Reversible addition of ethene to gallium(i) monomers and dimers.
Schwamm, Ryan J.; Bhide, Malavika A.; Nichol, Gary S.; Cowley, Michael J.; Chemical science 16 (2025) 13333–13344; doi:10.1039/d4sc06894g

data_1575304
_publ_section_title
;
 Reversible addition of ethene to gallium(i) monomers and dimers.
;
_journal_issue                   29
_journal_name_full               'Chemical science'
_journal_page_first              13333
_journal_page_last               13344
_journal_paper_doi               10.1039/d4sc06894g
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C48 H74 Ga2 N2 P2, 2(B C24 F20), 2(C6 H5 F)'
_chemical_formula_sum            'C108 H84 B2 F42 Ga2 N2 P2'
_chemical_formula_weight         2430.77
_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             2024-12-06
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-03-21 deposited with the CCDC.	2025-04-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 111.413(6)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   13.8266(9)
_cell_length_b                   24.9376(12)
_cell_length_c                   16.2676(7)
_cell_measurement_reflns_used    2694
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      53.7600
_cell_measurement_theta_min      3.4030
_cell_volume                     5221.9(5)
_computing_cell_refinement       'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-beta (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 100'
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.991
_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     -1.00  78.00   0.50    2.00    --   51.52 -99.00 -90.00  158
  2  \w   -124.00 -67.00   0.50    2.00    --  -52.02 -38.00-180.00  114
  3  \w    -72.00 -27.00   0.50    8.00    --  -87.44  77.00  90.00   90
  4  \w   -144.00-118.00   0.50    8.00    --  -87.44 -99.00-120.00   52
  5  \w   -158.00 -92.00   0.50    8.00    --  -87.44 -38.00-120.00  132
  6  \w    -44.00 -19.00   0.50    8.00    --  -87.44  57.00-120.00   50
  7  \w   -147.00 -99.00   0.50    8.00    --  -87.44 -99.00 -30.00   96
  8  \w   -148.00 -99.00   0.50    8.00    --  -87.44 -99.00  30.00   98
  9  \w    108.00 165.00   0.50    8.00    --  102.57  77.00 120.00  114
 10  \w     40.00  66.00   0.50    8.00    --  102.57 -77.00 120.00   52
 11  \w     41.00  92.00   0.50    8.00    --  102.57 -99.00  30.00  102
 12  \w     41.00  75.00   0.50    8.00    --  102.57 -77.00-120.00   68
 13  \w    106.00 149.00   0.50    8.00    --  102.57  77.00  60.00   86
 14  \w     41.00  75.00   0.50    8.00    --  102.57 -77.00 150.00   68
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix-Arc 100'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0982945000
_diffrn_orient_matrix_UB_12      -0.0008561000
_diffrn_orient_matrix_UB_13      -0.0235233000
_diffrn_orient_matrix_UB_21      -0.0396936000
_diffrn_orient_matrix_UB_22      -0.0510121000
_diffrn_orient_matrix_UB_23      -0.0555289000
_diffrn_orient_matrix_UB_31      -0.0556189000
_diffrn_orient_matrix_UB_32      0.0348434000
_diffrn_orient_matrix_UB_33      -0.0818828000
_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  0.1052
_diffrn_reflns_av_unetI/netI     0.0894
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            17135
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        50.432
_diffrn_reflns_theta_max         50.432
_diffrn_reflns_theta_min         3.414
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_current           30
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_diffrn_source_voltage           40
_exptl_absorpt_coefficient_mu    2.039
_exptl_absorpt_correction_T_max  0.92378
_exptl_absorpt_correction_T_min  0.92378
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.143a (Rigaku Oxford Diffraction, 2024)
Spherical absorption correction
using equivalent radius and absorption coefficient.
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.546
_exptl_crystal_description       needle
_exptl_crystal_F_000             2452
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of fluorobenzene and HMDSO  by slow evaporation'
_exptl_crystal_size_max          0.179
_exptl_crystal_size_mid          0.033
_exptl_crystal_size_min          0.021
_exptl_crystal_size_rad          0.026
_refine_diff_density_max         0.764
_refine_diff_density_min         -0.474
_refine_diff_density_rms         0.082
_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     785
_refine_ls_number_reflns         5425
_refine_ls_number_restraints     331
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.1186
_refine_ls_R_factor_gt           0.0754
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1137P)^2^+10.1842P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1922
_refine_ls_wR_factor_ref         0.2159
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3570
_reflns_number_total             5425
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc06894g3.cif
_cod_data_source_block           mc24012
_cod_database_code               1575304
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C104H89Ga2N2P2B2F40
_shelx_estimated_absorpt_t_max   0.958
_shelx_estimated_absorpt_t_min   0.712
_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
 F21-C49
 1.36 with sigma of 0.02
 C49-C54 = C49-C50
 1.38 with sigma of 0.02
 C54-C53 = C53-C52 = C52-C51 = C51-C50
 1.39 with sigma of 0.02
 F21-C54 = F21-C50
 2.35 with sigma of 0.04
 C49-C53 = C49-C51
 2.37 with sigma of 0.04
 C54-C52 = C52-C50
 2.41 with sigma of 0.04
 C53-C51
 2.4 with sigma of 0.04
 C49-C54 \\sim C54-C53 \\sim C53-C52 \\sim C52-C51 \\sim C51-C50 \\sim C50-C49
 with sigma of 0.02
 C49-C53 \\sim C49-C51 \\sim C53-C51 \\sim C54-C50 \\sim C54-C52 \\sim C52-C50
 with sigma of 0.04
 C54-F21 \\sim C50-F21
 with sigma of 0.04
 F21-C49 \\sim F21A-C49A
 with sigma of 0.02
 C49-C50 \\sim C49A-C50A
 with sigma of 0.02
 C49-C54 \\sim C49A-C54A
 with sigma of 0.02
 C50-C51 \\sim C50A-C51A
 with sigma of 0.02
 C51-C52 \\sim C51A-C52A
 with sigma of 0.02
 C52-C53 \\sim C52A-C53A
 with sigma of 0.02
 C53-C54 \\sim C53A-C54A
 with sigma of 0.02
 F21-C50 \\sim F21A-C50A
 with sigma of 0.04
 F21-C54 \\sim F21A-C54A
 with sigma of 0.04
 C49-C51 \\sim C49A-C51A
 with sigma of 0.04
 C49-C53 \\sim C49A-C53A
 with sigma of 0.04
 C50-C52 \\sim C50A-C52A
 with sigma of 0.04
 C50-C54 \\sim C50A-C54A
 with sigma of 0.04
 C51-C53 \\sim C51A-C53A
 with sigma of 0.04
 C52-C54 \\sim C52A-C54A
 with sigma of 0.04
3. Restrained planarity
 F21, C49, C50, C51, C52, C53, C54
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
F21 \\sim C49 \\sim C50 \\sim C51 \\sim C52 \\sim C53 \\sim C54: within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
F21A \\sim C49A \\sim C50A \\sim C51A \\sim C52A \\sim C53A \\sim C54A: within
2A with sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
5. Rigid body (RIGU) restrains
 F21, C49, C50, C51, C52, C53, C54
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 F21A, C49A, C50A, C51A, C52A, C53A, C54A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
6. Others
 Sof(F21A)=Sof(C49A)=Sof(C50A)=Sof(H50A)=Sof(C51A)=Sof(H51A)=Sof(C52A)=
 Sof(H52A)=Sof(C53A)=Sof(H53A)=Sof(C54A)=Sof(H54A)=1-FVAR(1)
 Sof(F21)=Sof(C49)=Sof(C50)=Sof(H50)=Sof(C51)=Sof(H51)=Sof(C52)=Sof(H52)=
 Sof(C53)=Sof(H53)=Sof(C54)=Sof(H54)=FVAR(1)
7.a Ternary CH refined with riding coordinates:
 C3(H3), C6(H6)
7.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C5(H5A,H5B), C7(H7A,H7B)
7.c Aromatic/amide H refined with riding coordinates:
 C18(H18), C20(H20), C50(H50), C51(H51), C52(H52), C53(H53), C54(H54),
 C50A(H50A), C51A(H51A), C52A(H52A), C53A(H53A), C54A(H54A)
7.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C13(H13A,H13B,
 H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C22(H22A,H22B,H22C), C23(H23A,
 H23B,H23C), C24(H24A,H24B,H24C)
;
_shelx_res_checksum              80371
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 1000'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a mitegen tip in Paratone oil.'
_olex2_submission_original_sample_id MAB311
_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 1.592
_oxdiff_exptl_absorpt_empirical_full_min 0.671