Cyclo-E5-bridged Trinuclear Triple-decker Complexes (E = P, As) Containing a Triply-bonded Mo2 Unit and Their Isomerisation
Lee, Meng-Wei; Balazs, Gabor; Reichl, Stephan; Zimmermann, Lisa; Scheer, Manfred; Tsai, Yi-Chou; Chemical Communications  (2023) –; doi:10.1039/D3CC03282E

data_7132043
_publ_section_title
;
 Cyclo-E5-bridged Trinuclear Triple-decker Complexes (E = P, As)
 Containing a Triply-bonded Mo2 Unit and Their Isomerisation
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D3CC03282E
_journal_year                    2023
_chemical_formula_moiety         'C70 H93 B2 Fe Mo2 N4 P5, C4 H10 O'
_chemical_formula_sum            'C74 H103 B2 Fe Mo2 N4 O P5'
_chemical_formula_weight         1488.80
_chemical_name_systematic
Cp*FeMo2[\k2-PhB(N-2,6-iPr2C6H3)2](?3,\k:\k:\h2-P2)[?3,\k:\k:\h3\k-P3PhB(N-2,6-iPr2C6H3)2]
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_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             2023-01-16
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-07-07 deposited with the CCDC.	2023-08-22 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.8890(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.15380(10)
_cell_length_b                   17.6318(2)
_cell_length_c                   37.3554(4)
_cell_measurement_reflns_used    45027
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.9860
_cell_measurement_theta_min      2.3350
_cell_volume                     7345.49(13)
_computing_cell_refinement       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_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     50.00 105.00   0.50    0.50    --   78.93-125.00-180.00  110
  2  \w     26.00  66.00   0.50    0.50    --   66.49-125.00-120.00   80
  3  \w     25.00  77.00   0.50    0.50    --   66.49-125.00 -30.00  104
  4  \w     37.00 105.00   0.50    0.50    --   78.93-125.00 -90.00  136
  5  \w     37.00  63.00   0.50    0.50    --   78.93-125.00 -60.00   52
  6  \w     49.00 105.00   0.50    0.50    --   78.93-125.00   0.00  112
  7  \w     31.00  56.00   0.50    0.50    --   69.02-102.00  30.00   50
  8  \w     37.00  73.00   0.50    0.50    --   66.49-102.00  30.00   72
  9  \w     77.00 105.00   0.50    0.50    --   78.93-125.00 120.00   56
 10  \w     38.00  67.00   0.50    0.50    --   78.93-125.00 120.00   58
 11  \w     40.00  65.00   0.50    0.50    --   77.43-102.00  30.00   50
 12  \w     57.00  82.00   0.50    0.50    --   78.93-102.00  30.00   50
 13  \w     54.00  92.00   0.50    0.50    --   77.43  15.00-150.00   76
 14  \w     43.00  98.00   0.50    0.50    --   77.43   0.00-180.00  110
 15  \w     70.00 103.00   0.50    0.50    --   78.93   0.00 -60.00   66
 16  \w     54.00  83.00   0.50    0.50    --   78.93  15.00  30.00   58
 17  \w     88.00 114.00   0.50    0.50    --   78.93  15.00  90.00   52
 18  \w    -91.00 -48.00   0.50    0.50    --  -68.43   0.00 -90.00   86
 19  \w   -102.00 -46.00   0.50    0.50    --  -74.09 128.00-135.56  112
 20  \w    -90.00 -64.00   0.50    0.50    --  -68.43 125.00  30.00   52
 21  \w    -63.00 -38.00   0.50    0.50    --  -68.43 125.00  60.00   50
 22  \w    -87.00 -29.00   0.50    0.50    --  -68.28 125.00  60.00  116
 23  \w    -79.00 -54.00   0.50    0.50    --  -68.43 102.00 133.00   50
 24  \w    -95.00 -33.00   0.50    0.50    --  -74.09 115.00 157.91  124
 25  \w   -103.00 -42.00   0.50    0.50    --  -68.28   0.00  30.00  122
 26  \w   -110.00 -42.00   0.50    0.50    --  -68.43 -15.00  90.00  136
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0050463000
_diffrn_orient_matrix_UB_12      0.0865935000
_diffrn_orient_matrix_UB_13      -0.0053357000
_diffrn_orient_matrix_UB_21      -0.0395797000
_diffrn_orient_matrix_UB_22      -0.0116731000
_diffrn_orient_matrix_UB_23      -0.0393049000
_diffrn_orient_matrix_UB_31      -0.1322563000
_diffrn_orient_matrix_UB_32      0.0001958000
_diffrn_orient_matrix_UB_33      0.0112953000
_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  0.0295
_diffrn_reflns_av_unetI/netI     0.0206
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       44
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            65913
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.079
_diffrn_reflns_theta_max         67.079
_diffrn_reflns_theta_min         2.366
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.685
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77992
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.58a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.346
_exptl_crystal_description       block
_exptl_crystal_F_000             3112
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.557
_refine_diff_density_min         -0.705
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     921
_refine_ls_number_reflns         13043
_refine_ls_number_restraints     381
_refine_ls_restrained_S_all      1.005
_refine_ls_R_factor_all          0.0285
_refine_ls_R_factor_gt           0.0268
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0426P)^2^+4.7547P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0701
_refine_ls_wR_factor_ref         0.0710
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12334
_reflns_number_total             13043
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc03282e2.cif
_cod_data_source_block           230119lt_auto
_cod_database_code               7132043
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N O Fe Mo P B'
_shelx_estimated_absorpt_t_max   0.549
_shelx_estimated_absorpt_t_min   0.445
_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. Rigid bond restraints
 C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C1A, C2A, C3A, C4A, C5A, C6A, C7A,
 C8A, C9A, C10A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9
\\sim C10 \\sim C1A \\sim C2A \\sim C3A \\sim C4A \\sim C5A \\sim C6A \\sim C7A
\\sim C8A \\sim C9A \\sim C10A: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
4. Same fragment restrains
{C1, C2, C3, C4, C5, C6, C7, C8, C9, C10} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C1A, C2A, C3A, C4A, C5A, C6A, C7A, C8A, C9A, C10A}
5. Others
 Sof(C1A)=Sof(C2A)=Sof(C3A)=Sof(C4A)=Sof(C5A)=Sof(C6A)=Sof(H6AA)=Sof(H6AB)=
 Sof(H6AC)=Sof(C7A)=Sof(H7AA)=Sof(H7AB)=Sof(H7AC)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=
 Sof(H8AC)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(H9AC)=Sof(C10A)=Sof(H10D)=Sof(H10E)=
 Sof(H10F)=1-FVAR(1)
 Sof(C1)=Sof(C2)=Sof(C3)=Sof(C4)=Sof(C5)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=
 Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(H7C)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=Sof(C9)=
 Sof(H9A)=Sof(H9B)=Sof(H9C)=Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C17(H17), C20(H20), C35(H35), C38(H38), C47(H47), C62(H62), C65(H65), C68(H68)
6.b Secondary CH2 refined with riding coordinates:
 C71(H71A,H71B), C73(H73A,H73B)
6.c Aromatic/amide H refined with riding coordinates:
 C13(H13), C14(H14), C15(H15), C24(H24), C25(H25), C26(H26), C27(H27),
 C28(H28), C31(H31), C32(H32), C33(H33), C43(H43), C44(H44), C45(H45), C51(H51),
  C52(H52), C53(H53), C54(H54), C55(H55), C58(H58), C59(H59), C60(H60)
6.d Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C22(H22A,H22B,
 H22C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C39(H39A,H39B,H39C), C40(H40A,
 H40B,H40C), C48(H48A,H48B,H48C), C49(H49A,H49B,H49C), C63(H63A,H63B,H63C),
 C64(H64A,H64B,H64C), C66(H66A,H66B,H66C), C67(H67A,H67B,H67C), C69(H69A,H69B,
 H69C), C70(H70A,H70B,H70C), C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C),
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C6A(H6AA,H6AB,H6AC), C7A(H7AA,H7AB,H7AC),
  C8A(H8AA,H8AB,H8AC), C9A(H9AA,H9AB,H9AC), C10A(H10D,H10E,H10F), C72(H72A,H72B,
 H72C), C74(H74A,H74B,H74C)
;
_shelx_res_checksum              85568
_shelx_hkl_checksum              99997
_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 1.360
_oxdiff_exptl_absorpt_empirical_full_min 0.786