Ferroelectricity and piezoelectric energy harvesting of an A<sub>3</sub>M<sub>2</sub>X<sub>9</sub>-type 0D bromobismuthate hybrid with a bulky organic quaternary amine.
Meena, Namonarayan; Sahoo, Supriya; Deka, Nilotpal; Gadagin, Vinayak B.; Zaręba, Jan K; Boomishankar, Ramamoorthy; Dalton transactions (Cambridge, England : 2003) 54 (2025) 2985–2990; doi:10.1039/d4dt03225j

data_7718267
_publ_section_title
;
 Ferroelectricity and piezoelectric energy harvesting of an
 A<sub>3</sub>M<sub>2</sub>X<sub>9</sub>-type 0D bromobismuthate hybrid
 with a bulky organic quaternary amine.
;
_journal_issue                   7
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              2985
_journal_page_last               2990
_journal_paper_doi               10.1039/d4dt03225j
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         'Bi2 Br9, 3(C16 H19 Br N), C O'
_chemical_formula_sum            'C49 H57 Bi2 Br12 N3 O'
_chemical_formula_weight         2080.85
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2024-10-04
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-11-18 deposited with the CCDC.	2025-01-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   28.426(12)
_cell_length_b                   11.954(5)
_cell_length_c                   18.491(8)
_cell_measurement_reflns_used    6149
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      19.39
_cell_measurement_theta_min      2.15
_cell_volume                     6283(5)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      150.15
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.2335
_diffrn_reflns_av_unetI/netI     0.1039
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            142841
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        25.186
_diffrn_reflns_theta_max         25.186
_diffrn_reflns_theta_min         1.433
_diffrn_source_current           20.0
_diffrn_source_power             0.8
_diffrn_source_voltage           40.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    13.260
_exptl_absorpt_correction_T_max  0.2831
_exptl_absorpt_correction_T_min  0.0335
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1282 before and 0.1047 after correction.
The Ratio of minimum to maximum transmission is 0.1183.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear yellowish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    2.200
_exptl_crystal_description       needle
_exptl_crystal_F_000             3864
_exptl_crystal_size_max          0.293
_exptl_crystal_size_mid          0.186
_exptl_crystal_size_min          0.088
_refine_diff_density_max         2.309
_refine_diff_density_min         -2.178
_refine_diff_density_rms         0.261
_refine_ls_abs_structure_details
;
 Flack x determined using 3147 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.024(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.100
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     622
_refine_ls_number_reflns         11222
_refine_ls_number_restraints     417
_refine_ls_restrained_S_all      1.087
_refine_ls_R_factor_all          0.1038
_refine_ls_R_factor_gt           0.0622
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0164P)^2^+106.1583P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1091
_refine_ls_wR_factor_ref         0.1238
_reflns_Friedel_coverage         0.930
_reflns_Friedel_fraction_full    0.992
_reflns_Friedel_fraction_max     0.992
_reflns_number_gt                8377
_reflns_number_total             11222
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt03225j2.cif
_cod_data_source_block           '[(p-BrPh)(p-MeBn)NMe2]3[Bi2Br9]_150K'
_cod_original_cell_volume        6283(4)
_cod_database_code               7718267
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.388
_shelx_estimated_absorpt_t_min   0.112
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O1-C1 \\sim O1-C1A
 with sigma of 0.02
 C48-C51 \\sim C48-C51A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms restrained to be isotropic: with sigma of 0.005 and
sigma for terminal atoms of 0.01
Uanis(C1) = Uanis(C1A)
Uanis(C51A) = Uanis(C51)
4. Others
 Sof(C1A)=1-FVAR(1)
 Sof(C1)=FVAR(1)
 Sof(C51A)=Sof(H51D)=Sof(H51E)=Sof(H51F)=1-FVAR(2)
 Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(H51C)=FVAR(2)
5.a Secondary CH2 refined with riding coordinates:
 C19(H19A,H19B), C27(H27A,H27B), C52(H52A,H52B)
5.b Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C15(H15), C16(H16), C21(H21), C22(H22), C24(H24),
 C25(H25), C29(H29), C30(H30), C32(H32), C33(H33), C38(H38), C39(H39), C41(H41),
  C42(H42), C46(H46), C47(H47), C49(H49), C50(H50), C54(H54), C55(H55),
 C57(H57), C58(H58)
5.c Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C26(H26A,H26B,H26C), C34(H34A,H34B,
 H34C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C43(H43A,H43B,H43C), C44(H44A,
 H44B,H44C), C51(H51A,H51B,H51C), C51A(H51D,H51E,H51F)
;
_shelx_res_checksum              43020
_olex2_submission_special_instructions 'No special instructions were received'