Directing the Self-Assembly of Conjugated Organic Ammonium Cations in Low-Dimensional Perovskites by Halide Substitution
Denis, Paul-Henry; Mertens, Martijn; Van Gompel, Wouter T. M.; Van Hecke, Kristof; Ruttens, Bart; D’Haen, Jan; Lutsen, Laurence; Vanderzande, Dirk; Chemistry of Materials  (2021) –; doi:10.1021/acs.chemmater.1c01221

data_4003968
_publ_section_title
;
 Directing the Self-Assembly of Conjugated Organic Ammonium Cations in
 Low-Dimensional Perovskites by Halide Substitution
;
_journal_name_full               'Chemistry of Materials'
_journal_paper_doi               10.1021/acs.chemmater.1c01221
_journal_year                    2021
_chemical_formula_moiety         'I10 Pb3, 4(C11 H14 N S2)'
_chemical_formula_sum            'C44 H56 I10 N4 Pb3 S8'
_chemical_formula_weight         2788.01
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-12-16
_audit_creation_method
;
Olex2 1.2
(compiled May 18 2018 14:05:52 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 93.989(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   19.2783(7)
_cell_length_b                   21.3335(7)
_cell_length_c                   8.4039(2)
_cell_measurement_reflns_used    5223
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      72.4670
_cell_measurement_theta_min      3.0710
_cell_volume                     3447.93(19)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4839
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.993
_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   -115.00 -17.00   1.00    4.00    --  -41.18 -38.00  60.00   98
  2  \w    -69.00  32.00   1.00    4.00    --  -41.18  57.00-150.00  101
  3  \w   -115.00 -17.00   1.00    4.00    --  -41.18 -38.00   0.00   98
  4  \w    -66.00  33.00   1.00    4.00    --  -41.18  38.00   0.00   99
  5  \w      6.00  82.00   1.00    4.00    --   41.18 -99.00-150.00   76
  6  \w    -21.00  74.00   1.00    4.00    --   41.18 -77.00   0.00   95
  7  \w     80.00 178.00   1.00   25.00    --  106.01  45.00 150.00   98
  8  \w     77.00 178.00   1.00   25.00    --  106.01  61.00  90.00  101
  9  \w    103.00 178.00   1.00   25.00    --  106.01  77.00 -90.00   75
 10  \w     33.00 112.00   1.00   25.00    --  106.01-125.00   0.00   79
 11  \w     97.00 147.00   1.00   25.00    --  106.01 125.00  30.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0713973000
_diffrn_orient_matrix_UB_12      -0.0304254000
_diffrn_orient_matrix_UB_13      0.0195722000
_diffrn_orient_matrix_UB_21      -0.0118858000
_diffrn_orient_matrix_UB_22      0.0449795000
_diffrn_orient_matrix_UB_23      0.1391382000
_diffrn_orient_matrix_UB_31      -0.0344840000
_diffrn_orient_matrix_UB_32      0.0475287000
_diffrn_orient_matrix_UB_33      -0.1186132000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0866
_diffrn_reflns_av_unetI/netI     0.0674
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            23374
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        66.593
_diffrn_reflns_theta_max         66.593
_diffrn_reflns_theta_min         3.094
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    51.674
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.367
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
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            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    2.685
_exptl_crystal_description       needle
_exptl_crystal_F_000             2504
_exptl_crystal_size_max          0.311
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.065
_refine_diff_density_max         4.460
_refine_diff_density_min         -2.344
_refine_diff_density_rms         0.362
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.089
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     348
_refine_ls_number_reflns         6039
_refine_ls_number_restraints     626
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.1091
_refine_ls_R_factor_gt           0.0877
_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^)+(0.0011P)^2^+282.4073P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1865
_refine_ls_wR_factor_ref         0.1995
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4600
_reflns_number_total             6039
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cm1c01221_si_005.cif
_cod_data_source_block           dvdz021
_cod_database_code               4003968
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C44 H56 I10 N4 Pb3 S8'
_shelx_estimated_absorpt_t_max   0.134
_shelx_estimated_absorpt_t_min   0.022
_reflns_odcompleteness_completeness 92.07
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.9888(8)
 0.0112(8)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H,H) groups
3. Restrained distances
 C1-S1
 1.73 with sigma of 0.01
 S1-C2
 1.729 with sigma of 0.01
 C2-C3
 1.365 with sigma of 0.01
 C3-C4
 1.407 with sigma of 0.01
 C4-C1
 1.367 with sigma of 0.01
 C1-C9
 1.456 with sigma of 0.01
 C2-C5A = C2-C5B
 1.453 with sigma of 0.01
 C5A-S2A = C5B-S2B
 1.73 with sigma of 0.01
 C6A-C7A = C6B-C7B
 1.365 with sigma of 0.01
 C7A-C8A = C7B-C8B
 1.407 with sigma of 0.01
 C8A-C5A = C8B-C5B
 1.367 with sigma of 0.01
 N1-C11
 1.487 with sigma of 0.01
 C11-C10
 1.51 with sigma of 0.01
 C10-C9
 1.521 with sigma of 0.01
 C9-C1
 1.518 with sigma of 0.01
 C21-S21
 1.73 with sigma of 0.01
 S21-C22
 1.729 with sigma of 0.01
 C22-C23
 1.365 with sigma of 0.01
 C23-C24
 1.407 with sigma of 0.01
 C24-C21
 1.367 with sigma of 0.01
 C25A-S22A = C25B-S22B
 1.73 with sigma of 0.01
 S22A-C26A = S22B-C26B
 1.729 with sigma of 0.01
 C26A-C27A = C26B-C27B
 1.365 with sigma of 0.01
 C27A-C28A = C27B-C28B
 1.407 with sigma of 0.01
 C28A-C25A = C28B-C25B
 1.367 with sigma of 0.01
 N21-C31
 1.487 with sigma of 0.01
 C31-C30
 1.51 with sigma of 0.01
 C30-C29
 1.521 with sigma of 0.01
 C29-C21
 1.518 with sigma of 0.01
 C1-C2
 2.494 with sigma of 0.02
 S1-C3
 2.55 with sigma of 0.02
 C2-C4
 2.316 with sigma of 0.01
 C3-C1
 2.319 with sigma of 0.02
 C4-S1
 2.551 with sigma of 0.02
 C5A-C6A = C5B-C6B
 2.494 with sigma of 0.02
 S2A-C7A = S2B-C7B
 2.55 with sigma of 0.02
 C6A-C8A = C6B-C8B
 2.316 with sigma of 0.01
 C7A-C5A = C7B-C5B
 2.319 with sigma of 0.02
 C8A-S2A = C8B-S2B
 2.551 with sigma of 0.02
 N1-C10
 2.478 with sigma of 0.02
 C11-C9
 2.511 with sigma of 0.02
 C10-C1
 2.533 with sigma of 0.02
 C21-C22
 2.494 with sigma of 0.02
 S21-C23
 2.55 with sigma of 0.02
 C22-C24
 2.316 with sigma of 0.01
 C23-C21
 2.319 with sigma of 0.02
 C24-S21
 2.551 with sigma of 0.02
 C25A-C26A = C25B-C26B
 2.494 with sigma of 0.02
 S22A-C27A = S22B-C27B
 2.55 with sigma of 0.02
 C26A-C28A = C26B-C28B
 2.316 with sigma of 0.01
 C27A-C25A = C27B-C25B
 2.319 with sigma of 0.02
 C28A-S22A = C28B-S22B
 2.551 with sigma of 0.02
 N21-C30
 2.478 with sigma of 0.02
 C31-C29
 2.511 with sigma of 0.02
 C30-C21
 2.533 with sigma of 0.02
4. Restrained planarity
 S1, C1, C2, C3, C4, C9, C5A, C5B
 with sigma of 0.01
 C2, S2A, C5A, C6A, C7A, C8A
 with sigma of 0.01
 C2, S2B, C5B, C6B, C7B, C8B
 with sigma of 0.01
 S21, C21, C22, C23, C24, C29, C25A
 with sigma of 0.01
 C22, S22A, C25A, C26A, C27A, C28A
 with sigma of 0.01
 C22, S22B, C25B, C26B, C27B, C28B
 with sigma of 0.01
5. Rigid bond restraints
 S21, N21, C21, C22, C23, C24, C29, C30, C31, S22A, C25A, C26A, C27A, C28A,
 S22B, C25B, C26B, C27B, C28B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.0005
 S1, N1, C1, C2, C3, C4, C9, C10, C11, S2A, C5A, C6A, C7A, C8A, S2B, C5B, C6B,
 C7B, C8B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
6. Uiso/Uaniso restraints and constraints
S21 \\sim N21 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim C29 \\sim C30 \\sim
C31 \\sim S22A \\sim C25A \\sim C26A \\sim C27A \\sim C28A \\sim S22B \\sim
C25B \\sim C26B \\sim C27B \\sim C28B: within 2A with sigma of 0.003 and sigma
for terminal atoms of 0.002
S1 \\sim N1 \\sim C1 \\sim C2 \\sim C3 \\sim C4 \\sim C9 \\sim C10 \\sim C11
\\sim S2A \\sim C5A \\sim C6A \\sim C7A \\sim C8A \\sim S2B \\sim C5B \\sim C6B
\\sim C7B \\sim C8B: within 2A with sigma of 0.003 and sigma for terminal atoms
of 0.006
Uanis(S2A) = Uanis(S2B)
Uanis(C5A) = Uanis(C5B)
Uanis(C6A) = Uanis(C6B)
Uanis(C7A) = Uanis(C7B)
Uanis(C8A) = Uanis(C8B)
Uanis(S22A) = Uanis(S22B)
Uanis(C26A) = Uanis(C26B)
Uanis(C27A) = Uanis(C27B)
Uanis(C28A) = Uanis(C28B)
Uanis(C25A) = Uanis(C25B)
7. Others
 Sof(S2B)=Sof(C5B)=Sof(C6B)=Sof(H6B)=Sof(C7B)=Sof(H7B)=Sof(C8B)=Sof(H8B)=1-
 FVAR(1)
 Sof(S2A)=Sof(C5A)=Sof(C6A)=Sof(H6A)=Sof(C7A)=Sof(H7A)=Sof(C8A)=Sof(H8A)=FVAR(1)
 Sof(S22B)=Sof(C25B)=Sof(C26B)=Sof(H26B)=Sof(C27B)=Sof(H27B)=Sof(C28B)=
 Sof(H28B)=1-FVAR(2)
 Sof(S22A)=Sof(C25A)=Sof(C26A)=Sof(H26A)=Sof(C27A)=Sof(H27A)=Sof(C28A)=
 Sof(H28A)=FVAR(2)
8.a Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B), C29(H29A,H29B), C30(H30A,H30B),
 C31(H31A,H31B)
8.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C23(H23), C24(H24), C6A(H6A), C7A(H7A), C8A(H8A), C26A(H26A),
 C27A(H27A), C28A(H28A), C6B(H6B), C7B(H7B), C8B(H8B), C26B(H26B), C27B(H27B),
 C28B(H28B)
8.c Idealised Me refined as rotating group:
 N1(H1A,H1B,H1C), N21(H21A,H21B,H21C)
;
_shelx_res_checksum              7374
_shelx_hkl_checksum              45710
_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
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 4.475
_oxdiff_exptl_absorpt_empirical_full_min 0.475