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_4003970
_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         '2(C11 H14 N S2),  Br4 Pb'
_chemical_formula_sum            'C22 H28 Br4 N2 Pb S4'
_chemical_formula_weight         975.50
_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     direct
_audit_creation_date             2020-07-13
_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                 91.330(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   23.5063(5)
_cell_length_b                   7.7046(2)
_cell_length_c                   8.2879(2)
_cell_measurement_reflns_used    16284
_cell_measurement_temperature    100(1)
_cell_measurement_theta_max      29.4240
_cell_measurement_theta_min      3.4440
_cell_volume                     1500.59(6)
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100(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 0.934
_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    -18.00  83.00   1.00   25.00    --   10.33  57.00-120.00  101
  2  \w    -15.00  51.00   1.00   25.00    --   10.33 -99.00  60.00   66
  3  \w    -64.00  35.00   1.00   25.00    --   10.33 -38.00  90.00   99
  4  \w    -18.00  83.00   1.00   25.00    --   10.33  57.00   0.00  101
  5  \w    -15.00  30.00   1.00   25.00    --  -11.26 -99.00   0.00   45
  6  \w    -42.00  43.00   1.00   25.00    --   10.33 -77.00-120.00   85
  7  \w    -42.00  43.00   1.00   25.00    --   10.33 -77.00-150.00   85
  8  \w    -64.00  35.00   1.00   25.00    --   10.33 -38.00 -90.00   99
  9  \w    -15.00  38.00   1.00   25.00    --   10.33 -99.00   0.00   53
 10  \w    -15.00  30.00   1.00   25.00    --  -11.26 -99.00  60.00   45
;
_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      -0.0015434000
_diffrn_orient_matrix_UB_12      -0.0868477000
_diffrn_orient_matrix_UB_13      -0.0281353000
_diffrn_orient_matrix_UB_21      0.0298424000
_diffrn_orient_matrix_UB_22      -0.0086933000
_diffrn_orient_matrix_UB_23      0.0119330000
_diffrn_orient_matrix_UB_31      -0.0042610000
_diffrn_orient_matrix_UB_32      -0.0292389000
_diffrn_orient_matrix_UB_33      0.0799717000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0595
_diffrn_reflns_av_unetI/netI     0.0320
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.934
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            32056
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.934
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.755
_diffrn_reflns_theta_min         2.600
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    11.241
_exptl_absorpt_correction_T_max  0.905
_exptl_absorpt_correction_T_min  0.336
_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    2.159
_exptl_crystal_description       plate
_exptl_crystal_F_000             920
_exptl_crystal_size_max          0.352
_exptl_crystal_size_mid          0.217
_exptl_crystal_size_min          0.129
_refine_diff_density_max         1.180
_refine_diff_density_min         -0.975
_refine_diff_density_rms         0.140
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     192
_refine_ls_number_reflns         4001
_refine_ls_number_restraints     178
_refine_ls_restrained_S_all      1.445
_refine_ls_R_factor_all          0.0353
_refine_ls_R_factor_gt           0.0281
_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^)+(0.0345P)^2^+1.6935P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0661
_refine_ls_wR_factor_ref         0.0706
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3510
_reflns_number_total             4001
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cm1c01221_si_002.cif
_cod_data_source_block           dvdz017
_cod_database_code               4003970
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C22 H28 Br4 N2 Pb S4'
_reflns_odcompleteness_completeness 99.94
_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,H,H,H) groups
2. Restrained distances
 S1A-C4A = S1A-C1A
 1.726 with sigma of 0.01
 C4A-C3A
 1.368 with sigma of 0.01
 C1A-C2A
 1.36 with sigma of 0.01
 C2A-C3A
 1.411 with sigma of 0.01
 S2A-C5A = S2A-C8A
 1.726 with sigma of 0.01
 C5A-C6A
 1.368 with sigma of 0.01
 C8A-C7A
 1.36 with sigma of 0.01
 C7A-C6A
 1.411 with sigma of 0.01
 S1B-C4B = S1B-C1B
 1.726 with sigma of 0.01
 C4B-C3B
 1.368 with sigma of 0.01
 C1B-C2B
 1.36 with sigma of 0.01
 C2B-C3B
 1.411 with sigma of 0.01
 S2B-C5B = S2B-C8B
 1.726 with sigma of 0.01
 C5B-C6B
 1.368 with sigma of 0.01
 C8B-C7B
 1.36 with sigma of 0.01
 C7B-C6B
 1.411 with sigma of 0.01
 S1A-C3A
 2.553 with sigma of 0.02
 C4A-C2A
 2.32 with sigma of 0.02
 C3A-C1A
 2.317 with sigma of 0.02
 C2A-S1A
 2.548 with sigma of 0.02
 C1A-C4A
 2.483 with sigma of 0.02
 S2A-C6A
 2.553 with sigma of 0.02
 C5A-C7A
 2.32 with sigma of 0.02
 C7A-C8A
 2.317 with sigma of 0.02
 C7A-S2A
 2.548 with sigma of 0.02
 C8A-C5A
 2.483 with sigma of 0.02
 S1B-C3B
 2.553 with sigma of 0.02
 C4B-C2B
 2.32 with sigma of 0.02
 C3B-C1B
 2.317 with sigma of 0.02
 C2B-S1B
 2.548 with sigma of 0.02
 C1B-C4B
 2.483 with sigma of 0.02
 S2B-C6B
 2.553 with sigma of 0.02
 C5B-C7B
 2.32 with sigma of 0.02
 C7B-C8B
 2.317 with sigma of 0.02
 C7B-S2B
 2.548 with sigma of 0.02
 C8B-C5B
 2.483 with sigma of 0.02
3. Restrained planarity
 S1A, C1A, C2A, C3A, C4A
 with sigma of 0.01
 S2A, C5A, C6A, C7A, C8A
 with sigma of 0.01
 S1B, C1B, C2B, C3B, C4B
 with sigma of 0.01
 S2B, C5B, C6B, C7B, C8B
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(C1A) = Uanis(C1B)
Uanis(C2A) = Uanis(C2B)
Uanis(C3A) = Uanis(C3B)
Uanis(C4A) = Uanis(C4B)
Uanis(C5A) = Uanis(C5B)
Uanis(C6A) = Uanis(C6B)
Uanis(C7A) = Uanis(C7B)
Uanis(C8A) = Uanis(C8B)
Uanis(S1A) = Uanis(S1B)
Uanis(S2A) = Uanis(S2B)
Uanis(C9A) = Uanis(C9B)
Uanis(C10A) = Uanis(C10B)
Uanis(C11A) = Uanis(C11B)
5. Rigid body (RIGU) restrains
 S1A, S2A, C1A, C2A, C3A, C4A, C5A, C6A, C7A, C8A
 with sigma for 1-2 distances of 0.003 and sigma for 1-3 distances of 0.003
 S1B, S2B, C1B, C2B, C3B, C4B, C5B, C6B, C7B, C8B
 with sigma for 1-2 distances of 0.003 and sigma for 1-3 distances of 0.003
6. Others
 Sof(H1BD)=Sof(H1BE)=Sof(H1BF)=Sof(S1B)=Sof(S2B)=Sof(C1B)=Sof(C2B)=Sof(H2B)=
 Sof(C3B)=Sof(H3B)=Sof(C4B)=Sof(C5B)=Sof(C6B)=Sof(H6B)=Sof(C7B)=Sof(H7B)=
 Sof(C8B)=Sof(H8B)=Sof(C9B)=Sof(H9BA)=Sof(H9BB)=Sof(C10B)=Sof(H10C)=Sof(H10D)=
 Sof(C11B)=Sof(H11C)=Sof(H11D)=1-FVAR(1)
 Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=Sof(S1A)=Sof(S2A)=Sof(C1A)=Sof(C2A)=Sof(H2A)=
 Sof(C3A)=Sof(H3A)=Sof(C4A)=Sof(C5A)=Sof(C6A)=Sof(H6A)=Sof(C7A)=Sof(H7A)=
 Sof(C8A)=Sof(H8A)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(C10A)=Sof(H10A)=Sof(H10B)=
 Sof(C11A)=Sof(H11A)=Sof(H11B)=FVAR(1)
7.a Secondary CH2 refined with riding coordinates:
 C9A(H9AA,H9AB), C10A(H10A,H10B), C11A(H11A,H11B), C9B(H9BA,H9BB), C10B(H10C,
 H10D), C11B(H11C,H11D)
7.b Aromatic/amide H refined with riding coordinates:
 C2A(H2A), C3A(H3A), C6A(H6A), C7A(H7A), C8A(H8A), C2B(H2B), C3B(H3B),
 C6B(H6B), C7B(H7B), C8B(H8B)
7.c Idealised Me refined as rotating group:
 N1(H1AA,H1AB,H1AC), N1(H1BD,H1BE,H1BF)
;
_shelx_res_checksum              37497
_shelx_hkl_checksum              98176
_olex2_exptl_crystal_mounting_method 'mounted on a LithoLoop'
_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 2.499
_oxdiff_exptl_absorpt_empirical_full_min 0.406