Lead-Halide Perovskites Meet Donor‒Acceptor Charge-Transfer Complexes
Marchal, Nadège; Van Gompel, Wouter; Gélvez-Rueda, María C.; Vandewal, Koen; Van Hecke, Kristof; Boyen, Hans-Gerd; Conings, Bert; Herckens, Roald; Maheshwari, Sudeep; Lutsen, Laurence; Quarti, Claudio; Grozema, Ferdinand C.; Vanderzande, Dirk; Beljonne, David; Chemistry of Materials 31 (2019) 6880–; doi:10.1021/acs.chemmater.9b01289

data_4002967
_publ_section_title
;
 Lead-Halide Perovskites Meet Donor--Acceptor Charge-Transfer Complexes
;
_journal_issue                   17
_journal_name_full               'Chemistry of Materials'
_journal_page_first              6880
_journal_paper_doi               10.1021/acs.chemmater.9b01289
_journal_volume                  31
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C20 H20 N, C12 H4 N4, I3 Pb'
_chemical_formula_sum            'C32 H24 I3 N5 Pb'
_chemical_formula_weight         1066.46
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'I -2ya'
_space_group_name_H-M_alt        'I 1 a 1'
_symmetry_space_group_name_Hall  'I -2ya'
_symmetry_space_group_name_H-M   'I 1 a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2018-04-02
_audit_creation_method
;
Olex2 1.2
(compiled Aug 10 2017 17:28:52 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 97.458(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.0302(2)
_cell_length_b                   42.3950(9)
_cell_length_c                   9.4390(2)
_cell_measurement_reflns_used    26322
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      29.3680
_cell_measurement_theta_min      2.6180
_cell_volume                     3186.23(13)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4839
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.946
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w     -7.00  60.00   1.00   45.00    --   10.40-114.00 145.00   67
  2  \w     39.00  96.00   1.00   45.00    --   10.40 174.00  15.00   57
  3  \w     31.00  95.00   1.00   45.00    --   10.40-174.00   5.00   64
  4  \w    -61.00 -14.00   1.00   45.00    --  -11.11 114.00-124.00   47
  5  \w    -70.00  51.00   1.00   45.00    --   10.40 -19.00-120.00  121
  6  \w    -20.00  51.00   1.00   45.00    --   10.40 -99.00 -90.00   71
  7  \w    -91.00 -44.00   1.00   45.00    --  -11.11 162.00-144.34   47
  8  \w    -71.00 -27.00   1.00   45.00    --  -11.11 132.00  -2.79   44
  9  \w    -67.00 -22.00   1.00   45.00    --  -11.11 124.00-161.76   45
 10  \w    -20.00  30.00   1.00   45.00    --  -11.11 -99.00  30.00   50
 11  \w    -87.00  21.00   1.00   45.00    --  -11.11 -77.00-150.00  108
 12  \w    -39.00  62.00   1.00   45.00    --  -11.11  57.00   0.00  101
 13  \w    -36.00  63.00   1.00   45.00    --  -11.11  38.00 120.00   99
 14  \w    -20.00   5.00   1.00   45.00    --  -11.11 -99.00  90.00   25
 15  \w    -85.00  13.00   1.00   45.00    --  -11.11 -38.00 -60.00   98
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0214661000
_diffrn_orient_matrix_UB_12      -0.0162209000
_diffrn_orient_matrix_UB_13      0.0045203000
_diffrn_orient_matrix_UB_21      -0.0672114000
_diffrn_orient_matrix_UB_22      -0.0028109000
_diffrn_orient_matrix_UB_23      0.0402451000
_diffrn_orient_matrix_UB_31      -0.0543959000
_diffrn_orient_matrix_UB_32      -0.0029359000
_diffrn_orient_matrix_UB_33      -0.0640385000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0523
_diffrn_reflns_av_unetI/netI     0.0370
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.946
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       56
_diffrn_reflns_limit_k_min       -56
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            46480
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.899
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.674
_diffrn_reflns_theta_min         2.603
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    8.232
_exptl_absorpt_correction_T_max  0.910
_exptl_absorpt_correction_T_min  0.427
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic pinkish violet'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   pinkish
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    2.223
_exptl_crystal_description       plate
_exptl_crystal_F_000             1968
_exptl_crystal_size_max          0.521
_exptl_crystal_size_mid          0.163
_exptl_crystal_size_min          0.042
_refine_diff_density_max         1.219
_refine_diff_density_min         -0.958
_refine_diff_density_rms         0.140
_refine_ls_abs_structure_details
;
 Flack x determined using 3508 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.017(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     371
_refine_ls_number_reflns         8105
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0286
_refine_ls_R_factor_gt           0.0260
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0289P)^2^+0.1739P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0541
_refine_ls_wR_factor_ref         0.0556
_reflns_Friedel_coverage         0.895
_reflns_Friedel_fraction_full    0.995
_reflns_Friedel_fraction_max     0.852
_reflns_number_gt                7729
_reflns_number_total             8105
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cm9b01289_si_001.cif
_cod_data_source_block           dvdz002
_cod_database_code               4002967
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C32 H24 I3 N5 Pb'
_reflns_odcompleteness_completeness 99.91
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B), C20(H20A,H20B)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C12(H12), C13(H13),
 C22(H22), C23(H23), C25(H25), C26(H26)
2.c Idealised Me refined as rotating group:
 N1(H1A,H1B,H1C)
;
_shelx_res_checksum              97519
_shelx_hkl_checksum              43721
_olex2_exptl_crystal_mounting_method 'mounted on a nylon loop'
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.390
_oxdiff_exptl_absorpt_empirical_full_min 0.679