Luminescent ionic heterobimetallic diphosphine-β-diketiminate complexes.
Kebernik, Steven; Krätschmer, Frederic; Sun, Xiaofei; Roesky, Peter W.; Dalton transactions (Cambridge, England : 2003) 54 (2025) 13192–13199; doi:10.1039/d5dt00977d

data_7719272
_publ_section_title
;
 Luminescent ionic heterobimetallic diphosphine-&#x3b2;-diketiminate
 complexes.
;
_journal_issue                   35
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              13192
_journal_page_last               13199
_journal_paper_doi               10.1039/d5dt00977d
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety
'C43 H38 Au Cu N3 P2, C41 H35 Au Cu N2 P2, C2 H3 N, 2(C F3 O3 S), 4[C4H8O]'
_chemical_formula_sum            'C104 H108 Au2 Cu2 F6 N6 O10 P4 S2'
_chemical_formula_weight         2424.97
_space_group_crystal_system      orthorhombic
_space_group_IT_number           62
_space_group_name_Hall           '-P 2ac 2n'
_space_group_name_H-M_alt        'P n m a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-04-14
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-04-24 deposited with the CCDC.	2025-07-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   40.8223(9)
_cell_length_b                   17.4125(4)
_cell_length_c                   14.3161(3)
_cell_measurement_reflns_used    42945
_cell_measurement_temperature    100
_cell_measurement_theta_max      27.72
_cell_measurement_theta_min      1.54
_cell_volume                     10176.1(4)
_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 (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      100
_diffrn_detector                 'EIGER2 1M CDTE'
_diffrn_detector_area_resol_mean 13.33
_diffrn_measured_fraction_theta_full 0.989
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_details
;
 660 frames, detector distance = 100 mm
;
_diffrn_measurement_device       'Eulerian 4-circle diffractometer'
_diffrn_measurement_device_type  'STOE STADIVARI'
_diffrn_measurement_method       'rotation method, \w scans'
_diffrn_radiation_collimation    '1.2 0.6 mm diameter'
_diffrn_radiation_monochromator  'Graded multilayer mirror'
_diffrn_radiation_polarisn_norm  270
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0330
_diffrn_reflns_av_unetI/netI     0.0356
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       50
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            49096
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.999
_diffrn_reflns_theta_min         1.842
_diffrn_source                   Axo_Mo
_diffrn_source_current           0.830
_diffrn_source_power             0.050
_diffrn_source_voltage           60
_exptl_absorpt_coefficient_mu    3.462
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.5389
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
STOE LANA, absorption correction by scaling of reflection intensities.
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    1.583
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             4864
_exptl_crystal_size_max          0.321
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.082
_refine_diff_density_max         1.383
_refine_diff_density_min         -1.950
_refine_diff_density_rms         0.113
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     740
_refine_ls_number_reflns         10198
_refine_ls_number_restraints     830
_refine_ls_restrained_S_all      1.105
_refine_ls_R_factor_all          0.0696
_refine_ls_R_factor_gt           0.0488
_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^)+(0.0737P)^2^+19.8130P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1243
_refine_ls_wR_factor_ref         0.1345
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7578
_reflns_number_total             10198
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt00977d2.cif
_cod_data_source_block           stk006_thf
_cod_depositor_comments
'Adding full bibliography for 7719271--7719275.cif.'
_cod_database_code               7719272
_shelx_shelxl_version_number     2019/2
_audit_contact_author
;
      Prof. Dr. Peter W. Roesky
      Karlsruher Institut fuer Technologie (KIT), CS
      Institut fuer Anorganische Chemie (AOC)
      Lehrstuhl fuer Anorganische Funktionsmaterialien
      Engesserstr. 15, Geb. 30.45
      76131 Karlsruhe 
      Bundesrepublik Deutschland
;
_audit_contact_letter
;
;
_shelx_estimated_absorpt_t_max   0.764
_shelx_estimated_absorpt_t_min   0.403
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C47-F6 = C47-F5 = C47-F4
 0.01 with sigma of 1.33
 C47-S2
 0.01 with sigma of 1.82
 S2-O5 = S2-O6 = S2-O4
 0.01 with sigma of 1.44
 N4-C45
 1.14 with sigma of 0.02
 C45-N4
 1.137 with sigma of 0.01
 C45-C46
 1.456 with sigma of 0.01
 C46-N4
 2.593 with sigma of 0.02
 C48-F1 = C48-F3 = C48-F2
 0.01 with sigma of 1.33
 C48-S1
 0.01 with sigma of 1.82
 S1-O3 = S1-O1 = S1-O2
 0.01 with sigma of 1.44
 N2-C22
 1.14 with sigma of 0.02
 C22-N2
 1.137 with sigma of 0.01
 C22-C23
 1.456 with sigma of 0.01
 C23-N2
 2.593 with sigma of 0.02
 C47-O5
 0.02 with sigma of 2.58
 C47-O6
 0.02 with sigma of 2.56
 C47-O4
 0.02 with sigma of 2.57
 N4-C46
 2.59 with sigma of 0.04
 C48-O3
 0.02 with sigma of 2.58
 C48-O1
 0.02 with sigma of 2.56
 C48-O2
 0.02 with sigma of 2.57
 N2-C23
 2.59 with sigma of 0.04
 P2A-C40A \\sim P2A-C39
 with sigma of 0.02
 P2A-C39A \\sim P2A-C44
 with sigma of 0.04
 P2A-C41A \\sim P2A-C40
 with sigma of 0.04
 P2A-C40A \\sim P2-C40A
 with sigma of 0.02
 N3-C39A \\sim N3-C44
 with sigma of 0.02
 P2A-C39 \\sim P2-C39
 with sigma of 0.02
 Au2A-P2A_$1 \\sim Au2-P2
 with sigma of 0.02
 C40A-C39A \\sim C39-C44
 with sigma of 0.02
 C40A-C41A \\sim C39-C40
 with sigma of 0.02
 C39A-C44A \\sim C44-C43
 with sigma of 0.02
 P2A-C27 \\sim P2-C27
 with sigma of 0.02
 C41A-C42A \\sim C40-C41
 with sigma of 0.02
 C44A-C43A \\sim C43-C42
 with sigma of 0.02
 C43A-C42A \\sim C42-C41
 with sigma of 0.02
 N3-C40A \\sim N3-C39
 with sigma of 0.04
 N3-C44A \\sim N3-C43
 with sigma of 0.04
 C40A-C44A \\sim C39-C43
 with sigma of 0.04
 Cu04-P2A_$1 \\sim Cu2-P2_$1
 with sigma of 0.04
 C40A-C42A \\sim C39-C41
 with sigma of 0.04
 C39A-C41A \\sim C44-C40
 with sigma of 0.04
 C39A-C43A \\sim C44-C42
 with sigma of 0.04
 C41A-C43A \\sim C40-C42
 with sigma of 0.04
 C44A-C42A \\sim C43-C41
 with sigma of 0.04
 Au2A-C40A_$1 \\sim Au2-C40A
 with sigma of 0.04
 Au2A-C39_$1 \\sim Au2-C39
 with sigma of 0.04
 Au2A-Cu04 \\sim Au2-Cu2
 with sigma of 0.02
 Cu04-N3_$1 \\sim Cu2-N3_$1
 with sigma of 0.02
 Au2A-N3_$1 \\sim Au2-N3
 with sigma of 0.04
 C47-F6 \\sim C47-F5 \\sim C47-F4
 with sigma of 0.02
 Au2A-C27_$1 \\sim Au2-C27
 with sigma of 0.04
 F6-F5 \\sim F5-F4 \\sim F4-F6
 with sigma of 0.04
 S2-F6 \\sim S2-F5 \\sim S2-F4
 with sigma of 0.04
 S2-O5 \\sim S2-O6 \\sim S2-O4
 with sigma of 0.02
 O5-O6 \\sim O6-O4 \\sim O5-O4
 with sigma of 0.04
 C47-O5 \\sim C47-O6 \\sim C47-O4
 with sigma of 0.04
 C48-F1 \\sim C48-F3 \\sim C48-F2
 with sigma of 0.02
 F1-F3 \\sim F3-F2 \\sim F2-F1
 with sigma of 0.04
 S1-F1 \\sim S1-F3 \\sim S1-F2
 with sigma of 0.04
 S1-O3 \\sim S1-O1 \\sim S1-O2
 with sigma of 0.02
 O3-O1 \\sim O1-O2 \\sim O3-O2
 with sigma of 0.04
 C48-O3 \\sim C48-O1 \\sim C48-O2
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C4 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
Cu04 \\sim P2A \\sim Au2 \\sim Cu2 \\sim P2: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
Au2A \\sim Cu04 \\sim P2A \\sim Au2 \\sim Cu2 \\sim P2: within 2A with sigma of
0.001 and sigma for terminal atoms of 0.002 within 2A
C39A \\sim C40A \\sim C41A \\sim C42A \\sim C43A \\sim C44A \\sim C39 \\sim C40
\\sim C41 \\sim C42 \\sim C43 \\sim C44: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
N4 \\sim C45 \\sim C46: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
S1 \\sim F1 \\sim F2 \\sim F3 \\sim O1 \\sim O2 \\sim O3 \\sim C48: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
S2 \\sim F4 \\sim F5 \\sim F6 \\sim O4 \\sim O5 \\sim O6 \\sim C47: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
N2 \\sim C22 \\sim C23: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Cu1 \\sim N2 \\sim C22 \\sim C23: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C33A \\sim C34A \\sim C35A \\sim C36A \\sim C37A \\sim C38A \\sim C33 \\sim C34
\\sim C35 \\sim C36 \\sim C37 \\sim C38: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
Uanis(C47) \\sim Ueq, Uanis(F6) \\sim Ueq, Uanis(F5) \\sim Ueq, Uanis(F4) \\sim
Ueq, Uanis(S2) \\sim Ueq, Uanis(O5) \\sim Ueq, Uanis(O6) \\sim Ueq, Uanis(O4)
\\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(F1) \\sim Ueq, Uanis(F3) \\sim Ueq,
Uanis(F2) \\sim Ueq, Uanis(S1) \\sim Ueq, Uanis(O3) \\sim Ueq, Uanis(O1) \\sim
Ueq, Uanis(O2) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of
0.02
4. Rigid body (RIGU) restrains
 S2, F4, F5, F6, O4, O5, O6, C47
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N4, C45, C46
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S1, F1, F2, F3, O1, O2, O3, C48
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N2, C22, C23
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: N2(0.5) C22(0.5) C23(0.5) H23A(0.5) H23B(0.5) H23C(0.5) Au2A(0.25)
 Cu04(0.25) P2A(0.5) C33A(0.5) C34A(0.5) H34A(0.5) C35A(0.5) H35A(0.5)
 C36A(0.5) H36A(0.5) C37A(0.5) H37A(0.5) C38A(0.5) H38A(0.5) C39A(0.5)
 C40A(0.5) C41A(0.5) H41A(0.5) C42A(0.5) H42A(0.5) C43A(0.5) H43A(0.5)
 C44A(0.5) H44A(0.5) Au2(0.25) Cu2(0.25) P2(0.5) C38(0.5) H38(0.5) C33(0.5)
 C34(0.5) H34(0.5) C35(0.5) H35(0.5) C36(0.5) H36(0.5) C37(0.5) H37(0.5)
 C39(0.5) C40(0.5) H40(0.5) C41(0.5) H41(0.5) C42(0.5) H42(0.5) C43(0.5)
 H43(0.5) C44(0.5) N4(0.5) C45(0.5) C46(0.5) H46A(0.5) H46B(0.5) H46C(0.5)
 S1(0.5) F1(0.5) F2(0.5) F3(0.5) O1(0.5) O2(0.5) O3(0.5) C48(0.5) S2(0.5)
 F4(0.5) F5(0.5) F6(0.5) O4(0.5) O5(0.5) O6(0.5) C47(0.5)
6.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C5(H5), C6(H6), C7(H7), C8(H8), C17(H17), C18(H18), C19(H19),
 C20(H20), C21(H21), C11(H11), C12(H12), C13(H13), C14(H14), C15(H15), C24(H24),
  C28(H28), C29(H29), C30(H30), C31(H31), C32(H32), C34A(H34A), C35A(H35A),
 C36A(H36A), C37A(H37A), C38A(H38A), C41A(H41A), C42A(H42A), C43A(H43A),
 C44A(H44A), C38(H38), C34(H34), C35(H35), C36(H36), C37(H37), C40(H40),
 C41(H41), C42(H42), C43(H43)
6.b Fitted hexagon refined as free rotating group:
 C33A(C34A,C35A,C36A,C37A,C38A), C38(C33,C34,C35,C36,C37)
6.c Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C23(H23A,H23B,H23C), C26(H26A,H26B,H26C), C46(H46A,H46B,H46C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              48604
_shelx_hkl_checksum              16761
_shelx_fab_checksum              31647
_olex2_submission_special_instructions 'No special instructions were received'