<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_7135305
_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         'C72.63 H99.89 La S2, C3 H7'
_chemical_formula_sum            'C75.63 H106.89 La S2'
_chemical_formula_weight         1219.08
_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     direct
_atom_sites_solution_secondary   difmap
_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                 91.790(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   21.1136(7)
_cell_length_b                   18.2758(6)
_cell_length_c                   36.1580(13)
_cell_measurement_reflns_used    9793
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      77.45
_cell_measurement_theta_min      3.67
_cell_volume                     13945.4(8)
_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 1.000
_diffrn_measured_fraction_theta_max 0.997
_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  0.0652
_diffrn_reflns_av_unetI/netI     0.0318
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_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            142504
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         77.522
_diffrn_reflns_theta_min         2.445
_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    5.571
_exptl_absorpt_correction_T_max  0.6577
_exptl_absorpt_correction_T_min  0.4861
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1293 before and 0.0934 after correction.
The Ratio of minimum to maximum transmission is 0.7391.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.161
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             5197
_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         0.461
_refine_diff_density_min         -0.723
_refine_diff_density_rms         0.075
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.225
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     908
_refine_ls_number_reflns         14804
_refine_ls_number_restraints     189
_refine_ls_restrained_S_all      1.224
_refine_ls_R_factor_all          0.0605
_refine_ls_R_factor_gt           0.0592
_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^)+(0.0187P)^2^+65.9012P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1383
_refine_ls_wR_factor_ref         0.1389
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14307
_reflns_number_total             14804
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc04945h2.cif
_cod_data_source_block           crs303
_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               7135305
_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. Uiso/Uaniso restraints and constraints
C50 \\sim C50A \\sim C51 \\sim C51A \\sim C52 \\sim C52A: within 2A with sigma
of 0.005 and sigma for terminal atoms of 0.01 within 2A
C9 \\sim C14 \\sim C14A \\sim C15 \\sim C15A \\sim C16A \\sim C57A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C53 \\sim C54 \\sim C54A \\sim C55 \\sim C55A: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
3. Rigid body (RIGU) restrains
 C50A, C51A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Fixed Sof: La1(0.63) La1A(0.37) S1(0.63) S1A(0.37) S2(0.63) S2A(0.37)
 C1(0.63) H1A(0.63) H1B(0.63) H1C(0.63) C12(0.63) H12(0.63) C12A(0.37)
 H12A(0.37) C13(0.63) C13A(0.37) C14(0.6) H14(0.6) C14A(0.4) H14A(0.4) C15(0.6)
 H15A(0.6) H15B(0.6) H15C(0.6) C15A(0.4) H15D(0.4) H15E(0.4) H15F(0.4)
 C16A(0.6) H16A(0.6) H16B(0.6) H16C(0.6) C20(0.63) H20(0.63) C20A(0.37)
 H20A(0.37) C21(0.63) H21A(0.63) H21B(0.63) H21C(0.63) C21A(0.37) H21D(0.37)
 H21E(0.37) H21F(0.37) C22(0.63) H22A(0.63) H22B(0.63) H22C(0.63) C22A(0.37)
 H22D(0.37) H22E(0.37) H22F(0.37) C50(0.65) H50(0.65) C50A(0.35) H50A(0.35)
 C51(0.65) H51A(0.65) H51B(0.65) H51C(0.65) C51A(0.35) H51D(0.35) H51E(0.35)
 H51F(0.35) C52(0.65) H52A(0.65) H52B(0.65) H52C(0.65) C52A(0.35) H52D(0.35)
 H52E(0.35) H52F(0.35) H53(0.85) H53A(0.15) C54(0.85) H54A(0.85) H54B(0.85)
 H54C(0.85) C54A(0.15) H54D(0.15) H54E(0.15) H54F(0.15) C55(0.85) H55A(0.85)
 H55B(0.85) H55C(0.85) C55A(0.15) H55D(0.15) H55E(0.15) H55F(0.15) C57A(0.4)
 H57D(0.4) H57E(0.4) H57F(0.4) H74A(0.65) H74B(0.65) H74C(0.65) H74D(0.35)
 H74E(0.35) H74F(0.35) C75(0.65) H75A(0.65) H75B(0.65) C75A(0.35) H75C(0.35)
 H75D(0.35) C76(0.65) H76A(0.65) H76B(0.65) C76A(0.35) H76C(0.35) H76D(0.35)
5.a Ternary CH refined with riding coordinates:
 C12A(H12A), C14(H14), C14A(H14A), C17(H17), C20(H20), C20A(H20A), C29(H29),
 C32(H32), C35(H35), C50(H50), C50A(H50A), C53(H53), C53(H53A), C56(H56),
 C65(H65), C68(H68), C71(H71)
5.b Secondary CH2 refined with riding coordinates:
 C75(H75A,H75B), C75A(H75C,H75D), C76(H76A,H76B), C76A(H76C,H76D)
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), C15A(H15D,H15E,H15F), C16A(H16A,H16B,
 H16C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,H21C),
 C21A(H21D,H21E,H21F), C22(H22A,H22B,H22C), C22A(H22D,H22E,H22F), 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), C51A(H51D,H51E,H51F),
 C52(H52A,H52B,H52C), C52A(H52D,H52E,H52F), C54(H54A,H54B,H54C), C54A(H54D,H54E,
 H54F), C55(H55A,H55B,H55C), C55A(H55D,H55E,H55F), C57(H57A,H57B,H57C),
 C57A(H57D,H57E,H57F), 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), C74(H74A,H74B,H74C), C74(H74D,H74E,H74F)
;
_shelx_res_checksum              75641
_shelx_hkl_checksum              10184
_olex2_submission_special_instructions 'No special instructions were received'