Formation of a cyclooctatetraenylsamarium(III) inverse sandwich that ring-opens tetrahydrofuran.
Peedika Paramban, Ramees; Guo, Zhifang; Deacon, Glen B.; Junk, Peter C.; Dalton transactions (Cambridge, England : 2003)  (2023) –; doi:10.1039/d2dt04164b

data_7712110
_publ_section_title
;
 Formation of a cyclooctatetraenylsamarium(III) inverse sandwich that
 ring-opens tetrahydrofuran.
;
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_paper_doi               10.1039/d2dt04164b
_journal_year                    2023
_chemical_formula_moiety         'C83 H121 N6 O2 Sm, C4 H8 O'
_chemical_formula_sum            'C87 H129 N6 O3 Sm'
_chemical_formula_weight         1457.30
_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             2022-11-15
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-11-15 deposited with the CCDC.	2023-01-05 downloaded from the CCDC.
;
_cell_angle_alpha                97.357(2)
_cell_angle_beta                 103.624(2)
_cell_angle_gamma                108.342(3)
_cell_formula_units_Z            2
_cell_length_a                   12.6902(4)
_cell_length_b                   17.9896(7)
_cell_length_c                   20.6655(4)
_cell_measurement_reflns_used    15021
_cell_measurement_temperature    122.99(12)
_cell_measurement_theta_max      76.1280
_cell_measurement_theta_min      3.8310
_cell_volume                     4246.3(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (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      122.99(12)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_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     35.00 119.00   0.50    0.30    --   47.95  46.00 -11.00  168
  2  \w     95.00 178.00   0.50    2.00    --  107.11  46.00 -11.00  166
  3  \w     95.00 178.00   0.50    2.00    --  107.11  30.00 120.00  166
  4  \w     94.00 178.00   0.50    2.00    --  107.11  15.00 -90.00  168
  5  \w     35.00  77.00   0.50    2.00    --  107.11 -46.00-161.00   84
  6  \w     35.00 106.00   0.50    2.00    --  107.11 -94.00-120.00  142
  7  \w     36.00  76.00   0.50    2.00    --  107.11 -45.00 -30.00   80
  8  \w     32.00  66.00   0.50    2.00    --  107.11 -30.00 -90.00   68
  9  \w     36.00  76.00   0.50    2.00    --  107.11 -45.00-120.00   80
 10  \w     35.00 105.00   0.50    2.00    --  107.11 -95.00 -59.63  140
 11  \w     35.00 107.00   0.50    2.00    --  107.11-105.00  72.02  144
 12  \w     34.00  96.00   0.50    0.30    --   47.95-125.00  60.00  124
 13  \w     32.00  66.00   0.50    2.00    --  107.11 -30.00 -30.00   68
 14  \w     36.00  76.00   0.50    2.00    --  107.11 -45.00  30.00   80
 15  \w     32.00  66.00   0.50    2.00    --  107.11 -30.00  60.00   68
 16  \w     36.00  76.00   0.50    2.00    --  107.11 -45.00  90.00   80
 17  \w     35.00 106.00   0.50    2.00    --  107.11 -94.00 150.00  142
 18  \w     35.00 106.00   0.50    2.00    --  107.11 -94.00  60.00  142
 19  \w     35.00 106.00   0.50    2.00    --  107.11 -94.00 -30.00  142
 20  \w     32.00  66.00   0.50    2.00    --  107.11 -30.00-180.00   68
 21  \w     32.00  66.00   0.50    2.00    --  107.11 -30.00-150.00   68
 22  \w     32.00  66.00   0.50    2.00    --  107.11 -30.00-120.00   68
 23  \w     32.00  66.00   0.50    2.00    --  107.11 -30.00 -60.00   68
 24  \w     32.00  66.00   0.50    2.00    --  107.11 -30.00   0.00   68
 25  \w     32.00  66.00   0.50    2.00    --  107.11 -30.00  30.00   68
 26  \w     35.00 106.00   0.50    2.00    --  107.11 -94.00 120.00  142
 27  \w     35.00 130.00   0.50    2.00    --  107.11 -77.00 150.00  190
 28  \w     35.00 106.00   0.50    2.00    --  107.11 -94.00  30.00  142
 29  \w     32.00  66.00   0.50    2.00    --  107.11 -30.00 120.00   68
 30  \w     25.00 120.00   0.50    0.30    --   47.95  77.00  60.00  190
 31  \w     35.00 106.00   0.50    2.00    --  107.11 -94.00-150.00  142
 32  \w     35.00 106.00   0.50    2.00    --  107.11 -94.00-180.00  142
 33  \w    -23.00  61.00   0.50    0.30    --   47.95 -46.00-161.00  168
 34  \w    -60.00  25.00   0.50    0.30    --  -47.95  38.00  60.00  170
 35  \w    -61.00  25.00   0.50    0.30    --  -47.95  46.00 -11.00  172
 36  \w    -79.00 -14.00   0.50    2.00    --  -86.25  46.00 -11.00  130
 37  \w    -71.00  25.00   0.50    0.30    --  -47.95  77.00-120.00  192
 38  \w    -68.00 -11.00   0.50    2.00    --  -86.25  30.00 -90.00  114
 39  \w    -86.00 -13.00   0.50    2.00    --  -86.25 125.00  60.00  146
 40  \w   -119.00 -35.00   0.50    0.30    --  -47.95 -46.00-161.00  168
 41  \w   -120.00 -73.00   0.50    0.30    --  -47.95-125.00 -30.00   94
 42  \w   -159.00 -73.00   0.50    2.00    --  -86.25 -46.00-161.00  172
 43  \w   -159.00 -83.00   0.50    2.00    --  -86.25 -94.00 -60.00  152
 44  \w   -120.00 -73.00   0.50    0.30    --  -47.95-125.00 150.00   94
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0269239000
_diffrn_orient_matrix_UB_12      0.0778918000
_diffrn_orient_matrix_UB_13      0.0028769000
_diffrn_orient_matrix_UB_21      0.0794737000
_diffrn_orient_matrix_UB_22      0.0283969000
_diffrn_orient_matrix_UB_23      -0.0448267000
_diffrn_orient_matrix_UB_31      -0.1041790000
_diffrn_orient_matrix_UB_32      -0.0409504000
_diffrn_orient_matrix_UB_33      -0.0645213000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1189
_diffrn_reflns_av_unetI/netI     0.0776
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            76924
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.000
_diffrn_reflns_theta_min         3.806
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.551
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.45835
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.140
_exptl_crystal_description       plate
_exptl_crystal_F_000             1558
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.01
_refine_diff_density_max         3.622
_refine_diff_density_min         -1.168
_refine_diff_density_rms         0.114
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.074
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     943
_refine_ls_number_reflns         16575
_refine_ls_number_restraints     165
_refine_ls_restrained_S_all      1.074
_refine_ls_R_factor_all          0.0925
_refine_ls_R_factor_gt           0.0763
_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^)+(0.0936P)^2^+10.7447P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1806
_refine_ls_wR_factor_ref         0.1904
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14020
_reflns_number_total             16575
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt04164b2.cif
_cod_data_source_block           rpp_t8c_g5
_cod_original_cell_volume        4246.3(2)
_cod_database_code               7712110
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Sm C H O N'
_shelx_estimated_absorpt_t_max   0.947
_shelx_estimated_absorpt_t_min   0.337
_reflns_odcompleteness_completeness 99.84
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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. Restrained distances
 O4-C88 = O4-C91
 1.44 with sigma of 0.02
 C88-C89 = C90-C91
 1.53 with sigma of 0.02
 C89-C90
 1.54 with sigma of 0.02
 O3-C84 = O3-C87
 1.44 with sigma of 0.02
 C84-C85 = C86-C87
 1.53 with sigma of 0.02
 C85-C86
 1.54 with sigma of 0.02
 O4-C89 = O4-C90 = C88-C90 = C89-C91
 2.38 with sigma of 0.04
 O3-C85 = O3-C86 = C84-C86 = C85-C87
 2.38 with sigma of 0.04
 C89-C91 \\sim C88-C90
 with sigma of 0.04
 O4-C89 \\sim O4-C90
 with sigma of 0.04
 C88-C89 \\sim C89-C90 \\sim C90-C91
 with sigma of 0.02
 O4-C88 \\sim O4-C91
 with sigma of 0.02
 O3-C85 \\sim O3-C86
 with sigma of 0.04
 C85-C87 \\sim C84-C86
 with sigma of 0.04
 O3-C84 \\sim O3-C87
 with sigma of 0.02
 C84-C85 \\sim C85-C86 \\sim C86-C87
 with sigma of 0.02
3. Rigid bond restraints
 C79, C78, C80
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Uiso/Uaniso restraints and constraints
O4 \\sim C88 \\sim C89 \\sim C90 \\sim C91: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
O3 \\sim C84 \\sim C85 \\sim C86 \\sim C87: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
C79 \\sim C78 \\sim C80: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.01 within 2A
5. Rigid body (RIGU) restrains
 O4, C88, C89, C90, C91
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O3, C84, C85, C86, C87
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: O4(0.5) C88(0.5) H88A(0.5) H88B(0.5) C89(0.5) H89A(0.5) H89B(0.5)
 C90(0.5) H90A(0.5) H90B(0.5) C91(0.5) H91A(0.5) H91B(0.5) O3(0.5) C84(0.5)
 H84A(0.5) H84B(0.5) C85(0.5) H85A(0.5) H85B(0.5) C86(0.5) H86A(0.5) H86B(0.5)
 C87(0.5) H87A(0.5) H87B(0.5)
7.a Ternary CH refined with riding coordinates:
 C3(H3), C35(H35), C20(H20), C10(H10), C45(H45), C28(H28), C48(H48), C23(H23),
 C61(H61), C81(H81), C68(H68), C78(H78)
7.b Secondary CH2 refined with riding coordinates:
 C56(H56A,H56B), C55(H55A,H55B), C57(H57A,H57B), C58(H58A,H58B), C51(H51A,
 H51B), C53(H53A,H53B), C52(H52A,H52B), C54(H54A,H54B), C88(H88A,H88B),
 C89(H89A,H89B), C90(H90A,H90B), C91(H91A,H91B), C84(H84A,H84B), C85(H85A,H85B),
  C86(H86A,H86B), C87(H87A,H87B)
7.c Aromatic/amide H refined with riding coordinates:
 C13(H13), C38(H38), C71(H71), C41(H41), C42(H42), C43(H43), C7(H7), C32(H32),
 C17(H17), C5(H5), C31(H31), C6(H6), C30(H30), C65(H65), C16(H16), C18(H18),
 C63(H63), C64(H64), C74(H74), C76(H76), C75(H75)
7.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C),
 C47(H47A,H47B,H47C), C12(H12A,H12B,H12C), C22(H22A,H22B,H22C), C46(H46A,H46B,
 H46C), C11(H11A,H11B,H11C), C21(H21A,H21B,H21C), C26(H26A,H26B,H26C), C25(H25A,
 H25B,H25C), C24(H24A,H24B,H24C), C59(H59A,H59B,H59C), C60(H60A,H60B,H60C),
 C27(H27A,H27B,H27C), C69(H69A,H69B,H69C), C50(H50A,H50B,H50C), C49(H49A,H49B,
 H49C), C83(H83A,H83B,H83C), C82(H82A,H82B,H82C), C80(H80A,H80B,H80C), C70(H70A,
 H70B,H70C), C79(H79A,H79B,H79C)
;
_shelx_res_checksum              74798
_shelx_hkl_checksum              62377
_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 2.867
_oxdiff_exptl_absorpt_empirical_full_min 0.610