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_1575299
_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         'C68 H82 Ga2 N2 P2, C7 H8'
_chemical_formula_sum            'C75 H90 Ga2 N2 P2'
_chemical_formula_weight         1220.86
_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
_audit_creation_date             2022-08-24
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-09-16 deposited with the CCDC.	2025-04-10 downloaded from the CCDC.
;
_cell_angle_alpha                91.413(2)
_cell_angle_beta                 96.822(2)
_cell_angle_gamma                96.004(2)
_cell_formula_units_Z            2
_cell_length_a                   12.0391(3)
_cell_length_b                   12.1205(3)
_cell_length_c                   22.5729(6)
_cell_measurement_reflns_used    13402
_cell_measurement_temperature    120.00(10)
_cell_measurement_theta_max      28.1330
_cell_measurement_theta_min      3.6010
_cell_volume                     3250.28(14)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_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      120.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0521
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -41.00  51.00   1.00   30.00    --  -16.47  69.00 -76.00   92
  2  \w    -84.00   8.00   1.00   30.00    --  -16.47 -69.00 151.00   92
  3  \w    -45.00  39.00   1.00   30.00    --  -16.47  77.00 150.00   84
  4  \w    -39.00  12.00   1.00   30.00    --  -16.47 -77.00 -90.00   51
  5  \w    -90.00 -39.00   1.00   30.00    --  -16.47-178.00 -60.00   51
  6  \w    -39.00  12.00   1.00   30.00    --  -16.47 -77.00  90.00   51
  7  \w    -45.00  39.00   1.00   30.00    --  -16.47  77.00  60.00   84
  8  \w     -4.00  89.00   1.00   30.00    --   18.18  38.00 -90.00   93
  9  \w      0.00  87.00   1.00   30.00    --   18.18  57.00  60.00   87
 10  \w    -20.00   7.00   1.00   30.00    --   18.18 -99.00-150.00   27
 11  \w      0.00  87.00   1.00   30.00    --   18.18  57.00 -30.00   87
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku Oxford Diffraction XCalibur'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0221399000
_diffrn_orient_matrix_UB_12      -0.0391105000
_diffrn_orient_matrix_UB_13      0.0197485000
_diffrn_orient_matrix_UB_21      0.0385198000
_diffrn_orient_matrix_UB_22      0.0428403000
_diffrn_orient_matrix_UB_23      0.0150108000
_diffrn_orient_matrix_UB_31      -0.0398580000
_diffrn_orient_matrix_UB_32      0.0101245000
_diffrn_orient_matrix_UB_33      0.0196876000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0565
_diffrn_reflns_av_unetI/netI     0.0599
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            53072
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.371
_diffrn_reflns_theta_min         3.383
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.922
_exptl_absorpt_correction_T_max  0.622
_exptl_absorpt_correction_T_min  0.061
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear red'
_exptl_crystal_density_diffrn    1.247
_exptl_crystal_description       needle
_exptl_crystal_F_000             1292
_exptl_crystal_size_max          0.522
_exptl_crystal_size_mid          0.091
_exptl_crystal_size_min          0.071
_refine_diff_density_max         0.611
_refine_diff_density_min         -0.540
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     805
_refine_ls_number_reflns         13265
_refine_ls_number_restraints     272
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0690
_refine_ls_R_factor_gt           0.0485
_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^)+(0.0450P)^2^+1.8074P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1008
_refine_ls_wR_factor_ref         0.1089
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10443
_reflns_number_total             13265
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc06894g3.cif
_cod_data_source_block           rjs351_tol_autored
_cod_database_code               1575299
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N P Ga'
_chemical_oxdiff_usercomment
'@ 120 K, red-purple needles, toluene recryst crop 2'
_shelx_estimated_absorpt_t_max   0.937
_shelx_estimated_absorpt_t_min   0.645
_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. Shared sites
{C73, C69A}
3. Restrained distances
 C69-C70
 1.51 with sigma of 0.02
 C70-C71 = C70-C75 = C72-C73
 1.39 with sigma of 0.02
 C71-C72 = C73-C74 = C74-C75
 1.38 with sigma of 0.02
 C69A-C70A
 1.51 with sigma of 0.02
 C71A-C72A = C73A-C74A = C74A-C75A
 1.38 with sigma of 0.02
 C70A-C71A = C70A-C75A = C72A-C73A
 1.39 with sigma of 0.02
 C70-C72
 2.42 with sigma of 0.04
 C71-C73
 2.39 with sigma of 0.04
 C70-C74
 2.41 with sigma of 0.04
 C72-C74 = C73-C75
 2.4 with sigma of 0.04
 C69-C71 = C69-C75
 2.52 with sigma of 0.04
 C70A-C72A
 2.42 with sigma of 0.04
 C71A-C73A
 2.39 with sigma of 0.04
 C72A-C74A = C73A-C75A
 2.4 with sigma of 0.04
 C70A-C74A
 2.41 with sigma of 0.04
 C69A-C71A = C69A-C75A
 2.52 with sigma of 0.04
 C70-C71 \\sim C71-C72 \\sim C72-C73 \\sim C73-C74 \\sim C74-C75 \\sim C75-C70
 with sigma of 0.02
 C70-C74 \\sim C70-C72 \\sim C75-C73 \\sim C71-C75 \\sim C72-C74 \\sim C71-C73
 with sigma of 0.04
 C69-C75 \\sim C69-C71
 with sigma of 0.04
 C70A-C71A \\sim C71A-C72A \\sim C72A-C73A \\sim C73A-C74A \\sim C74A-C75A
\\sim C75A-C70A
 with sigma of 0.02
 C69A-C75A \\sim C69A-C71A
 with sigma of 0.04
 C70A-C74A \\sim C70A-C72A \\sim C75A-C73A \\sim C71A-C75A \\sim C72A-C74A
\\sim C71A-C73A
 with sigma of 0.04
4. Restrained planarity
 C69, C70, C71, C72, C73, C74, C75
 with sigma of 0.1
 C69A, C70A, C71A, C72A, C73A, C74A, C75A
 with sigma of 0.1
5. Uiso/Uaniso restraints and constraints
C69 \\sim C70 \\sim C71 \\sim C72 \\sim C73 \\sim C74 \\sim C75: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C69A \\sim C70A \\sim C71A \\sim C72A \\sim C73A \\sim C74A \\sim C75A: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(C73) = Uanis(C69A)
6. Rigid body (RIGU) restrains
 C69, C70, C71, C72, C73, C74, C75
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C69A, C70A, C71A, C72A, C73A, C74A, C75A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Others
 Sof(C69A)=Sof(H69D)=Sof(H69E)=Sof(H69F)=Sof(C70A)=Sof(C71A)=Sof(H71A)=
 Sof(C72A)=Sof(H72A)=Sof(C73A)=Sof(H73A)=Sof(C74A)=Sof(H74A)=Sof(C75A)=
 Sof(H75A)=1-FVAR(1)
 Sof(C69)=Sof(H69A)=Sof(H69B)=Sof(H69C)=Sof(C70)=Sof(C71)=Sof(H71)=Sof(C72)=
 Sof(H72)=Sof(C73)=Sof(H73)=Sof(C74)=Sof(H74)=Sof(C75)=Sof(H75)=FVAR(1)
8.a Ternary CH refined with riding coordinates:
 C2(H2), C5(H5), C36(H36), C39(H39)
8.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C6(H6A,H6B), C37(H37A,H37B), C38(H38A,H38B),
 C40(H40A,H40B)
8.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C19(H19), C21(H21), C28(H28), C30(H30), C44(H44), C53(H53),
 C55(H55), C62(H62), C64(H64), C12(H12), C46(H46), C71(H71), C72(H72), C73(H73),
  C74(H74), C75(H75), C71A(H71A), C72A(H72A), C73A(H73A), C74A(H74A), C75A(H75A)
8.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,
 H25C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C48(H48A,
 H48B,H48C), C57(H57A,H57B,H57C), C58(H58A,H58B,H58C), C59(H59A,H59B,H59C),
 C66(H66A,H66B,H66C), C67(H67A,H67B,H67C), C68(H68A,H68B,H68C), C15(H15A,H15B,
 H15C), C16(H16A,H16B,H16C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C69(H69A,
 H69B,H69C), C69A(H69D,H69E,H69F)
;
_shelx_res_checksum              85600
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 700+'
_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 1.523
_oxdiff_exptl_absorpt_empirical_full_min 0.381