Annulated carbocyclic gallylene and bis-gallylene with two-coordinated Ga(i) atoms.
Merschel, Arne; Heda, Shkelqim; Vishnevskiy, Yury V.; Neumann, Beate; Stammler, Hans-Georg; Ghadwal, Rajendra S.; Chemical science 16 (2025) 2222–2230; doi:10.1039/d4sc06782g

data_1573164
_publ_section_title
;
 Annulated carbocyclic gallylene and bis-gallylene with two-coordinated
 Ga(i) atoms.
;
_journal_issue                   5
_journal_name_full               'Chemical science'
_journal_page_first              2222
_journal_page_last               2230
_journal_paper_doi               10.1039/d4sc06782g
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C33 H17 Ga N2, C33 Ga N2, [+ solvents]'
_chemical_formula_sum            'C73 H86 Ga2 N4'
_chemical_formula_weight         1158.89
_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             2023-05-17
_audit_creation_method
;
Olex2 1.5-ac5-024
(compiled 2022.04.12 svn.rca3783a0 for Rigaku Oxford Diffraction, GUI svn.r6498)
;
_audit_update_record
;
2024-02-23 deposited with the CCDC.	2024-11-14 downloaded from the CCDC.
;
_cell_angle_alpha                80.487(4)
_cell_angle_beta                 79.632(4)
_cell_angle_gamma                85.811(4)
_cell_formula_units_Z            2
_cell_length_a                   12.7988(7)
_cell_length_b                   14.6243(7)
_cell_length_c                   18.1282(9)
_cell_measurement_reflns_used    13212
_cell_measurement_temperature    220.0(1)
_cell_measurement_theta_max      23.4630
_cell_measurement_theta_min      3.8950
_cell_volume                     3288.5(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-024 (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      220.0(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1773
_diffrn_detector_type            Atlas
_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    -75.00  15.00   1.00   55.50    --   -6.77 -61.00  49.00   90
  2  \w      0.00  62.00   1.00   55.50    --   -6.77  61.00-171.00   62
  3  \w     14.00  76.00   1.00   55.50    --    7.16  61.00-171.00   62
  4  \w    -61.00  33.00   1.00   55.50    --    7.16 -61.00  49.00   94
  5  \w    -80.00 -20.00   1.00   55.50    --   -6.77 153.00 130.72   60
  6  \w    -77.00  13.00   1.00   55.50    --   -6.77 -38.00-120.00   90
  7  \w    -40.00  10.00   1.00   55.50    --   -6.77 -77.00   0.00   50
  8  \w    -80.00 -31.00   1.00   55.50    --   -6.77 153.00  36.12   49
  9  \w    -80.00 -20.00   1.00   55.50    --   -6.77 153.00-110.46   60
 10  \w     20.00  45.00   1.00   55.50    --    7.16-153.00 -12.56   25
 11  \w     55.00  80.00   1.00   55.50    --    7.16-153.00 -12.56   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset/far, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0203268000
_diffrn_orient_matrix_UB_12      -0.0368147000
_diffrn_orient_matrix_UB_13      -0.0134082000
_diffrn_orient_matrix_UB_21      -0.0485261000
_diffrn_orient_matrix_UB_22      0.0044231000
_diffrn_orient_matrix_UB_23      0.0254097000
_diffrn_orient_matrix_UB_31      -0.0203098000
_diffrn_orient_matrix_UB_32      0.0323791000
_diffrn_orient_matrix_UB_33      -0.0282084000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0486
_diffrn_reflns_av_unetI/netI     0.0402
_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       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            64721
_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         25.682
_diffrn_reflns_theta_min         3.217
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.862
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.530
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.90a (Rigaku Oxford Diffraction, 2023)
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            'dull light violet'
_exptl_crystal_colour_lustre     dull
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.170
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1228
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.953
_refine_diff_density_min         -0.717
_refine_diff_density_rms         0.056
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     897
_refine_ls_number_reflns         12461
_refine_ls_number_restraints     648
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.1001
_refine_ls_R_factor_gt           0.0645
_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^)+(0.0703P)^2^+4.1695P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1573
_refine_ls_wR_factor_ref         0.1789
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8211
_reflns_number_total             12461
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc06782g2.cif
_cod_data_source_block           8
_cod_depositor_comments
'Adding full bibliography for 1573160--1573166.cif.'
_cod_database_code               1573164
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C11 H10 N O'
_shelx_estimated_absorpt_t_max   0.882
_shelx_estimated_absorpt_t_min   0.794
_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. Uiso/Uaniso restraints and constraints
C55 \\sim C56 \\sim C57 \\sim C58 \\sim C59 \\sim C60 \\sim C61 \\sim C62 \\sim
C63 \\sim C64 \\sim C65 \\sim C66: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C55 \\sim C56B \\sim C57B \\sim C58B \\sim C59B \\sim C60B \\sim C61B \\sim
C62B \\sim C63B \\sim C64B \\sim C65B \\sim C66B: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 2A
C43 \\sim C45 \\sim C46 \\sim C47 \\sim C49 \\sim C50 \\sim C51 \\sim C52 \\sim
C53 \\sim C54 \\sim C44B \\sim C48B: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C43 \\sim C44B \\sim C45B \\sim C46B \\sim C47B \\sim C48B \\sim C49B \\sim
C50B \\sim C51B \\sim C52B \\sim C53B \\sim C54B: within 2A with sigma of 0.001
and sigma for terminal atoms of 0.002 within 2A
C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim C48 \\sim C49 \\sim C50 \\sim
C51 \\sim C52 \\sim C53 \\sim C54: within 2A with sigma of 0.001 and sigma for
terminal atoms of 0.002 within 2A
Uanis(C48) = Uanis(C48B)
Uanis(C44) = Uanis(C44B)
Uanis(Ga1B) = Uanis(Ga1)
3. Rigid body (RIGU) restrains
 C55, C56, C57, C58, C59, C60, C61, C62, C63, C64, C65, C66
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C55, C56B, C57B, C58B, C59B, C60B, C61B, C62B, C63B, C64B, C65B, C66B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C43, C45, C46, C47, C49, C50, C51, C52, C53, C54, C44B, C48B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C43, C44, C45, C46, C47, C48, C49, C50, C51, C52, C53, C54
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C43, C44B, C45B, C46B, C47B, C48B, C49B, C50B, C51B, C52B, C53B, C54B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 Ga1, Ga1B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Others
 Sof(H40A)=Sof(Ga2B)=Sof(C38B)=Sof(H38B)=Sof(C39B)=Sof(H39B)=Sof(C41B)=
 Sof(H41B)=Sof(C42B)=Sof(H42B)=Sof(C44B)=Sof(C45B)=Sof(H45B)=Sof(C46B)=
 Sof(H46B)=Sof(C47B)=Sof(H47B)=Sof(C48B)=Sof(C49B)=Sof(H49B)=Sof(C50B)=
 Sof(H50D)=Sof(H50E)=Sof(H50F)=Sof(C51B)=Sof(H51D)=Sof(H51E)=Sof(H51F)=
 Sof(C52B)=Sof(H52B)=Sof(C53B)=Sof(H53D)=Sof(H53E)=Sof(H53F)=Sof(C54B)=
 Sof(H54D)=Sof(H54E)=Sof(H54F)=Sof(C56B)=Sof(C57B)=Sof(H57B)=Sof(C58B)=
 Sof(H58B)=Sof(C59B)=Sof(H59B)=Sof(C60B)=Sof(C61B)=Sof(H61B)=Sof(C62B)=
 Sof(H62D)=Sof(H62E)=Sof(H62F)=Sof(C63B)=Sof(H63D)=Sof(H63E)=Sof(H63F)=
 Sof(C64B)=Sof(H64B)=Sof(C65B)=Sof(H65D)=Sof(H65E)=Sof(H65F)=Sof(C66B)=
 Sof(H66D)=Sof(H66E)=Sof(H66F)=1-FVAR(1)
 Sof(H40)=Sof(Ga2)=Sof(C38)=Sof(H38)=Sof(C39)=Sof(H39)=Sof(C41)=Sof(H41)=
 Sof(C42)=Sof(H42)=Sof(C44)=Sof(C45)=Sof(H45)=Sof(C46)=Sof(H46)=Sof(C47)=
 Sof(H47)=Sof(C48)=Sof(C49)=Sof(H49)=Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(H50C)=
 Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(H51C)=Sof(C52)=Sof(H52)=Sof(C53)=Sof(H53A)=
 Sof(H53B)=Sof(H53C)=Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(H54C)=Sof(C56)=Sof(C57)=
 Sof(H57)=Sof(C58)=Sof(H58)=Sof(C59)=Sof(H59)=Sof(C60)=Sof(C61)=Sof(H61)=
 Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(H62C)=Sof(C63)=Sof(H63A)=Sof(H63B)=Sof(H63C)=
 Sof(C64)=Sof(H64)=Sof(C65)=Sof(H65A)=Sof(H65B)=Sof(H65C)=Sof(C66)=Sof(H66A)=
 Sof(H66B)=Sof(H66C)=FVAR(1)
 Sof(Ga1B)=1-FVAR(2)
 Sof(Ga1)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C16(H16), C19(H19), C28(H28), C31(H31), C49(H49), C52(H52), C61(H61),
 C64(H64), C49B(H49B), C52B(H52B), C61B(H61B), C64B(H64B)
5.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C8(H8), C9(H9), C12(H12), C13(H13), C14(H14),
 C24(H24), C25(H25), C26(H26), C40(H40), C40(H40A), C38(H38), C39(H39),
 C41(H41), C42(H42), C45(H45), C46(H46), C47(H47), C57(H57), C58(H58), C59(H59),
  C38B(H38B), C39B(H39B), C41B(H41B), C42B(H42B), C45B(H45B), C46B(H46B),
 C47B(H47B), C57B(H57B), C58B(H58B), C59B(H59B)
5.c Fitted hexagon refined as free rotating group:
 C44(C45,C46,C47,C48,C43)
5.d Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C20(H20A,H20B,H20C), C21(H21A,H21B,
 H21C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C32(H32A,H32B,H32C), C33(H33A,
 H33B,H33C), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C), C53(H53A,H53B,H53C),
 C54(H54A,H54B,H54C), C62(H62A,H62B,H62C), C63(H63A,H63B,H63C), C65(H65A,H65B,
 H65C), C66(H66A,H66B,H66C), C50B(H50D,H50E,H50F), C51B(H51D,H51E,H51F),
 C53B(H53D,H53E,H53F), C54B(H54D,H54E,H54F), C62B(H62D,H62E,H62F), C63B(H63D,
 H63E,H63F), C65B(H65D,H65E,H65F), C66B(H66D,H66E,H66F)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              56146
_shelx_hkl_checksum              6911
_shelx_fab_checksum              27476
_olex2_date_sample_data_collection 2023-05-11
_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 1.205
_oxdiff_exptl_absorpt_empirical_full_min 0.881