Pyrylenes: A New Class of Tunable, Redox-Switchable, Photoexcitable Pyrylium-Carbene Hybrids with Three Stable Redox-States.
Antoni, Patrick W.; Hansmann, Max M.; Journal of the American Chemical Society 140 (2018) 14823–14835; doi:10.1021/jacs.8b08545

data_4133122
_publ_section_title
;
 Pyrylenes: A New Class of Tunable, Redox-Switchable, Photoexcitable
 Pyrylium-Carbene Hybrids with Three Stable Redox-States.
;
_journal_issue                   44
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              14823
_journal_page_last               14835
_journal_paper_doi               10.1021/jacs.8b08545
_journal_volume                  140
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C34 H44 N2 O'
_chemical_formula_sum            'C34 H44 N2 O'
_chemical_formula_weight         496.71
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-05-25
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.18 svn.r3508 for OlexSys, GUI svn.r5497)
;
_cell_angle_alpha                90
_cell_angle_beta                 128.754(2)
_cell_angle_gamma                90
_cell_formula_units_Z            24
_cell_length_a                   29.162(2)
_cell_length_b                   37.089(3)
_cell_length_c                   21.3845(16)
_cell_measurement_reflns_used    9295
_cell_measurement_temperature    149.93
_cell_measurement_theta_max      32.60
_cell_measurement_theta_min      2.60
_cell_volume                     18037(2)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      149.93
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0357
_diffrn_reflns_av_unetI/netI     0.0365
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       44
_diffrn_reflns_limit_h_min       -44
_diffrn_reflns_limit_k_max       56
_diffrn_reflns_limit_k_min       -56
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            243600
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.623
_diffrn_reflns_theta_min         2.081
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.065
_exptl_absorpt_correction_T_max  0.9012
_exptl_absorpt_correction_T_min  0.8492
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0773 before and 0.0509 after correction. The Ratio of minimum to maximum transmission is 0.9423. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.098
_exptl_crystal_description       block
_exptl_crystal_F_000             6480
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of thf and pentane  by slow evaporation'
_exptl_crystal_size_max          0.437
_exptl_crystal_size_mid          0.385
_exptl_crystal_size_min          0.247
_refine_diff_density_max         0.369
_refine_diff_density_min         -0.212
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.6(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2072
_refine_ls_number_reflns         60427
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0702
_refine_ls_R_factor_gt           0.0503
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0776P)^2^+4.7996P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1360
_refine_ls_wR_factor_ref         0.1503
_reflns_Friedel_coverage         0.999
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                46463
_reflns_number_total             60427
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b08545_si_002.cif
_cod_data_source_block           c2c_supercell
_cod_database_code               4133122
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.984
_shelx_estimated_absorpt_t_min   0.972
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.4(13)
 0.6(13)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C9(H9), C17(H17), C19(H19), C24(H24), C25(H25), C28(H28), C30(H30),
 C37(H37), C43(H43), C51(H51), C53(H53), C58(H58), C59(H59), C62(H62), C64(H64),
  C71(H71), C77(H77), C85(H85), C87(H87), C92(H92), C93(H93), C96(H96),
 C98(H98), C105(H105), C111(H111), C119(H119), C121(H121), C126(H126),
 C127(H127), C130(H130), C132(H132), C139(H139), C145(H145), C153(H153),
 C155(H155), C160(H160), C161(H161), C164(H164), C166(H166), C173(H173),
 C179(H179), C187(H187), C189(H189), C194(H194), C195(H195), C198(H198),
 C200(H200)
3.b Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C12(H12A,H12B,H12C),
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C21(H21A,H21B,H21C), C22(H22A,H22B,
 H22C), C23(H23A,H23B,H23C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C34(H34A,
 H34B,H34C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C),
 C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C55(H55A,H55B,
 H55C), C56(H56A,H56B,H56C), C57(H57A,H57B,H57C), C66(H66A,H66B,H66C), C67(H67A,
 H67B,H67C), C68(H68A,H68B,H68C), C74(H74A,H74B,H74C), C75(H75A,H75B,H75C),
 C76(H76A,H76B,H76C), C80(H80A,H80B,H80C), C81(H81A,H81B,H81C), C82(H82A,H82B,
 H82C), C89(H89A,H89B,H89C), C90(H90A,H90B,H90C), C91(H91A,H91B,H91C),
 C100(H10A,H10B,H10C), C101(H10D,H10E,H10F), C102(H10G,H10H,H10I), C108(H10J,
 H10K,H10L), C109(H10M,H10N,H10O), C110(H11A,H11B,H11C), C114(H11D,H11E,H11F),
 C115(H11G,H11H,H11I), C116(H11J,H11K,H11L), C123(H12D,H12E,H12F), C124(H12G,
 H12H,H12I), C125(H12J,H12K,H12L), C134(H13D,H13E,H13F), C135(H13G,H13H,H13I),
 C136(H13J,H13K,H13L), C142(H14D,H14E,H14F), C143(H14G,H14H,H14I), C144(H14J,
 H14K,H14L), C148(H14M,H14N,H14O), C149(H14P,H14Q,H14R), C150(H15A,H15B,H15C),
 C157(H15D,H15E,H15F), C158(H15G,H15H,H15I), C159(H15J,H15K,H15L), C168(H16A,
 H16B,H16C), C169(H16D,H16E,H16F), C170(H17A,H17B,H17C), C176(H17D,H17E,H17F),
 C177(H17G,H17H,H17I), C178(H17J,H17K,H17L), C182(H18A,H18B,H18C), C183(H18D,
 H18E,H18F), C184(H18G,H18H,H18I), C191(H19A,H19B,H19C), C192(H19D,H19E,H19F),
 C193(H19G,H19H,H19I), C202(H20A,H20B,H20C), C203(H20D,H20E,H20F), C204(H20G,
 H20H,H20I)
;
_shelx_res_checksum              91817
_shelx_hkl_checksum              39328
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 800'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in perfluoroether oil'
_olex2_submission_special_instructions 'No special instructions were received'