Thionated perylene diimides with intense absorbance in the near-IR.
Llewellyn, Ben A.; Davies, E. Stephen; Pfeiffer, Constance R.; Cooper, Mick; Lewis, William; Champness, Neil R.; Chemical communications (Cambridge, England) 52 (2016) 2099–2102; doi:10.1039/c5cc09962e

data_7118633
_publ_section_title
;
 Thionated perylene diimides with intense absorbance in the near-IR.
;
_journal_issue                   10
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              2099
_journal_page_last               2102
_journal_paper_doi               10.1039/c5cc09962e
_journal_volume                  52
_journal_year                    2016
_chemical_formula_moiety         'C40 H40 N4 O2 S4'
_chemical_formula_sum            'C40.5 H40.5 Cl1.5 N4 O2 S4'
_chemical_formula_weight         796.68
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2015-09-01
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2015-11-03 deposited with the CCDC.
2015-12-15 downloaded from the CCDC.
;
_cell_angle_alpha                96.008(5)
_cell_angle_beta                 95.267(6)
_cell_angle_gamma                118.650(11)
_cell_formula_units_Z            4
_cell_length_a                   12.8268(14)
_cell_length_b                   13.2644(13)
_cell_length_c                   24.5245(7)
_cell_measurement_reflns_used    7909
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      73.4990
_cell_measurement_theta_min      3.8720
_cell_volume                     3593.1(7)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120(2)
_diffrn_crystal_treatment        'flash frozen in gaseous N2'
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 4.2207
_diffrn_detector_type            TitanS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.969
_diffrn_measurement_details
;
  1 omega   74.00  164.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      103.6263   15.0000   30.0000 90

  2 omega   68.00  173.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      103.6263   15.0000  120.0000 105

  3 omega   97.00  122.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      103.6263 -125.0000  150.0000 25

  4 omega   55.00   91.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      103.6263  -30.0000  150.0000 36

  5 omega   51.00  134.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      103.6263  -77.0000  150.0000 83

  6 omega   35.00  101.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      103.6263  -94.0000    0.0000 66

  7 omega   58.00  109.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      103.6263  -94.0000  -60.0000 51

  8 omega   94.00  122.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      103.6263 -125.0000 -120.0000 28

  9 omega   58.00   90.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      103.6263  -30.0000 -180.0000 32

 10 omega   40.00   94.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      103.6263  -45.0000 -120.0000 54

 11 omega   56.00   84.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      103.6263  -30.0000  -60.0000 28

 12 omega   41.00   98.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      103.6263  -45.0000   30.0000 57

 13 omega   59.00  114.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       43.0601   38.0000  -90.0000 55

 14 omega   34.00  134.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      103.6263  -77.0000   30.0000 100

 15 omega   32.00   77.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      103.6263 -125.0000 -120.0000 45

 16 omega    3.00   96.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       43.0601 -125.0000   30.0000 93

 17 omega   32.00   82.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      103.6263  -30.0000   90.0000 50

 18 omega  -27.00   50.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       43.0601  -38.0000   90.0000 77

 19 omega  -50.00  -10.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.0601   38.0000  120.0000 40

 20 omega   20.00  110.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       43.0601   57.0000 -150.0000 90
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'GV1000, TitanS2'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'MiTeGen micromount'
_diffrn_orient_matrix_UB_11      0.1030182000
_diffrn_orient_matrix_UB_12      0.0280196000
_diffrn_orient_matrix_UB_13      -0.0339511000
_diffrn_orient_matrix_UB_21      0.0374102000
_diffrn_orient_matrix_UB_22      0.1302517000
_diffrn_orient_matrix_UB_23      0.0116366000
_diffrn_orient_matrix_UB_31      0.0850188000
_diffrn_orient_matrix_UB_32      0.0169487000
_diffrn_orient_matrix_UB_33      0.0530104000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1332
_diffrn_reflns_av_unetI/netI     0.1383
_diffrn_reflns_laue_measured_fraction_full 0.999
_diffrn_reflns_laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            28315
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.969
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.166
_diffrn_reflns_theta_min         3.673
_diffrn_source                   'rotating-anode X-ray tube'
_diffrn_source_type              'GV1000 (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.808
_exptl_absorpt_correction_T_max  0.928
_exptl_absorpt_correction_T_min  0.780
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
;
_exptl_crystal_colour            'clear dark red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.473
_exptl_crystal_description       plank
_exptl_crystal_F_000             1668
_exptl_crystal_size_max          0.1513
_exptl_crystal_size_mid          0.0405
_exptl_crystal_size_min          0.035
_refine_diff_density_max         1.455
_refine_diff_density_min         -0.658
_refine_diff_density_rms         0.148
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.264
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     974
_refine_ls_number_reflns         14170
_refine_ls_number_restraints     243
_refine_ls_restrained_S_all      1.268
_refine_ls_R_factor_all          0.1863
_refine_ls_R_factor_gt           0.1488
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3777
_refine_ls_wR_factor_ref         0.4157
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8945
_reflns_number_total             14170
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5cc09962e2.cif
_cod_data_source_block           perblm_sq
_cod_original_cell_volume        3593.1(6)
_cod_original_formula_sum        'C40.50 H40.50 Cl1.50 N4 O2 S4'
_cod_database_code               7118633
_nottingham_internal_coll_name   PERBLM
_nottingham_internal_coll_number 15090
_nottingham_internal_coll_client BL/NRC
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method 'omega scans'
_nottingham_internal_coll_frame_time '120.0000, 30.0000'
_nottingham_internal_coll_frame_width 1.0000
_nottingham_internal_coll_user   pcxbl1
_nottingham_internal_coll_date   18/08/2015
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'GVA, PL13110002'
_nottingham_internal_process_date 26/08/2015
_nottingham_internal_process_user pcxbl1
_nottingham_internal_solution_date 26/8/2015
_nottingham_internal_solution_user pcxbl1
_nottingham_internal_refinement_date 1/9/2015
_nottingham_internal_refinement_user pcxbl1/pczcrp/pczwl
_nottingham_internal_self_archive_date 1/9/2015
_nottingham_internal_self_validation_date 1/9/2015
_nottingham_internal_self_validation_user pczcrp/pczwl
_nottingham_internal_validation_date 30/10/2015
_nottingham_internal_validation_user pczwl
_nottingham_internal_archive_date 30/10/2015
_platon_squeeze_void_probe_radius 1.20
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C40H40N4O2S4
_chemical_oxdiff_usercomment
'PERBLM, 15090, on micromount in fomblin, for BL/NRC'
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C64B-C63 \\sim C64-C63B \\sim C64Z-C63Z \\sim C64A-C63A \\sim C54B-C53B \\sim
C54-C53 \\sim C54A-C53A
 with sigma of 0.02
 C53A-C52A \\sim C53-C52 \\sim C53B-C52B \\sim C63A-C62A \\sim C63Z-C62A \\sim
C63-C62B \\sim C63B-C62B
 with sigma of 0.02
 C52-C51A \\sim C52A-C51A \\sim C52B-C51B \\sim C62A-C61A \\sim C62B-C61B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C62B \\sim C63B \\sim C64 \\sim C63 \\sim C64B: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02
C51A \\sim C52A \\sim C53A \\sim C54A \\sim C52 \\sim C53 \\sim C54: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C62B, C63B, C64, C63, C64B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C51A, C52A, C53A, C54A, C52, C53, C54
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H62G)=Sof(H62H)=Sof(C63)=Sof(H63G)=Sof(H63H)=Sof(C64B)=Sof(H64J)=
 Sof(H64K)=Sof(H64L)=1-FVAR(1)
 Sof(H62E)=Sof(H62F)=Sof(C63B)=Sof(H63E)=Sof(H63F)=Sof(C64)=Sof(H64G)=
 Sof(H64H)=Sof(H64I)=FVAR(1)
 Sof(H62C)=Sof(H62D)=Sof(C63Z)=Sof(H63C)=Sof(H63D)=Sof(C64Z)=Sof(H64D)=
 Sof(H64E)=Sof(H64F)=1-FVAR(2)
 Sof(H62A)=Sof(H62B)=Sof(C63A)=Sof(H63A)=Sof(H63B)=Sof(C64A)=Sof(H64A)=
 Sof(H64B)=Sof(H64C)=FVAR(2)
 Sof(H51C)=Sof(H51D)=Sof(C52)=Sof(H52C)=Sof(H52D)=Sof(C53)=Sof(H53C)=Sof(H53D)=
 Sof(C54)=Sof(H54D)=Sof(H54E)=Sof(H54F)=1-FVAR(3)
 Sof(H51A)=Sof(H51B)=Sof(C52A)=Sof(H52A)=Sof(H52B)=Sof(C53A)=Sof(H53A)=
 Sof(H53B)=Sof(C54A)=Sof(H54A)=Sof(H54B)=Sof(H54C)=FVAR(3)
6.a Secondary CH2 refined with riding coordinates:
 C32A(H32A,H32B), C32B(H32C,H32D), C33A(H33A,H33B), C33B(H33C,H33D), C35A(H35A,
 H35B), C35B(H35C,H35D), C36A(H36A,H36B), C36B(H36C,H36D), C42A(H42A,H42B),
 C42B(H42C,H42D), C43A(H43A,H43B), C43B(H43C,H43D), C45A(H45A,H45B), C45B(H45C,
 H45D), C46A(H46A,H46B), C46B(H46C,H46D), C51A(H51A,H51B), C51A(H51C,H51D),
 C51B(H51E,H51F), C52B(H52E,H52F), C53B(H53E,H53F), C61A(H61A,H61B), C61B(H61C,
 H61D), C62A(H62A,H62B), C62A(H62C,H62D), C62B(H62E,H62F), C62B(H62G,H62H),
 C52A(H52A,H52B), C53A(H53A,H53B), C63A(H63A,H63B), C63B(H63E,H63F), C52(H52C,
 H52D), C53(H53C,H53D), C63(H63G,H63H), C63Z(H63C,H63D)
6.b Aromatic/amide H refined with riding coordinates:
 C2A(H2A), C2B(H2B), C5A(H5A), C5B(H5B), C6A(H6A), C6B(H6B), C8A(H8A),
 C8B(H8B), C11A(H11A), C11B(H11B), C12A(H12A), C12B(H12B)
6.c Idealised Me refined as rotating group:
 C54B(H54G,H54H,H54I), C54A(H54A,H54B,H54C), C64(H64G,H64H,H64I), C64A(H64A,
 H64B,H64C), C54(H54D,H54E,H54F), C64B(H64J,H64K,H64L), C64Z(H64D,H64E,H64F)
;
_shelx_res_checksum              41916
_shelx_fab_checksum              88976
_olex2_exptl_crystal_mounting_method 'in fomblin film on a micromount'
_olex2_submission_special_instructions 'No special instructions were received'