Novel synthetic route towards heteroleptic pnictogen-rich organometallic-inorganic coordination compounds
Shelyganov, Pavel; El Sayed Moussa, Mehdi; Seidl, Michael; Zimmermann, Lisa; Silva, Wagner; Scheer, Manfred; Dalton Transactions  (2023) –; doi:10.1039/D3DT03490A

data_7714528
_publ_section_title
;
 Novel synthetic route towards heteroleptic pnictogen-rich
 organometallic-inorganic coordination compounds
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT03490A
_journal_year                    2023
_chemical_formula_moiety
'C56 H40 As3.24 Cu2 Mo8 O16 P4.76, 2(Al C16 F36 O4), 2(C7 H8)'
_chemical_formula_sum            'C102 H56 Al2 As3.24 Cu2 F72 Mo8 O24 P4.76'
_chemical_formula_weight         4372.18
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-02-18
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6270)
;
_audit_update_record
;
2023-10-12 deposited with the CCDC.	2023-11-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 111.6100(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   16.6487(2)
_cell_length_b                   23.0766(2)
_cell_length_c                   19.1463(2)
_cell_measurement_reflns_used    40903
_cell_measurement_temperature    123.01(10)
_cell_measurement_theta_max      66.6070
_cell_measurement_theta_min      4.5370
_cell_volume                     6838.89(13)
_computing_cell_refinement       'CrysAlisPro 1.171.41.90a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.90a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.90a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      123.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 4.2047
_diffrn_detector_type            TitanS2
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_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    -51.00 -26.00   1.00    3.17    --  -43.23  78.00  33.00   25
  2  \w    -16.00  44.00   1.00    3.17    --   43.23 -78.00 -91.00   60
  3  \w     41.00  66.00   1.00    9.99    --   86.50 -78.00 -91.00   25
  4  \w     96.00 121.00   1.00    9.99    --   86.50  78.00  33.00   25
  5  \w    -69.00 -20.00   1.00    9.99    --  -90.00  78.00  33.00   49
  6  \w   -129.00-104.00   1.00    9.99    --  -90.00 -78.00 -91.00   25
  7  \w    -69.00  26.00   1.00    3.17    --  -43.23  57.00 -30.00   95
  8  \w     -7.00  18.00   1.00    3.17    --  -43.23  37.00  60.00   25
  9  \w     19.00 114.00   1.00    3.17    --   43.23  37.00  30.00   95
 10  \w   -130.00-104.00   1.00    9.99    --  -90.00 -77.00   0.00   26
 11  \w   -164.00-103.00   1.00    9.99    --  -90.00 -77.00  30.00   61
 12  \w   -173.00-119.00   1.00    9.99    --  -90.00 -94.00 -60.00   54
 13  \w    -92.00 -34.00   1.00    9.99    --  -90.00  45.00  30.00   58
 14  \w    -66.00 -40.00   1.00    9.99    --  -90.00  61.00  30.00   26
 15  \w   -113.00 -25.00   1.00    9.99    --  -90.00  25.00-159.21   88
 16  \w   -122.00 -77.00   1.00    9.99    --  -90.00  77.00  90.00   45
 17  \w   -120.00 -88.00   1.00    9.99    --  -90.00  15.00  30.00   32
 18  \w    -68.00 -21.00   1.00    9.99    --  -90.00  15.00  30.00   47
 19  \w   -124.00 -97.00   1.00    9.99    --  -90.00-125.00 150.00   27
 20  \w   -117.00 -81.00   1.00    9.99    --  -90.00  61.00 150.00   36
 21  \w   -127.00-102.00   1.00    9.99    --  -90.00   0.00 -60.00   25
 22  \w    -52.00 -26.00   1.00    9.99    --  -90.00  61.00 150.00   26
 23  \w    -72.00 -21.00   1.00    9.99    --  -90.00   0.00 -60.00   51
 24  \w   -109.00 -84.00   1.00    9.99    --  -90.00  61.00  60.00   25
 25  \w    -66.00 -28.00   1.00    9.99    --  -90.00  61.00  60.00   38
 26  \w   -167.00-142.00   1.00    9.99    --  -90.00 -94.00-180.00   25
 27  \w   -163.00-123.00   1.00    9.99    --  -90.00-125.00 120.00   40
 28  \w    -43.00 -16.00   1.00    9.99    --  -90.00  77.00  90.00   27
 29  \w   -124.00 -36.00   1.00    9.99    --  -90.00  88.00 -29.84   88
 30  \w   -151.00-126.00   1.00    9.99    --  -90.00 -94.00   0.00   25
 31  \w   -103.00 -78.00   1.00    9.99    --  -90.00 125.00 150.00   25
 32  \w   -127.00 -97.00   1.00    9.99    --  -90.00 145.00  87.44   30
 33  \w   -161.00-136.00   1.00    9.99    --  -90.00-125.00  90.00   25
 34  \w    -94.00 -68.00   1.00    9.99    --  -90.00  61.00 -30.00   26
 35  \w   -109.00 -84.00   1.00    9.99    --  -90.00  30.00 -90.00   25
 36  \w   -136.00-108.00   1.00    9.99    --  -90.00-125.00  60.00   28
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dualflex, TitanS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0508693000
_diffrn_orient_matrix_UB_12      0.0494849000
_diffrn_orient_matrix_UB_13      -0.0187667000
_diffrn_orient_matrix_UB_21      0.0853927000
_diffrn_orient_matrix_UB_22      -0.0274765000
_diffrn_orient_matrix_UB_23      0.0520992000
_diffrn_orient_matrix_UB_31      0.0048833000
_diffrn_orient_matrix_UB_32      -0.0354435000
_diffrn_orient_matrix_UB_33      -0.0664767000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0918
_diffrn_reflns_av_unetI/netI     0.0494
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            66757
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        66.694
_diffrn_reflns_theta_max         66.694
_diffrn_reflns_theta_min         3.438
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.157
_exptl_absorpt_correction_T_max  0.520
_exptl_absorpt_correction_T_min  0.106
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.90a (Rigaku Oxford Diffraction, 2020)
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    2.123
_exptl_crystal_description       block
_exptl_crystal_F_000             4213
_exptl_crystal_size_max          0.411
_exptl_crystal_size_mid          0.306
_exptl_crystal_size_min          0.223
_refine_diff_density_max         1.040
_refine_diff_density_min         -1.031
_refine_diff_density_rms         0.157
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1776
_refine_ls_number_reflns         12040
_refine_ls_number_restraints     1302
_refine_ls_restrained_S_all      1.070
_refine_ls_R_factor_all          0.0529
_refine_ls_R_factor_gt           0.0500
_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^)+(0.0962P)^2^+8.3638P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1346
_refine_ls_wR_factor_ref         0.1386
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11151
_reflns_number_total             12040
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt03490a2.cif
_cod_data_source_block           psh_194_pr_b_mp_abs
_cod_database_code               7714528
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         Mo4As2P2AlO12F36C51
_shelx_estimated_absorpt_t_max   0.235
_shelx_estimated_absorpt_t_min   0.117
_reflns_odcompleteness_completeness 98.56
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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
 C38C-C37A \\sim C38A-C37A \\sim C38B-C37B \\sim C40C-C37A \\sim C40A-C37A
\\sim C40B-C37B \\sim C39A-
 C37A \\sim C39B-C37B
 with sigma of 0.02
 C46-C45B \\sim C46-C45A
 with sigma of 0.02
 C47A-C46 \\sim C47B-C46 \\sim C48A-C47A \\sim C48B-C47B \\sim C49A-C48A \\sim
C49B-C48B \\sim C50A-
 C49A \\sim C50B-C49B \\sim C51A-C50A \\sim C51B-C50B \\sim C51A-C46 \\sim
C51B-C46
 with sigma of 0.02
 O12A-C41A \\sim O12B-C41B
 with sigma of 0.02
 F22B-C39B \\sim F24B-C39B \\sim F23B-C39B
 with sigma of 0.02
 F24B-F22B \\sim F22B-F23B \\sim F23B-F24B
 with sigma of 0.02
 F35C-C44C \\sim F36B-C44B \\sim F34C-C44C \\sim F36C-C44C \\sim F35B-C44B
\\sim F34B-C44B
 with sigma of 0.02
 C41B-F36B \\sim C41B-F34B \\sim C41B-F35B
 with sigma of 0.02
 F7B-C32B \\sim F8B-C32B \\sim F9B-C32B
 with sigma of 0.02
 F26C-F27C \\sim F27C-F25C \\sim F25C-F26C
 with sigma of 0.02
 C41A-C44C \\sim C44A-C41A \\sim C41A-C42A \\sim C41A-C42C \\sim C41A-C43C
\\sim C43A-C41A \\sim C41B-
 C44B \\sim C41B-C43B \\sim C41B-C42B
 with sigma of 0.02
 C33A-C36A \\sim C35B-C33B \\sim C33A-C35A \\sim C34A-C33A \\sim C34B-C33B
\\sim C36B-C33B
 with sigma of 0.02
 C42C-C41A \\sim C42A-C41A \\sim C42B-C41B \\sim C43C-C41A \\sim C43A-C41A
\\sim C43B-C41B \\sim C44C-
 C41A \\sim C44B-C41B \\sim C44A-C41A
 with sigma of 0.02
 F19C-C38C \\sim F21C-C38C \\sim F20C-C38C
 with sigma of 0.02
 F12B-C34B \\sim F10B-C34B \\sim F11B-C34B
 with sigma of 0.02
 F20C-F21C \\sim F21C-F19C \\sim F19C-F20C
 with sigma of 0.02
 F19B-C38B \\sim F20B-C38B \\sim F21B-C38B
 with sigma of 0.02
 F27B-C40B \\sim F25B-C40B \\sim F26B-C40B
 with sigma of 0.02
 F26A-C40A \\sim F25A-C40A \\sim F27A-C40A
 with sigma of 0.02
 F25C-C40C \\sim F27C-C40C \\sim F26C-C40C
 with sigma of 0.02
 C5B-C1 \\sim C5B-C4B \\sim C4B-C3B \\sim C2-C3B \\sim C2-C1
 with sigma of 0.02
3. Restrained planarity
 C5B, C1, C2, C3B, H1B, H2B
 with sigma of 0.1
 C1, C2, C3A, C5A, H1A, H2A
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C51B \\sim C51A \\sim C50B \\sim C50A \\sim C49B \\sim C49A \\sim C48B \\sim
C48A \\sim C47B \\sim C47A \\sim C46 \\sim C45A \\sim C45B: within 1.7A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 1.7A
P4 \\sim P3 \\sim As1 \\sim As2: within 2.4A with sigma of 0.005 and sigma for
terminal atoms of 0.01 within 2.4A
C39B \\sim F24B \\sim F22B \\sim F23B \\sim C38B \\sim F20B \\sim F21B \\sim
F19B \\sim C40B \\sim F27B \\sim F25B \\sim F26B: within 1.9A with sigma of
0.01 and sigma for terminal atoms of 0.01 within 1.9A
C38C \\sim F20C \\sim F21C \\sim F19C \\sim C40C \\sim F26C \\sim F27C \\sim
F25C: within 1.9A with sigma of 0.01 and sigma for terminal atoms of 0.01
within 1.9A
C39A \\sim F24A \\sim F22A \\sim F23A \\sim C38A \\sim F20A \\sim F21A \\sim
F19A \\sim C40A \\sim F27A \\sim F25A \\sim F26A: within 1.9A with sigma of
0.01 and sigma for terminal atoms of 0.01 within 1.9A
C41A \\sim C44A \\sim F35A \\sim F36A \\sim F34A \\sim C43A \\sim F32A \\sim
F33A \\sim F31A \\sim C42A \\sim F30A \\sim F28A \\sim F29A: within 1.9A with
sigma of 0.01 and sigma for terminal atoms of 0.01 within 1.9A
C44B \\sim F36B \\sim F34B \\sim F35B \\sim C43B \\sim F32B \\sim F33B \\sim
F31B \\sim C42B \\sim F29B \\sim F30B \\sim F28B: within 1.9A with sigma of
0.01 and sigma for terminal atoms of 0.01 within 1.9A
O11B \\sim O11A \\sim C37B \\sim C37A \\sim C40B \\sim C40A \\sim C40C \\sim
C38B \\sim C38A \\sim C38C \\sim C39A \\sim C39B: within 1.9A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 1.9A
C33B \\sim C36B \\sim F17B \\sim F18B \\sim F16B \\sim C34B \\sim F10B \\sim
F12B \\sim F11B \\sim C35B \\sim F15B \\sim F13B \\sim F14B \\sim C33A: within
1.9A with sigma of 0.01 and sigma for terminal atoms of 0.01 within 1.9A
C44C \\sim F36C \\sim F34C \\sim F35C \\sim C43C \\sim F32C \\sim F33C \\sim
F31C \\sim C42C \\sim F29C \\sim F30C \\sim F28C: within 1.9A with sigma of
0.01 and sigma for terminal atoms of 0.01 within 1.9A
C41B \\sim C41A \\sim C42A \\sim C42C \\sim C42B \\sim C43C \\sim C43A \\sim
C43B \\sim C44C \\sim C44A \\sim C44B: within 1.9A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 1.9A
F18A \\sim C36A \\sim F16A \\sim F17A \\sim C33A: within 1.9A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 1.9A
O11A \\sim O11B: within 1.9A with sigma of 0.01 and sigma for terminal atoms of
0.01 within 1.9A
F7B \\sim C32B \\sim F9B \\sim F8B \\sim C29 \\sim F6B \\sim C31B \\sim F5B
\\sim F4B \\sim F1B \\sim F3B \\sim C30B \\sim F2B: within 1.9A with sigma of
0.005 and sigma for terminal atoms of 0.01 within 1.9A
C1 \\sim C2 \\sim C3B \\sim C5B \\sim C4B \\sim C6A \\sim C4A \\sim C6B \\sim
O1B: within 1.9A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
1.9A
Uanis(O12B) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.008
5. Others
 Fixed Sof: As1(0.81) As2(0.81) H1A(0.75) H1B(0.25) O1A(0.75) H2A(0.75)
 H2B(0.25) C4A(0.75) H4A(0.75) C6A(0.75) C5A(0.75) H5A(0.75) C3A(0.75)
 H3A(0.75) O12A(0.73) C41A(0.73) C44A(0.41) F35A(0.41) F36A(0.41) F34A(0.41)
 C43A(0.41) F32A(0.41) F33A(0.41) F31A(0.41) C42A(0.41) F30A(0.41) F28A(0.41)
 F29A(0.41) O11A(0.76) C37A(0.76) C39A(0.76) F24A(0.76) F22A(0.76) F23A(0.76)
 C38A(0.46) F20A(0.46) F21A(0.46) F19A(0.46) C40A(0.46) F27A(0.46) F25A(0.46)
 F26A(0.46) O10A(0.75) C33A(0.75) C34A(0.75) F11A(0.75) F12A(0.75) F10A(0.75)
 C36A(0.75) F17A(0.75) F18A(0.75) F16A(0.75) C35A(0.75) F14A(0.75) F15A(0.75)
 F13A(0.75) O9A(0.75) C32A(0.75) F9A(0.75) F7A(0.75) F8A(0.75) C31A(0.75)
 F4A(0.75) F5A(0.75) F6A(0.75) C30A(0.75) F2A(0.75) F3A(0.75) F1A(0.75)
 C45A(0.55) H45A(0.55) H45B(0.55) H45C(0.55) C47A(0.55) H47A(0.55) C48A(0.55)
 H48A(0.55) C49A(0.55) H49A(0.55) C50A(0.55) H50A(0.55) C51A(0.55) H51A(0.55)
 O12B(0.27) C44B(0.27) F36B(0.27) F34B(0.27) F35B(0.27) C43B(0.27) F32B(0.27)
 F33B(0.27) F31B(0.27) C42B(0.27) F29B(0.27) F30B(0.27) F28B(0.27) O11B(0.24)
 C37B(0.24) C39B(0.24) F24B(0.24) F22B(0.24) F23B(0.24) C38B(0.24) F20B(0.24)
 F21B(0.24) F19B(0.24) C40B(0.24) F27B(0.24) F25B(0.24) F26B(0.24) O9B(0.25)
 C32B(0.25) F9B(0.25) F7B(0.25) F8B(0.25) C31B(0.25) F5B(0.25) F6B(0.25)
 F4B(0.25) C30B(0.25) F3B(0.25) F1B(0.25) F2B(0.25) O10B(0.25) C33B(0.25)
 C36B(0.25) F18B(0.25) F16B(0.25) F17B(0.25) C35B(0.25) F14B(0.25) F15B(0.25)
 F13B(0.25) C34B(0.25) F11B(0.25) F12B(0.25) F10B(0.25) C4B(0.25) H4B(0.25)
 C5B(0.25) H5B(0.25) C3B(0.25) H3B(0.25) C6B(0.25) O1B(0.25) C38C(0.3)
 F20C(0.3) F21C(0.3) F19C(0.3) C40C(0.3) F26C(0.3) F27C(0.3) F25C(0.3)
 C44C(0.32) F36C(0.32) F34C(0.32) F35C(0.32) C43C(0.32) F32C(0.32) F33C(0.32)
 F31C(0.32) C42C(0.32) F29C(0.32) F30C(0.32) F28C(0.32) C48B(0.45) H48B(0.45)
 C50B(0.45) H50B(0.45) C49B(0.45) H49B(0.45) C51B(0.45) H51B(0.45) C47B(0.45)
 H47B(0.45) C45B(0.45) H45D(0.45) H45E(0.45) H45F(0.45) C41B(0.27) P3(0.19)
 P4(0.19)
6.a Ternary CH refined with riding coordinates:
 C1(H1A), C1(H1B), C2(H2A), C2(H2B), C4B(H4B)
6.b Aromatic/amide H refined with riding coordinates:
 C25(H25), C15(H15), C17(H17), C26(H26), C18(H18), C11(H11), C16(H16), C9(H9),
 C8(H8), C12(H12), C22(H22), C4A(H4A), C24(H24), C19(H19), C10(H10), C5A(H5A),
 C23(H23), C3A(H3A), C47A(H47A), C48A(H48A), C49A(H49A), C50A(H50A), C51A(H51A),
  C5B(H5B), C3B(H3B), C48B(H48B), C50B(H50B), C49B(H49B), C51B(H51B), C47B(H47B)
6.c Idealised Me refined as rotating group:
 C45A(H45A,H45B,H45C), C45B(H45D,H45E,H45F)
;
_shelx_res_checksum              19970
_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 4.863
_oxdiff_exptl_absorpt_empirical_full_min 0.298