled 2014.03.20 svn.r2914 for OlexSys, GUI svn.r4816),
 SHELXL-2014,
 and manual edit
;
_cell_angle_alpha                90
_cell_angle_beta                 111.074(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   44.228(10)
_cell_length_b                   13.454(3)
_cell_length_c                   46.847(10)
_cell_measurement_reflns_used    9715
_cell_measurement_temperature    100
_cell_measurement_theta_max      26.06
_cell_measurement_theta_min      2.22
_cell_volume                     26012(10)
_computing_cell_refinement       'SAINT V8.34A (Bruker-AXS, 2007)'
_computing_data_collection       'Bruker SMART v5.054 (Bruker-AXS, 2007)'
_computing_data_reduction        'SAINT V8.34A (Bruker-AXS, 2007)'
_computing_molecular_graphics    'DIAMOND 3 (Crystal Impact, 1999)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2014/2 (Sheldrick, 2014)'
_computing_structure_solution    'XT-2014/1 (Sheldrick, 2012)'
_diffrn_ambient_temperature      100
_diffrn_detector_area_resol_mean 8.19
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.931
_diffrn_measurement_device_type  'Bruker SMART 1000 ccd'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1355
_diffrn_reflns_av_unetI/netI     0.1160
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.931
_diffrn_reflns_limit_h_max       57
_diffrn_reflns_limit_h_min       -60
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       63
_diffrn_reflns_limit_l_min       -60
_diffrn_reflns_number            204260
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.931
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         29.170
_diffrn_reflns_theta_min         0.932
_diffrn_source_current           30
_diffrn_source_power             1.5
_diffrn_source_target            Mo
_diffrn_source_voltage           50
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.943
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.7630
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0992 before and 0.0684 after correction.
The Ratio of minimum to maximum transmission is 0.7630.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_density_diffrn    1.211
_exptl_crystal_F_000             10000
_exptl_crystal_size_max          0.8
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.18
_refine_diff_density_max         1.993
_refine_diff_density_min         -1.552
_refine_diff_density_rms         0.116
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.104
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1577
_refine_ls_number_reflns         32718
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.105
_refine_ls_R_factor_all          0.1430
_refine_ls_R_factor_gt           0.0804
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0514P)^2^+106.9853P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1411
_refine_ls_wR_factor_ref         0.1609
_reflns_Friedel_coverage         0.000
_reflns_number_gt                21032
_reflns_number_total             32718
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja510973h_si_003.cif
_cod_data_source_block           s13029
_cod_depositor_comments
'Adding full bibliography for 4123295--4123298.cif.'
_cod_database_code               4123298
_shelxl_version_number           2014-2
_shelx_estimated_absorpt_t_max   0.849
_shelx_estimated_absorpt_t_min   0.519
_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. Shared sites
{C15C, C45C}
3. Uiso/Uaniso restraints and constraints
Uanis(C15C) = Uanis(C45C)
4. Same fragment restrains
{C8, C9, C10, C11, C12}
as
{C7', C8', C9', C10', C11'}
5. Others
 Sof(H23C)=Sof(C55B)=Sof(H55A)=Sof(H55B)=Sof(H55C)=1-FVAR(1)
 Sof(H23B)=Sof(C25B)=Sof(H25D)=Sof(H25E)=Sof(H25F)=FVAR(1)
 Sof(C7')=Sof(H7'A)=Sof(H7'B)=Sof(H7'C)=Sof(C8')=Sof(H8'A)=Sof(H8'B)=Sof(C9')=
 Sof(H9'A)=Sof(H9'B)=Sof(C10')=Sof(H10I)=Sof(H10J)=Sof(C11')=Sof(H11C)=
 Sof(H11D)=Sof(H11E)=1-FVAR(2)
 Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=Sof(C9)=Sof(H9G)=Sof(H9H)=Sof(C10)=
 Sof(H10G)=Sof(H10H)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(C12)=Sof(H12G)=Sof(H12H)=
 Sof(H12I)=FVAR(2)
 Uiso(C8)=Uiso(C9)=Uiso(C10)=Uiso(C11)=Uiso(C12)=FVAR(3)
 Uiso(C7')=Uiso(C8')=Uiso(C9')=Uiso(C10')=Uiso(C11')=FVAR(4)
 Sof(C44C)=Sof(C45C)=Sof(H45C)=Sof(C46C)=Sof(H46C)=Sof(C47C)=Sof(H47C)=
 Sof(C48C)=Sof(H48C)=Sof(C49C)=Sof(H49C)=1-FVAR(5)
 Sof(C14C)=Sof(C15C)=Sof(H15C)=Sof(C16C)=Sof(H16C)=Sof(C17C)=Sof(H17C)=
 Sof(C18C)=Sof(H18C)=Sof(C19C)=Sof(H19C)=FVAR(5)
 Sof(H23G)=Sof(C54E)=Sof(H54A)=Sof(H54B)=Sof(H54C)=Sof(C55E)=Sof(H55D)=
 Sof(H55E)=Sof(H55F)=1-FVAR(6)
 Sof(H23F)=Sof(C24E)=Sof(H24M)=Sof(H24N)=Sof(H24O)=Sof(C25E)=Sof(H25M)=
 Sof(H25N)=Sof(H25O)=FVAR(6)
6.a Ternary CH refined with riding coordinates:
 C20A(H20A), C23A(H23A), C20B(H20B), C23B(H23B), C23B(H23C), C20C(H20C),
 C23C(H23D), C20D(H20D), C23D(H23E), C20E(H20E), C23E(H23F), C23E(H23G),
 C20F(H20F), C23F(H23H)
6.b Secondary CH2 refined with riding coordinates:
 C9(H9G,H9H), C10(H10G,H10H), C11(H11A,H11B), C8'(H8'A,H8'B), C9'(H9'A,H9'B),
 C10'(H10I,H10J)
6.c Aromatic/amide H refined with riding coordinates:
 C4A(H4A), C6A(H6A), C9A(H9A), C10A(H10A), C12A(H12A), C13A(H13A), C19A(H19A),
 C15A(H15A), C16A(H16A), C17A(H17A), C18A(H18A), C4B(H4B), C6B(H6B), C9B(H9B),
 C10B(H10B), C12B(H12B), C13B(H13B), C15B(H15B), C16B(H16B), C17B(H17B),
 C18B(H18B), C19B(H19B), C4C(H4C), C6C(H6C), C9C(H9C), C10C(H10C), C12C(H12C),
 C13C(H13C), C15C(H15C), C16C(H16C), C17C(H17C), C18C(H18C), C19C(H19C),
 C45C(H45C), C46C(H46C), C47C(H47C), C48C(H48C), C49C(H49C), C4D(H4D), C6D(H6D),
  C9D(H9D), C10D(H10D), C12D(H12D), C13D(H13D), C15D(H15D), C16D(H16D),
 C17D(H17D), C18D(H18D), C19D(H19D), C4E(H4E), C6E(H6E), C9E(H9E), C10E(H10E),
 C12E(H12E), C13E(H13E), C15E(H15E), C16E(H16E), C17E(H17E), C18E(H18E),
 C19E(H19E), C4F(H4F), C6F(H6F), C9F(H9F), C10F(H10F), C12F(H12F), C13F(H13F),
 C15F(H15F), C16F(H16F), C17F(H17F), C18F(H18F), C19F(H19F), C2(H2), C3(H3),
 C4(H4), C5(H5), C6(H6), C7(H7)
6.d Idealised Me refined as rotating group:
 C21A(H21A,H21B,H21C), C22A(H22A,H22B,H22C), C24A(H24A,H24B,H24C), C25A(H25A,
 H25B,H25C), C21B(H21D,H21E,H21F), C22B(H22D,H22E,H22F), C24B(H24D,H24E,H24F),
 C25B(H25D,H25E,H25F), C55B(H55A,H55B,H55C), C21C(H21G,H21H,H21I), C22C(H22G,
 H22H,H22I), C24C(H24G,H24H,H24I), C25C(H25G,H25H,H25I), C21D(H21J,H21K,H21L),
 C22D(H22J,H22K,H22L), C24D(H24J,H24K,H24L), C25D(H25J,H25K,H25L), C21E(H21M,
 H21N,H21O), C22E(H22M,H22N,H22O), C24E(H24M,H24N,H24O), C25E(H25M,H25N,H25O),
 C54E(H54A,H54B,H54C), C55E(H55D,H55E,H55F), C21F(H21P,H21Q,H21R), C22F(H22P,
 H22Q,H22R), C24F(H24P,H24Q,H24R), C25F(H25P,H25Q,H25R), C8(H8A,H8B,H8C),
 C12(H12G,H12H,H12I), C7'(H7'A,H7'B,H7'C), C11'(H11C,H11D,H11E)
;