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_4003967
_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         'I7 Pb2, 3(C11 H14 N S2), H2 O'
_chemical_formula_sum            'C33 H44 I7 N3 O Pb2 S6'
_chemical_formula_weight         1993.77
_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   mixed
_audit_creation_date             2020-01-03
_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                 91.9300(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.4912(2)
_cell_length_b                   8.37690(10)
_cell_length_c                   40.0997(5)
_cell_measurement_reflns_used    13856
_cell_measurement_temperature    100(1)
_cell_measurement_theta_max      73.8410
_cell_measurement_theta_min      2.8130
_cell_volume                     5200.72(11)
_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 2018/2 (Sheldrick, 2018)'
_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 0.998
_diffrn_measured_fraction_theta_max 0.975
_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    -66.00  33.00   1.00    5.00    --  -41.68  38.00 -30.00   99
  2  \w   -115.00 -14.00   1.00    5.00    --  -41.68 -57.00-180.00  101
  3  \w     27.00  98.00   1.00    5.00    --   41.68-125.00-180.00   71
  4  \w     97.00 178.00   1.00   20.00    --  106.01 125.00 -60.00   81
  5  \w     78.00 178.00   1.00   20.00    --  106.01  30.00   0.00  100
  6  \w     33.00 112.00   1.00   20.00    --  106.01-125.00 120.00   79
  7  \w     33.00 112.00   1.00   20.00    --  106.01-125.00  30.00   79
  8  \w     33.00 132.00   1.00   20.00    --  106.01 -45.00-180.00   99
  9  \w    103.00 178.00   1.00   20.00    --  106.01  77.00-120.00   75
 10  \w   -115.00 -14.00   1.00    5.00    --  -41.68 -57.00 -60.00  101
 11  \w   -115.00 -14.00   1.00    5.00    --  -41.68 -57.00  60.00  101
 12  \w     78.00 178.00   1.00   20.00    --  106.01  30.00-180.00  100
 13  \w     53.00 178.00   1.00   20.00    --  106.01  15.00 -60.00  125
 14  \w     77.00 178.00   1.00   20.00    --  106.01  61.00 120.00  101
 15  \w     78.00 178.00   1.00   20.00    --  106.01  30.00  90.00  100
 16  \w   -115.00 -14.00   1.00    5.00    --  -41.68 -57.00   0.00  101
 17  \w    -70.00  31.00   1.00    5.00    --  -41.68  57.00  90.00  101
 18  \w     77.00 102.00   1.00   20.00    --  106.01  61.00-180.00   25
;
_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      -0.0873246000
_diffrn_orient_matrix_UB_12      -0.0168975000
_diffrn_orient_matrix_UB_13      0.0169692000
_diffrn_orient_matrix_UB_21      -0.0431117000
_diffrn_orient_matrix_UB_22      -0.0500777000
_diffrn_orient_matrix_UB_23      -0.0335660000
_diffrn_orient_matrix_UB_31      0.0205615000
_diffrn_orient_matrix_UB_32      -0.1761473000
_diffrn_orient_matrix_UB_33      0.0078795000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0725
_diffrn_reflns_av_unetI/netI     0.0503
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       49
_diffrn_reflns_limit_l_min       -49
_diffrn_reflns_number            50163
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.429
_diffrn_reflns_theta_min         2.854
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    47.543
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.653
_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 yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    2.546
_exptl_crystal_description       plate
_exptl_crystal_F_000             3608
_exptl_crystal_size_max          0.177
_exptl_crystal_size_mid          0.113
_exptl_crystal_size_min          0.066
_refine_diff_density_max         1.634
_refine_diff_density_min         -1.262
_refine_diff_density_rms         0.228
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     518
_refine_ls_number_reflns         10362
_refine_ls_number_restraints     171
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.0535
_refine_ls_R_factor_gt           0.0420
_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^)+(0.0425P)^2^+20.2094P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0963
_refine_ls_wR_factor_ref         0.1030
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8635
_reflns_number_total             10362
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cm1c01221_si_001.cif
_cod_data_source_block           dvdz015
_cod_database_code               4003967
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C33 H44 I7 N3 O Pb2 S6'
_reflns_odcompleteness_completeness 99.86
_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, All N(H,H,H) groups
 At 1.5 times of:
  All O(H,H) groups
2. Restrained distances
 C1A-S1A
 1.725 with sigma of 0.01
 S1A-C2A
 1.725 with sigma of 0.01
 C2A-C3A
 1.365 with sigma of 0.01
 C3A-C4A
 1.409 with sigma of 0.01
 C4A-C1A
 1.365 with sigma of 0.01
 C1B-S1B
 1.725 with sigma of 0.01
 S1B-C2B
 1.725 with sigma of 0.01
 C2B-C3B
 1.365 with sigma of 0.01
 C3B-C4B
 1.409 with sigma of 0.01
 C4B-C1B
 1.365 with sigma of 0.01
 C23A-S5A
 1.725 with sigma of 0.01
 S5A-C24A
 1.725 with sigma of 0.01
 C24A-C25A
 1.365 with sigma of 0.01
 C25A-C26A
 1.409 with sigma of 0.01
 C26A-C23A
 1.365 with sigma of 0.01
 C23B-S5B
 1.725 with sigma of 0.01
 S5B-C24B
 1.725 with sigma of 0.01
 C24B-C25B
 1.365 with sigma of 0.01
 C25B-C26B
 1.409 with sigma of 0.01
 C26B-C23B
 1.365 with sigma of 0.01
 C5-C1B
 1.451 with sigma of 0.01
 C27-C23B
 1.451 with sigma of 0.01
 C10-C11A = C10-C11B
 1.513 with sigma of 0.01
 C11A-N1A = C11B-N1B
 1.485 with sigma of 0.01
 S1A-C3A
 2.483 with sigma of 0.02
 C2A-C4A
 2.553 with sigma of 0.02
 C3A-C1A
 2.314 with sigma of 0.02
 C4A-S1A
 2.314 with sigma of 0.02
 C1A-C2A
 2.553 with sigma of 0.02
 S1B-C3B
 2.483 with sigma of 0.02
 C2B-C4B
 2.553 with sigma of 0.02
 C3B-C1B
 2.314 with sigma of 0.02
 C4B-S1B
 2.314 with sigma of 0.02
 C1B-C2B
 2.553 with sigma of 0.02
 S5A-C25A
 2.483 with sigma of 0.02
 C24A-C26A
 2.553 with sigma of 0.02
 C25A-C23A
 2.314 with sigma of 0.02
 C26A-S5A
 2.314 with sigma of 0.02
 C23A-C24A
 2.553 with sigma of 0.02
 S5B-C25B
 2.483 with sigma of 0.02
 C24B-C26B
 2.553 with sigma of 0.02
 C25B-C23B
 2.314 with sigma of 0.02
 C26B-S5B
 2.314 with sigma of 0.02
 C23B-C24B
 2.553 with sigma of 0.02
 C10-N1A = C10-N1B
 2.476 with sigma of 0.02
3. Restrained planarity
 C5, S1B, C1B, C2B, C3B, C4B
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
S1B \\sim C1B \\sim C2B \\sim C3B \\sim C4B: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02
S1A \\sim C1A \\sim C2A \\sim C3A \\sim C4A: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02
S5A \\sim C23A \\sim C24A \\sim C25A \\sim C26A: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02
S5B \\sim C23B \\sim C24B \\sim C25B \\sim C26B: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02
Uanis(C1A) = Uanis(C1B)
Uanis(S1A) = Uanis(S1B)
Uanis(C2A) = Uanis(C2B)
Uanis(C4A) = Uanis(C4B)
Uanis(C3A) = Uanis(C3B)
Uanis(N1A) = Uanis(N1B)
Uanis(C11A) = Uanis(C11B)
Uanis(C23A) = Uanis(C23B)
Uanis(S5A) = Uanis(S5B)
Uanis(C24A) = Uanis(C24B)
Uanis(C25A) = Uanis(C25B)
Uanis(C26A) = Uanis(C26B)
5. Others
 Sof(S1B)=Sof(C1B)=Sof(C2B)=Sof(H2B)=Sof(C3B)=Sof(H3B)=Sof(C4B)=Sof(H4B)=1-
 FVAR(1)
 Sof(S1A)=Sof(C1A)=Sof(C2A)=Sof(H2A)=Sof(C3A)=Sof(H3A)=Sof(C4A)=Sof(H4A)=FVAR(1)
 Sof(H10C)=Sof(H10D)=Sof(N1B)=Sof(H1BA)=Sof(H1BB)=Sof(H1BC)=Sof(C11B)=
 Sof(H11C)=Sof(H11D)=1-FVAR(2)
 Sof(H10A)=Sof(H10B)=Sof(N1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=Sof(C11A)=
 Sof(H11A)=Sof(H11B)=FVAR(2)
 Sof(S5B)=Sof(C23B)=Sof(C24B)=Sof(H24B)=Sof(C25B)=Sof(H25B)=Sof(C26B)=
 Sof(H26B)=1-FVAR(3)
 Sof(S5A)=Sof(C23A)=Sof(C24A)=Sof(H24A)=Sof(C25A)=Sof(H25A)=Sof(C26A)=
 Sof(H26A)=FVAR(3)
6.a Free rotating group:
 O1(H1A,H1B)
6.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C10(H10A,H10B), C10(H10C,H10D), C11A(H11A,H11B), C11B(H11C,H11D),
  C20(H20A,H20B), C21(H21A,H21B), C22(H22A,H22B), C31(H31A,H31B), C32(H32A,
 H32B), C33(H33A,H33B)
6.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C2A(H2A), C3A(H3A), C4A(H4A), C2B(H2B), C3B(H3B), C4B(H4B),
 C13(H13), C14(H14), C15(H15), C17(H17), C18(H18), C28(H28), C29(H29),
 C24A(H24A), C25A(H25A), C26A(H26A), C24B(H24B), C25B(H25B), C26B(H26B)
6.d Idealised Me refined as rotating group:
 N1A(H1AA,H1AB,H1AC), N1B(H1BA,H1BB,H1BC), N2(H2C,H2D,H2E), N3(H3C,H3D,H3E)
;
_shelx_res_checksum              88351
_shelx_hkl_checksum              64309
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 4.880
_oxdiff_exptl_absorpt_empirical_full_min 0.461