Phenylimido Complexes of Rhenium: Fluorine Substituents Provide Protection, Reactivity and Solubility
Claude, Guilhem; Kulitzki, Erika; Hagenbach, Adelheid; Roca Jungfer, Maximilian; Figueroa, Joshua S.; Abram, Ulrich; Dalton Transactions  (2023) –; doi:10.1039/D3DT00446E

data_7712554
_publ_section_title
;
 Phenylimido Complexes of Rhenium: Fluorine Substituents Provide
 Protection, Reactivity and Solubility
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT00446E
_journal_year                    2023
_chemical_formula_moiety         '2(C68 H78 Cl3 F N3 Re), 2.5(C7 H8), C H2 Cl2'
_chemical_formula_sum            'C154.5 H178 Cl8 F2 N6 Re2'
_chemical_formula_weight         2813.02
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2021-12-16
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2023-01-17 deposited with the CCDC.	2023-03-07 downloaded from the CCDC.
;
_cell_angle_alpha                84.392(8)
_cell_angle_beta                 82.455(9)
_cell_angle_gamma                63.855(5)
_cell_formula_units_Z            1
_cell_length_a                   14.706(3)
_cell_length_b                   16.346(3)
_cell_length_c                   17.419(5)
_cell_measurement_reflns_used    9801
_cell_measurement_temperature    100
_cell_measurement_theta_max      27.88
_cell_measurement_theta_min      2.49
_cell_volume                     3722.5(15)
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'CMOS area detector'
_diffrn_detector_area_resol_mean 10.42
_diffrn_detector_type            'PHOTON 100'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device       'Bruker D8 Venture Duo'
_diffrn_measurement_device_type  'D8 Venture'
_diffrn_measurement_method       '\f and \w scans''
_diffrn_radiation_monochromator  'W/C multilayer mirrors'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~2,3~
_diffrn_reflns_av_R_equivalents  0.0455
_diffrn_reflns_av_unetI/netI     0.0472
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            167349
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.989
_diffrn_reflns_theta_min         2.361
_diffrn_source                   'micro-focus sealed tube'
_diffrn_source_target            Mo
_diffrn_source_type              'Incoatec I\mS 1.0'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.820
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5344
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1041 before and 0.0801 after correction.
The Ratio of minimum to maximum transmission is 0.7167.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.255
_exptl_crystal_description       block
_exptl_crystal_F_000             1451
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.18
_refine_diff_density_max         1.744
_refine_diff_density_min         -1.488
_refine_diff_density_rms         0.098
_refine_ls_abs_structure_details
;
 Flack x determined using 14560 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.009(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1479
_refine_ls_number_reflns         35322
_refine_ls_number_restraints     1904
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0460
_refine_ls_R_factor_gt           0.0396
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0519P)^2^+4.1256P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0993
_refine_ls_wR_factor_ref         0.1039
_reflns_Friedel_coverage         0.980
_reflns_Friedel_fraction_full    0.984
_reflns_Friedel_fraction_max     0.975
_reflns_number_gt                32118
_reflns_number_total             35322
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt00446e2.cif
_cod_data_source_block           renphf_dipp2
_cod_original_cell_volume        3722.5(16)
_cod_original_formula_sum        'C154.50 H178 Cl8 F2 N6 Re2'
_cod_database_code               7712554
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.735
_shelx_estimated_absorpt_t_min   0.669
_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
 C52-C51 \\sim C52A-C51
 with sigma of 0.02
 C23-C24 \\sim C23-C25
 with sigma of 0.02
 C51-C53 \\sim C51-C53A
 with sigma of 0.02
 C54-C56 \\sim C54-C56A
 with sigma of 0.02
 C54-C55 \\sim C54-C55A
 with sigma of 0.02
3. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(C25) = Uanis(C23) = Uanis(C24)
Uanis(C47) = Uanis(C48) = Uanis(C49) = Uanis(C50) = Uanis(C45) = Uanis(C46)
Uanis(C146) = Uanis(C141) = Uanis(C148) = Uanis(C140) = Uanis(C147) =
Uanis(C157) = Uanis(C142)
Uanis(C53A) = Uanis(C53) = Uanis(C52) = Uanis(C52A)
Uanis(C56) = Uanis(C56A) = Uanis(C55A) = Uanis(C55)
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(H51A)=Sof(C52A)=Sof(H52D)=Sof(H52E)=Sof(H52F)=Sof(C53A)=Sof(H53D)=
 Sof(H53E)=Sof(H53F)=1-FVAR(1)
 Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(H52C)=Sof(H51)=Sof(C53)=Sof(H53A)=Sof(H53B)=
 Sof(H53C)=FVAR(1)
 Sof(H54A)=Sof(C56A)=Sof(H56D)=Sof(H56E)=Sof(H56F)=Sof(C55A)=Sof(H55D)=
 Sof(H55E)=Sof(H55F)=1-FVAR(2)
 Sof(H54)=Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(H56C)=Sof(C55)=Sof(H55A)=Sof(H55B)=
 Sof(H55C)=FVAR(2)
 Fixed Sof: C136(0.5) C154(0.5) H154(0.5) C137(0.5) H137(0.5) C139(0.5)
 H139(0.5) C155(0.5) H155(0.5) C135(0.5) H135(0.5) C138(0.5) H13J(0.5)
 H13K(0.5) H13L(0.5)
7.a Ternary CH refined with riding coordinates:
 C35(H35), C150(H150), C20(H20), C88(H88), C128(H128), C32(H32), C131(H131),
 C23(H23), C63(H63), C51(H51), C51(H51A), C103(H103), C91(H91), C100(H100),
 C54(H54), C54(H54A), C66(H66), C119(H119)
7.b Secondary CH2 refined with riding coordinates:
 C145(H14J,H14K)
7.c Me refined with riding coordinates:
 C149(H14A,H14B,H14C), C36(H36A,H36B,H36C), C133(H13A,H13B,H13C), C22(H22A,
 H22B,H22C), C90(H90A,H90B,H90C), C65(H65A,H65B,H65C), C130(H13D,H13E,H13F),
 C37(H37A,H37B,H37C), C132(H13G,H13H,H13I), C129(H12A,H12B,H12C), C64(H64A,H64B,
 H64C), C152(H15A,H15B,H15C), C120(H12D,H12E,H12F), C101(H10A,H10B,H10C),
 C93(H93A,H93B,H93C), C121(H12G,H12H,H12I), C34(H34A,H34B,H34C), C89(H89A,H89B,
 H89C), C67(H67A,H67B,H67C), C92(H92A,H92B,H92C), C68(H68A,H68B,H68C),
 C102(H10D,H10E,H10F), C56(H56A,H56B,H56C), C21(H21A,H21B,H21C), C104(H10G,H10H,
 H10I), C105(H10J,H10K,H10L), C55(H55A,H55B,H55C), C142(H14G,H14H,H14I),
 C144(H14D,H14E,H14F), C33(H33A,H33B,H33C), C138(H13J,H13K,H13L), C56A(H56D,
 H56E,H56F), C55A(H55D,H55E,H55F)
7.d Aromatic/amide H refined with riding coordinates:
 C29(H29), C12(H12), C11(H11), C41(H41), C85(H85), C2(H2), C86(H86), C16(H16),
 C84(H84), C71(H71), C30(H30), C5(H5), C6(H6), C70(H70), C115(H115), C3(H3),
 C79(H79), C126(H126), C42(H42), C116(H116), C80(H80), C111(H111), C47(H47),
 C59(H59), C48(H48), C110(H110), C28(H28), C78(H78), C117(H117), C17(H17),
 C109(H109), C18(H18), C49(H49), C74(H74), C61(H61), C73(H73), C60(H60),
 C43(H43), C96(H96), C10(H10), C125(H125), C151(H151), C143(H143), C158(H158),
 C156(H156), C153(H153), C98(H98), C97(H97), C124(H124), C146(H146), C141(H141),
  C148(H148), C140(H140), C147(H147), C154(H154), C137(H137), C139(H139),
 C155(H155), C135(H135)
7.e Fitted hexagon refined as free rotating group:
 C151(C143,C158,C156,C153,C134), C146(C141,C148,C140,C147,C157), C136(C154,
 C137,C139,C155,C135)
7.f Idealised Me refined as rotating group:
 C52(H52A,H52B,H52C), C24(H24A,H24B,H24C), C53(H53A,H53B,H53C), C25(H25A,H25B,
 H25C), C52A(H52D,H52E,H52F), C53A(H53D,H53E,H53F)
;
_shelx_res_checksum              93441
_olex2_submission_special_instructions 'No special instructions were received'