Heteroleptic samarium(iii) halide complexes probed by fluorescence-detected L<sub>3</sub>-edge X-ray absorption spectroscopy.
Goodwin, Conrad A. P.; Réant, Benjamin L L; Kragskow, Jon G. C.; DiMucci, Ida M.; Lancaster, Kyle M.; Mills, David P.; Sproules, Stephen; Dalton transactions (Cambridge, England : 2003) 47 (2018) 10613–10625; doi:10.1039/c8dt01452c

data_7046253
_publ_section_title
;
 Heteroleptic samarium(iii) halide complexes probed by
 fluorescence-detected L<sub>3</sub>-edge X-ray absorption spectroscopy.
;
_journal_issue                   31
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              10613
_journal_page_last               10625
_journal_paper_doi               10.1039/c8dt01452c
_journal_volume                  47
_journal_year                    2018
_chemical_formula_moiety         'C36 H84 Br N2 Si4 Sm'
_chemical_formula_sum            'C36 H84 Br N2 Si4 Sm'
_chemical_formula_weight         887.67
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_symmetry_space_group_name_Hall  '-P 2ac 2ab'
_symmetry_space_group_name_H-M   'P b c a'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2018-03-28
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-03-29 deposited with the CCDC.
2018-05-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   20.6319(9)
_cell_length_b                   20.1603(11)
_cell_length_c                   21.9662(10)
_cell_measurement_reflns_used    7912
_cell_measurement_temperature    150.01(1)
_cell_measurement_theta_max      25.7600
_cell_measurement_theta_min      2.8970
_cell_volume                     9136.7(8)
_computing_cell_refinement       'CrysAlisPro 1.171.39.30c (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.30c (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.30c (Rigaku OD, 2017)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      150.01(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1636
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.992
_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     35.00 101.40   0.80   12.50    --   11.54 178.00 120.00   83
  2  \w    -79.00  11.40   0.80   12.50    --  -12.00 -57.00-120.00  113
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0043460000
_diffrn_orient_matrix_UB_12      -0.0318670000
_diffrn_orient_matrix_UB_13      -0.0129763000
_diffrn_orient_matrix_UB_21      -0.0163630000
_diffrn_orient_matrix_UB_22      0.0144471000
_diffrn_orient_matrix_UB_23      -0.0251130000
_diffrn_orient_matrix_UB_31      0.0299499000
_diffrn_orient_matrix_UB_32      0.0032782000
_diffrn_orient_matrix_UB_33      -0.0156382000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0675
_diffrn_reflns_av_unetI/netI     0.0743
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            32776
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.350
_diffrn_reflns_theta_min         2.404
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.289
_exptl_absorpt_correction_T_max  0.945
_exptl_absorpt_correction_T_min  0.913
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.30c (Rigaku Oxford Diffraction, 2017)
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 yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.291
_exptl_crystal_description       block
_exptl_crystal_F_000             3736
_exptl_crystal_preparation       'By Benjamin Reant and CAPG.'
_exptl_crystal_recrystallization_method 'From hexane.'
_exptl_crystal_size_max          0.494
_exptl_crystal_size_mid          0.356
_exptl_crystal_size_min          0.259
_refine_diff_density_max         0.698
_refine_diff_density_min         -1.119
_refine_diff_density_rms         0.105
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     467
_refine_ls_number_reflns         8310
_refine_ls_number_restraints     914
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0857
_refine_ls_R_factor_gt           0.0459
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0361P)^2^+3.7975P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0889
_refine_ls_wR_factor_ref         0.1063
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5518
_reflns_number_total             8310
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8dt01452c2.cif
_cod_data_source_block           2-Br
_cod_depositor_comments
'Adding full bibliography for 7046250--7046253.cif.'
_cod_database_code               7046253
_manchester_internal_coll_name   odpm74
_manchester_internal_coll_client CAPG
_manchester_internal_coll_type   custom
_manchester_internal_coll_frame_time 12.5
_manchester_internal_coll_frame_width 0.8
_manchester_internal_coll_frame_method '\w scans'
_manchester_internal_coll_user   CAPG
_manchester_internal_coll_date   29/9/16
_manchester_internal_process_user CAPG
_manchester_internal_process_date 27/3/18
_manchester_internal_solution_user CAPG
_manchester_internal_solution_date 27/3/18
_manchester_internal_refinement_user CAPG
_manchester_internal_refinement_date 27/3/18
_manchester_internal_validation_user CAPG
_manchester_internal_validation_date 28/3/18
_manchester_internal_archive_date 28/3/18
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         Sm(N(SiC9H21)2)2Br
_reflns_odcompleteness_completeness 98.62
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(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
 C26B-C25B \\sim C27B-C25B \\sim C26A-C25A \\sim C27A-C25A \\sim C20-C19 \\sim
C21-C19 \\sim C32-C31 ~
 C33-C31 \\sim C29-C28 \\sim C30-C28 \\sim C35-C34 \\sim C36-C34 \\sim C2-C1
\\sim C3-C1 \\sim C9-C7 \\sim C8-
 C7 \\sim C5-C4 \\sim C6-C4 \\sim C23-C22A \\sim C24A-C22A \\sim C14-C13 \\sim
C15-C13 \\sim C12-C10 \\sim C11-
 C10 \\sim C17-C16 \\sim C18-C16
 with sigma of 0.008
 Si3-C22A \\sim Si3-C22B \\sim Si3-C25A \\sim Si3-C25B \\sim Si3-C19 \\sim
Si4-C31 \\sim Si4-C34 \\sim Si2-
 C10 \\sim Si2-C16 \\sim Si2-C13 \\sim Si1-C1 \\sim Si1-C7 \\sim Si1-C4 \\sim
Si4-C28
 with sigma of 0.008
3. Uiso/Uaniso restraints and constraints
Si3 \\sim C19 \\sim C20 \\sim C21 \\sim C23 \\sim C25A \\sim C27A \\sim C26A
\\sim C22B \\sim C24B \\sim C22A \\sim C24A \\sim C25B \\sim C26B \\sim C27B:
within 2A with sigma of 0.008 and sigma for terminal atoms of 0.008
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Others
 Sof(C25B)=Sof(H25B)=Sof(C26B)=Sof(H26D)=Sof(H26E)=Sof(H26F)=Sof(C27B)=
 Sof(H27D)=Sof(H27E)=Sof(H27F)=1-FVAR(1)
 Sof(C25A)=Sof(H25A)=Sof(C27A)=Sof(H27A)=Sof(H27B)=Sof(H27C)=Sof(C26A)=
 Sof(H26A)=Sof(H26B)=Sof(H26C)=FVAR(1)
 Sof(H23D)=Sof(H23E)=Sof(H23F)=Sof(C22A)=Sof(H22A)=Sof(C24A)=Sof(H24D)=
 Sof(H24E)=Sof(H24F)=1-FVAR(2)
 Sof(H23A)=Sof(H23B)=Sof(H23C)=Sof(C22B)=Sof(H22B)=Sof(C24B)=Sof(H24A)=
 Sof(H24B)=Sof(H24C)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C1(H1), C4(H4), C7(H7), C10(H10), C13(H13), C16(H16), C19(H19), C28(H28),
 C31(H31), C34(H34), C25A(H25A), C22B(H22B), C22A(H22A), C25B(H25B)
6.b Me refined with riding coordinates:
 C27A(H27A,H27B,H27C), C26A(H26A,H26B,H26C), C26B(H26D,H26E,H26F), C27B(H27D,
 H27E,H27F)
6.c Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C8(H8A,
 H8B,H8C), C9(H9A,H9B,H9C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C14(H14A,
 H14B,H14C), C15(H15A,H15B,H15C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C),
 C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C23(H23D,H23E,H23F), C23(H23A,H23B,
 H23C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C32(H32A,H32B,H32C), C33(H33A,
 H33B,H33C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C24B(H24A,H24B,H24C),
 C24A(H24D,H24E,H24F)
;
_shelx_res_checksum              44402
_olex2_exptl_crystal_mounting_method 'From fomblin on a microscope slide.'
_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 1.877
_oxdiff_exptl_absorpt_empirical_full_min 0.475