Heteroleptic copper(I) complexes with coumarin-substituted aminodiphosphine and diimine ligands: synthesis and photophysical studies.
Naina, Vanitha R.; Singh, Akhil K.; Shubham, ?; Krätschmer, Frederic; Lebedkin, Sergei; Kappes, Manfred M.; Roesky, Peter W.; Dalton transactions (Cambridge, England : 2003)  (2023) –; doi:10.1039/d3dt02317f

data_7713816
_publ_section_title
;
 Heteroleptic copper(I) complexes with coumarin-substituted
 aminodiphosphine and diimine ligands: synthesis and photophysical
 studies.
;
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_paper_doi               10.1039/d3dt02317f
_journal_year                    2023
_chemical_formula_moiety         'C62 H67 Cu N3 O2 P2 S, B F4, 3(C H2 Cl2)'
_chemical_formula_sum            'C65 H73 B Cl6 Cu F4 N3 O2 P2 S'
_chemical_formula_weight         1385.31
_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_creation_date             2023-01-18
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2022.11.02 svn.ra8b101fa for OlexSys, GUI svn.r6635)
;
_audit_update_record
;
2023-06-01 deposited with the CCDC.	2023-07-31 downloaded from the CCDC.
;
_cell_angle_alpha                77.69(2)
_cell_angle_beta                 65.656(19)
_cell_angle_gamma                87.432(18)
_cell_formula_units_Z            2
_cell_length_a                   14.757(2)
_cell_length_b                   15.000(4)
_cell_length_c                   16.552(5)
_cell_measurement_reflns_used    67537
_cell_measurement_temperature    110
_cell_measurement_theta_max      31.87
_cell_measurement_theta_min      1.96
_cell_volume                     3257.5(15)
_computing_cell_refinement
;
X-Area Recipe 1.33.0.0 (STOE, 2015)
;
_computing_data_collection
;
X-Area Pilatus3_SV 1.31.150.0 (STOE, 2018)
;
_computing_data_reduction
;
X-Area Integrate 1.73.1.0 (STOE, 2018)
X-Area LANA 1.73.2.0 (STOE, 2018)
;
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material
;
STOE & Cie GmbH, X-Area, software package for collecting single-crystal or
multi-domain crystal data on STOE area-detector diffractometers, for image 
processing, for the correction and scaling of reflection intensities and 
for outlier rejection, version 1.84, Darmstadt 2018
;
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      110
_diffrn_detector                 Pilatus200K
_diffrn_detector_area_resol_mean 5.81
_diffrn_detector_type            'DECTRIS PILATUS 200K'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.784
_diffrn_measurement_details
;
 675 frames, detector distance = 40 mm
;
_diffrn_measurement_device       'Eulerian 4-circle diffractometer'
_diffrn_measurement_device_type  'STOE STADIVARI'
_diffrn_measurement_method       'rotation method, \w scans'
_diffrn_radiation_collimation    '0.5 mm diameter, monocapillary'
_diffrn_radiation_monochromator  'plane graphite'
_diffrn_radiation_polarisn_norm  0
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0484
_diffrn_reflns_av_unetI/netI     0.0465
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.784
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            45610
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.784
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.233
_diffrn_reflns_theta_min         1.949
_diffrn_source                   'Mo Genix 3D HF'
_diffrn_source_current           1.000
_diffrn_source_power             0.050
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    0.720
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.5170
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
STOE X-Red32, absorption correction by Gaussian integration, analogous to
P. Coppens, "The Evaluation of Absorption and Extinction in Single-Crystal
Structure Analysis", published in: F. R. Ahmed (Editor), "Crystallographic
Computing", Munksgaard, Copenhagen (1970), 255 - 270.
Afterwards scaling of reflection intensities was performed within STOE LANA.
J. Koziskova, F. Hahn, J. Richter, J. Kozisek, "Comparison of different
absorption corrections on the model structure of tetrakis(\m~2~-acetato)-
diaqua-di-copper(II)", Acta Chimica Slovaca, vol. 9, no. 2, 2016, pp. 136 - 140.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.412
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       fragment
_exptl_crystal_F_000             1436
_exptl_crystal_size_max          0.394
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.169
_refine_diff_density_max         1.639
_refine_diff_density_min         -1.441
_refine_diff_density_rms         0.116
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.083
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1016
_refine_ls_number_reflns         18077
_refine_ls_number_restraints     714
_refine_ls_restrained_S_all      1.087
_refine_ls_R_factor_all          0.0995
_refine_ls_R_factor_gt           0.0716
_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^)+(0.1086P)^2^+6.0860P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1857
_refine_ls_wR_factor_ref         0.2256
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13303
_reflns_number_total             18077
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02317f2.cif
_cod_data_source_block           nv274
_cod_original_cell_volume        3257.7(15)
_cod_database_code               7713816
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.888
_shelx_estimated_absorpt_t_min   0.765
_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
 N1-C1A \\sim N1-C1B
 with sigma of 0.02
 O2A-C5A \\sim O2B-C5B
 with sigma of 0.02
 O2A-C7A \\sim O2B-C7B
 with sigma of 0.02
 O1A-C7A \\sim O1B-C7B
 with sigma of 0.02
 C1A-C2A \\sim C1B-C2B
 with sigma of 0.02
 C1A-C6A \\sim C1B-C6B
 with sigma of 0.02
 C2A-C3A \\sim C2B-C3B
 with sigma of 0.02
 C6A-C5A \\sim C6B-C5B
 with sigma of 0.02
 C4A-C5A \\sim C4B-C5B
 with sigma of 0.02
 C4A-C3A \\sim C4B-C3B
 with sigma of 0.02
 C4A-C9A \\sim C4B-C9B
 with sigma of 0.02
 C8A-C7A \\sim C8B-C7B
 with sigma of 0.02
 C8A-C9A \\sim C8B-C9B
 with sigma of 0.02
 C9A-C10A \\sim C9B-C10B
 with sigma of 0.02
 N1-C2A \\sim N1-C2B
 with sigma of 0.04
 N1-C6A \\sim N1-C6B
 with sigma of 0.04
 O2A-O1A \\sim O2B-O1B
 with sigma of 0.04
 O2A-C6A \\sim O2B-C6B
 with sigma of 0.04
 O2A-C4A \\sim O2B-C4B
 with sigma of 0.04
 O2A-C8A \\sim O2B-C8B
 with sigma of 0.04
 O1A-C8A \\sim O1B-C8B
 with sigma of 0.04
 C1A-C5A \\sim C1B-C5B
 with sigma of 0.04
 C1A-C3A \\sim C1B-C3B
 with sigma of 0.04
 C2A-C6A \\sim C2B-C6B
 with sigma of 0.04
 C2A-C4A \\sim C2B-C4B
 with sigma of 0.04
 C6A-C4A \\sim C6B-C4B
 with sigma of 0.04
 C4A-C8A \\sim C4B-C8B
 with sigma of 0.04
 C4A-C10A \\sim C4B-C10B
 with sigma of 0.04
 C5A-C3A \\sim C5B-C3B
 with sigma of 0.04
 C5A-C7A \\sim C5B-C7B
 with sigma of 0.04
 C5A-C9A \\sim C5B-C9B
 with sigma of 0.04
 C3A-C9A \\sim C3B-C9B
 with sigma of 0.04
 C8A-C10A \\sim C8B-C10B
 with sigma of 0.04
 C7A-C9A \\sim C7B-C9B
 with sigma of 0.04
 Cl1A-C63A \\sim Cl1B-C63B
 with sigma of 0.02
 Cl2A-C63A \\sim Cl2B-C63B
 with sigma of 0.02
 Cl1A-Cl2A \\sim Cl1B-Cl2B
 with sigma of 0.04
 Cl5A-C65A \\sim Cl5B-C65B
 with sigma of 0.02
 Cl6A-C65A \\sim Cl6B-C65B
 with sigma of 0.02
 Cl5A-Cl6A \\sim Cl5B-Cl6B
 with sigma of 0.04
 F4A-B \\sim F4B-B
 with sigma of 0.02
 F1A-B \\sim F1B-B
 with sigma of 0.02
 F2A-B \\sim F2B-B
 with sigma of 0.02
 F3A-B \\sim F3B-B
 with sigma of 0.02
 Cl3A-C64A \\sim Cl3B-C64B
 with sigma of 0.02
 Cl4A-C64A \\sim Cl4B-C64B
 with sigma of 0.02
 Cl3A-Cl4A \\sim Cl3B-Cl4B
 with sigma of 0.04
 C47-C48A \\sim C47-C48B
 with sigma of 0.02
 C47-C49A \\sim C47-C49B
 with sigma of 0.02
 C47-C50A \\sim C47-C50B
 with sigma of 0.02
3. Rigid bond restraints
 O2A, C8A, C5A, O1A, C9A, C1A, C3A, C2A, C7A, C6A, C10A, C4A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C1B, O1B, O2B, C2B, C9B, C3B, C7B, C4B, C8B, C5B, C10B, C6B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Cl4A, Cl3A, C64A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Cl2B, C63B, Cl1B, Cl2A, Cl1A, C63A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Cl5B, C65B, Cl6B, Cl5A, C65A, Cl6A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F2A, F4A, B, F2B, F1A, F1B, F4B, F3B, F3A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Cl3B, C64B, Cl4B, Cl3A, C64A, Cl4A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C49A, C49B, C50A, C50B, C48B, C48A, C47
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
O2A \\sim C8A \\sim C5A \\sim O1A \\sim C9A \\sim C1A \\sim C3A \\sim C2A \\sim
C7A \\sim C6A \\sim C10A \\sim C4A: within 0.1A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 0.1A
C1B \\sim O1B \\sim O2B \\sim C2B \\sim C9B \\sim C3B \\sim C7B \\sim C4B \\sim
C8B \\sim C5B \\sim C10B \\sim C6B: within 0.1A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 0.1A
Cl4A \\sim Cl3A \\sim C64A: within 2.5A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2.5A
Cl2A \\sim Cl1A \\sim C63A \\sim Cl2B \\sim C63B \\sim Cl1B: within 2.5A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2.5A
C65A \\sim Cl5A \\sim Cl6A \\sim C65B \\sim Cl5B \\sim Cl6B: within 2.5A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2.5A
B \\sim F4A \\sim F2B \\sim F2A \\sim F1A \\sim F1B \\sim F4B \\sim F3B \\sim
F3A: within 2.5A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
2.5A
Cl3A \\sim C64A \\sim Cl4A \\sim Cl3B \\sim C64B \\sim Cl4B: within 2.5A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2.5A
C47 \\sim C49A \\sim C49B \\sim C50A \\sim C50B \\sim C48B \\sim C48A: within
2.5A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2.5A
Uanis(C1B) \\sim Ueq, Uanis(C2B) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(C6B) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C2B) \\sim Ueq, Uanis(C1B) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(C1B) \\sim Ueq, Uanis(C6B) \\sim Ueq, Uanis(C5B) \\sim Ueq, Uanis(C4B)
\\sim Ueq, Uanis(C3B) \\sim Ueq, Uanis(C2B) \\sim Ueq: with sigma of 0.02 and
sigma for terminal atoms of 0.04
Uanis(C3B) \\sim Ueq, Uanis(C4B) \\sim Ueq, Uanis(C2B) \\sim Ueq, Uanis(C1B)
\\sim Ueq, Uanis(C6B) \\sim Ueq, Uanis(C5B) \\sim Ueq: with sigma of 0.02 and
sigma for terminal atoms of 0.04
Uanis(Cl4A) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C1B) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C64A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 F2A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C63B)=Sof(H63C)=Sof(H63D)=Sof(Cl1B)=Sof(Cl2B)=1-FVAR(1)
 Sof(Cl1A)=Sof(Cl2A)=Sof(C63A)=Sof(H63A)=Sof(H63B)=FVAR(1)
 Sof(Cl5B)=Sof(C65B)=Sof(H65C)=Sof(H65D)=Sof(Cl6B)=1-FVAR(2)
 Sof(Cl5A)=Sof(Cl6A)=Sof(C65A)=Sof(H65A)=Sof(H65B)=FVAR(2)
 Sof(F4B)=Sof(F3B)=Sof(F1B)=Sof(F2B)=1-FVAR(3)
 Sof(F4A)=Sof(F1A)=Sof(F2A)=Sof(F3A)=FVAR(3)
 Sof(Cl3B)=Sof(C64B)=Sof(H64C)=Sof(H64D)=Sof(Cl4B)=1-FVAR(4)
 Sof(Cl3A)=Sof(Cl4A)=Sof(C64A)=Sof(H64A)=Sof(H64B)=FVAR(4)
 Sof(C49B)=Sof(H49D)=Sof(H49E)=Sof(H49F)=Sof(C48B)=Sof(H48D)=Sof(H48E)=
 Sof(H48F)=Sof(C50B)=Sof(H50D)=Sof(H50E)=Sof(H50F)=1-FVAR(5)
 Sof(C48A)=Sof(H48A)=Sof(H48B)=Sof(H48C)=Sof(C49A)=Sof(H49A)=Sof(H49B)=
 Sof(H49C)=Sof(C50A)=Sof(H50A)=Sof(H50B)=Sof(H50C)=FVAR(5)
 Fixed Sof: O2A(0.78) O1A(0.78) C1A(0.78) C2A(0.78) H2A(0.78) C3A(0.78)
 H3A(0.78) C4A(0.78) C5A(0.78) C6A(0.78) H6A(0.78) C8A(0.78) H8A(0.78)
 C7A(0.78) C9A(0.78) C10A(0.78) H10A(0.78) H10B(0.78) H10C(0.78) C1B(0.22)
 C6B(0.22) H6B(0.22) C5B(0.22) C4B(0.22) C3B(0.22) H3B(0.22) C2B(0.22)
 H2B(0.22) O2B(0.22) C7B(0.22) O1B(0.22) C8B(0.22) H8B(0.22) C9B(0.22)
 C10B(0.22) H10D(0.22) H10E(0.22) H10F(0.22)
7.a Secondary CH2 refined with riding coordinates:
 C64A(H64A,H64B), C65A(H65A,H65B), C63A(H63A,H63B), C63B(H63C,H63D), C65B(H65C,
 H65D), C64B(H64C,H64D)
7.b Aromatic/amide H refined with riding coordinates:
 C46(H46), C45(H45), C26(H26), C2A(H2A), C3A(H3A), C6A(H6A), C16(H16),
 C15(H15), C32(H32), C25(H25), C33(H33), C62(H62), C35(H35), C42(H42), C36(H36),
  C52(H52), C23(H23), C53(H53), C59(H59), C22(H22), C54(H54), C43(H43),
 C13(H13), C55(H55), C61(H61), C12(H12), C60(H60), C8A(H8A), C6B(H6B), C3B(H3B),
  C2B(H2B), C8B(H8B)
7.c Fitted hexagon refined as free rotating group:
 C1A(C2A,C3A,C4A,C5A,C6A), C1B(C6B,C5B,C4B,C3B,C2B)
7.d Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C18(H18A,H18B,H18C), C39(H39A,H39B,H39C), C19(H19A,H19B,
 H19C), C38(H38A,H38B,H38C), C30(H30A,H30B,H30C), C48A(H48A,H48B,H48C),
 C29(H29A,H29B,H29C), C40(H40A,H40B,H40C), C28(H28A,H28B,H28C), C10A(H10A,H10B,
 H10C), C49A(H49A,H49B,H49C), C50A(H50A,H50B,H50C), C10B(H10D,H10E,H10F),
 C49B(H49D,H49E,H49F), C48B(H48D,H48E,H48F), C50B(H50D,H50E,H50F)
;
_shelx_res_checksum              31498
_olex2_submission_special_instructions 'No special instructions were received'