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_7713815
_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         '2(C46 H35 Cu N3 O2 P2), 2(B F4), 3(C H2 Cl2)'
_chemical_formula_sum            'C95 H76 B2 Cl6 Cu2 F8 N6 O4 P4'
_chemical_formula_weight         2002.89
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_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                90
_cell_angle_beta                 115.037(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   40.1317(18)
_cell_length_b                   14.1718(4)
_cell_length_c                   17.4639(8)
_cell_measurement_reflns_used    30094
_cell_measurement_temperature    150
_cell_measurement_theta_max      27.29
_cell_measurement_theta_min      1.54
_cell_volume                     8999.1(7)
_computing_cell_refinement
;
X-Area Recipe 1.33.0.0 (STOE, 2015)
;
_computing_data_collection
;
X-Area WinXpose 2.0.22.0 (STOE, 2016)
;
_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    'olex2.solve 1.5-alpha (Bourhis et al., 2015)'
_diffrn_ambient_temperature      150
_diffrn_detector                 'image plate (34 cm diameter)'
_diffrn_detector_area_resol_mean 6.67
_diffrn_detector_type            'STOE Imaging Plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_details
;
 183 frames, detector distance = 120 mm
;
_diffrn_measurement_device       '2-circle diffractometer'
_diffrn_measurement_device_type  'STOE IPDS II'
_diffrn_measurement_method       'rotation method, \w scans'
_diffrn_radiation_collimation    '0.5 mm diameter, multiple pinhole'
_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  0.0278
_diffrn_reflns_av_unetI/netI     0.0309
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       51
_diffrn_reflns_limit_h_min       -51
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            27976
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.159
_diffrn_reflns_theta_min         1.542
_diffrn_source
'sealed X-ray tube, 12 x 0.4 mm long-fine focus'
_diffrn_source_current           40
_diffrn_source_power             2.000
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    0.795
_exptl_absorpt_correction_T_max  0.8087
_exptl_absorpt_correction_T_min  0.4220
_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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.478
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       fragment
_exptl_crystal_F_000             4088
_exptl_crystal_size_max          0.628
_exptl_crystal_size_mid          0.403
_exptl_crystal_size_min          0.247
_refine_diff_density_max         0.433
_refine_diff_density_min         -0.478
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     710
_refine_ls_number_reflns         9958
_refine_ls_number_restraints     735
_refine_ls_restrained_S_all      1.083
_refine_ls_R_factor_all          0.0725
_refine_ls_R_factor_gt           0.0485
_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^)+(0.0436P)^2^+25.4827P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1079
_refine_ls_wR_factor_ref         0.1208
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7605
_reflns_number_total             9958
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02317f2.cif
_cod_data_source_block           nv198
_cod_database_code               7713815
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.828
_shelx_estimated_absorpt_t_min   0.635
_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
 Cl3A-C47A
 1.78 with sigma of 0.02
 Cl4A-C47A
 1.77 with sigma of 0.02
 Cl3A-C47A = Cl4A-C47A
 1.771 with sigma of 0.01
 Cl3A-Cl4A
 2.916 with sigma of 0.03
 Cl3A-Cl4A
 2.92 with sigma of 0.04
 Cl3A-C47A \\sim Cl3B-C47B
 with sigma of 0.02
 Cl4A-C47A \\sim Cl4B-C47B
 with sigma of 0.02
 Cl3A-Cl4A \\sim Cl3B-Cl4B
 with sigma of 0.04
 P1-C40A \\sim P1-C40B
 with sigma of 0.02
 C40A-C41A \\sim C40B-C41B
 with sigma of 0.02
 C40A-C45A \\sim C40B-C45B
 with sigma of 0.02
 C41A-C42A \\sim C41B-C42B
 with sigma of 0.02
 C45A-C44A \\sim C45B-C44B
 with sigma of 0.02
 C42A-C43A \\sim C42B-C43B
 with sigma of 0.02
 C44A-C43A \\sim C44B-C43B
 with sigma of 0.02
 P1-C41A \\sim P1-C41B
 with sigma of 0.04
 P1-C45A \\sim P1-C45B
 with sigma of 0.04
 C40A-C42A \\sim C40B-C42B
 with sigma of 0.04
 C40A-C44A \\sim C40B-C44B
 with sigma of 0.04
 C41A-C45A \\sim C41B-C45B
 with sigma of 0.04
 C41A-C43A \\sim C41B-C43B
 with sigma of 0.04
 C45A-C43A \\sim C45B-C43B
 with sigma of 0.04
 C42A-C44A \\sim C42B-C44B
 with sigma of 0.04
 Cl2A-C46A \\sim Cl2B-C46B
 with sigma of 0.02
 Cl1A-C46A \\sim Cl1B-C46B
 with sigma of 0.02
 Cl2A-Cl1A \\sim Cl2B-Cl1B
 with sigma of 0.04
 Cl4A-C47A \\sim C47A-Cl3B
 with sigma of 0.02
 F1A-B \\sim F1B-B
 with sigma of 0.02
 F3A-B \\sim F3B-B
 with sigma of 0.02
 F2B-B \\sim F2A-B
 with sigma of 0.02
 F4A-B \\sim F4B-B
 with sigma of 0.02
 F1A-F4A \\sim F3B-F2A \\sim F1B-F4B \\sim F2B-F3A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Cl3A \\sim Cl4A \\sim C47A: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Cl4B \\sim Cl3A \\sim C47A \\sim Cl4A \\sim Cl3B \\sim C47B: within 2.5A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2.5A
C40A \\sim C40B \\sim C45B \\sim C45A \\sim C44B \\sim C44A \\sim C43A \\sim
C43B \\sim C42B \\sim C42A \\sim C41B \\sim C41A: within 2.5A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2.5A
C46A \\sim Cl2A \\sim Cl1A \\sim Cl2B \\sim C46B \\sim Cl1B: within 2.5A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2.5A
B \\sim F1A \\sim F3A \\sim F3B \\sim F4A \\sim F2A \\sim F2B \\sim F4B \\sim
F1B: within 2.5A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
2.5A
Uanis(Cl4A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Cl3A) \\sim Ueq, Uanis(Cl4A) \\sim Ueq, Uanis(C47A) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(Cl2B) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F4B) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(F4A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(B) \\sim Ueq, Uanis(F1A) \\sim Ueq, Uanis(F4A) \\sim Ueq, Uanis(F3B)
\\sim Ueq, Uanis(F2A) \\sim Ueq, Uanis(F1B) \\sim Ueq, Uanis(F4B) \\sim Ueq,
Uanis(F3A) \\sim Ueq, Uanis(F2B) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 Cl3A, Cl4A, C47A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C40B)=Sof(C45B)=Sof(H45B)=Sof(C44B)=Sof(H44B)=Sof(C43B)=Sof(H43B)=
 Sof(C42B)=Sof(H42B)=Sof(C41B)=Sof(H41B)=1-FVAR(1)
 Sof(C40A)=Sof(C45A)=Sof(H45A)=Sof(C44A)=Sof(H44A)=Sof(C43A)=Sof(H43A)=
 Sof(C42A)=Sof(H42A)=Sof(C41A)=Sof(H41A)=FVAR(1)
 Sof(C46B)=Sof(H46C)=Sof(H46D)=Sof(Cl1B)=Sof(Cl2B)=1-FVAR(2)
 Sof(Cl2A)=Sof(Cl1A)=Sof(C46A)=Sof(H46A)=Sof(H46B)=FVAR(2)
 Sof(F3B)=Sof(F2A)=Sof(F1B)=1-FVAR(3)
 Sof(F1A)=Sof(F3A)=Sof(F2B)=FVAR(3)
 Fixed Sof: F4A(0.7) Cl3A(0.25) Cl4A(0.25) C47A(0.25) H47A(0.25) H47B(0.25)
 Cl3B(0.25) C47B(0.25) H47C(0.25) H47D(0.25) Cl4B(0.25) F4B(0.3)
6.a Secondary CH2 refined with riding coordinates:
 C46A(H46A,H46B), C47A(H47A,H47B), C47B(H47C,H47D), C46B(H46C,H46D)
6.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C3(H3), C35(H35), C33(H33), C29(H29), C2(H2), C8(H8), C23(H23),
 C45A(H45A), C44A(H44A), C43A(H43A), C42A(H42A), C41A(H41A), C31(H31), C39(H39),
  C32(H32), C37(H37), C38(H38), C27(H27), C30(H30), C11(H11), C36(H36),
 C26(H26), C24(H24), C25(H25), C21(H21), C12(H12), C19(H19), C17(H17), C13(H13),
  C20(H20), C16(H16), C45B(H45B), C44B(H44B), C43B(H43B), C42B(H42B), C41B(H41B)
6.c Fitted hexagon refined as free rotating group:
 C40A(C45A,C44A,C43A,C42A,C41A), C40B(C45B,C44B,C43B,C42B,C41B)
6.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C)
;
_shelx_res_checksum              80276
_olex2_submission_special_instructions 'No special instructions were received'