Synthesis and Reactivity of Dinuclear Copper(I) Pyridine, Diimine Complexes
Stephan, Michel; Dammannn, Wiebke; Burger, Peter; Dalton Transactions  (2022) –; doi:10.1039/D2DT02307E

data_7710974
_publ_section_title
;
 Synthesis and Reactivity of Dinuclear Copper(I) Pyridine, Diimine
 Complexes
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT02307E
_journal_year                    2022
_chemical_formula_moiety         'C48 H66 Cl Cu2 N6, C32 H12 B F23.97, 8(C3 H3)'
_chemical_formula_sum            'C104 H102 B Cl Cu2 F23.97 N6'
_chemical_formula_weight         2064.68
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2c807x
_audit_creation_date             2021-11-08
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-06-28 deposited with the CCDC.	2022-08-15 downloaded from the CCDC.
;
_cell_angle_alpha                93.893(2)
_cell_angle_beta                 99.600(2)
_cell_angle_gamma                94.627(2)
_cell_formula_units_Z            2
_cell_length_a                   14.0607(19)
_cell_length_b                   18.845(3)
_cell_length_c                   19.069(3)
_cell_measurement_reflns_used    6923
_cell_measurement_temperature    100
_cell_measurement_theta_max      22.69
_cell_measurement_theta_min      2.35
_cell_volume                     4948.8(13)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1101
_diffrn_reflns_av_unetI/netI     0.1416
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            74086
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.499
_diffrn_reflns_theta_min         1.087
_diffrn_source_current           0.6
_diffrn_source_power             0.03
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.552
_exptl_absorpt_correction_T_max  0.7458
_exptl_absorpt_correction_T_min  0.5919
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2012/1 (Bruker,2012) was used for absorption correction. wR2(int) was 0.1673 before and 0.0478 after correction. The Ratio of minimum to maximum transmission is 0.7936. The \l/2 correction factor is 0.0015.'
_exptl_crystal_colour            'clear reddish orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.386
_exptl_crystal_description       plate
_exptl_crystal_F_000             2127
_exptl_crystal_preparation       benzene
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: benzene'
_exptl_crystal_size_max          0.229
_exptl_crystal_size_mid          0.154
_exptl_crystal_size_min          0.032
_refine_diff_density_max         0.479
_refine_diff_density_min         -0.642
_refine_diff_density_rms         0.071
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.995
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1490
_refine_ls_number_reflns         22478
_refine_ls_number_restraints     460
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.1554
_refine_ls_R_factor_gt           0.0629
_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^)+(0.0399P)^2^+2.0196P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1011
_refine_ls_wR_factor_ref         0.1273
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11602
_reflns_number_total             22478
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt02307e2.cif
_cod_data_source_block           mv_ms100_first
_cod_original_cell_volume        4948.9(11)
_cod_database_code               7710974
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.983
_shelx_estimated_absorpt_t_min   0.884
_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
 C99-C97 \\sim C98-C108
 with sigma of 0.02
 C99-C101 \\sim C98-C100
 with sigma of 0.02
 C107-C97 \\sim C106-C108
 with sigma of 0.02
 C107-C105 \\sim C106-C104
 with sigma of 0.02
 C99-C107 \\sim C98-C106
 with sigma of 0.04
 C97-C105 \\sim C108-C104
 with sigma of 0.04
 C97-C101 \\sim C108-C100
 with sigma of 0.04
 C105-C101 \\sim C104-C100
 with sigma of 0.04
 C103-C105 \\sim C102-C104
 with sigma of 0.02
 C103-C101 \\sim C102-C100
 with sigma of 0.02
 C99-C103 \\sim C98-C102
 with sigma of 0.04
 C107-C103 \\sim C106-C102
 with sigma of 0.04
 C82-F30 \\sim C82-F29
 with sigma of 0.02
 C82-F32 \\sim C82-F31
 with sigma of 0.02
 C77-F24 \\sim C77-F25
 with sigma of 0.02
 C77-F28 \\sim C77-F23
 with sigma of 0.02
 C77-F26 \\sim C77-F27
 with sigma of 0.02
 F6-C80 \\sim F5-C80
 with sigma of 0.02
 C80-F4 \\sim C80-F3
 with sigma of 0.02
 F22-C76 \\sim F17-C76
 with sigma of 0.02
 F20-C76 \\sim F21-C76
 with sigma of 0.02
 F18-C76 \\sim F19-C76
 with sigma of 0.02
 F19-F21 \\sim F19-F17
 with sigma of 0.04
 C76-C67 \\sim C76-F19 \\sim C76-F21 \\sim C76-F17
 with sigma of 0.02
 F2-C80 \\sim F7-C80
 with sigma of 0.02
 F2-F6 \\sim F2-F4 \\sim F6-F4 \\sim F3-F7 \\sim F3-F5 \\sim F7-F5
 with sigma of 0.04
 C80-C64 \\sim C80-F2 \\sim C80-F6 \\sim C80-F4 \\sim C80-F3 \\sim C80-F7 \\sim
C80-F5
 with sigma of 0.02
 C82-F34 \\sim C82-F33
 with sigma of 0.02
 F31-F33 \\sim F32-F34 \\sim F30-F34 \\sim F33-F29
 with sigma of 0.04
 C82-F31 \\sim C82-F32 \\sim C82-F30 \\sim C82-F33 \\sim C82-F29 \\sim C82-F34
\\sim C82-C70
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
F35 \\sim F36 \\sim F37 \\sim F38 \\sim F39 \\sim F40: within 0.1A with sigma
of 0.01 and sigma for terminal atoms of 0.01 within 0.1A
Uanis(C104) \\sim Ueq, Uanis(C105) \\sim Ueq, Uanis(C106) \\sim Ueq,
Uanis(C107) \\sim Ueq, Uanis(C108) \\sim Ueq, Uanis(C97) \\sim Ueq, Uanis(C98)
\\sim Ueq, Uanis(C99) \\sim Ueq, Uanis(C100) \\sim Ueq, Uanis(C101) \\sim Ueq,
Uanis(C102) \\sim Ueq, Uanis(C103) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(C104) \\sim Ueq, Uanis(C103) \\sim Ueq, Uanis(C102) \\sim Ueq,
Uanis(C101) \\sim Ueq, Uanis(C100) \\sim Ueq, Uanis(C99) \\sim Ueq, Uanis(C98)
\\sim Ueq, Uanis(C97) \\sim Ueq, Uanis(C108) \\sim Ueq, Uanis(C107) \\sim Ueq,
Uanis(C106) \\sim Ueq, Uanis(C105) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(F5) \\sim Ueq, Uanis(F3) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(F40) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F20) \\sim Ueq, Uanis(F21) \\sim Ueq, Uanis(F22) \\sim Ueq, Uanis(F17)
\\sim Ueq, Uanis(F18) \\sim Ueq, Uanis(F19) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(F33) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.2
4. Rigid body (RIGU) restrains
 C82
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F32, F34, C82, F30, C70
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C64
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C66, C77, F26, F24, F28
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C66, C77, F27, F23, F25
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F4, F6, F2, C80, C64
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F18, F20, F22, C76, C67
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F20, F22, C76, F18, C67
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F19, F21, C76, F17, C67
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F31, F33, F29, C82, C70
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F3, F7, F5, C80, C64
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(H40C)=Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)=
 1-FVAR(1)
 Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(H39C)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(H42C)=
 FVAR(1)
 Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(H38C)=1-FVAR(2)
 Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=FVAR(2)
 Sof(F38)=1-FVAR(3)
 Sof(F37)=FVAR(3)
 Sof(F35)=1-FVAR(4)
 Sof(F36)=FVAR(4)
 Sof(F40)=1-FVAR(5)
 Sof(F39)=FVAR(5)
 Sof(C100)=Sof(H100)=Sof(C98)=Sof(H98)=Sof(C108)=Sof(H108)=Sof(C106)=Sof(H106)=
 Sof(C104)=Sof(H104)=Sof(C102)=Sof(H102)=1-FVAR(6)
 Sof(C99)=Sof(H99)=Sof(C107)=Sof(H107)=Sof(C97)=Sof(H97)=Sof(C103)=Sof(H103)=
 Sof(C105)=Sof(H105)=Sof(C101)=Sof(H101)=FVAR(6)
 Sof(F19)=Sof(F21)=Sof(F17)=1-FVAR(7)
 Sof(F22)=Sof(F18)=Sof(F20)=FVAR(7)
 Sof(F31)=Sof(F29)=1-FVAR(8)
 Sof(F30)=Sof(F32)=Sof(F34)=FVAR(8)
 Sof(F3)=Sof(F5)=1-FVAR(9)
 Sof(F2)=Sof(F6)=Sof(F4)=FVAR(9)
 Sof(F23)=Sof(F25)=Sof(F27)=1-FVAR(10)
 Sof(F24)=Sof(F28)=Sof(F26)=FVAR(10)
6.a Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C47(H47A,H47B), C15(H15A,H15B), C35(H35A,H35B)
6.b Aromatic/amide H refined with riding coordinates:
 C56(H56), C61(H61), C62(H62), C9(H9), C57(H57), C11(H11), C43(H43), C63(H63),
 C58(H58), C72(H72), C75(H75), C23(H23), C73(H73), C60(H60), C59(H59), C31(H31),
  C21(H21), C74(H74), C22(H22), C92(H92), C91(H91), C25(H25), C27(H27),
 C90(H90), C26(H26), C94(H94), C95(H95), C032(H032), C038(H038), C039(H039),
 C85(H85), C93(H93), C03D(H03D), C03E(H03E), C86(H86), C87(H87), C84(H84),
 C88(H88), C03K(H03K), C89(H89), C99(H99), C107(H107), C97(H97), C103(H103),
 C105(H105), C101(H101), C100(H100), C98(H98), C108(H108), C106(H106),
 C104(H104), C102(H102)
6.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C7(H7A,H7B,H7C), C34(H34A,H34B,H34C), C49(H49A,H49B,
 H49C), C46(H46A,H46B,H46C), C2(H2A,H2B,H2C), C19(H19A,H19B,H19C), C1(H1A,H1B,
 H1C), C50(H50A,H50B,H50C), C17(H17A,H17B,H17C), C3(H3A,H3B,H3C), C51(H51A,H51B,
 H51C), C18(H18A,H18B,H18C), C39(H39A,H39B,H39C), C42(H42A,H42B,H42C), C40(H40A,
 H40B,H40C), C37(H37A,H37B,H37C), C41(H41A,H41B,H41C), C38(H38A,H38B,H38C)
;
_olex2_exptl_crystal_mounting_method 'cactus needle under polybutenes'
_olex2_submission_special_instructions 'No special instructions were received'