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_7718268
_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             2024-10-09
_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                   28.880(7)
_cell_length_b                   12.092(3)
_cell_length_c                   18.540(4)
_cell_measurement_reflns_used    9938
_cell_measurement_temperature    298.15
_cell_measurement_theta_max      19.17
_cell_measurement_theta_min      2.20
_cell_volume                     6474(3)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_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      298.15
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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  0.1648
_diffrn_reflns_av_unetI/netI     0.0771
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -34
_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            144236
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         1.410
_diffrn_source_current           30.0
_diffrn_source_power             1.2
_diffrn_source_voltage           40.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    12.868
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.2230
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1648 before and 0.0914 after correction.
The Ratio of minimum to maximum transmission is 0.2992.
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    2.135
_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         1.474
_refine_diff_density_min         -1.321
_refine_diff_density_rms         0.180
_refine_ls_abs_structure_details
;
 Flack x determined using 3152 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.021(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.192
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     548
_refine_ls_number_reflns         11398
_refine_ls_number_restraints     29
_refine_ls_restrained_S_all      1.191
_refine_ls_R_factor_all          0.1034
_refine_ls_R_factor_gt           0.0596
_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^)+73.4198P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0996
_refine_ls_wR_factor_ref         0.1179
_reflns_Friedel_coverage         0.933
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                8680
_reflns_number_total             11398
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt03225j2.cif
_cod_data_source_block           '[(p-BrPh)(p-MeBn)NMe2]3[Bi2Br9]_298K'
_cod_original_cell_volume        6475(3)
_cod_database_code               7718268
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.397
_shelx_estimated_absorpt_t_min   0.117
_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 O1A-C1A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(O1A) \\sim Ueq, Uanis(O1) \\sim Ueq, Uanis(C1A) \\sim Ueq, Uanis(C1)
\\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(O1A) = Uanis(O1)
Uanis(C1A) = Uanis(C1)
4. Rigid body (RIGU) restrains
 C15, C16
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(O1A)=Sof(C1A)=1-FVAR(1)
 Sof(O1)=Sof(C1)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C19(H19A,H19B), C35(H35A,H35B), C52(H52A,H52B)
6.b Aromatic/amide H refined with riding coordinates:
 C16(H16), C15(H15), C13(H13), C12(H12), C42(H42), C41(H41), C39(H39),
 C38(H38), C33(H33), C32(H32), C30(H30), C29(H29), C58(H58), C57(H57), C55(H55),
  C54(H54), C25(H25), C24(H24), C22(H22), C21(H21), C50(H50), C49(H49),
 C47(H47), C46(H46)
6.c Fitted hexagon refined as free rotating group:
 C11(C16,C15,C14,C13,C12), C4(C42,C41,C40,C39,C38), C28(C33,C32,C31,C30,C29),
 C53(C58,C57,C56,C55,C54), C20(C25,C24,C23,C22,C21), C3(C50,C49,C48,C47,C46)
6.d Idealised Me refined as rotating group:
 C36(H36A,H36B,H36C), C17(H17A,H17B,H17C), C2(H2A,H2B,H2C), C34(H34A,H34B,
 H34C), C26(H26A,H26B,H26C), C37(H37A,H37B,H37C), C5(H5A,H5B,H5C), C18(H18A,
 H18B,H18C), C51(H51A,H51B,H51C)
;
_shelx_res_checksum              24270
_olex2_submission_special_instructions 'No special instructions were received'