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_4003971
_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         'I30 Pb9, 12(C11 H14 N S2)'
_chemical_formula_sum            'C132 H168 I30 N12 Pb9 S24'
_chemical_formula_weight         8364.02
_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             2021-02-09
_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                 117.507(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   37.2172(7)
_cell_length_b                   8.52620(10)
_cell_length_c                   38.7318(8)
_cell_measurement_reflns_used    18865
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      73.3720
_cell_measurement_theta_min      3.3760
_cell_volume                     10901.0(4)
_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 0.999
_diffrn_measured_fraction_theta_max 0.986
_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    -70.00  31.00   1.00    5.00    --  -41.68  57.00 -90.00  101
  2  \w    -70.00  31.00   1.00    5.00    --  -41.68  57.00  60.00  101
  3  \w    -66.00  33.00   1.00    5.00    --  -41.68  38.00-180.00   99
  4  \w     27.00  98.00   1.00    5.00    --   41.68-125.00 -60.00   71
  5  \w    103.00 178.00   1.00   20.00    --  106.01  77.00  30.00   75
  6  \w     30.00 139.00   1.00   20.00    --  106.01 -77.00  30.00  109
  7  \w     80.00 178.00   1.00   20.00    --  106.01  45.00-180.00   98
  8  \w     97.00 178.00   1.00   20.00    --  106.01 125.00 120.00   81
  9  \w     23.00 107.00   1.00   20.00    --  106.01 -94.00 -60.00   84
 10  \w     97.00 178.00   1.00   20.00    --  106.01 125.00   0.00   81
 11  \w     14.00 115.00   1.00    5.00    --   41.68  57.00-120.00  101
 12  \w     14.00 115.00   1.00    5.00    --   41.68  57.00   0.00  101
 13  \w     14.00 115.00   1.00    5.00    --   41.68  57.00 120.00  101
 14  \w     77.00 178.00   1.00   20.00    --  106.01  61.00   0.00  101
 15  \w     78.00 178.00   1.00   20.00    --  106.01  30.00 120.00  100
 16  \w     80.00 178.00   1.00   20.00    --  106.01  45.00-120.00   98
 17  \w     25.00  69.00   1.00   20.00    --  106.01 -99.00-169.00   44
 18  \w     53.00 142.00   1.00   20.00    --  106.01  15.00 -30.00   89
;
_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      0.0117191000
_diffrn_orient_matrix_UB_12      -0.1348625000
_diffrn_orient_matrix_UB_13      -0.0193063000
_diffrn_orient_matrix_UB_21      -0.0397204000
_diffrn_orient_matrix_UB_22      0.0239760000
_diffrn_orient_matrix_UB_23      -0.0378331000
_diffrn_orient_matrix_UB_31      0.0215288000
_diffrn_orient_matrix_UB_32      0.1178258000
_diffrn_orient_matrix_UB_33      -0.0143813000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0915
_diffrn_reflns_av_unetI/netI     0.0645
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       45
_diffrn_reflns_limit_h_min       -45
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       47
_diffrn_reflns_limit_l_min       -48
_diffrn_reflns_number            105246
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.994
_diffrn_reflns_theta_min         2.725
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    49.033
_exptl_absorpt_correction_T_max  0.761
_exptl_absorpt_correction_T_min  0.300
_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    2.548
_exptl_crystal_description       'rect. Prism'
_exptl_crystal_F_000             7512
_exptl_crystal_size_max          0.147
_exptl_crystal_size_mid          0.061
_exptl_crystal_size_min          0.047
_refine_diff_density_max         4.233
_refine_diff_density_min         -2.081
_refine_diff_density_rms         0.283
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     940
_refine_ls_number_reflns         21838
_refine_ls_number_restraints     750
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.1041
_refine_ls_R_factor_gt           0.0691
_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^)+(0.1039P)^2^+104.5382P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1801
_refine_ls_wR_factor_ref         0.2107
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14445
_reflns_number_total             21838
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cm1c01221_si_004.cif
_cod_data_source_block           dvdz020b
_cod_original_cell_volume        10901.1(4)
_cod_database_code               4003971
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C132 H168 I30 N12 Pb9 S24'
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     42.79
_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. 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-C5
 1.453 with sigma of 0.01
 C5-S2
 1.73 with sigma of 0.01
 S2-C6
 1.729 with sigma of 0.01
 C6-C7
 1.365 with sigma of 0.01
 C7-C8
 1.407 with sigma of 0.01
 C8-C5
 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
 C25-S22
 1.73 with sigma of 0.01
 S22-C26
 1.729 with sigma of 0.01
 C26-C27
 1.365 with sigma of 0.01
 C27-C28
 1.407 with sigma of 0.01
 C28-C25
 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
 C41-S41
 1.73 with sigma of 0.01
 S41-C42
 1.729 with sigma of 0.01
 C42-C43
 1.365 with sigma of 0.01
 C43-C44
 1.407 with sigma of 0.01
 C44-C41
 1.367 with sigma of 0.01
 C45-S42
 1.73 with sigma of 0.01
 S42-C48
 1.729 with sigma of 0.01
 C48-C47
 1.365 with sigma of 0.01
 C47-C46
 1.407 with sigma of 0.01
 C46-C45
 1.367 with sigma of 0.01
 N41-C51
 1.487 with sigma of 0.01
 C51-C50
 1.51 with sigma of 0.01
 C50-C49
 1.521 with sigma of 0.01
 C49-C41
 1.518 with sigma of 0.01
 C61-S61
 1.73 with sigma of 0.01
 S61-C62
 1.729 with sigma of 0.01
 C62-C63
 1.365 with sigma of 0.01
 C63-C64
 1.407 with sigma of 0.01
 C64-C61
 1.367 with sigma of 0.01
 C61-C69
 1.456 with sigma of 0.01
 C62-C65
 1.453 with sigma of 0.01
 C65-S62
 1.73 with sigma of 0.01
 S62-C66
 1.729 with sigma of 0.01
 C66-C67
 1.365 with sigma of 0.01
 C67-C68
 1.407 with sigma of 0.01
 C68-C65
 1.367 with sigma of 0.01
 N61-C71
 1.487 with sigma of 0.01
 C71-C70
 1.51 with sigma of 0.01
 C70-C69
 1.521 with sigma of 0.01
 C69-C61
 1.518 with sigma of 0.01
 C81-S81
 1.73 with sigma of 0.01
 S81-C82
 1.729 with sigma of 0.01
 C82-C83
 1.365 with sigma of 0.01
 C83-C84
 1.407 with sigma of 0.01
 C84-C81
 1.367 with sigma of 0.01
 C81-C89
 1.456 with sigma of 0.01
 C82-C85
 1.453 with sigma of 0.01
 C85-S82
 1.73 with sigma of 0.01
 S82-C86
 1.729 with sigma of 0.01
 C86-C87
 1.365 with sigma of 0.01
 C87-C88
 1.407 with sigma of 0.01
 C88-C85
 1.367 with sigma of 0.01
 N81-C91
 1.487 with sigma of 0.01
 C91-C90
 1.51 with sigma of 0.01
 C90-C89
 1.521 with sigma of 0.01
 C89-C81
 1.518 with sigma of 0.01
 C101-S101
 1.73 with sigma of 0.01
 S101-C102
 1.729 with sigma of 0.01
 C102-C103
 1.365 with sigma of 0.01
 C103-C104
 1.407 with sigma of 0.01
 C104-C101
 1.367 with sigma of 0.01
 C102-C105
 1.453 with sigma of 0.01
 C105-S102
 1.73 with sigma of 0.01
 S102-C106
 1.729 with sigma of 0.01
 C106-C107
 1.365 with sigma of 0.01
 C107-C108
 1.407 with sigma of 0.01
 C108-C105
 1.367 with sigma of 0.01
 N101-C111
 1.487 with sigma of 0.01
 C111-C110
 1.51 with sigma of 0.01
 C110-C109
 1.521 with sigma of 0.01
 C109-C101
 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
 C5-C6
 2.494 with sigma of 0.02
 S2-C7
 2.55 with sigma of 0.02
 C6-C8
 2.316 with sigma of 0.01
 C7-C5
 2.319 with sigma of 0.02
 C8-S2
 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
 C25-C26
 2.494 with sigma of 0.02
 S22-C27
 2.55 with sigma of 0.02
 C26-C28
 2.316 with sigma of 0.01
 C27-C25
 2.319 with sigma of 0.02
 C28-S22
 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
 C41-C42
 2.494 with sigma of 0.02
 S41-C43
 2.55 with sigma of 0.02
 C42-C44
 2.316 with sigma of 0.01
 C43-C41
 2.319 with sigma of 0.02
 C44-S41
 2.551 with sigma of 0.02
 C45-C48
 2.494 with sigma of 0.02
 S42-C47
 2.55 with sigma of 0.02
 C48-C46
 2.316 with sigma of 0.01
 C47-C45
 2.319 with sigma of 0.02
 C46-S42
 2.551 with sigma of 0.02
 N41-C50
 2.478 with sigma of 0.02
 C51-C49
 2.511 with sigma of 0.02
 C50-C41
 2.533 with sigma of 0.02
 C61-C62
 2.494 with sigma of 0.02
 S61-C63
 2.55 with sigma of 0.02
 C62-C64
 2.316 with sigma of 0.01
 C63-C61
 2.319 with sigma of 0.02
 C64-S61
 2.551 with sigma of 0.02
 C65-C66
 2.494 with sigma of 0.02
 S62-C67
 2.55 with sigma of 0.02
 C66-C68
 2.316 with sigma of 0.01
 C67-C65
 2.319 with sigma of 0.02
 C68-S62
 2.551 with sigma of 0.02
 N61-C70
 2.478 with sigma of 0.02
 C71-C69
 2.511 with sigma of 0.02
 C70-C61
 2.533 with sigma of 0.02
 C81-C82
 2.494 with sigma of 0.02
 S81-C83
 2.55 with sigma of 0.02
 C82-C84
 2.316 with sigma of 0.01
 C83-C81
 2.319 with sigma of 0.02
 C84-S81
 2.551 with sigma of 0.02
 C85-C86
 2.494 with sigma of 0.02
 S82-C87
 2.55 with sigma of 0.02
 C86-C88
 2.316 with sigma of 0.01
 C87-C85
 2.319 with sigma of 0.02
 C88-S82
 2.551 with sigma of 0.02
 N81-C90
 2.478 with sigma of 0.02
 C91-C89
 2.511 with sigma of 0.02
 C90-C81
 2.533 with sigma of 0.02
 C101-C102
 2.494 with sigma of 0.02
 S101-C103
 2.55 with sigma of 0.02
 C102-C104
 2.316 with sigma of 0.01
 C103-C101
 2.319 with sigma of 0.02
 C104-S101
 2.551 with sigma of 0.02
 C105-C106
 2.494 with sigma of 0.02
 S102-C107
 2.55 with sigma of 0.02
 C106-C108
 2.316 with sigma of 0.01
 C107-C105
 2.319 with sigma of 0.02
 C108-S102
 2.551 with sigma of 0.02
 N101-C110
 2.478 with sigma of 0.02
 C111-C109
 2.511 with sigma of 0.02
 C110-C101
 2.533 with sigma of 0.02
 C49-C44
 2.584 with sigma of 0.02
 C49-S41
 2.801 with sigma of 0.02
3. Restrained planarity
 S1, C1, C2, C3, C4, C5, C9
 with sigma of 0.01
 S21, C21, C22, C23, C24, C25, C29
 with sigma of 0.01
 S22, C22, C25, C26, C27, C28
 with sigma of 0.01
 S41, C41, C42, C43, C44, C45, C49
 with sigma of 0.01
 S42, C42, C45, C46, C47, C48
 with sigma of 0.01
 S61, C61, C62, C63, C64, C65, C69
 with sigma of 0.01
 S62, C62, C65, C66, C67, C68
 with sigma of 0.01
 S81, C81, C82, C83, C84, C85, C89
 with sigma of 0.01
 S82, C82, C85, C86, C87, C88
 with sigma of 0.01
 S101, C101, C102, C103, C104, C105, C109
 with sigma of 0.01
 S102, C102, C105, C106, C107, C108
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
S1 \\sim S2 \\sim N1 \\sim C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6
\\sim C7 \\sim C8 \\sim C9 \\sim C10 \\sim C11: within 2A with sigma of 0.003
and sigma for terminal atoms of 0.006
S21 \\sim S22 \\sim N21 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25 \\sim
C26 \\sim C27 \\sim C28 \\sim C29 \\sim C30 \\sim C31: within 2A with sigma of
0.003 and sigma for terminal atoms of 0.006
S41 \\sim S42 \\sim N41 \\sim C41 \\sim C42 \\sim C43 \\sim C44 \\sim C45 \\sim
C46 \\sim C47 \\sim C48 \\sim C49 \\sim C50 \\sim C51: within 2A with sigma of
0.003 and sigma for terminal atoms of 0.006
S61 \\sim S62 \\sim N61 \\sim C61 \\sim C62 \\sim C63 \\sim C64 \\sim C65 \\sim
C66 \\sim C67 \\sim C68 \\sim C69 \\sim C70 \\sim C71: within 2A with sigma of
0.003 and sigma for terminal atoms of 0.006
S81 \\sim S82 \\sim N81 \\sim C81 \\sim C82 \\sim C83 \\sim C84 \\sim C85 \\sim
C86 \\sim C87 \\sim C88 \\sim C89 \\sim C90 \\sim C91: within 2A with sigma of
0.003 and sigma for terminal atoms of 0.006
S101 \\sim S102 \\sim N101 \\sim C101 \\sim C102 \\sim C103 \\sim C104 \\sim
C105 \\sim C106 \\sim C107 \\sim C108 \\sim C109 \\sim C110 \\sim C111: within
2A with sigma of 0.003 and sigma for terminal atoms of 0.006
5.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), C49(H49A,H49B), C50(H50A,H50B), C51(H51A,H51B), C69(H69A,H69B),
  C70(H70A,H70B), C71(H71A,H71B), C89(H89A,H89B), C90(H90A,H90B), C91(H91A,
 H91B), C109(H10F,H10G), C110(H11C,H11D), C111(H11E,H11F)
5.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C8(H8), C23(H23), C24(H24), C26(H26),
 C27(H27), C28(H28), C43(H43), C44(H44), C46(H46), C47(H47), C48(H48), C63(H63),
  C64(H64), C66(H66), C67(H67), C68(H68), C83(H83), C84(H84), C86(H86),
 C87(H87), C88(H88), C103(H103), C104(H104), C106(H106), C107(H107), C108(H108)
5.c Idealised Me refined as rotating group:
 N1(H1A,H1B,H1C), N21(H21A,H21B,H21C), N41(H41A,H41B,H41C), N61(H61A,H61B,
 H61C), N81(H81A,H81B,H81C), N101(H10C,H10D,H10E)
;
_shelx_res_checksum              99623
_shelx_hkl_checksum              24313
_shelx_fab_checksum              68226
_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 13.394
_oxdiff_exptl_absorpt_empirical_full_min 0.416