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

data_7710975
_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, Cl2 Cu, 0.5(C4 H8 O)'
_chemical_formula_sum            'C50 H70 Cl3 Cu3 N6 O0.5'
_chemical_formula_weight         1060.09
_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
_audit_block_doi                 10.5517/ccdc.csd.cc2c806w
_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                111.2060(10)
_cell_angle_beta                 92.281(2)
_cell_angle_gamma                99.549(2)
_cell_formula_units_Z            4
_cell_length_a                   12.9709(3)
_cell_length_b                   18.3585(3)
_cell_length_c                   24.0138(4)
_cell_measurement_reflns_used    36338
_cell_measurement_temperature    99.9(2)
_cell_measurement_theta_max      75.8410
_cell_measurement_theta_min      3.7930
_cell_volume                     5226.17(18)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53a (Rigaku OD, 2019)'
_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 2018/3 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.9(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2063
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.971
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -71.00  30.00   1.00    5.00    --  -42.82  57.00   0.00  101
  2  \w   -124.00 -79.00   1.00    5.00    --  -42.82 -99.00 -30.00   45
  3  \w   -124.00 -79.00   1.00    5.00    --  -42.82 -99.00   0.00   45
  4  \w   -115.00 -15.00   1.00    5.00    --  -42.82 -57.00-150.00  100
  5  \w   -124.00 -79.00   1.00    5.00    --  -42.82 -99.00 -90.00   45
  6  \w     23.00  99.00   1.00    5.00    --   42.82-125.00  60.00   76
  7  \w      1.00  84.00   1.00    5.00    --   42.82 -99.00 120.00   83
  8  \w     85.00 178.00   1.00   20.00    --  111.00  45.00  30.00   93
  9  \w     85.00 178.00   1.00   20.00    --  111.00  45.00-180.00   93
 10  \w     35.00 139.00   1.00   20.00    --  111.00 -30.00   0.00  104
 11  \w     86.00 178.00   1.00   20.00    --  111.00  42.00  -2.61   92
 12  \w     38.00 118.00   1.00   20.00    --  111.00-125.00 -60.00   80
 13  \w     58.00 178.00   1.00   20.00    --  111.00  15.00 -30.00  120
 14  \w     28.00 110.00   1.00   20.00    --  111.00 -94.00 150.00   82
 15  \w     39.00 140.00   1.00   20.00    --  111.00 -61.00 150.00  101
 16  \w     83.00 178.00   1.00   20.00    --  111.00  30.00-120.00   95
 17  \w     28.00 110.00   1.00   20.00    --  111.00 -94.00 -60.00   82
 18  \w     38.00 118.00   1.00   20.00    --  111.00-125.00  60.00   80
 19  \w     28.00 110.00   1.00   20.00    --  111.00 -94.00-180.00   82
 20  \w     38.00 118.00   1.00   20.00    --  111.00-125.00 150.00   80
 21  \w     39.00 140.00   1.00   20.00    --  111.00 -61.00 -90.00  101
 22  \w     38.00 118.00   1.00   20.00    --  111.00-125.00 -90.00   80
 23  \w     94.00 178.00   1.00   20.00    --  111.00 125.00 -60.00   84
 24  \w     38.00 118.00   1.00   20.00    --  111.00-125.00-180.00   80
 25  \w     39.00 140.00   1.00   20.00    --  111.00 -61.00 -60.00  101
 26  \w     85.00 178.00   1.00   20.00    --  111.00  45.00 -90.00   93
 27  \w     38.00 118.00   1.00   20.00    --  111.00-125.00  90.00   80
 28  \w     93.00 139.00   1.00   20.00    --  111.00 -30.00-180.00   46
 29  \w     64.00  96.00   1.00   20.00    --  111.00-125.00  30.00   32
 30  \w     72.00 118.00   1.00   20.00    --  111.00-125.00-150.00   46
 31  \w     90.00 117.00   1.00   20.00    --  111.00-125.00 -30.00   27
 32  \w     43.00 113.00   1.00   20.00    --  111.00-125.00 120.00   70
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1156963000
_diffrn_orient_matrix_UB_12      -0.0061144000
_diffrn_orient_matrix_UB_13      0.0103987000
_diffrn_orient_matrix_UB_21      0.0294188000
_diffrn_orient_matrix_UB_22      0.0389325000
_diffrn_orient_matrix_UB_23      -0.0457337000
_diffrn_orient_matrix_UB_31      0.0206794000
_diffrn_orient_matrix_UB_32      0.0828496000
_diffrn_orient_matrix_UB_33      0.0509116000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0512
_diffrn_reflns_av_unetI/netI     0.0428
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            84178
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.638
_diffrn_reflns_theta_min         3.476
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.127
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.487
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53a (Rigaku Oxford Diffraction, 2019)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.347
_exptl_crystal_description       block
_exptl_crystal_F_000             2216
_exptl_crystal_recrystallization_method 'THF/n-hexane diffusion'
_exptl_crystal_size_max          0.247
_exptl_crystal_size_mid          0.207
_exptl_crystal_size_min          0.067
_refine_diff_density_max         1.025
_refine_diff_density_min         -1.029
_refine_diff_density_rms         0.083
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.069
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1203
_refine_ls_number_reflns         21635
_refine_ls_number_restraints     99
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0564
_refine_ls_R_factor_gt           0.0476
_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^)+(0.0382P)^2^+10.4135P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1188
_refine_ls_wR_factor_ref         0.1268
_reflns_Friedel_coverage         0.000
_reflns_number_gt                18545
_reflns_number_total             21635
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt02307e2.cif
_cod_data_source_block           ms127-3-face
_cod_original_cell_volume        5226.16(18)
_cod_original_formula_sum        'C50 H70 Cl3 Cu3 N6 O0.50'
_cod_database_code               7710975
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C192 H264 Cl12 Cu12 N24 '
_chemical_oxdiff_usercomment     'Stephan/Burger, Cu, 100 K'
_reflns_odcompleteness_completeness 99.83
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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
 O80A-C84A
 1.434 with sigma of 0.001
 C81A-O80A
 1.434 with sigma of 0.001
 C81A-C82A
 1.528 with sigma of 0.001
 C82A-C83A
 1.533 with sigma of 0.001
 C83A-C84A
 1.528 with sigma of 0.001
 O80B-C84B
 1.434 with sigma of 0.001
 O80B-C81B
 1.434 with sigma of 0.001
 C83B-C84B
 1.528 with sigma of 0.001
 C81B-C82B
 1.528 with sigma of 0.001
 C83B-C82B
 1.533 with sigma of 0.001
 O80A-C82A
 2.371 with sigma of 0.001
 O80A-C83A
 2.371 with sigma of 0.001
 C81A-C84A
 2.351 with sigma of 0.001
 C83A-C81A
 2.377 with sigma of 0.001
 C82A-C84A
 2.377 with sigma of 0.001
 C83B-O80B
 2.371 with sigma of 0.001
 O80B-C83B
 2.371 with sigma of 0.001
 C82B-O80B
 2.371 with sigma of 0.001
 C84B-C81B
 2.351 with sigma of 0.001
 C82B-C84B
 2.377 with sigma of 0.001
 C83B-C81B
 2.377 with sigma of 0.001
3. Uiso/Uaniso restraints and constraints
Uanis(C82A) \\sim Ueq, Uanis(C83B) \\sim Ueq, Uanis(C84B) \\sim Ueq: with sigma
of 0.007 and sigma for terminal atoms of 0.014
4. Rigid body (RIGU) restrains
 O80A, C81A, C82A, C83A, C84A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O80B, C81B, C82B, C83B, C84B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: O80A(0.5) O80B(0.5) C81A(0.5) H81A(0.5) H81B(0.5) C81B(0.5)
 H81C(0.5) H81D(0.5) C82A(0.5) H82A(0.5) H82B(0.5) C82B(0.5) H82C(0.5)
 H82D(0.5) C83A(0.5) H83A(0.5) H83B(0.5) C83B(0.5) H83C(0.5) H83D(0.5)
 C84A(0.5) H84A(0.5) H84B(0.5) C84B(0.5) H84C(0.5) H84D(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C29A(H29A,H29B), C29B(H29C,H29D), C37A(H37A,H37B), C37B(H37C,H37D), C51A(H51A,
 H51B), C51B(H51C,H51D), C59A(H59A,H59B), C59B(H59C,H59D), C81A(H81A,H81B),
 C81B(H81C,H81D), C82A(H82A,H82B), C82B(H82C,H82D), C83A(H83A,H83B), C83B(H83C,
 H83D), C84A(H84A,H84B), C84B(H84C,H84D)
6.b Aromatic/amide H refined with riding coordinates:
 C11A(H11A), C11B(H11B), C12A(H12A), C12B(H12B), C13A(H13A), C13B(H13B),
 C17A(H17A), C17B(H17B), C18A(H18A), C18B(H18B), C19A(H19A), C19B(H19B),
 C21A(H21A), C21B(H21B), C25A(H25A), C25B(H25B), C43A(H43A), C43B(H43B),
 C47A(H47A), C47B(H47B)
6.c Idealised Me refined as rotating group:
 C27A(H27A,H27B,H27C), C27B(H27D,H27E,H27F), C31A(H31A,H31B,H31C), C31B(H31D,
 H31E,H31F), C32A(H32A,H32B,H32C), C32B(H32D,H32E,H32F), C33A(H33A,H33B,H33C),
 C33B(H33D,H33E,H33F), C35A(H35A,H35B,H35C), C35B(H35D,H35E,H35F), C39A(H39A,
 H39B,H39C), C39B(H39D,H39E,H39F), C40A(H40A,H40B,H40C), C40B(H40D,H40E,H40F),
 C41A(H41A,H41B,H41C), C41B(H41D,H41E,H41F), C49A(H49A,H49B,H49C), C49B(H49D,
 H49E,H49F), C53A(H53A,H53B,H53C), C53B(H53D,H53E,H53F), C54A(H54A,H54B,H54C),
 C54B(H54D,H54E,H54F), C55A(H55A,H55B,H55C), C55B(H55D,H55E,H55F), C57A(H57A,
 H57B,H57C), C57B(H57D,H57E,H57F), C61A(H61A,H61B,H61C), C61B(H61D,H61E,H61F),
 C62A(H62A,H62B,H62C), C62B(H62D,H62E,H62F), C63A(H63A,H63B,H63C), C63B(H63D,
 H63E,H63F)
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.762
_oxdiff_exptl_absorpt_empirical_full_min 0.653