Reductive dehydrocoupling of diphenyltin dihydride with LiAlH<sub>4</sub>: selective synthesis and structures of the first bicyclo[2.2.1]heptastannane-1,4-diide and bicyclo[2.2.2]octastannane-1,4-diide.
Steller, Beate G.; Fischer, Roland C.; Flock, Michaela; Hill, Michael S.; Liptrot, David J.; McMullin, Claire L.; Rajabi, Nasir A.; Tiefling, Kathrin; Wilson, Andrew S. S.; Chemical communications (Cambridge, England) 56 (2020) 336–339; doi:10.1039/c9cc07976a

data_7125626
_publ_section_title
;
 Reductive dehydrocoupling of diphenyltin dihydride with
 LiAlH<sub>4</sub>: selective synthesis and structures of the first
 bicyclo[2.2.1]heptastannane-1,4-diide and
 bicyclo[2.2.2]octastannane-1,4-diide.
;
_journal_issue                   3
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              336
_journal_page_last               339
_journal_paper_doi               10.1039/c9cc07976a
_journal_volume                  56
_journal_year                    2020
_chemical_formula_moiety         'C60 H50 Sn7, 2(C16 H32 Li O8), C2 H4 O0.5'
_chemical_formula_sum            'C98 H126 Li2 O17.5 Sn7'
_chemical_formula_weight         2428.69
_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     direct
_audit_creation_date             2017-05-22
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_audit_update_record
;
2017-07-11 deposited with the CCDC.	2019-11-28 downloaded from the CCDC.
;
_cell_angle_alpha                82.634(2)
_cell_angle_beta                 76.623(3)
_cell_angle_gamma                70.379(2)
_cell_formula_units_Z            2
_cell_length_a                   14.3301(9)
_cell_length_b                   15.1075(10)
_cell_length_c                   26.1181(19)
_cell_measurement_reflns_used    5511
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.20
_cell_measurement_theta_min      2.61
_cell_volume                     5173.7(6)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_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_temperature      100.01
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0279
_diffrn_reflns_av_unetI/netI     0.0275
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            145924
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.034
_diffrn_reflns_theta_min         1.875
_diffrn_source                   'sealed tube'
_exptl_absorpt_coefficient_mu    1.722
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.723
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'Bruker software'
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.559
_exptl_crystal_description       Block
_exptl_crystal_F_000             2420
_exptl_crystal_size_max          0.354
_exptl_crystal_size_mid          0.211
_exptl_crystal_size_min          0.136
_refine_diff_density_max         1.633
_refine_diff_density_min         -1.389
_refine_diff_density_rms         0.125
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1399
_refine_ls_number_reflns         30024
_refine_ls_number_restraints     833
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0568
_refine_ls_R_factor_gt           0.0372
_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^)+(0.0434P)^2^+16.6424P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0912
_refine_ls_wR_factor_ref         0.1067
_reflns_Friedel_coverage         0.000
_reflns_number_gt                23308
_reflns_number_total             30024
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc07976a2.cif
_cod_data_source_block           rf244_0m
_cod_depositor_comments
'Adding full bibliography for 7125626--7125630.cif.'
_cod_original_formula_sum        'C98 H126 Li2 O17.50 Sn7'
_cod_database_code               7125626
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.800
_shelx_estimated_absorpt_t_min   0.581
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
2. Restrained distances
 Sn6-C49A \\sim Sn6-C49
 with sigma of 0.005
 Sn2-C7A \\sim Sn2-C7
 with sigma of 0.005
 O7A-C71A \\sim O7-C72 \\sim O7-C73 \\sim O7A-C73A \\sim O8-C74 \\sim O8A-C74A
\\sim O8A-C75A \\sim O8-C75
 \\sim O5A-C76A \\sim O5A-C69A \\sim O5-C76 \\sim O5-C69 \\sim O6-C70 \\sim
O6A-C70A \\sim O6-C71 \\sim O6A-C72A
 with sigma of 0.005
 C72A-C71A \\sim C72-C71 \\sim C74A-C73A \\sim C74-C73 \\sim C76A-C75A \\sim
C76-C75 \\sim C70-C69 
 C70A-C69A
 with sigma of 0.005
 O5A-Li1 \\sim O5-Li1
 with sigma of 0.005
 O8-Li1 \\sim O8A-Li1
 with sigma of 0.005
 O7A-Li1 \\sim O7-Li1
 with sigma of 0.005
 O6A-Li1 \\sim O6-Li1
 with sigma of 0.005
 O9A-Li2 \\sim O9-Li2
 with sigma of 0.005
 O10-Li2 \\sim O10A-Li2
 with sigma of 0.005
 O11-Li2 \\sim O11A-Li2
 with sigma of 0.005
 O12-Li2 \\sim O12A-Li2
 with sigma of 0.005
 O9A-C77A \\sim O9-C77 \\sim O9-C84 \\sim O9A-C84A \\sim O12-C83 \\sim
O12A-C83A \\sim O12-C82 \\sim O12A-
 C82A \\sim O11-C81 \\sim O11A-C81A \\sim O11-C80 \\sim O11A-C80A \\sim O10-C79
\\sim O10A-C79A \\sim O10A-
 C78A \\sim O10-C78
 with sigma of 0.005
 C80-C79 \\sim C80A-C79A \\sim C82A-C81A \\sim C82-C81 \\sim C84A-C83A \\sim
C84-C83 \\sim C78A-C77A 
 C78-C77
 with sigma of 0.005
 C95B-C94A \\sim C95A-C94
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
O9 \\sim O10 \\sim O11 \\sim O12 \\sim C77 \\sim C78 \\sim C79 \\sim C80 \\sim
C81 \\sim C82 \\sim C83 \\sim C84: within 2A with sigma of 0.02 and sigma for
terminal atoms of 0.01
O9A \\sim O10A \\sim O11A \\sim O12A \\sim C77A \\sim C78A \\sim C79A \\sim
C80A \\sim C81A \\sim C82A \\sim C83A \\sim C84A: within 2A with sigma of 0.02
and sigma for terminal atoms of 0.01
C94 \\sim C95A \\sim C94A \\sim C95B: within 2A with sigma of 0.02 and sigma
for terminal atoms of 0.01
Uanis(C81A) \\sim Ueq, Uanis(C81) \\sim Ueq, Uanis(C82A) \\sim Ueq, Uanis(C82)
\\sim Ueq, Uanis(O12A) \\sim Ueq, Uanis(O12) \\sim Ueq, Uanis(C83A) \\sim Ueq,
Uanis(C83) \\sim Ueq, Uanis(O11) \\sim Ueq, Uanis(O11A) \\sim Ueq, Uanis(C80)
\\sim Ueq, Uanis(C80A) \\sim Ueq, Uanis(C84A) \\sim Ueq, Uanis(C84) \\sim Ueq,
Uanis(O10) \\sim Ueq, Uanis(O10A) \\sim Ueq, Uanis(C78) \\sim Ueq, Uanis(C78A)
\\sim Ueq, Uanis(C77A) \\sim Ueq, Uanis(C77) \\sim Ueq, Uanis(O9A) \\sim Ueq,
Uanis(O9) \\sim Ueq, Uanis(C79) \\sim Ueq, Uanis(C79A) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C90) \\sim Ueq, Uanis(C92) \\sim Ueq, Uanis(C63) \\sim Ueq, Uanis(C64)
\\sim Ueq, Uanis(O3) \\sim Ueq, Uanis(C65) \\sim Ueq, Uanis(C66) \\sim Ueq,
Uanis(C62) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O5) \\sim Ueq, Uanis(O6) \\sim Ueq, Uanis(O7) \\sim Ueq, Uanis(O8) \\sim
Ueq, Uanis(C69) \\sim Ueq, Uanis(C70) \\sim Ueq, Uanis(C71) \\sim Ueq,
Uanis(C72) \\sim Ueq, Uanis(C73) \\sim Ueq, Uanis(C74) \\sim Ueq, Uanis(C75)
\\sim Ueq, Uanis(C76) \\sim Ueq, Uanis(C74A) \\sim Ueq, Uanis(O8A) \\sim Ueq,
Uanis(C76A) \\sim Ueq, Uanis(O5A) \\sim Ueq, Uanis(C75A) \\sim Ueq, Uanis(C69A)
\\sim Ueq, Uanis(C70A) \\sim Ueq, Uanis(O6A) \\sim Ueq, Uanis(C71A) \\sim Ueq,
Uanis(C72A) \\sim Ueq, Uanis(O7A) \\sim Ueq, Uanis(C73A) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(O6) = Uanis(O6A)
4. Others
 Fixed Sof: C7(0.5) C8(0.5) H8(0.5) C9(0.5) H9(0.5) C10(0.5) H10(0.5) C11(0.5)
 H11(0.5) C12(0.5) H12(0.5) C49(0.65) C50(0.65) H50(0.65) C51(0.65) H51(0.65)
 C52(0.65) H52(0.65) C53(0.65) H53(0.65) C54(0.65) H54(0.65) C7A(0.5) C12A(0.5)
 H12A(0.5) C11A(0.5) H11A(0.5) C10A(0.5) H10A(0.5) C9A(0.5) H9A(0.5) C8A(0.5)
 H8A(0.5) C49A(0.35) C50A(0.35) H50A(0.35) C51A(0.35) H51A(0.35) C52A(0.35)
 H52A(0.35) C53A(0.35) H53A(0.35) C54A(0.35) H54A(0.35) O5(0.6) O6(0.6) O7(0.6)
 O8(0.6) O5A(0.4) O6A(0.4) O7A(0.4) O8A(0.4) C69(0.6) H69A(0.6) H69B(0.6)
 C70(0.6) H70A(0.6) H70B(0.6) C71(0.6) H71A(0.6) H71B(0.6) C72(0.6) H72A(0.6)
 H72B(0.6) C73(0.6) H73A(0.6) H73B(0.6) C74(0.6) H74A(0.6) H74B(0.6) C75(0.6)
 H75A(0.6) H75B(0.6) C76(0.6) H76A(0.6) H76B(0.6) C69A(0.4) H69C(0.4) H69D(0.4)
 C70A(0.4) H70C(0.4) H70D(0.4) C71A(0.4) H71C(0.4) H71D(0.4) C72A(0.4)
 H72C(0.4) H72D(0.4) C73A(0.4) H73C(0.4) H73D(0.4) C74A(0.4) H74C(0.4)
 H74D(0.4) C75A(0.4) H75C(0.4) H75D(0.4) C76A(0.4) H76C(0.4) H76D(0.4) O9(0.65)
 O10(0.65) O11(0.65) O12(0.65) O9A(0.35) O10A(0.35) O11A(0.35) O12A(0.35)
 C77(0.65) H77A(0.65) H77B(0.65) C78(0.65) H78A(0.65) H78B(0.65) C79(0.65)
 H79A(0.65) H79B(0.65) C80(0.65) H80A(0.65) H80B(0.65) C81(0.65) H81A(0.65)
 H81B(0.65) C82(0.65) H82A(0.65) H82B(0.65) C83(0.65) H83A(0.65) H83B(0.65)
 C84(0.65) H84A(0.65) H84B(0.65) C77A(0.35) H77C(0.35) H77D(0.35) C78A(0.35)
 H78C(0.35) H78D(0.35) C79A(0.35) H79C(0.35) H79D(0.35) C80A(0.35) H80C(0.35)
 H80D(0.35) C81A(0.35) H81C(0.35) H81D(0.35) C82A(0.35) H82C(0.35) H82D(0.35)
 C83A(0.35) H83C(0.35) H83D(0.35) C84A(0.35) H84C(0.35) H84D(0.35) O20(0.5)
 C93(0.5) H93A(0.5) H93B(0.5) C95(0.5) H95A(0.25) H95B(0.25) H95C(0.25)
 H95D(0.25) C94(0.25) H94A(0.25) H94B(0.25) C95A(0.25) H95E(0.25) H95F(0.25)
 C94A(0.25) H94C(0.25) H94D(0.25) C95B(0.25) H95G(0.25) H95H(0.25)
5.a Secondary CH2 refined with riding coordinates:
 C61(H61A,H61B), C62(H62A,H62B), C63(H63A,H63B), C64(H64A,H64B), C65(H65A,
 H65B), C66(H66A,H66B), C67(H67A,H67B), C68(H68A,H68B), C69(H69A,H69B),
 C70(H70A,H70B), C71(H71A,H71B), C72(H72A,H72B), C73(H73A,H73B), C74(H74A,H74B),
  C75(H75A,H75B), C76(H76A,H76B), C69A(H69C,H69D), C70A(H70C,H70D), C71A(H71C,
 H71D), C72A(H72C,H72D), C73A(H73C,H73D), C74A(H74C,H74D), C75A(H75C,H75D),
 C76A(H76C,H76D), C85(H85A,H85B), C86(H86A,H86B), C87(H87A,H87B), C88(H88A,
 H88B), C89(H89A,H89B), C90(H90A,H90B), C91(H91A,H91B), C92(H92A,H92B),
 C77(H77A,H77B), C78(H78A,H78B), C79(H79A,H79B), C80(H80A,H80B), C81(H81A,H81B),
  C82(H82A,H82B), C83(H83A,H83B), C84(H84A,H84B), C77A(H77C,H77D), C78A(H78C,
 H78D), C79A(H79C,H79D), C80A(H80C,H80D), C81A(H81C,H81D), C82A(H82C,H82D),
 C83A(H83C,H83D), C84A(H84C,H84D), C93(H93A,H93B), C95(H95A,H95B), C95(H95C,
 H95D), C94(H94A,H94B), C95A(H95E,H95F), C94A(H94C,H94D), C95B(H95G,H95H)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C14(H14), C15(H15), C16(H16),
 C17(H17), C18(H18), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24), C26(H26),
  C27(H27), C28(H28), C29(H29), C30(H30), C32(H32), C33(H33), C34(H34),
 C35(H35), C36(H36), C38(H38), C39(H39), C40(H40), C41(H41), C42(H42), C44(H44),
  C45(H45), C46(H46), C47(H47), C48(H48), C60(H60), C59(H59), C58(H58),
 C57(H57), C56(H56), C8(H8), C9(H9), C10(H10), C11(H11), C12(H12), C50(H50),
 C51(H51), C52(H52), C53(H53), C54(H54), C12A(H12A), C11A(H11A), C10A(H10A),
 C9A(H9A), C8A(H8A), C50A(H50A), C51A(H51A), C52A(H52A), C53A(H53A), C54A(H54A)
5.c Fitted hexagon refined as free rotating group:
 C60(C59,C58,C57,C56,C55), C7A(C12A,C11A,C10A,C9A,C8A), C49A(C50A,C51A,C52A,
 C53A,C54A)
;
_olex2_submission_special_instructions 'No special instructions were received'