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_1513671
_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         'C33 H34 O2 Si, 0.25(C4 H10 O)'
_chemical_formula_sum            'C34 H36.5 O3.25 Si'
_chemical_formula_weight         525.22
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-07-22
_audit_creation_method
;
  Olex2 1.2-beta
  (compiled 2013.04.25 svn.r2679, GUI svn.r4466)
;
_cell_angle_alpha                90
_cell_angle_beta                 90.665(4)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   38.218(8)
_cell_length_b                   19.296(4)
_cell_length_c                   8.5140(18)
_cell_measurement_reflns_used    9264
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.27
_cell_measurement_theta_min      2.66
_cell_volume                     6278(2)
_computing_cell_refinement
;
Bruker (2010). SAINT Release 7.68A. Integration Software for Single Crystal
Data. Bruker AXS Inc., Madison, USA.
;
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction
;
Bruker (2010). SAINT Release 7.68A. Integration Software for Single Crystal
Data. Bruker AXS Inc., Madison, USA.
;
_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
'SHELXS-97 (Sheldrick, G.M. (2008). Acta Cryst. A64, 112-122.'
_computing_structure_solution
'SHELXS-97 (Sheldrick, G.M. (2008). Acta Cryst. A64, 112-122.'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0494
_diffrn_reflns_av_sigmaI/netI    0.0437
_diffrn_reflns_limit_h_max       48
_diffrn_reflns_limit_h_min       -49
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            42742
_diffrn_reflns_theta_full        27.61
_diffrn_reflns_theta_max         27.61
_diffrn_reflns_theta_min         1.92
_exptl_absorpt_coefficient_mu    0.106
_exptl_absorpt_correction_T_max  0.9921
_exptl_absorpt_correction_T_min  0.9748
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.111
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             2244
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.281
_refine_diff_density_min         -0.421
_refine_diff_density_rms         0.063
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.240
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     331
_refine_ls_number_reflns         7289
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.240
_refine_ls_R_factor_all          0.0832
_refine_ls_R_factor_gt           0.0599
_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^)+(0.1000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1802
_refine_ls_wR_factor_ref         0.1886
_reflns_number_gt                5487
_reflns_number_total             7289
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c3sc52623b.txt
_cod_data_source_block           mo_d050413_0m
_cod_original_formula_sum        'C34 H36.50 O3.25 Si'
_cod_database_code               1513671
_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.a Ternary CH refined with riding coordinates:
 C2(H2), C28(H28), C31(H31)
2.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C7(H7), C8(H8), C10(H10), C11(H11), C14(H14), C15(H15), C17(H17),
 C18(H18), C19(H19), C20(H20), C26(H26), C27(H27)
2.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C12(H12A,H12B,H12C), C29(H29A,H29B,H29C), C30(H30A,H30B,
 H30C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C)
;
_olex_mask_details
;
Total solvent accessible volume / cell = 1238.7 Ang^3 [19.7%]
Total electron count / cell = 86.9

gridding: (200,108,48)
Void #Grid points Vol/A^3 Vol/%  Centre of mass (frac)   Eigenvectors (frac)
 1   98492   596.4   9.5  (-0.000, 0.000,-0.331)  1  (-0.004, 1.000,-0.000)
                                                  2  ( 0.998, 0.004, 0.062)
                                                  3  (-0.062, 0.000, 0.998)
 2    1894    11.5   0.2  (-0.000, 0.448, 0.250)  1  ( 0.006, 0.000, 1.000)
                                                  2  ( 0.000, 1.000, 0.000)
                                                  3  ( 1.000, 0.000,-0.006)
 3    1894    11.5   0.2  ( 0.000, 0.552, 0.750)  1  ( 0.006, 0.000, 1.000)
                                                  2  ( 0.000, 1.000, 0.000)
                                                  3  ( 1.000, 0.000,-0.006)
 4   98492   596.4   9.5  ( 0.500, 0.500,-0.383)  1  ( 0.002, 1.000, 0.000)
                                                  2  ( 0.996,-0.002, 0.087)
                                                  3  (-0.087,-0.000, 0.996)
 5    1894    11.5   0.2  ( 0.500, 0.052, 0.750)  1  ( 0.006, 0.000, 1.000)
                                                  2  ( 0.000, 1.000, 0.000)
                                                  3  ( 1.000, 0.000,-0.006)
 6    1894    11.5   0.2  ( 0.500, 0.948, 0.250)  1  ( 0.006, 0.000, 1.000)
                                                  2  ( 0.000, 1.000, 0.000)
                                                  3  ( 1.000, 0.000,-0.006)

Void  Vol/Ang^3  #Electrons
   1      596.4         41.0
   2       11.5          1.2
   3       11.5          1.2
   4      596.4         41.0
   5       11.5          1.2
   6       11.5          1.2
;
_shelx_estimated_absorpt_t_max   0.992
_shelx_estimated_absorpt_t_min   0.973
_shelxl_version_number           2013-4