Pentalenes with novel topologies: exploiting the cascade carbopalladation reaction between alkynes and gem-dibromoolefins
London, Gábor; von Wantoch Rekowski, Margarete; Dumele, Oliver; Schweizer, W. Bernd; Gisselbrecht, Jean-Paul; Boudon, Corinne; Diederich, François; Chemical Science 5 (2014) 965–; doi:10.1039/c3sc52623b

data_1513669
_publ_section_title
;
 Pentalenes with novel topologies: exploiting the cascade carbopalladation
 reaction between alkynes and gem-dibromoolefins
;
_journal_issue                   3
_journal_name_full               'Chemical Science'
_journal_page_first              965
_journal_paper_doi               10.1039/c3sc52623b
_journal_volume                  5
_journal_year                    2014
_chemical_formula_moiety         'C41 H34 Cl2 N2 O2 Si, C4 H8 O2'
_chemical_formula_sum            'C45 H42 Cl2 N2 O4 Si'
_chemical_formula_weight         773.79
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-07-24
_audit_creation_method
;
  Olex2 1.2-beta
  (compiled 2013.04.25 svn.r2679, GUI svn.r4466)
;
_cell_angle_alpha                90
_cell_angle_beta                 112.452(5)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   20.094(7)
_cell_length_b                   17.545(6)
_cell_length_c                   24.430(8)
_cell_measurement_reflns_used    9897
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      21.22
_cell_measurement_theta_min      2.47
_cell_volume                     7960(5)
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.689
_diffrn_measured_fraction_theta_max 0.971
_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_unetI/netI     0.0676
_diffrn_reflns_Laue_measured_fraction_full 0.689
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            9907
_diffrn_reflns_point_group_measured_fraction_full 0.689
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         22.342
_diffrn_reflns_theta_min         1.597
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.239
_exptl_absorpt_correction_T_max  0.7447
_exptl_absorpt_correction_T_min  0.4429
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.1189 before and 0.0858 after correction.
The Ratio of minimum to maximum transmission is 0.5947.
The \l/2 correction factor is 0.0000.
;
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.291
_exptl_crystal_description       prism
_exptl_crystal_F_000             3248
_exptl_crystal_recrystallization_method 'EtOAc, hexane'
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.06
_refine_diff_density_max         1.691
_refine_diff_density_min         -1.068
_refine_diff_density_rms         0.211
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   3.589
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     475
_refine_ls_number_reflns         9907
_refine_ls_number_restraints     34
_refine_ls_restrained_S_all      3.587
_refine_ls_R_factor_all          0.2916
_refine_ls_R_factor_gt           0.2692
_refine_ls_shift/su_max          0.034
_refine_ls_shift/su_mean         0.004
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1500P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.6166
_refine_ls_wR_factor_ref         0.6271
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8219
_reflns_number_total             9907
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c3sc52623b.txt
_cod_data_source_block           mo_d201212_0ma
_cod_depositor_comments
;

2019-02-17
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C90 H84 Cl4 N4 O8 Si2'
_cod_original_formula_weight         1547.59
_cod_original_formula_moiety         '2(C41 H34 Cl2 N2 O2 Si), 2(C4 H8 O2)'
_cod_original_formula_units_Z            4
_cod_database_code               1513669
_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
 Si1-C1 = Si1-C36 = Si1-C33 = Si1-C39
 1.88 with sigma of 0.02
 C36-C38
 1.54 with sigma of 0.02
 Si1A-C1A = Si1A-C36A = Si1A-C39A = Si1A-C33A
 1.88 with sigma of 0.02
 O56-C54 = O56A-C54A
 1.2 with sigma of 0.02
 O53A-C54A = O53-C54
 1.3 with sigma of 0.02
 C52A-C51A = C52-C51
 1.52 with sigma of 0.02
 C55A-C54A = C55-C54
 1.44 with sigma of 0.02
 C35-C33 = C33-C34 = C41-C39 = C40-C39 = C36-C37
 1.54 with sigma of 0.02
 C41A-C39A = C40A-C39A = C33A-C35A = C34A-C33A = C36A-C37A = C36A-C38A
 1.54 with sigma of 0.02
 Si1-C35
 2.86 with sigma of 0.04
 Si1-C34
 2.86 with sigma of 0.04
 Si1-C38
 2.86 with sigma of 0.04
 Si1-C37
 2.86 with sigma of 0.04
 Si1-C40
 2.86 with sigma of 0.04
 Si1-C41
 2.86 with sigma of 0.04
3.a Ternary CH refined with riding coordinates:
 C33(H33), C36(H36), C39(H39), C3A(H3A), C33A(H33A), C36A(H36A), C39A(H39A)
3.b Secondary CH2 refined with riding coordinates:
 C52(H52A,H52B), C52A(H52C,H52D)
3.c Me refined with riding coordinates:
 C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C38A(H38D,H38E,H38F), C41A(H41D,
 H41E,H41F), C51(H51A,H51B,H51C), C55(H55A,H55B,H55C), C51A(H51D,H51E,H51F),
 C55A(H55D,H55E,H55F)
3.d Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11), C17(H17), C18(H18),
 C19(H19), C20(H20), C22(H22), C23(H23), C5A(H5A), C6A(H6A), C8A(H8A), C9A(H9A),
  C10A(H10A), C11A(H11A), C17A(H17A), C18A(H18A), C19A(H19A), C20A(H20A),
 C22A(H22A), C23A(H23A)
3.e Idealised Me refined as rotating group:
 C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C37(H37A,H37B,H37C), C38(H38A,H38B,
 H38C), C34A(H34D,H34E,H34F), C35A(H35D,H35E,H35F), C37A(H37D,H37E,H37F),
 C40A(H40D,H40E,H40F)
;
_shelx_res_checksum              21196
_shelxl_version_number           2013-4