Revealing the Role of Bifunctional Molecules in Crystallizing Methylammonium Lead Iodide through Geometric Isomers
Zhang, Wenhao; Zhang, Weihua; Wang, Kai; Chu, Yanmeng; Du, Jiankang; Mei, Anyi; Rong, Yaoguang; Hu, Yue; Han, Hongwei; Chemistry of Materials  (2021) –; doi:10.1021/acs.chemmater.1c00391

data_4003946
_publ_section_title
;
 Revealing the Role of Bifunctional Molecules in Crystallizing
 Methylammonium Lead Iodide through Geometric Isomers
;
_journal_name_full               'Chemistry of Materials'
_journal_paper_doi               10.1021/acs.chemmater.1c00391
_journal_year                    2021
_chemical_formula_moiety         '4(C7 H14 N O2), I10 Pb3'
_chemical_formula_sum            'C28 H56 I10 N4 O8 Pb3'
_chemical_formula_weight         2467.33
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-12-11
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 107.6090(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.96490(10)
_cell_length_b                   23.28940(10)
_cell_length_c                   14.05910(10)
_cell_measurement_reflns_used    36832
_cell_measurement_temperature    295.53(11)
_cell_measurement_theta_max      73.6500
_cell_measurement_theta_min      3.7940
_cell_volume                     2797.82(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.28b (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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      295.53(11)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.988
_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    -33.00  31.00   0.50    0.50    --    0.00 -82.00  90.00  128
  2  \w      6.00  92.00   0.50    0.50    --   32.00  72.00-152.55  172
  3  \w    -46.00  56.00   0.50    0.50    --   36.00 -55.00 -57.40  204
  4  \w      9.00  75.00   0.50    0.50    --   36.00  72.00  24.32  132
  5  \w     28.00  76.00   0.50    0.50    --   52.00  73.00-119.54   96
  6  \w     31.00  56.00   0.50    0.50    --   56.00  74.00  86.22   50
  7  \w    114.00 144.00   0.50    0.50    --   56.00  75.00  -7.10   60
  8  \w     33.00  69.00   0.50    0.50    --   56.00  75.00  -7.10   72
  9  \w     32.00  57.00   0.50    0.50    --   60.00  74.00 -44.26   50
 10  \w     32.00  65.00   0.50    0.50    --   60.00  75.00 156.78   66
 11  \w     93.00 119.00   0.50    0.50    --   60.00  75.00 156.78   52
 12  \w     32.00  77.00   0.50    0.50    --   60.00  75.00  42.36   90
 13  \w     36.00  63.00   0.50    0.50    --   64.00  75.00-142.17   54
 14  \w     97.00 123.00   0.50    0.50    --   64.00  75.00 -93.52   52
 15  \w     36.00  76.00   0.50    0.50    --   64.00  75.00 -93.52   80
 16  \w     40.00  71.00   0.50    0.50    --   68.00  75.00 102.38   62
 17  \w     44.00  73.00   0.50    0.50    --   72.00  74.00  78.20   58
 18  \w     44.00  86.00   0.50    0.50    --   72.00  74.00  -2.17   84
 19  \w     44.00  86.00   0.50    0.50    --   72.00  75.00 128.29   84
 20  \w     91.00 122.00   0.50    0.50    --   72.00  75.00 128.29   62
 21  \w     44.00  72.00   0.50    0.50    --   72.00  74.00 -60.54   56
 22  \w    110.00 159.00   0.50    0.50    --   72.00  74.00  -2.17   98
 23  \w     48.00 110.00   0.50    0.50    --   76.00  74.00-117.75  124
 24  \w     49.00  81.00   0.50    0.50    --   76.00  73.00 171.03   64
 25  \w    125.00 165.00   0.50    0.50    --   76.00  74.00-117.75   80
 26  \w     60.00 172.00   0.50    0.50    --   84.00  65.00 -74.23  224
 27  \w    126.00 153.00   0.50    0.50    --   94.60  70.00 -30.42   54
 28  \w     67.00 162.00   0.50    0.50    --   94.60  74.00-124.81  190
 29  \w     69.00 113.00   0.50    0.50    --   94.60  70.00 -30.42   88
 30  \w      6.00 117.00   0.50    0.50    --   94.60 -82.00 -30.00  222
 31  \w      6.00 103.00   0.50    0.50    --   94.60 -61.00-150.00  194
 32  \w     71.00 171.00   0.50    0.50    --   94.60  62.00  76.92  200
 33  \w    133.00 175.00   0.50    0.50    --   94.60  71.00 111.70   84
 34  \w     69.00 166.00   0.50    0.50    --   94.60  68.00-136.87  194
 35  \w     30.00 124.00   0.50    0.50    --   94.60 -82.00  90.00  188
 36  \w     67.00 130.00   0.50    0.50    --   94.60  71.00 111.70  126
 37  \w    101.00 126.00   0.50    0.50    --   94.60 -82.00   0.00   50
 38  \w     36.00  76.00   0.50    0.50    --   94.60 -82.00   0.00   80
 39  \w     68.00 174.00   0.50    0.50    --   94.60  69.00 -54.30  212
 40  \w     22.00 119.00   0.50    0.50    --   94.60 -82.00-150.00  194
 41  \w     44.00  78.00   0.50    0.50    --   94.60 -77.00  30.00   68
 42  \w     73.00 123.00   0.50    0.50    --   94.60  54.00 119.39  100
 43  \w    128.00 184.00   0.50    0.50    --   94.60  63.00 162.46  112
 44  \w     74.00 168.00   0.50    0.50    --   94.60  61.00   0.00  188
 45  \w     71.00 104.00   0.50    0.50    --   94.60  61.00-150.00   66
 46  \w     78.00 178.00   0.50    0.50    --   94.60  61.00-180.00  200
 47  \w     70.00 124.00   0.50    0.50    --   94.60  63.00 162.46  108
 48  \w     73.00 162.00   0.50    0.50    --   94.60  61.00  60.00  178
 49  \w     66.00 100.00   0.50    0.50    --   94.60  75.00  21.56   68
 50  \w     34.00 109.00   0.50    0.50    --   94.60 -61.00  90.00  150
 51  \w     68.00 167.00   0.50    0.50    --   94.60  70.00  15.62  198
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1114307000
_diffrn_orient_matrix_UB_12      -0.0004459000
_diffrn_orient_matrix_UB_13      0.1076415000
_diffrn_orient_matrix_UB_21      -0.0339857000
_diffrn_orient_matrix_UB_22      -0.0643001000
_diffrn_orient_matrix_UB_23      0.0087985000
_diffrn_orient_matrix_UB_31      0.1376033000
_diffrn_orient_matrix_UB_32      -0.0155331000
_diffrn_orient_matrix_UB_33      -0.0394020000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0661
_diffrn_reflns_av_unetI/netI     0.0365
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            68096
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.934
_diffrn_reflns_theta_min         3.298
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    60.910
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.04495
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.28b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    2.929
_exptl_crystal_description       plate
_exptl_crystal_F_000             2184
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.018
_refine_diff_density_min         -1.199
_refine_diff_density_rms         0.148
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.026(9)
_refine_ls_extinction_coef       0.000168(11)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.007
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     488
_refine_ls_number_reflns         11059
_refine_ls_number_restraints     10
_refine_ls_restrained_S_all      1.007
_refine_ls_R_factor_all          0.0303
_refine_ls_R_factor_gt           0.0290
_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^)+(0.0469P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0732
_refine_ls_wR_factor_ref         0.0739
_reflns_Friedel_coverage         0.921
_reflns_Friedel_fraction_full    0.994
_reflns_Friedel_fraction_max     0.959
_reflns_number_gt                10575
_reflns_number_total             11059
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cm1c00391_si_001.cif
_cod_data_source_block           20201122_1rt
_cod_database_code               4003946
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.262
_shelx_estimated_absorpt_t_min   0.039
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.974(9)
 0.026(9)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H,H) groups
 At 1.5 times of:
  All O(H) groups
3. Rigid body (RIGU) restrains
 O8, C28, O7
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4.a Ternary CH refined with riding coordinates:
 C1(H1), C6(H6), C8(H8), C13(H13), C15(H15), C20(H20), C22(H22), C27(H27)
4.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C9(H9A,H9B), C10(H10A,
 H10B), C11(H11A,H11B), C12(H12A,H12B), C16(H16A,H16B), C17(H17A,H17B),
 C18(H18A,H18B), C19(H19A,H19B), C23(H23A,H23B), C24(H24A,H24B), C25(H25A,H25B),
  C26(H26A,H26B)
4.c Idealised Me refined as rotating group:
 N1(H1A,H1B,H1C), N2(H2C,H2D,H2E), N3(H3C,H3D,H3E), N4(H4C,H4D,H4E)
4.d Idealised tetrahedral OH refined as rotating group:
 O2(H2), O4(H4), O5(H5), O8(H8A)
;
_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 15.372
_oxdiff_exptl_absorpt_empirical_full_min 0.503