<i>In crystallo</i> homolytic cleavage of a terminal lanthanum(III)-methyl bond by Cu Kα X-radiation forms a La(II) complex.
Stennett, Cary R.; Luevano, Makayla R.; Ziller, Joseph W.; Evans, William J.; Chemical communications (Cambridge, England)  (2025) –; doi:10.1039/d5cc04945h

data_7135306
_publ_section_title
;
 <i>In crystallo</i> homolytic cleavage of a terminal
 lanthanum(III)-methyl bond by Cu K&#x3b1; X-radiation forms a La(II)
 complex.
;
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_paper_doi               10.1039/d5cc04945h
_journal_year                    2025
_chemical_formula_moiety         'C72.53 H99.59 La S2, C3 H7'
_chemical_formula_sum            'C75.53 H106.59 La S2'
_chemical_formula_weight         1217.58
_chemical_melting_point          ?
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Oxygen-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-10-15
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)

Dolomanov, O.V., Bourhis, L.J., Gildea, R.J, Howard, J.A.K. & Puschmann, H.
 (2009), J. Appl. Cryst. 42, 339-341.

Sheldrick, G.M. (2008). Acta Cryst. A64, 112-122.

Sheldrick, G.M. (2015). Acta Cryst. A71, 3-8.
;
_audit_update_record
;
2025-10-15 deposited with the CCDC.	2025-11-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.017(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   21.0895(8)
_cell_length_b                   18.2926(6)
_cell_length_c                   36.1914(16)
_cell_measurement_reflns_used    9529
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      77.21
_cell_measurement_theta_min      2.44
_cell_volume                     13953.3(9)
_computing_cell_refinement       'Bruker SAINT 8.40b, 2013'
_computing_data_collection       'Bruker APEX6 2024.9-1, 2024'
_computing_data_reduction        'Bruker SAINT 8.40b, 2013'
_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, 2014)'
_computing_structure_solution    'Bruker SHELXTL 2014/7 (XT)'
_diffrn_ambient_temperature      100.00
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device_type  'Bruker PHOTON III'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0686
_diffrn_reflns_av_unetI/netI     0.0348
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       45
_diffrn_reflns_limit_l_min       -45
_diffrn_reflns_number            139288
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         77.754
_diffrn_reflns_theta_min         2.443
_diffrn_source                   'Bruker IuS DIAMOND II'
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    5.567
_exptl_absorpt_correction_T_max  0.5895
_exptl_absorpt_correction_T_min  0.4229
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1313 before and 0.0949 after correction.
The Ratio of minimum to maximum transmission is 0.7174.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.159
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             5190
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: hexane'
_exptl_crystal_size_max          0.155
_exptl_crystal_size_mid          0.151
_exptl_crystal_size_min          0.138
_refine_diff_density_max         0.534
_refine_diff_density_min         -0.722
_refine_diff_density_rms         0.081
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.201
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     918
_refine_ls_number_reflns         14812
_refine_ls_number_restraints     210
_refine_ls_restrained_S_all      1.203
_refine_ls_R_factor_all          0.0720
_refine_ls_R_factor_gt           0.0699
_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^)+(0.0290P)^2^+72.5558P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1628
_refine_ls_wR_factor_ref         0.1637
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14055
_reflns_number_total             14812
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc04945h2.cif
_cod_data_source_block           crs304
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_chemical_melting_point' value 'not measured' was changed
to '?' -- the value is undefined or not given.

data item '_exptl_crystal_density_meas' value 'not measured' was
changed to '?' -- the value is perceived as not measured.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 
;
_cod_original_sg_symbol_H-M      C2/c
_cod_database_code               7135306
_shelx_estimated_absorpt_t_max   0.514
_shelx_estimated_absorpt_t_min   0.479
_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, All C(H,H,H,H,H,H) groups
2. Restrained distances
 C75-C74A \\sim C75A-C74 \\sim C76-C75A \\sim C76-C75
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C18 \\sim C18A \\sim C19 \\sim C83: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01 within 2A
C13 \\sim C19A \\sim C20 \\sim C20A \\sim C21 \\sim C21A \\sim C22: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C45 \\sim C50 \\sim C51 \\sim C52 \\sim C79 \\sim C80 \\sim C81: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C74 \\sim C74A \\sim C75 \\sim C75A \\sim C76: within 2A with sigma of 0.005
and sigma for terminal atoms of 0.01 within 2A
4. Others
 Fixed Sof: La1(0.53) La1A(0.47) S1(0.53) S1A(0.47) S2(0.53) S2A(0.47)
 C1(0.53) H1A(0.53) H1B(0.53) H1C(0.53) C8A(0.47) C9(0.53) C9A(0.47) H9A(0.47)
 C10(0.53) H10(0.53) C14(0.53) H14(0.53) C15(0.53) H15A(0.53) H15B(0.53)
 H15C(0.53) C16(0.53) H16A(0.53) H16B(0.53) H16C(0.53) H17(0.55) H17A(0.45)
 C18(0.55) H18A(0.55) H18B(0.55) H18C(0.55) C18A(0.45) H18D(0.45) H18E(0.45)
 H18F(0.45) C19(0.55) H19A(0.55) H19B(0.55) H19C(0.55) C19A(0.45) H19D(0.45)
 C20(0.55) H20(0.55) C20A(0.45) H20A(0.45) H20B(0.45) H20C(0.45) C21(0.55)
 H21A(0.55) H21B(0.55) H21C(0.55) C21A(0.45) H21D(0.45) H21E(0.45) H21F(0.45)
 C22(0.55) H22A(0.55) H22B(0.55) H22C(0.55) C50(0.55) H50(0.55) C51(0.55)
 H51A(0.55) H51B(0.55) H51C(0.55) C52(0.55) H52A(0.55) H52B(0.55) H52C(0.55)
 H53(0.75) H53A(0.25) C54(0.75) H54A(0.75) H54B(0.75) H54C(0.75) C54A(0.25)
 H54D(0.25) H54E(0.25) H54F(0.25) C74(0.75) H74A(0.75) H74B(0.75) C74A(0.25)
 H74C(0.25) H74D(0.25) C75(0.6) H75A(0.6) H75B(0.6) C75A(0.4) H75C(0.4)
 H75D(0.4) H76A(0.6) H76B(0.6) H76C(0.6) H76D(0.4) H76E(0.4) H76F(0.4)
 C77(0.47) H77A(0.47) H77B(0.47) H77C(0.47) C78(0.47) H78A(0.47) H78B(0.47)
 H78C(0.47) C79(0.45) H79(0.45) C80(0.45) H80A(0.45) H80B(0.45) H80C(0.45)
 C81(0.45) H81A(0.45) H81B(0.45) H81C(0.45) C82(0.47) H82(0.47) C83(0.45)
 H83A(0.45) H83B(0.45) H83C(0.45)
5.a Ternary CH refined with riding coordinates:
 C9A(H9A), C14(H14), C17(H17), C17(H17A), C19A(H19D), C20(H20), C29(H29),
 C32(H32), C35(H35), C50(H50), C53(H53), C53(H53A), C56(H56), C65(H65),
 C68(H68), C71(H71), C79(H79), C82(H82)
5.b Secondary CH2 refined with riding coordinates:
 C74(H74A,H74B), C74A(H74C,H74D), C75(H75A,H75B), C75A(H75C,H75D)
5.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C10(H10), C12(H12), C25(H25), C27(H27), C40(H40),
 C41(H41), C42(H42), C46(H46), C48(H48), C61(H61), C63(H63)
5.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C18(H18A,H18B,
 H18C), C18A(H18D,H18E,H18F), C19(H19A,H19B,H19C), C20A(H20A,H20B,H20C),
 C21(H21A,H21B,H21C), C21A(H21D,H21E,H21F), C22(H22A,H22B,H22C), C30(H30A,H30B,
 H30C), C31(H31A,H31B,H31C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C36(H36A,
 H36B,H36C), C37(H37A,H37B,H37C), C51(H51A,H51B,H51C), C52(H52A,H52B,H52C),
 C54(H54A,H54B,H54C), C54A(H54D,H54E,H54F), C55(H55A,H55B,H55C), C57(H57A,H57B,
 H57C), C58(H58A,H58B,H58C), C66(H66A,H66B,H66C), C67(H67A,H67B,H67C), C69(H69A,
 H69B,H69C), C70(H70A,H70B,H70C), C72(H72A,H72B,H72C), C73(H73A,H73B,H73C),
 C76(H76A,H76B,H76C), C76(H76D,H76E,H76F), C77(H77A,H77B,H77C), C78(H78A,H78B,
 H78C), C80(H80A,H80B,H80C), C81(H81A,H81B,H81C), C83(H83A,H83B,H83C)
;
_shelx_res_checksum              70567
_shelx_hkl_checksum              88790
_olex2_submission_special_instructions 'No special instructions were received'