Synthesis, Structure, and Resolution of Exceptionally Twisted Pentacenes
Jun Lu; Douglas M. Ho; Nancy J. Vogelaar; Christina M. Kraml; Stefan Bernhard; Neal Byrne; Laura R. Kim; Robert A. Pascal; Journal of the American Chemical Society 128 (2006) 17043–17050; doi:10.1021/ja065935f

data_4111265
_publ_contact_author_address
;
Princeton University
Department of Chemistry
Princeton, NJ   08544-1009
USA
;
_publ_contact_author_email       snake@princeton.edu
_publ_contact_author_fax         '(609) 258 6746'
_publ_contact_author_name        'Professor Robert A. Pascal, Jr.'
_publ_contact_author_phone       '(609) 258 5417'
_publ_section_title
;
 Synthesis, Structure, and Resolution of Exceptionally Twisted Pentacenes
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              17043
_journal_page_last               17050
_journal_paper_doi               10.1021/ja065935f
_journal_volume                  128
_journal_year                    2006
_chemical_absolute_configuration unk
_chemical_compound_source        'chemical synthesis'
_chemical_formula_iupac          'C76 H50 . 2.5(C4 H8 O2)'
_chemical_formula_moiety         'C76 H50, 2.5(C4 H8 O2)'
_chemical_formula_structural     'C76 H50 . 2.5(C4 H8 O2)'
_chemical_formula_sum            'C84 H70 O5'
_chemical_formula_weight         1159.40
_chemical_name_systematic
;
9,11,20,22-Tetraphenyl-10,21-di-p-tolyltetrabenzo[a,c,l,n]pentacene
Ethyl Acetate Solvate
;
_space_group_IT_number           4
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      4
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             'July 7, 2006'
_audit_creation_method
;
SHELXL and manual editing of form.cif
;
_audit_update_record
;
July 7, 2006  rap135f.cif         Initial CIF created by DMH.

July 7, 2006  Sent to Checkcif.   See rap135f_checkcif.pdf for
                                  the alerts that were generated.
                                  Selected responses follow.

-------------------------------------------------------------------------

CHEMW03_ALERT_2_A The ratio of given/expected molecular weight as
                  calculated from the _atom_site* data lies outside the
                  range 0.90 <> 1.10.
                  From _chemical_formula_weight                   1159.40
                  Calculated formula weight                        963.24
PLAT043_ALERT_1_A Check Reported Molecular Weight ............... 1159.40
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ ............ ?
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)........ ?
PLAT602_ALERT_4_C VERY LARGE Solvent Accessible VOID(S) in Structure    !
FORMU01_ALERT_1_G There is a discrepancy between the atom counts in the
                  _chemical_formula_sum and _chemical_formula_ moiety.
FORMU01_ALERT_2_G There is a discrepancy between the atom counts in the
                  _chemical_formula_sum and the formula from the _atom_
                  site* data.
CELLZ01_ALERT_1_G Difference between formula and atom_site contents
                  detected.
CELLZ01_ALERT_1_G Large difference may be due to a symmetry error.

                  The alerts CHEMW03_ALERT_2_A to CELLZ01_ALERT_1_G
                  indicated above are not a problem.  They simply reflect
                  the fact that the solvent atoms were excluded from the
                  _atom_site* data because the SQUEEZE/BYPASS procedure
                  was used.  See the _refine_special_details section
                  below.  It follows that the correctly Reported MW and
                  Dx values (which include those solvent atoms) of
                  1159.40 and 1.215 "would" be larger than the incor-
                  rectly Calculated values based on the _atom_site* data.
                  Similarly, the correctly Reported F000 value of 2456 is
                  (as it should be) larger than the incorrectly Calcu-
                  lated value of 2024.  none of these discrepancies and
                  differences are due to a symmetry error.

THETM01_ALERT_3_A The value of sine(theta_max)/wavelength is      < 0.550
                  Calculated sin(theta_max)/wavelength =           0.5387
PLAT027_ALERT_3_A _diffrn_reflns_theta_full (too) Low ........ 22.51 Deg.

                  The alerts THETM01_ALERT_3_A and PLAT027_ALERT_3_A are
                  not a problem.  They simply reflect the fact that the
                  crystal available for the experiment was not of
                  sufficient quality to provide usable data to higher
                  angles.  As indicated above, the solvent sites within
                  the crystal were particularly ill-behaved.  It is not
                  uncommon to find that the presence of badly disordered
                  solvents will diminish the effective resolution of a
                  data set.  Therefore, only a 0.93 Angstrom resolution
                  data set was targeted.  Nevertheless, such a data set
                  is still considered to be of "atomic resolution", and
                  still meets the community's standards of acceptability
                  in such severe disorder cases.

PLAT220_ALERT_2_A Large Non-Solvent C Ueq(max)/Ueq(min) ...... 4.79 Ratio
PLAT222_ALERT_3_A Large Non-Solvent H Ueq(max)/Ueq(min) ...... 5.05 Ratio
PLAT220_ALERT_2_B Large Non-Solvent C Ueq(max)/Ueq(min) ...... 4.24 Ratio
PLAT222_ALERT_3_B Large Non-Solvent H Ueq(max)/Ueq(min) ...... 4.20 Ratio
PLAT230_ALERT_2_B Hirshfeld Test Diff for C3 - C4 ............... 8.66 su
PLAT230_ALERT_2_B Hirshfeld Test Diff for C19A - C19B ........... 7.52 su
PLAT230_ALERT_2_B Hirshfeld Test Diff for C22 - C53 ............. 7.47 su
PLAT230_ALERT_2_B Hirshfeld Test Diff for C79A - C79B ........... 7.01 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for C4B - C8A ............. 5.38 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for C11A - C19B ........... 5.17 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for C13 - C14 ............. 5.95 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for C23 - C28 ............. 5.60 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for C33 - C34 ............. 5.44 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for C38 - C39 ............. 5.65 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for C71A - C79B ........... 5.36 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for C73 - C74 ............. 5.84 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for C76 - C77 ............. 5.54 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for C80A - C81 ............ 5.49 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for C87 - C88 ............. 6.63 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for C98 - C99 ............. 6.89 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for C107 - C112 ........... 5.83 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for C114 - C115 ........... 5.34 su
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors ........ for C32
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors ........ for C92
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ........ 6
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ............. 6

                  The alerts PLAT220_ALERT_2_A to PLAT720_ALERT_4_C are
                  not unexpected, and given the situation are acceptable.
                  The observed variations in the displacement parameters
                  are attributable to neighboring effects of disordered
                  solvent molecules and on pseudo-symmetry effects.  The
                  high levels of thermal motion in various parts of the
                  molecules seem to be chemically and physically reason-
                  able, so no attempt was made to artificially mask those
                  variations through the use of restraints.  The 6 labels
                  flagged by CheckCif as unusual are H1ME, H2ME, H3ME,
                  H4ME, H5ME and H6ME, i.e., the methyl hydrogens on C119
                  and C120.  Due to the 4 character limit in Siemens
                  SHELXTL, labels such as H119A, H119B, H119C, H120A,
                  H120B and H120C were unavailable to us.  Hence, the 6
                  hydrogens were labelled H1 through H6 with a ME suffix
                  to differentiate them from the aromatic H1 through H6
                  atoms.  CheckCif considers the H1ME to H6ME labels to
                  be unusual, and we simply indicate here that there was
                  a reason for their selection and use.  Using the labels
                  H1ME through H6ME does not alter the final numeric
                  crystallographic results, so there is no overwhelming
                  justification to say that they are not fine as is.

PLAT024_ALERT_4_B Merging of Friedel Pairs is STRONGLY Indicated ...... !
REFLT03_ALERT_4_G MoKa measured Friedel data cannot be used to determine
                  absolute structure in a light-atom study EXCEPT under
                  VERY special conditions. It is preferred that Friedel
                  data is merged in such cases.

                  PLAT024_ALERT_4_B and REFLT03_ALERT_4_G are the same,
                  and is only a recommendation.  In truth and on theoret-
                  ical grounds, Friedel data is unique and should not be
                  merged.  Therefore, it is not wrong to ignore this
                  CheckCif recommendation, and to exercise our right to
                  retain the data as unmerged.

STRVA01_ALERT_4_C Flack parameter is too small
                  From the CIF: _refine_ls_abs_structure_Flack     -5.120
                  From the CIF: _refine_ls_abs_structure_Flack_su   7.210
PLAT032_ALERT_4_C Std. Uncertainty in Flack Parameter too High ..... 7.00
PLAT033_ALERT_2_C Flack Parameter Value Deviates from Zero ........ -5.00

                  STRVA01_ALERT_4_C, PLAT032_ALERT_4_C and PLAT033_ALERT_
                  2_C are obviously all saying the same thing.  Yes, we
                  agree that the absolute structure cannot be determined
                  based on the intensity data, and no attempt is made on
                  our part to suggest that it has.  In fact, both left-
                  and right-handed twistomers are present in the crystal,
                  and solutions at equilibrium are expected to be racemic.
                  That the compound has crystallized in a chiral space
                  groups seems to be due simply to the molecules being
                  unable to pack and efficiently fill space based on a
                  centrosymmetric motif.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 105.778(1)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   14.8577(3)
_cell_length_b                   29.2657(6)
_cell_length_c                   15.1524(5)
_cell_measurement_reflns_used    74302
_cell_measurement_temperature    200(2)
_cell_measurement_theta_max      22.51
_cell_measurement_theta_min      1.39
_cell_volume                     6340.3(3)
_computing_cell_refinement       'DENZO-SMN (Otwinowski & Minor, 1997)'
_computing_data_collection       'COLLECT (Nonius, 1998)'
_computing_data_reduction
;
DENZO-SMN (Otwinowski & Minor, 1997), PLATON (Spek, 2003),
Siemens SHELXTL (Sheldrick, 1996)
;
_computing_molecular_graphics    'Siemens SHELXTL (Sheldrick, 1996)'
_computing_publication_material  'Siemens SHELXTL (Sheldrick, 1996)'
_computing_structure_refinement  'Siemens SHELXTL (Sheldrick, 1996)'
_computing_structure_solution    'Siemens SHELXTL (Sheldrick, 1996)'
_diffrn_ambient_temperature      200(2)
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device       'Nonius KappaCCD'
_diffrn_measurement_method       '\w scans, 1760 0.5\% rotations'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0800
_diffrn_reflns_av_sigmaI/netI    0.0605
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            74302
_diffrn_reflns_theta_full        22.51
_diffrn_reflns_theta_max         22.51
_diffrn_reflns_theta_min         1.39
_diffrn_standards_decay_%        0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.074
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            Orange
_exptl_crystal_density_diffrn    1.215
_exptl_crystal_description       Prism
_exptl_crystal_F_000             2456
_exptl_crystal_size_max          0.33
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.13
_refine_diff_density_max         0.295
_refine_diff_density_min         -0.208
_refine_diff_density_rms         0.051
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -5.12(721)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_all   1.038
_refine_ls_goodness_of_fit_ref   1.092
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1373
_refine_ls_number_reflns         16570
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.038
_refine_ls_restrained_S_gt       1.092
_refine_ls_R_factor_all          0.0767
_refine_ls_R_factor_gt           0.0630
_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^)+(0.0874P)^2^+0.9666P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.1531
_refine_ls_wR_factor_ref         0.1460
_reflns_number_gt                13774
_reflns_number_total             16570
_reflns_threshold_expression     I>2\s(I)
_cod_data_source_file            ja065935fsi20060815_063926.cif
_cod_data_source_block           rap135f
_cod_original_sg_symbol_H-M      'P 21'
_cod_database_code               4111265