Synthesis and electronic properties of A3B-thienyl porphyrins: experimental and computational investigations
Kumar, Poomani Ram; Britto, Neethinathan Johnee; Kathiravan, Arunkumar; Neels, Antonia; Jaccob, Madhavan; Mothi, Ebrahim M.; New Journal of Chemistry 43 (2019) 1569–; doi:10.1039/C8NJ04289F

data_7058040
_publ_section_title
;
 Synthesis and electronic properties of A3B-thienyl porphyrins:
 experimental and computational investigations
;
_journal_issue                   3
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              1569
_journal_paper_doi               10.1039/C8NJ04289F
_journal_volume                  43
_journal_year                    2019
_chemical_formula_moiety         'C41 H30 N4 O3 S3'
_chemical_formula_sum            'C44 H33 N4 O3 S3'
_chemical_formula_weight         761.92
_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
_audit_creation_date             2018-10-10
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-10-09 deposited with the CCDC.
2018-12-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.247(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.3276(11)
_cell_length_b                   13.0193(7)
_cell_length_c                   23.939(2)
_cell_measurement_reflns_used    36440
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      25.58
_cell_measurement_theta_min      1.65
_cell_volume                     3836.0(5)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector_area_resol_mean 6.67
_diffrn_measured_fraction_theta_full 0.984
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_device_type  'STOE IPDS 2'
_diffrn_measurement_method       'rotation method'
_diffrn_radiation_monochromator  'plane graphite'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0610
_diffrn_reflns_av_unetI/netI     0.0310
_diffrn_reflns_Laue_measured_fraction_full 0.984
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            48920
_diffrn_reflns_point_group_measured_fraction_full 0.984
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        25.232
_diffrn_reflns_theta_max         25.232
_diffrn_reflns_theta_min         1.655
_exptl_absorpt_coefficient_mu    0.240
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            'clear dark blue'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.319
_exptl_crystal_description       rod
_exptl_crystal_F_000             1588
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.45
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.202
_refine_diff_density_min         -0.288
_refine_diff_density_rms         0.041
_refine_ls_extinction_coef       0.0020(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.012
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     498
_refine_ls_number_reflns         6839
_refine_ls_number_restraints     26
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.0527
_refine_ls_R_factor_gt           0.0377
_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^)+(0.0694P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1027
_refine_ls_wR_factor_ref         0.1090
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5036
_reflns_number_total             6839
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8nj04289f2.cif
_cod_data_source_block           mr68
_cod_depositor_comments
'Adding full bibliography for 7058040--7058041.cif.'
_cod_database_code               7058040
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.932
_shelx_estimated_absorpt_t_min   0.890
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H,H) groups
2. Restrained distances
 C15-C16 = C15-C16A = C24-C25 = C24-C25A
 1.38 with sigma of 0.02
 C25-C26 = C26-C27 = C16-C17 = C17-C18
 1.43 with sigma of 0.02
 C25A-C26A = C26A-C27A = C16A-C17A = C17A-C18A
 1.43 with sigma of 0.02
 C15-S2 = C15-S2A = S2-C18 = S2A-C18A
 1.72 with sigma of 0.02
 C24-S3 = C24-S3A = S3-C27 = S3A-C27A
 1.72 with sigma of 0.02
 S2A-C16A = S2A-C17A
 2.56 with sigma of 0.02
 S3A-C26A = S3A-C25A
 2.56 with sigma of 0.02
 C16A-C18A
 2.3 with sigma of 0.02
 C25A-C27A
 2.3 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(S2) = Uanis(C16A)
Uanis(S2A) = Uanis(C16)
Uanis(C17) = Uanis(C18A)
Uanis(C17A) = Uanis(C18)
Uanis(S3) = Uanis(C25A)
Uanis(S3A) = Uanis(C25)
Uanis(C26) = Uanis(C27A)
Uanis(C26A) = Uanis(C27)
4. Others
 Sof(C16A)=Sof(H16A)=Sof(C17A)=Sof(H17A)=Sof(C18A)=Sof(H18A)=1-FVAR(1)
 Sof(C16)=Sof(H16)=Sof(C17)=Sof(H17)=Sof(C18)=Sof(H18)=FVAR(1)
 Sof(C25A)=Sof(H25A)=Sof(C26A)=Sof(H26A)=Sof(C27A)=Sof(H27A)=1-FVAR(2)
 Sof(C25)=Sof(H25)=Sof(C26)=Sof(H26)=Sof(C27)=Sof(H27)=FVAR(2)
 Fixed Sof: S2(0.7) S2A(0.3) S3(0.8) S3A(0.2)
5.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C7(H7), C8(H8), C9(H9), C11(H11), C12(H12), C16(H16),
 C17(H17), C18(H18), C16A(H16A), C17A(H17A), C18A(H18A), C20(H20), C21(H21),
 C25(H25), C26(H26), C27(H27), C25A(H25A), C26A(H26A), C27A(H27A), C29(H29),
 C30(H30), C34(H34), C38(H38)
5.b Idealised Me refined as rotating group:
 C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C)
;
_shelx_res_checksum              84901
_shelx_hkl_checksum              23632
_shelx_fab_checksum              13417
_olex2_submission_original_sample_id 'Compound 8'
_olex2_submission_special_instructions 'No special instructions were received'