Principles of Melting in Hybrid Organic-Inorganic Perovskite and Polymorphic ABX3 Structures
Shaw, Bikash Kumar; Bennett, Thomas Douglas; Castillo Blas, Celia; Thorne, Michael Francis; Gómez, María Laura Ríos; Forrest, Thomas; Keen, David A.; Diaz-Lopez, Maria; Chater, Philip A.; McHugh, Lauren Nicole; Chemical Science  (2022) –; doi:10.1039/D1SC07080K

data_1566083
_publ_section_title
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 Principles of Melting in Hybrid Organic-Inorganic Perovskite and
 Polymorphic ABX3 Structures
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC07080K
_journal_year                    2022
_chemical_formula_moiety
'0.13(C48 Fe8 N72), 0.25(C32.02 H72.2 N2), 0.5(C16 H35.64 N)'
_chemical_formula_sum            'C22.01 H35.86 Fe N10'
_chemical_formula_weight         496.39
_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_Hall           'P 2 2ab'
_space_group_name_H-M_alt        'P 21 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2020-08-29
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-08-31 deposited with the CCDC.	2022-01-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   15.7971(7)
_cell_length_b                   15.8093(9)
_cell_length_c                   21.4138(11)
_cell_measurement_reflns_used    8450
_cell_measurement_temperature    240
_cell_measurement_theta_max      64.632
_cell_measurement_theta_min      3.475
_cell_volume                     5347.9(5)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      240
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device_type  'Vantec 500'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.1126
_diffrn_reflns_av_unetI/netI     0.0817
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            55212
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        65.338
_diffrn_reflns_theta_max         65.338
_diffrn_reflns_theta_min         2.063
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.747
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.6634
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1429 before and 0.0966 after correction. The Ratio of minimum to maximum transmission is 0.6634. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'yellowish colourless'
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.233
_exptl_crystal_description       prism
_exptl_crystal_F_000             2111
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.534
_refine_diff_density_min         -0.582
_refine_diff_density_rms         0.130
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.07(3)
_refine_ls_extinction_coef       0.0008(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     626
_refine_ls_number_reflns         9065
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.1405
_refine_ls_R_factor_gt           0.1063
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1523P)^2^+21.3446P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2999
_refine_ls_wR_factor_ref         0.3279
_reflns_Friedel_coverage         0.806
_reflns_Friedel_fraction_full    0.993
_reflns_Friedel_fraction_max     0.993
_reflns_number_gt                6196
_reflns_number_total             9065
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc07080k2.cif
_cod_data_source_block           celiap21212
_cod_database_code               1566083
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.764
_shelx_estimated_absorpt_t_min   0.648
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.93(3)
 0.07(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups
3. Rigid bond restraints
 N11
 with sigma for 1-2 distances of 0.05 and sigma for 1-3 distances of 0.05
4. Uiso/Uaniso restraints and constraints
Uanis(C62B) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.2
Uiso(C51B) = Uiso(C51A)
Uanis(C54B) = Uanis(C54A)
Uanis(C50A) = Uanis(C62B)
Uanis(C72) = Uanis(C71B)
5. Others
 Sof(C55B)=Sof(H55A)=Sof(H55B)=Sof(H55C)=1-FVAR(1)
 Sof(C55A)=Sof(H55D)=Sof(H55E)=Sof(H55F)=FVAR(1)
 Sof(H42C)=Sof(H42D)=Sof(C43A)=Sof(H43A)=Sof(H43B)=Sof(H43C)=1-FVAR(2)
 Sof(H42A)=Sof(H42B)=Sof(C43B)=Sof(H43D)=Sof(H43E)=Sof(H43F)=FVAR(2)
 Sof(C51B)=Sof(H51A)=Sof(H51B)=1-FVAR(3)
 Sof(C51A)=Sof(H51C)=Sof(H51D)=Sof(H51E)=FVAR(3)
 Fixed Sof: C63B(0.33333) H63A(0.33333) H63B(0.33333) H63C(0.33333) C62A(0.67)
 H62A(0.67) H62B(0.67) H70C(0.7) H70D(0.7) H70A(0.33333) H70B(0.33333)
 H53C(0.5) H53D(0.5) H53A(0.5) H53B(0.5) C50A(0.33333) H50A(0.33333)
 H50B(0.33333) C50B(0.67) H50C(0.67) H50D(0.67) C54B(0.5) H54A(0.5) H54B(0.5)
 H72D(0.67) H72E(0.67) H72F(0.67) H72A(0.33333) H72B(0.33333) H72C(0.33333)
 C71B(0.67) H71A(0.67) H71B(0.67) C54A(0.5) H54C(0.5) H54D(0.5) C62B(0.33333)
 H62C(0.33333) H62D(0.33333) C71A(0.33333) H71C(0.33333) H71D(0.33333)
 C63A(0.67) H63D(0.67) H63E(0.67) H63F(0.67)
6.a Secondary CH2 refined with riding coordinates:
 C61(H61A,H61B), C60(H60A,H60B), C66(H66A,H66B), C62A(H62A,H62B), C48(H48A,
 H48B), C70(H70C,H70D), C70(H70A,H70B), C40(H40A,H40B), C42(H42C,H42D),
 C42(H42A,H42B), C69(H69A,H69B), C65(H65A,H65B), C53(H53C,H53D), C53(H53A,H53B),
  C50A(H50A,H50B), C52(H52A,H52B), C45(H45A,H45B), C50B(H50C,H50D), C49(H49A,
 H49B), C44(H44A,H44B), C54B(H54A,H54B), C46(H46A,H46B), C73(H73A,H73B),
 C75(H75A,H75B), C71B(H71A,H71B), C74(H74A,H74B), C67(H67A,H67B), C51B(H51A,
 H51B), C54A(H54C,H54D), C41(H41A,H41B), C62B(H62C,H62D), C71A(H71C,H71D)
6.b Idealised Me refined as rotating group:
 C63B(H63A,H63B,H63C), C55B(H55A,H55B,H55C), C47(H47A,H47B,H47C), C72(H72D,
 H72E,H72F), C72(H72A,H72B,H72C), C76(H76A,H76B,H76C), C43A(H43A,H43B,H43C),
 C68(H68A,H68B,H68C), C63A(H63D,H63E,H63F), C55A(H55D,H55E,H55F), C43B(H43D,
 H43E,H43F), C51A(H51C,H51D,H51E)
;
_olex2_submission_special_instructions 'No special instructions were received'