A Stable Aromatic Tetrasilacyclobutadiene Dication.
Sun, Xiaofei; Simler, Thomas; Yadav, Ravi; Köppe, Ralf; Roesky, Peter W.; Journal of the American Chemical Society 141 (2019) 14987–14990; doi:10.1021/jacs.9b08018

data_4129013
_publ_contact_author
;
      Prof. Dr. Peter W. Roesky
      Karlsruher Institut fuer Technologie (KIT), CS
      Institut fuer Anorganische Chemie (AOC)
      Lehrstuhl fuer Anorganische Funktionsmaterialien
      Engesserstr. 15, Geb. 30.45
      76131 Karlsruhe 
      Bundesrepublik Deutschland
;
_publ_section_title
;
 A Stable Aromatic Tetrasilacyclobutadiene Dication.
;
_journal_issue                   38
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              14987
_journal_page_last               14990
_journal_paper_doi               10.1021/jacs.9b08018
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety
'C61.34 H92.02 N8 Si4, 2(C24 H20 B), 2(C2 H3 N)'
_chemical_formula_sum            'C113.34 H138.02 B2 N10 Si4'
_chemical_formula_weight         1774.41
_space_group_crystal_system      orthorhombic
_space_group_IT_number           60
_space_group_name_Hall           '-P 2n 2ab'
_space_group_name_H-M_alt        'P b c n'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-06-07
_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                   23.0452(2)
_cell_length_b                   17.8779(2)
_cell_length_c                   25.1244(3)
_cell_measurement_reflns_used    90314
_cell_measurement_temperature    130
_cell_measurement_theta_max      64.33
_cell_measurement_theta_min      2.15
_cell_volume                     10351.25(19)
_computing_cell_refinement
;
X-Area Recipe 1.33.0.0 (STOE, 2015)
PLATON (A.L.Spek, 2009)
;
_computing_data_collection       'X-Area Pilatus3_SV 1.31.150.0 (STOE, 2018)'
_computing_data_reduction
;
X-Area Integrate 1.73.1.0 (STOE, 2018)
X-Area LANA 1.73.2.0 (STOE, 2018)
PLATON (A.L.Spek, 2009)
;
_computing_molecular_graphics    'Diamond 4, Olex2 (Dolomanov et al., 2009)'
_computing_publication_material
;
STOE & Cie GmbH, X-Area, software package for collecting single-crystal or
multi-domain crystal data on STOE area-detector diffractometers, for image 
processing, for the correction and scaling of reflection intensities and 
for outlier rejection, version 1.84, Darmstadt 2018
MS Word (Microsoft)
Olex2 (Dolomanov et al., 2009)
;
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS-2018/3 (Sheldrick, 2015)'
_diffrn_ambient_temperature      130
_diffrn_detector_area_resol_mean 13.33
_diffrn_detector_type            Dectris
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device       'Eulerian 4-circle diffractometer'
_diffrn_measurement_device_type  StadiVari
_diffrn_measurement_method       'rotation method, \w scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34143
_diffrn_reflns_av_R_equivalents  0.0176
_diffrn_reflns_av_unetI/netI     0.0123
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            61881
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        53.597
_diffrn_reflns_theta_max         62.497
_diffrn_reflns_theta_min         2.722
_exptl_absorpt_coefficient_mu    0.599
_exptl_absorpt_correction_T_max  0.8041
_exptl_absorpt_correction_T_min  0.2450
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'STOE XRED, XSHAPE & LANA'
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.139
_exptl_crystal_description       block
_exptl_crystal_F_000             3816
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.17
_refine_diff_density_max         0.664
_refine_diff_density_min         -0.402
_refine_diff_density_rms         0.047
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     767
_refine_ls_number_reflns         12453
_refine_ls_number_restraints     159
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0693
_refine_ls_R_factor_gt           0.0610
_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^)+(0.0758P)^2^+6.7470P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1648
_refine_ls_wR_factor_ref         0.1707
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10662
_reflns_number_total             12453
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b08018_si_004.cif
_cod_data_source_block           tsxf13
_cod_database_code               4129013
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.905
_shelx_estimated_absorpt_t_min   0.890
_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
2. Restrained distances
 H41-H8AA
 2 with sigma of 0.001
 C8B-C5B \\sim C8A-C5A
 with sigma of 0.001
 C4A-C8A \\sim C8A-C6A
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C2B \\sim C7B \\sim C6B \\sim C5B \\sim C4B \\sim C3B \\sim C8B: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
C2A \\sim C3A \\sim C4A \\sim C5A \\sim C6A \\sim C7A \\sim C8A: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
C51A \\sim C52A \\sim C53A \\sim C54A \\sim C55A \\sim C56A: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
C51B \\sim C52B \\sim C53B \\sim C54B \\sim C55B \\sim C56B: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Fixed Sof: C24(0.45) H24A(0.45) H24B(0.45) H24C(0.45) C2A(0.88) C7A(0.88)
 H7A(0.88) C6A(0.88) H6A(0.88) C5A(0.88) C4A(0.88) H4A(0.88) C3A(0.88)
 H3A(0.88) C26A(0.5) H26A(0.5) H26B(0.5) H26C(0.5) C27A(0.5) H27A(0.5)
 H27B(0.5) H27C(0.5) C28A(0.5) H28A(0.5) H28B(0.5) H28C(0.5) C30A(0.667)
 H30A(0.667) H30B(0.667) H30C(0.667) C31A(0.667) H31A(0.667) H31B(0.667)
 H31C(0.667) C32A(0.667) H32A(0.667) H32B(0.667) H32C(0.667) C26B(0.5)
 H26D(0.5) H26E(0.5) H26F(0.5) C27B(0.5) H27D(0.5) H27E(0.5) H27F(0.5)
 C28B(0.5) H28D(0.5) H28E(0.5) H28F(0.5) C30B(0.333) H30D(0.333) H30E(0.333)
 H30F(0.333) C31B(0.333) H31D(0.333) H31E(0.333) H31F(0.333) C32B(0.333)
 H32D(0.333) H32E(0.333) H32F(0.333) C51A(0.5) C56A(0.5) H56A(0.5) C55A(0.5)
 H55A(0.5) C54A(0.5) H54A(0.5) C53A(0.5) H53A(0.5) C52A(0.5) H52A(0.5)
 C51B(0.5) C56B(0.5) H56B(0.5) C55B(0.5) H55B(0.5) C54B(0.5) H54B(0.5)
 C53B(0.5) H53B(0.5) C52B(0.5) H52B(0.5) N6(0.5) C59(0.5) C60(0.5) H60A(0.5)
 H60B(0.5) H60C(0.5) N5(0.5) C57(0.5) C58(0.5) H58A(0.5) H58B(0.5) H58C(0.5)
 C8B(0.12) H8BA(0.12) H8BB(0.12) H8BC(0.12) C2B(0.12) C7B(0.12) H7B(0.12)
 C6B(0.12) H6B(0.12) C5B(0.12) C4B(0.12) H4B(0.12) C3B(0.12) H3B(0.12) C8A(0.1)
 H8AA(0.1) H8AB(0.1) H8AC(0.1)
5.a Me refined with riding coordinates:
 C8B(H8BA,H8BB,H8BC)
5.b Aromatic/amide H refined with riding coordinates:
 C23(H23), C22(H22), C20(H20), C19(H19), C7A(H7A), C6A(H6A), C4A(H4A),
 C3A(H3A), C34(H34), C35(H35), C36(H36), C37(H37), C38(H38), C40(H40), C41(H41),
  C42(H42), C43(H43), C44(H44), C46(H46), C47(H47), C48(H48), C49(H49),
 C50(H50), C56A(H56A), C55A(H55A), C54A(H54A), C53A(H53A), C52A(H52A),
 C56B(H56B), C55B(H55B), C54B(H54B), C53B(H53B), C52B(H52B), C7B(H7B), C6B(H6B),
  C4B(H4B), C3B(H3B)
5.c Fitted hexagon refined as free rotating group:
 C2A(C7A,C6A,C5A,C4A,C3A), C51A(C56A,C55A,C54A,C53A,C52A), C51B(C56B,C55B,C54B,
 C53B,C52B), C2B(C7B,C6B,C5B,C4B,C3B)
5.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C14(H14A,H14B,
 H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C24(H24A,H24B,H24C),
 C26A(H26A,H26B,H26C), C27A(H27A,H27B,H27C), C28A(H28A,H28B,H28C), C30A(H30A,
 H30B,H30C), C31A(H31A,H31B,H31C), C32A(H32A,H32B,H32C), C26B(H26D,H26E,H26F),
 C27B(H27D,H27E,H27F), C28B(H28D,H28E,H28F), C30B(H30D,H30E,H30F), C31B(H31D,
 H31E,H31F), C32B(H32D,H32E,H32F), C60(H60A,H60B,H60C), C58(H58A,H58B,H58C),
 C8A(H8AA,H8AB,H8AC)
;
_shelx_res_checksum              50125
_shelx_hkl_checksum              40778
_olex2_submission_special_instructions 'No special instructions were received'