Bis(Imido) Tungsten Complexes: Efficient Precatalysts for the Homogeneous Dimerization of Ethylene
Messinis, Antonis M.; Batsanov, Andrei S.; Wright, William R. H.; Howard, Judith A. K.; Hanton, Martin J.; Dyer, Philip W.; ACS Catalysis 8 (2018) 11249–; doi:10.1021/acscatal.8b02202

data_4515804
_publ_section_title
;
 Bis(Imido) Tungsten Complexes: Efficient Precatalysts for the Homogeneous
 Dimerization of Ethylene
;
_journal_issue                   12
_journal_name_full               'ACS Catalysis'
_journal_page_first              11249
_journal_paper_doi               10.1021/acscatal.8b02202
_journal_volume                  8
_journal_year                    2018
_chemical_formula_moiety         'C52 H44 Cl2 N2 O2 W,0.1(C4 H10 O2)'
_chemical_formula_sum            'C52.4 H45 Cl2 N2 O2.2 W'
_chemical_formula_weight         992.65
_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_Hall           '-R 3'
_space_group_name_H-M_alt        'R -3 :H'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2017-10-27
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            18
_cell_length_a                   32.8492(13)
_cell_length_b                   32.8492(13)
_cell_length_c                   20.7376(9)
_cell_measurement_reflns_used    9973
_cell_measurement_temperature    120
_cell_measurement_theta_max      23.69
_cell_measurement_theta_min      2.15
_cell_volume                     19379.3(14)
_computing_cell_refinement       'SAINT v7.46A (Bruker, 2008)'
_computing_data_collection       'SMART v5.625 (Bruker, 2001)'
_computing_data_reduction        'SAINT v7.46A (Bruker, 2008)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL 2016/6 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      120
_diffrn_detector_area_resol_mean 5.6
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART CCD 6000 area detector'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0958
_diffrn_reflns_av_unetI/netI     0.0689
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       42
_diffrn_reflns_limit_h_min       -42
_diffrn_reflns_limit_k_max       42
_diffrn_reflns_limit_k_min       -42
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            80646
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.505
_diffrn_reflns_theta_min         1.215
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_current           35.0
_diffrn_source_power             1.75
_diffrn_source_target            Mo
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    2.851
_exptl_absorpt_correction_T_max  0.8460
_exptl_absorpt_correction_T_min  0.7302
_exptl_absorpt_correction_type   integration
_exptl_absorpt_process_details
;
 SADABS-2009/1 (Bruker,2010) was used for absorption correction. 
 R(int) was 0.0998 before and 0.0737 after correction. The Ratio 
 of minimum to maximum transmission is 0.8631. The \l/2 correction 
 factor is 0.0015.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.531
_exptl_crystal_description       rhombohedron
_exptl_crystal_F_000             8982
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.844
_refine_diff_density_min         -1.734
_refine_diff_density_rms         0.111
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.965
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     534
_refine_ls_number_reflns         9910
_refine_ls_number_restraints     39
_refine_ls_restrained_S_all      0.968
_refine_ls_R_factor_all          0.0752
_refine_ls_R_factor_gt           0.0414
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0370P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0761
_refine_ls_wR_factor_ref         0.0840
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6704
_reflns_number_total             9910
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            W-bisimido.cif
_cod_data_source_block           8_12srv093
_cod_original_cell_volume        19379.3(17)
_cod_original_sg_symbol_H-M      'R -3'
_cod_database_code               4515804
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.825
_shelx_estimated_absorpt_t_min   0.658
_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, All C(H,H,H,H,H,H) groups
2. Restrained distances
 W-O2A \\sim W-O2B
 with sigma of 0.02
 C19B-C18B \\sim C19B-C20B \\sim C20B-C21B \\sim C22B-C21B \\sim C18B-C17A
\\sim C22B-C17A
 with sigma of 0.02
 O2A-C3B \\sim O2B-C3B
 with sigma of 0.02
 O1B-C2A \\sim O1B-C2B
 with sigma of 0.02
 C3B-C2B \\sim C3B-C2A
 with sigma of 0.02
 W-O2B \\sim W-O2A
 with sigma of 0.02
 O2B-C3B \\sim O2A-C3B
 with sigma of 0.02
 C3B-C2B \\sim C3A-C2A
 with sigma of 0.02
 O2B-C3B \\sim O2A-C3A
 with sigma of 0.02
 O1B-C2B \\sim O1B-C2A
 with sigma of 0.02
 O1B-C2B \\sim O1A-C2A
 with sigma of 0.02
 O1B-C1 \\sim O1A-C1
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C41C \\sim C42C \\sim C43C \\sim C44C \\sim C45C \\sim C46C: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
Uiso(C17B) = Uiso(C17A)
Uiso(C41B) = Uiso(C41A)
Uiso(C46B) = Uiso(C46A)
Uiso(C42B) = Uiso(C42A)
Uiso(C43B) = Uiso(C43A)
Uiso(C45B) = Uiso(C45A)
Uiso(C44B) = Uiso(C44A)
4. Rigid body (RIGU) restrains
 O1B, C2A, C3A, O2A, W, C4A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: O1B(0.33) O2A(0.67) O2B(0.33) H1BD(0.33) H1BE(0.33) H1BF(0.33)
 H1AA(0.67) H1AB(0.67) H1AC(0.67) C2A(0.67) H2AA(0.67) H2AB(0.67) C2B(0.33)
 H2BA(0.33) H2BB(0.33) C3B(0.33) H3BA(0.33) H3BB(0.33) C4A(0.67) H4AA(0.67)
 H4AB(0.67) H4AC(0.67) C4B(0.33) H4BA(0.33) H4BB(0.33) H4BC(0.33) C17A(0.85)
 C18A(0.85) H18A(0.85) C19A(0.85) H19A(0.85) C20A(0.85) H20A(0.85) C21A(0.85)
 H21A(0.85) C22A(0.85) H22A(0.85) C47A(0.6) C48A(0.6) H48A(0.6) C49A(0.6)
 H49A(0.6) C50A(0.6) H50A(0.6) C51A(0.6) H51A(0.6) C52A(0.6) H52A(0.6)
 C47B(0.4) C48B(0.4) H48B(0.4) C49B(0.4) H49B(0.4) C50B(0.4) H50B(0.4)
 C51B(0.4) H51B(0.4) C52B(0.4) H52B(0.4) C41C(0.15) C42C(0.15) H42C(0.15)
 C43C(0.15) H43C(0.15) C44C(0.15) H44C(0.15) C45C(0.15) H45C(0.15) C46C(0.15)
 H46C(0.15) C17B(0.15) C18B(0.15) H18B(0.15) C19B(0.15) H19B(0.15) C20B(0.15)
 H20B(0.15) C21B(0.15) H21B(0.15) C22B(0.15) H22B(0.15) C41A(0.425) C42A(0.425)
 H42A(0.425) C43A(0.425) H43A(0.425) C44A(0.425) H44A(0.425) C45A(0.425)
 H45A(0.425) C46A(0.425) H46A(0.425) C41B(0.425) C42B(0.425) H42B(0.425)
 C43B(0.425) H43B(0.425) C44B(0.425) H44B(0.425) C45B(0.425) H45B(0.425)
 C46B(0.425) H46B(0.425) C3A(0.67) H3AA(0.67) H3AB(0.67) O1A(0.67)
6.a Riding coordinates:
 C7(H7), C9(H9), C12(H12), C13(H13), C14(H14), C15(H15), C16(H16), C18A(H18A),
 C19A(H19A), C20A(H20A), C21A(H21A)
6.b Free rotating group:
 C41A(C42A,H42A,C43A,H43A,C44A,H44A,C45A,H45A,C46A,H46A), C41B(C42B,H42B,C43B,
 H43B,C44B,H44B,C45B,H45B,C46B,H46B)
6.c Secondary CH2 refined with riding coordinates:
 C2A(H2AA,H2AB), C2B(H2BA,H2BB), C3B(H3BA,H3BB), C3A(H3AA,H3AB)
6.d Me refined with riding coordinates:
 C1(H1BD,H1BE,H1BF), C1(H1AA,H1AB,H1AC), C4A(H4AA,H4AB,H4AC), C4B(H4BA,H4BB,
 H4BC)
6.e Aromatic/amide H refined with riding coordinates:
 C22A(H22A), C48A(H48A), C49A(H49A), C50A(H50A), C51A(H51A), C52A(H52A),
 C48B(H48B), C49B(H49B), C50B(H50B), C51B(H51B), C52B(H52B), C42C(H42C),
 C43C(H43C), C44C(H44C), C45C(H45C), C46C(H46C), C18B(H18B), C19B(H19B),
 C20B(H20B), C21B(H21B), C22B(H22B)
6.f Fitted hexagon refined as free rotating group:
 C41C(C42C,C43C,C44C,C45C,C46C), C17B(C18B,C19B,C20B,C21B,C22B)
;
_shelx_res_checksum              72226
_shelx_hkl_checksum              38826
_shelx_fab_checksum              55078