Reshaping aromatic frameworks: expansion of aromatic system drives metallabenzenoids to metallapentalenes.
Li, Qian; Fei, Jiawei; Ruan, Kaidong; Hua, Yuhui; Chen, Dafa; Luo, Ming; Xia, Haiping; Chemical science 14 (2023) 5672–5680; doi:10.1039/d3sc01491f

data_1568944
_publ_section_title
;
 Reshaping aromatic frameworks: expansion of aromatic system drives
 metallabenzenoids to metallapentalenes.
;
_journal_issue                   21
_journal_name_full               'Chemical science'
_journal_page_first              5672
_journal_page_last               5680
_journal_paper_doi               10.1039/d3sc01491f
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C63 H52 Cl2 O Os P3, C H2 Cl2, B F4'
_chemical_formula_sum            'C64 H54 B Cl4 F4 O Os P3'
_chemical_formula_weight         1350.79
_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             2022-09-20
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-09-23 deposited with the CCDC.	2023-04-24 downloaded from the CCDC.
;
_cell_angle_alpha                102.3440(10)
_cell_angle_beta                 99.8500(10)
_cell_angle_gamma                97.6070(10)
_cell_formula_units_Z            2
_cell_length_a                   10.15200(10)
_cell_length_b                   12.5705(2)
_cell_length_c                   23.1569(3)
_cell_measurement_reflns_used    35042
_cell_measurement_temperature    100.00(12)
_cell_measurement_theta_max      74.2210
_cell_measurement_theta_min      4.5130
_cell_volume                     2800.15(7)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(12)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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     30.00  56.00   0.50    0.08    --   62.00  80.00-154.74   52
  2  \w     38.00  66.00   0.50    0.08    --   70.00  80.00-149.85   56
  3  \w    127.00 171.00   0.50    0.30    --  107.76  77.00  30.00   88
  4  \w     89.00 172.00   0.50    0.30    --  107.76  77.00  60.00  166
  5  \w     77.00 112.00   0.50    0.30    --  107.76  77.00  30.00   70
  6  \w     79.00 110.00   0.50    0.30    --  107.76  77.00   0.00   62
  7  \w    113.00 177.00   0.50    0.30    --  107.76  77.00   0.00  128
  8  \w     78.00 176.00   0.50    0.30    --  107.76  77.00 120.00  196
  9  \w     77.00 178.00   0.50    0.30    --  107.76  77.00 150.00  202
 10  \w     87.00 147.00   0.50    0.30    --  107.76  61.00  30.00  120
 11  \w     90.00 177.00   0.50    0.30    --  107.76  61.00  90.00  174
 12  \w     78.00 148.00   0.50    0.30    --  107.76  77.00 -90.00  140
 13  \w     83.00 113.00   0.50    0.30    --  107.76  61.00-150.00   60
 14  \w    130.00 160.00   0.50    0.30    --  107.76  61.00-150.00   60
 15  \w     84.00 143.00   0.50    0.30    --  107.76  61.00 -90.00  118
 16  \w     32.00  60.00   0.50    0.08    --   43.10  38.00 -90.00   56
 17  \w     81.00 178.00   0.50    0.30    --  107.76  30.00-120.00  194
 18  \w     87.00 177.00   0.50    0.30    --  107.76  45.00 -30.00  180
 19  \w    113.00 156.00   0.50    0.30    --  107.76  45.00 150.00   86
 20  \w     83.00 108.00   0.50    0.30    --  107.76  45.00 150.00   50
 21  \w     21.00  90.00   0.50    0.08    --   43.10  38.00 150.00  138
 22  \w    108.00 161.00   0.50    0.30    --  107.76 110.00 -33.00  106
 23  \w     29.00  64.00   0.50    0.08    --   62.00  83.00 -60.68   70
 24  \w     19.00  45.00   0.50    0.08    --   54.00  88.00-117.04   52
 25  \w     16.00  41.00   0.50    0.08    --   54.00  92.00 -31.45   50
 26  \w     29.00  55.00   0.50    0.08    --   62.00  83.00 -17.93   52
 27  \w     30.00  64.00   0.50    0.08    --   62.00  81.00-103.73   68
 28  \w     17.00  42.00   0.50    0.08    --   54.00  90.00 159.74   50
 29  \w     29.00  56.00   0.50    0.08    --   62.00  82.00 169.59   54
 30  \w     64.00  91.00   0.50    0.08    --   62.00  82.00 169.59   54
 31  \w     42.00  67.00   0.50    0.08    --   74.00  81.00 116.75   50
 32  \w     15.00  41.00   0.50    0.08    --   50.00  88.00  84.62   52
 33  \w      7.00  32.00   0.50    0.08    --   42.00  89.00 171.89   50
 34  \w      2.00  27.00   0.50    0.08    --   42.00  97.00 129.09   50
 35  \w     -4.00  24.00   0.50    0.08    --   38.00 100.00 -36.00   56
 36  \w    -66.00  31.00   0.50    0.08    --  -43.10  57.00  60.00  194
 37  \w    -49.00 -24.00   0.50    0.30    --  -90.25 110.00 -33.00   50
 38  \w    -84.00 -31.00   0.50    0.08    --  -43.10 110.00 -33.00  106
 39  \w    -26.00   2.00   0.50    0.08    --  -43.10 110.00 -33.00   56
 40  \w     78.00 105.00   0.50    0.30    --  107.76 -77.00 -30.00   54
 41  \w     42.00  69.00   0.50    0.30    --  107.76 -61.00 -90.00   54
 42  \w     34.00  90.00   0.50    0.30    --  107.76 -77.00-150.00  112
 43  \w     35.00  69.00   0.50    0.30    --  107.76 -77.00 -30.00   68
 44  \w     35.00  70.00   0.50    0.30    --  107.76 -61.00  30.00   70
 45  \w     34.00  65.00   0.50    0.30    --  107.76 -61.00  90.00   62
 46  \w     34.00  70.00   0.50    0.30    --  107.76 -61.00 150.00   72
 47  \w     36.00  99.00   0.50    0.08    --   43.10-125.00 150.00  126
 48  \w     34.00 113.00   0.50    0.30    --  107.76-125.00 120.00  158
 49  \w     90.00 116.00   0.50    0.30    --  107.76-125.00 -30.00   52
 50  \w     34.00 109.00   0.50    0.30    --  107.76-125.00-180.00  150
 51  \w     34.00 117.00   0.50    0.30    --  107.76-125.00-150.00  166
 52  \w     21.00  63.00   0.50    0.08    --   43.10-110.00-128.00   84
 53  \w     37.00  68.00   0.50    0.30    --  107.76-125.00 -30.00   62
 54  \w     67.00 111.00   0.50    0.30    --  107.76-110.00-128.00   88
 55  \w     49.00 108.00   0.50    0.30    --  107.76 -94.00 -90.00  118
 56  \w     44.00 103.00   0.50    0.30    --  107.76 -94.00 -30.00  118
 57  \w     44.00  80.00   0.50    0.30    --  107.76 -94.00  60.00   72
 58  \w     35.00  78.00   0.50    0.30    --  107.76-125.00  60.00   86
 59  \w     87.00 114.00   0.50    0.30    --  107.76-125.00  60.00   54
 60  \w     69.00  94.00   0.50    0.30    --  107.76-125.00 150.00   50
 61  \w    -75.00 -20.00   0.50    0.08    --  -43.10 -57.00 -60.00  110
 62  \w    -83.00 -20.00   0.50    0.08    --  -43.10 -57.00  30.00  126
 63  \w    -57.00 -20.00   0.50    0.08    --  -43.10 -57.00  90.00   74
 64  \w    -59.00 -19.00   0.50    0.08    --  -43.10 -38.00  60.00   80
 65  \w   -121.00 -76.00   0.50    0.08    --  -43.10 -38.00  60.00   90
 66  \w   -116.00 -86.00   0.50    0.08    --  -43.10 -57.00  30.00   60
 67  \w   -117.00 -78.00   0.50    0.08    --  -43.10 -57.00 -60.00   78
 68  \w   -132.00-105.00   0.50    0.30    --  -90.25 -69.00   1.81   54
 69  \w   -134.00-108.00   0.50    0.08    --  -66.00 -79.00 -47.78   52
 70  \w    -66.00 -34.00   0.50    0.08    --  -66.00 -79.00 -47.78   64
 71  \w   -120.00 -95.00   0.50    0.08    --  -66.00 -79.00  26.57   50
 72  \w    -78.00 -50.00   0.50    0.30    --  -82.00 -79.00  78.72   56
 73  \w    -74.00 -34.00   0.50    0.08    --  -66.00 -79.00  26.57   80
 74  \w    -73.00 -47.00   0.50    0.30    --  -78.00 -78.00  54.61   52
 75  \w    -73.00 -46.00   0.50    0.30    --  -78.00 -79.00 146.18   54
 76  \w    -69.00 -43.00   0.50    0.30    --  -74.00 -78.00 159.28   52
 77  \w   -102.00 -58.00   0.50    0.30    --  -90.25 -80.00 167.75   88
 78  \w   -138.00-105.00   0.50    0.30    --  -90.25 -80.00 167.75   66
 79  \w   -165.00 -97.00   0.50    0.30    --  -90.25 -77.00  30.00  136
 80  \w    -67.00 -35.00   0.50    0.08    --  -66.00 -78.00  -8.18   64
 81  \w    -85.00 -59.00   0.50    0.30    --  -90.25 -77.00  50.02   52
 82  \w    -84.00 -59.00   0.50    0.30    --  -90.25 -77.00   0.00   50
 83  \w    -89.00 -59.00   0.50    0.30    --  -90.25 -77.00  30.00   60
 84  \w   -140.00-101.00   0.50    0.30    --  -90.25 -77.00   0.00   78
 85  \w   -149.00-123.00   0.50    0.30    --  -90.25 -77.00  50.02   52
 86  \w   -155.00-129.00   0.50    0.30    --  -82.00 -76.00 116.52   52
 87  \w    -73.00 -48.00   0.50    0.30    --  -78.00 -76.00  29.56   50
 88  \w   -141.00-115.00   0.50    0.08    --  -66.00 -78.00  -8.18   52
 89  \w   -155.00-129.00   0.50    0.30    --  -90.25 -76.00  -7.79   52
 90  \w   -141.00 -61.00   0.50    0.30    --  -90.25 -77.00-120.00  160
 91  \w    -86.00 -59.00   0.50    0.30    --  -90.25 -77.00-180.00   54
 92  \w    -71.00 -44.00   0.50    0.30    --  -74.00 -76.00-138.37   54
 93  \w    -96.00 -60.00   0.50    0.30    --  -90.25 -75.00-107.76   72
 94  \w    -88.00 -55.00   0.50    0.30    --  -86.00 -76.00 -93.71   66
 95  \w   -102.00 -60.00   0.50    0.30    --  -90.25 -75.00 -88.83   84
 96  \w    -94.00 -64.00   0.50    0.30    --  -90.25 -75.00-139.99   60
 97  \w   -157.00-130.00   0.50    0.30    --  -90.25 -75.00-107.76   54
 98  \w   -104.00 -60.00   0.50    0.30    --  -90.25 -74.00 -48.30   88
 99  \w    -70.00 -45.00   0.50    0.30    --  -74.00 -71.00 -50.16   50
100  \w   -100.00 -60.00   0.50    0.30    --  -90.25 -76.00  -7.79   80
101  \w   -108.00 -61.00   0.50    0.30    --  -90.25 -75.00  80.24   94
102  \w    -77.00 -51.00   0.50    0.30    --  -82.00 -76.00 116.52   52
103  \w    -87.00 -62.00   0.50    0.30    --  -90.25 -71.00  57.85   50
104  \w    -71.00 -46.00   0.50    0.30    --  -74.00 -70.00 -20.52   50
105  \w    -89.00 -63.00   0.50    0.30    --  -90.25 -69.00   1.81   52
106  \w   -155.00-128.00   0.50    0.30    --  -90.25 -74.00 -48.30   54
107  \w    -99.00 -70.00   0.50    0.08    --  -43.10-125.00  30.00   58
108  \w   -148.00-123.00   0.50    0.30    --  -90.25-110.00-128.00   50
109  \w    -74.00 -48.00   0.50    0.30    --  -82.00 -83.00-141.40   52
110  \w    -73.00 -48.00   0.50    0.30    --  -82.00 -83.00-162.68   50
111  \w    -77.00 -48.00   0.50    0.30    --  -82.00 -83.00 -47.55   58
112  \w   -132.00 -57.00   0.50    0.30    --  -90.25 -83.00 -12.14  150
113  \w    -57.00 -32.00   0.50    0.08    --  -66.00 -83.00  70.43   50
114  \w    -82.00 -57.00   0.50    0.30    --  -90.25 -82.00 110.49   50
115  \w   -152.00-100.00   0.50    0.30    --  -90.25 -81.00 144.18  104
116  \w   -152.00-114.00   0.50    0.30    --  -90.25 -82.00 110.49   76
117  \w   -130.00-105.00   0.50    0.08    --  -62.00 -81.00  97.58   50
118  \w    -82.00 -57.00   0.50    0.30    --  -90.25 -81.00 144.18   50
119  \w    -54.00 -29.00   0.50    0.08    --  -62.00 -81.00  97.58   50
120  \w    -82.00 -57.00   0.50    0.30    --  -90.25 -81.00 -64.39   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1262204000
_diffrn_orient_matrix_UB_12      -0.0898944000
_diffrn_orient_matrix_UB_13      -0.0102290000
_diffrn_orient_matrix_UB_21      0.0333132000
_diffrn_orient_matrix_UB_22      -0.0018045000
_diffrn_orient_matrix_UB_23      0.0671970000
_diffrn_orient_matrix_UB_31      -0.0862269000
_diffrn_orient_matrix_UB_32      0.0903039000
_diffrn_orient_matrix_UB_33      0.0149355000
_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  0.1429
_diffrn_reflns_av_unetI/netI     0.0617
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            67098
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        62.495
_diffrn_reflns_theta_max         62.495
_diffrn_reflns_theta_min         3.656
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.337
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.074
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
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            'clear light brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.602
_exptl_crystal_description       plate
_exptl_crystal_F_000             1352
_exptl_crystal_size_max          0.494
_exptl_crystal_size_mid          0.247
_exptl_crystal_size_min          0.047
_refine_diff_density_max         1.887
_refine_diff_density_min         -1.324
_refine_diff_density_rms         0.147
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     703
_refine_ls_number_reflns         8941
_refine_ls_number_restraints     99
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0596
_refine_ls_R_factor_gt           0.0550
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0819P)^2^+10.9656P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1463
_refine_ls_wR_factor_ref         0.1489
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8386
_reflns_number_total             8941
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc01491f2.cif
_cod_data_source_block           1
_cod_depositor_comments
'Adding full bibliography for 1568944--1568946.cif.'
_cod_database_code               1568944
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C63 H52Cl2OOsP3CH2Cl2BF4'
_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 O(H) groups
2. Uiso/Uaniso restraints and constraints
C01O \\sim C01V \\sim C024 \\sim C023 \\sim C025 \\sim C01X: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
Uanis(Cl00) \\sim Ueq, Uanis(C026) \\sim Ueq, Uanis(Cl07) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
3. Rigid body (RIGU) restrains
 Cl00, C026, Cl07
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C01O, C01V, C024, C023, C025, C01X
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Others
 Sof(H3B)=Sof(O01Q)=Sof(H01Q)=1-FVAR(1)
 Sof(H3A)=Sof(O1)=Sof(H1A)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C3(H3B), C3(H3A)
5.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C026(H02A,H02B)
5.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C00E(H00E), C00F(H00F), C00H(H00H), C00I(H00I), C00J(H00J),
 C00O(H00O), C00P(H00P), C00R(H00R), C00T(H00T), C00U(H00U), C00V(H00V),
 C00W(H00W), C00X(H00X), C00Y(H00Y), C00Z(H00Z), C010(H010), C011(H011),
 C012(H012), C015(H015), C7(H7), C019(H019), C01A(H01A), C01B(H01B), C01C(H01C),
  C6(H6), C01E(H01E), C01F(H01F), C01I(H01I), C01J(H01J), C01K(H01K),
 C01L(H01L), C01M(H01M), C01V(H01V), C024(H024), C023(H023), C025(H025),
 C01X(H01X), C01P(H01P), C01R(H01R), C01S(H01S), C01T(H01T), C01U(H01U),
 C01W(H01W), C01Y(H01Y), C01Z(H01Z), C020(H020), C022(H022)
5.d Fitted hexagon refined as free rotating group:
 C01O(C01V,C024,C023,C025,C01X)
5.e Idealised tetrahedral OH refined as rotating group:
 O01Q(H01Q), O1(H1A)
;
_shelx_res_checksum              13228
_shelx_hkl_checksum              64283
_shelx_fab_checksum              29876
_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 4.922
_oxdiff_exptl_absorpt_empirical_full_min 0.480