Methylamine-Dimer-Induced Phase Transition toward MAPbI<sub>3</sub> Films and High-Efficiency Perovskite Solar Modules.
Huang, Xiaofeng; Chen, Ruihao; Deng, Guocheng; Han, Faming; Ruan, Pengpeng; Cheng, Fangwen; Yin, Jun; Wu, Binghui; Zheng, Nanfeng; Journal of the American Chemical Society 142 (2020) 6149–6157; doi:10.1021/jacs.9b13443

data_4134507
_publ_section_title
;
 Methylamine-Dimer-Induced Phase Transition toward MAPbI<sub>3</sub> Films
 and High-Efficiency Perovskite Solar Modules.
;
_journal_issue                   13
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              6149
_journal_page_last               6157
_journal_paper_doi               10.1021/jacs.9b13443
_journal_volume                  142
_journal_year                    2020
_chemical_formula_moiety         'I8.77 Pb2, 5(C H6 N), 2(C H5 N), 0.23(Cl1)'
_chemical_formula_sum            'C7 H40 Cl0.23 I8.77 N7 Pb2'
_chemical_formula_weight         1757.68
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2019-11-11
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 69.247(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.7722(4)
_cell_length_b                   14.9103(4)
_cell_length_c                   19.1625(8)
_cell_measurement_reflns_used    8063
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      28.5200
_cell_measurement_theta_min      3.4980
_cell_volume                     3679.7(2)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4741
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.883
_diffrn_measurement_details
;
  1 omega  -87.00   12.00   1.0000   22.5000
omega____ theta____ kappa____ phi______ frames
    -      -14.0012  -37.0000  -30.0000 99

  2 omega  -60.00   26.00   1.0000   22.5000
omega____ theta____ kappa____ phi______ frames
    -       14.4699  -77.0000  150.0000 86

  3 omega   46.00   72.00   1.0000   22.5000
omega____ theta____ kappa____ phi______ frames
    -       14.4699  178.0000  -90.0000 26

  4 omega    9.00   57.00   1.0000   22.5000
omega____ theta____ kappa____ phi______ frames
    -       14.4699   57.0000    0.0000 48

  5 omega  -19.00   44.00   1.0000   22.5000
omega____ theta____ kappa____ phi______ frames
    -       14.4699  -99.0000  -90.0000 63
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0455359000
_diffrn_orient_matrix_UB_12      0.0136395000
_diffrn_orient_matrix_UB_13      -0.0295193000
_diffrn_orient_matrix_UB_21      -0.0309466000
_diffrn_orient_matrix_UB_22      0.0218304000
_diffrn_orient_matrix_UB_23      -0.0176010000
_diffrn_orient_matrix_UB_31      0.0013440000
_diffrn_orient_matrix_UB_32      0.0399886000
_diffrn_orient_matrix_UB_33      0.0196701000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0743
_diffrn_reflns_av_unetI/netI     0.0890
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.883
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            30849
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.883
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.468
_diffrn_reflns_theta_min         3.446
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    16.520
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.57409
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    3.173
_exptl_crystal_description       block
_exptl_crystal_F_000             3055
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         7.725
_refine_diff_density_min         -4.273
_refine_diff_density_rms         0.434
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     256
_refine_ls_number_reflns         9888
_refine_ls_number_restraints     11
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.1030
_refine_ls_R_factor_gt           0.0621
_refine_ls_shift/su_max          0.042
_refine_ls_shift/su_mean         0.003
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0692P)^2^+33.1841P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1389
_refine_ls_wR_factor_ref         0.1633
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6777
_reflns_number_total             9888
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b13443_si_002.cif
_cod_data_source_block           Pb2I9(CH3NH2)2(CH3NH3)5
_cod_depositor_comments
'Adding full bibliography for 4134506--4134507.cif.'
_cod_database_code               4134507
_shelxl_version_number           2013-2
_reflns_odcompleteness_completeness 99.74
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.42
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All N(H,H) groups, All N(H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Shared sites
{Cl1, I008}
{Cl3, I007}
{Cl2, I006}
{Cl6, I00A}
{Cl0, I5}
{Cl4, I00B}
3. Restrained distances
 N2-H2A
 0.89 with sigma of 0.02
 N2-H2B
 0.89 with sigma of 0.02
 H7B-N7
 0.89 with sigma of 0.02
 H7A-N7
 0.89 with sigma of 0.02
 H2A-C2
 2 with sigma of 0.01
 H2B-C2
 2 with sigma of 0.01
 H2A-H2B
 1.45 with sigma of 0.01
 N6-H7A
 2.6 with sigma of 0.01
 H7B-H7A
 1.55 with sigma of 0.01
 H2B-H3A
 2.2 with sigma of 0.01
 H7A-H6C
 2.2 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(I008) = Uanis(Cl1)
Uanis(Cl1) = Uanis(I008)
Uanis(Cl3) = Uanis(I007)
Uanis(I007) = Uanis(Cl3)
Uanis(Cl2) = Uanis(I006)
Uanis(I006) = Uanis(Cl2)
Uanis(Cl6) = Uanis(I00A)
Uanis(I00A) = Uanis(Cl6)
Uanis(Cl0) = Uanis(I5)
Uanis(I5) = Uanis(Cl0)
Uanis(Cl4) = Uanis(I00B)
Uanis(I00B) = Uanis(Cl4)
5. Others
 Sof(I008)=1-FVAR(1)
 Sof(Cl1)=FVAR(1)
 Sof(Cl3)=1-FVAR(2)
 Sof(I007)=FVAR(2)
 Sof(Cl2)=1-FVAR(3)
 Sof(I006)=FVAR(3)
 Sof(Cl6)=1-FVAR(4)
 Sof(I00A)=FVAR(4)
 Sof(Cl0)=1-FVAR(5)
 Sof(I5)=FVAR(5)
 Sof(Cl4)=1-FVAR(6)
 Sof(I00B)=FVAR(6)
6.a Idealised Me refined as rotating group:
 N5(H5A,H5B,H5C), N3(H3A,H3B,H3C), N1(H1A,H1B,H1C), C5(H5D,H5E,H5F), C3(H3D,
 H3E,H3F), N6(H6A,H6B,H6C), N4(H4A,H4B,H4C), C4(H4D,H4E,H4F), C1(H1D,H1E,H1F),
 C2(H2C,H2D,H2E), C7(H7C,H7D,H7E), C6(H6D,H6E,H6F)
;
_olex2_date_sample_data_collection 2019-10-19
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.465
_oxdiff_exptl_absorpt_empirical_full_min 0.346