Well-Defined Scandacyclopropenes: Synthesis, Structure, and Reactivity.
Lv, Ze-Jie; Huang, Zhe; Shen, Jinghang; Zhang, Wen-Xiong; Xi, Zhenfeng; Journal of the American Chemical Society 141 (2019) 20547–20555; doi:10.1021/jacs.9b11631

data_4133782
_publ_section_title
;
 Well-Defined Scandacyclopropenes: Synthesis, Structure, and Reactivity.
;
_journal_issue                   51
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              20547
_journal_page_last               20555
_journal_paper_doi               10.1021/jacs.9b11631
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         '2(C39 H56 K N2 O Sc), C4 H8 O'
_chemical_formula_sum            'C82 H120 K2 N4 O3 Sc2'
_chemical_formula_weight         1377.93
_space_group_crystal_system      orthorhombic
_space_group_IT_number           39
_space_group_name_Hall           'A 2 -2b'
_space_group_name_H-M_alt        'A e m 2'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2019-10-27
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.13686(18)
_cell_length_b                   27.9904(5)
_cell_length_c                   29.4130(7)
_cell_measurement_reflns_used    26225
_cell_measurement_temperature    179.99(10)
_cell_measurement_theta_max      28.6150
_cell_measurement_theta_min      3.5430
_cell_volume                     8345.5(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      179.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.972
_diffrn_measured_fraction_theta_max 0.974
_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      3.00  29.00   0.50   30.00    --   -9.50 -77.00-150.00   52
  2  \w    -46.00 -14.00   0.50   30.00    --   -9.50 -77.00-150.00   64
  3  \w    -32.00  20.00   0.50   30.00    --   -9.50 -82.00   0.00  104
  4  \w    -45.00 -10.00   0.50   30.00    --   -9.50 -38.00-180.00   70
  5  \w    -94.00 -53.00   0.50   30.00    --   -9.50 -57.00  30.00   82
  6  \w    -19.00  10.00   0.50   30.00    --   -9.50 -57.00  30.00   58
  7  \w    -28.00  13.00   0.50   30.00    --   -9.50 -82.00 120.00   82
  8  \w     -9.00  43.00   0.50   30.00    --    9.60 -82.00-180.00  104
  9  \w    -80.00  40.00   0.50   30.00    --    9.60 -57.00 -30.00  240
 10  \w    -34.00  50.00   0.50   30.00    --    9.60 -82.00 -60.00  168
 11  \w    -14.00  52.00   0.50   30.00    --    9.60 -82.00  60.00  132
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0389829000
_diffrn_orient_matrix_UB_12      0.0184584000
_diffrn_orient_matrix_UB_13      0.0095895000
_diffrn_orient_matrix_UB_21      -0.0285705000
_diffrn_orient_matrix_UB_22      0.0044781000
_diffrn_orient_matrix_UB_23      -0.0216023000
_diffrn_orient_matrix_UB_31      -0.0505818000
_diffrn_orient_matrix_UB_32      -0.0167732000
_diffrn_orient_matrix_UB_33      0.0048148000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0685
_diffrn_reflns_av_unetI/netI     0.0408
_diffrn_reflns_Laue_measured_fraction_full 0.972
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       34
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            58477
_diffrn_reflns_point_group_measured_fraction_full 0.975
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.021
_diffrn_reflns_theta_min         3.423
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.307
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.74336
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.097
_exptl_crystal_description       block
_exptl_crystal_F_000             2976
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.553
_refine_diff_density_min         -2.905
_refine_diff_density_rms         0.125
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.51(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.185
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     624
_refine_ls_number_reflns         8115
_refine_ls_number_restraints     220
_refine_ls_restrained_S_all      1.191
_refine_ls_R_factor_all          0.1094
_refine_ls_R_factor_gt           0.1040
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2451
_refine_ls_wR_factor_ref         0.2549
_reflns_Friedel_coverage         0.962
_reflns_Friedel_fraction_full    0.978
_reflns_Friedel_fraction_max     0.980
_reflns_number_gt                7420
_reflns_number_total             8115
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b11631_si_002.cif
_cod_data_source_block           2a_THF
_cod_depositor_comments
'Adding full bibliography for 4133782--4133791.cif.'
_cod_original_sg_symbol_Hall     'A 2 -2c'
_cod_database_code               4133782
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'Sc N C H'
_shelx_estimated_absorpt_t_max   0.970
_shelx_estimated_absorpt_t_min   0.970
_reflns_odcompleteness_completeness 99.66
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.42
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.49(6)
 0.51(6)
2. 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
3. Restrained distances
 O3-C65 = O3-C65_$1 = C65_$1-C66_$1 = C66_$1-C66 = C65-C66
 1.48 with sigma of 0.02
 C44-C43 = C45-C44 = C45-C46 = C47-C46
 1.54 with sigma of 0.02
 C63-C64 = C62-C63 = C62-C61 = O2-C64 = O2-C61
 1.48 with sigma of 0.02
 O3-C66_$1
 2.5 with sigma of 0.02
 C65_$1-C66
 2.5 with sigma of 0.02
 C66_$1-C65
 2.5 with sigma of 0.02
 C66-O3
 2.5 with sigma of 0.02
 C65-C65_$1
 2.5 with sigma of 0.02
 C43-C45
 2.5 with sigma of 0.02
 C44-C46
 2.5 with sigma of 0.02
 C45-C47
 2.5 with sigma of 0.02
 O2-C62
 2.5 with sigma of 0.02
 C61-C63
 2.5 with sigma of 0.02
 C62-C64
 2.5 with sigma of 0.02
 C63-O2
 2.5 with sigma of 0.02
 C64-C61
 2.5 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
C22 \\sim C23 \\sim C24 \\sim C25: within 3A with sigma of 0.02 and sigma for
terminal atoms of 0.04
C28 \\sim C33 \\sim C32 \\sim C31 \\sim C30 \\sim C29: within 3A with sigma of
0.02 and sigma for terminal atoms of 0.04
C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47: within 3A with sigma of 0.02 and
sigma for terminal atoms of 0.04
C48 \\sim C49 \\sim C50: within 3A with sigma of 0.02 and sigma for terminal
atoms of 0.04
Uanis(C50) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.006
5. Others
 Fixed Sof: H14A(0.5) H14B(0.5) H12A(0.5) H12B(0.5) H13A(0.5) H13B(0.5)
 H15B(0.5) H15C(0.5) H21A(0.5) H21B(0.5) H21C(0.5) O1(0.5) C22(0.5) H22A(0.5)
 H22B(0.5) C23(0.5) H23A(0.5) H23B(0.5) C24(0.5) H24A(0.5) H24B(0.5) C25(0.5)
 H25A(0.5) H25B(0.5) K2(0.5) Sc1(0.5) C54(0.5) C53(0.5) C52(0.5) C51(0.5)
 C55(0.5) C60(0.5) H60A(0.5) H60B(0.5) H60C(0.5) C58(0.5) H58A(0.5) H58B(0.5)
 H58C(0.5) C57(0.5) H57A(0.5) H57B(0.5) H57C(0.5) C59(0.5) H59A(0.5) H59B(0.5)
 H59C(0.5) C56(0.5) H56A(0.5) H56B(0.5) H56C(0.5) C62(0.5) H62A(0.5) H62B(0.5)
 C34(0.5) C39(0.5) H39(0.5) C38(0.5) H38(0.5) C37(0.5) H37(0.5) C36(0.5)
 H36(0.5) C35(0.5) H35(0.5) C63(0.5) H63A(0.5) H63B(0.5) O2(0.5) C28(0.5)
 C29(0.5) H29(0.5) C30(0.5) H30(0.5) C31(0.5) H31(0.5) C32(0.5) H32(0.5)
 C33(0.5) H33(0.5) C64(0.5) H64A(0.5) H64B(0.5) C61(0.5) H61A(0.5) H61B(0.5)
 C50(0.5) H50A(0.5) H50B(0.5) H50C(0.5) C47(0.5) H47A(0.5) H47B(0.5) H47C(0.5)
 C27(0.5) N3(0.5) C40(0.5) H40(0.5) N2(0.5) C48(0.5) H48(0.5) C26(0.5) C49(0.5)
 H49A(0.5) H49B(0.5) H49C(0.5) C42(0.5) H42A(0.5) H42B(0.5) H42C(0.5) C44(0.5)
 H44A(0.5) H44B(0.5) C45(0.5) H45A(0.5) H45B(0.5) C43(0.5) C41(0.5) H41A(0.5)
 H41B(0.5) H41C(0.5) C46(0.5) H46A(0.5) H46B(0.5)
6.a Ternary CH refined with riding coordinates:
 C8(H8), C40(H40), C48(H48)
6.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C12(H12A,H12B), C13(H13A,H13B), C22(H22A,H22B), C23(H23A,
 H23B), C24(H24A,H24B), C25(H25A,H25B), C62(H62A,H62B), C63(H63A,H63B),
 C64(H64A,H64B), C61(H61A,H61B), C44(H44A,H44B), C45(H45A,H45B), C66(H66A,H66B),
  C65(H65A,H65B), C46(H46A,H46B)
6.c Me refined with riding coordinates:
 C15(H15A,H15B,H15C), C21(H21A,H21B,H21C)
6.d Aromatic/amide H refined with riding coordinates:
 C3(H3), C7(H7), C4(H4), C5(H5), C6(H6), C39(H39), C38(H38), C37(H37),
 C36(H36), C35(H35), C29(H29), C30(H30), C31(H31), C32(H32), C33(H33)
6.e Fitted pentagon refined as free rotating group:
 C54(C53,C52,C51,C55)
6.f Fitted hexagon refined as free rotating group:
 C34(C39,C38,C37,C36,C35), C28(C29,C30,C31,C32,C33)
6.g Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C10(H10A,H10B,H10C), C9(H9A,H9B,H9C), C19(H19A,H19B,
 H19C), C60(H60A,H60B,H60C), C58(H58A,H58B,H58C), C57(H57A,H57B,H57C), C59(H59A,
 H59B,H59C), C56(H56A,H56B,H56C), C50(H50A,H50B,H50C), C47(H47A,H47B,H47C),
 C49(H49A,H49B,H49C), C42(H42A,H42B,H42C), C41(H41A,H41B,H41C)
;
_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 1.461
_oxdiff_exptl_absorpt_empirical_full_min 0.528