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_1566082
_publ_section_title
;
 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(C48.01 Co8 N72.01), 0.25(C32 H70.35 N2), 0.25(C31.94 H72.29 N2)'
_chemical_formula_sum            'C21.99 H35.67 Co N10'
_chemical_formula_weight         499.06
_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                   15.7659(6)
_cell_length_b                   15.7712(5)
_cell_length_c                   21.2815(7)
_cell_measurement_reflns_used    6708
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      64.356
_cell_measurement_theta_min      3.488
_cell_volume                     5291.6(3)
_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      296.15
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.992
_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  0.1251
_diffrn_reflns_av_unetI/netI     0.0954
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            54532
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        65.370
_diffrn_reflns_theta_max         65.370
_diffrn_reflns_theta_min         2.076
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    5.311
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.6571
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1350 before and 0.0892 after correction. The Ratio of minimum to maximum transmission is 0.6571. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            pink
_exptl_crystal_colour_primary    pink
_exptl_crystal_density_diffrn    1.253
_exptl_crystal_description       prism
_exptl_crystal_F_000             2117
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.495
_refine_diff_density_min         -0.602
_refine_diff_density_rms         0.093
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.09(2)
_refine_ls_extinction_coef       0.00011(8)
_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   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     598
_refine_ls_number_reflns         8979
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.1507
_refine_ls_R_factor_gt           0.1093
_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^)+(0.0005P)^2^+42.7522P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2309
_refine_ls_wR_factor_ref         0.2542
_reflns_Friedel_coverage         0.806
_reflns_Friedel_fraction_full    0.993
_reflns_Friedel_fraction_max     0.993
_reflns_number_gt                6063
_reflns_number_total             8979
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc07080k2.cif
_cod_data_source_block           celiaco
_cod_database_code               1566082
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.619
_shelx_estimated_absorpt_t_min   0.523
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.91(2)
 0.09(2)
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
3. Uiso/Uaniso restraints and constraints
Uanis(C5B) \\sim Ueq, Uanis(C5A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.2
Uanis(C52) = Uanis(C51)
Uanis(C56) = Uanis(C55)
Uanis(C66) = Uanis(C67)
Uiso(C75B) = Uiso(C75A)
Uanis(C5B) = Uanis(C5A)
4. Others
 Sof(C71B)=Sof(H71A)=Sof(H71B)=Sof(H70C)=Sof(H70D)=1-FVAR(1)
 Sof(H70A)=Sof(H70B)=Sof(C71A)=Sof(H71C)=Sof(H71D)=FVAR(1)
 Sof(C75B)=Sof(H75A)=Sof(H75B)=Sof(H74C)=Sof(H74D)=1-FVAR(2)
 Sof(H74A)=Sof(H74B)=Sof(C75A)=Sof(H75C)=Sof(H75D)=FVAR(2)
 Sof(C43B)=Sof(H43A)=Sof(H43B)=Sof(H43C)=1-FVAR(3)
 Sof(C43A)=Sof(H43D)=Sof(H43E)=Sof(H43F)=FVAR(3)
 Sof(C48A)=Sof(H48D)=Sof(H48E)=Sof(H48F)=1-FVAR(4)
 Sof(C47A)=Sof(H47A)=Sof(H47B)=FVAR(4)
 Sof(H62A)=Sof(H62B)=Sof(C63B)=Sof(H63C)=Sof(H63D)=1-FVAR(5)
 Sof(H62C)=Sof(H62D)=Sof(C63A)=Sof(H63A)=Sof(H63B)=FVAR(5)
 Sof(C64B)=Sof(H64A)=Sof(H64B)=Sof(H64C)=1-FVAR(6)
 Sof(C64A)=Sof(H64D)=Sof(H64E)=Sof(H64F)=FVAR(6)
 Sof(C48B)=Sof(H48A)=Sof(H48B)=Sof(H48C)=1-FVAR(7)
 Sof(H46A)=Sof(H46B)=Sof(C5)=Sof(H5A)=Sof(H5B)=FVAR(7)
 Sof(C72B)=Sof(H72A)=Sof(H72B)=Sof(H72C)=1-FVAR(8)
 Fixed Sof: C5B(0.67) N15A(0.33333) C42A(0.5) H42A(0.5) H42B(0.5) N10A(0.5)
 H41A(0.5) H41B(0.5) H41C(0.5) H41D(0.5) C76B(0.8) H76A(0.8) H76B(0.8)
 H76C(0.8) C5A(0.33333) N15B(0.67) C42B(0.5) H42C(0.5) H42D(0.5) N10B(0.5)
 H72D(0.63) H72E(0.63) H72F(0.63) C76A(0.2) H76D(0.2) H76E(0.2) H76F(0.2)
5.a Secondary CH2 refined with riding coordinates:
 C42A(H42A,H42B), C65(H65A,H65B), C54(H54A,H54B), C66(H66A,H66B), C67(H67A,
 H67B), C46(H46A,H46B), C62(H62A,H62B), C62(H62C,H62D), C75B(H75A,H75B),
 C61(H61A,H61B), C69(H69A,H69B), C74(H74C,H74D), C74(H74A,H74B), C49(H49A,H49B),
  C55(H55A,H55B), C50(H50A,H50B), C40(H40A,H40B), C73(H73A,H73B), C71B(H71A,
 H71B), C70(H70C,H70D), C70(H70A,H70B), C51(H51A,H51B), C41(H41A,H41B),
 C41(H41C,H41D), C53(H53A,H53B), C63B(H63C,H63D), C45(H45A,H45B), C42B(H42C,
 H42D), C71A(H71C,H71D), C75A(H75C,H75D), C47A(H47A,H47B), C63A(H63A,H63B),
 C5(H5A,H5B)
5.b Idealised Me refined as rotating group:
 C43B(H43A,H43B,H43C), C48B(H48A,H48B,H48C), C64B(H64A,H64B,H64C), C56(H56A,
 H56B,H56C), C52(H52A,H52B,H52C), C68(H68A,H68B,H68C), C76B(H76A,H76B,H76C),
 C72B(H72A,H72B,H72C), C48A(H48D,H48E,H48F), C72A(H72D,H72E,H72F), C43A(H43D,
 H43E,H43F), C64A(H64D,H64E,H64F), C76A(H76D,H76E,H76F)
;
_olex2_submission_special_instructions 'No special instructions were received'