Tuning covalent bonding in zinc-based hybrid halides towards tunable room-temperature phosphorescence
Cui, Yibo; Lin, Jiawei; Liu, Kunjie; Shao, Yuhe; Zhao, Dong; Guo, Zhongnan; Zhao, Jing; Xia, Zhiguo; Liu, Quanlin; Chemical Science 16 (2025) 8291–8301; doi:10.1039/D5SC00931F

data_1574379
_publ_section_title
;
 Tuning covalent bonding in zinc-based hybrid halides towards tunable
 room-temperature phosphorescence
;
_journal_issue                   19
_journal_name_full               'Chemical Science'
_journal_page_first              8291
_journal_page_last               8301
_journal_paper_doi               10.1039/D5SC00931F
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         '0.5(Cl6 Zn2.04), C6 H9.01 N2'
_chemical_formula_sum            'C6 H9.01 Cl3 N2 Zn1.01'
_chemical_formula_weight         281.32
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-10-11
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2024-12-30 deposited with the CCDC.	2025-04-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 127.717(7)
_cell_angle_gamma                90
_cell_formula_units_Z            12
_cell_length_a                   9.909(2)
_cell_length_b                   63.672(16)
_cell_length_c                   6.3765(15)
_cell_measurement_reflns_used    9902
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      28.130
_cell_measurement_theta_min      2.770
_cell_volume                     3182.4(13)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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_temperature      150.15
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.994
_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  0.0563
_diffrn_reflns_av_unetI/netI     0.0746
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       90
_diffrn_reflns_limit_k_min       -90
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            38851
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.957
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.590
_diffrn_reflns_theta_min         2.559
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.032
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.5499
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0964 before and 0.0625 after correction. The Ratio of minimum to maximum transmission is 0.7370. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'clear whiteish white'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   whiteish
_exptl_crystal_colour_primary    white
_exptl_crystal_density_diffrn    1.761
_exptl_crystal_description       block
_exptl_crystal_F_000             1683
_refine_diff_density_max         1.186
_refine_diff_density_min         -0.874
_refine_diff_density_rms         0.122
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.44(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     310
_refine_ls_number_reflns         9345
_refine_ls_number_restraints     116
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.1208
_refine_ls_R_factor_gt           0.0546
_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^)+(0.0418P)^2^+13.6228P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1048
_refine_ls_wR_factor_ref         0.1348
_reflns_Friedel_coverage         0.917
_reflns_Friedel_fraction_full    0.983
_reflns_Friedel_fraction_max     0.920
_reflns_number_gt                5478
_reflns_number_total             9345
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc00931f2.cif
_cod_data_source_block           c2-c
_cod_depositor_comments
'Adding full bibliography for 1574378--1574388.cif.'
_cod_original_cell_volume        3182.5(14)
_cod_database_code               1574379
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.56(3)
 0.44(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H,H,H,H) groups
3. Rigid bond restraints
 C6, C2
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C18, C17, C15, C16, C14
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C3, C4, C5, C2, C6, N3
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C6 \\sim C2: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C15 \\sim C18 \\sim C17 \\sim C16: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
C2 \\sim C3 \\sim C4 \\sim C5 \\sim N3 \\sim C6: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08
Uanis(C6) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C5) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C2) \\sim
Ueq, Uanis(C6) \\sim Ueq, Uanis(N3) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(N8) = Uanis(N7)
Uanis(N5) = Uanis(N4)
Uanis(N1) = Uanis(N2)
Uanis(Zn3) = Uanis(Zn4)
Uanis(C8) = Uanis(N6)
Uanis(N9) = Uanis(C18)
Uanis(C9) = Uanis(C8)
Uanis(N9) = Uanis(C14)
5. Others
 1*[Sof(H13D)+Sof(H13E)+Sof(H13F)+Sof(N8)]+1*[Sof(N7)+Sof(H13A)+Sof(H13B)+
 Sof(H13C)]=1 with esd of 0.01
 1*[Sof(H7AA)+Sof(H7AB)+Sof(H7AC)+Sof(N4)]+1*[Sof(N5)+Sof(H7BD)+Sof(H7BE)+
 Sof(H7BF)]=1 with esd of 0.01
 1*[Sof(H1AA)+Sof(H1AB)+Sof(H1AC)+Sof(N2)+Sof(H2A)]+1*[Sof(H1BD)+Sof(H1BE)+
 Sof(H1BF)+Sof(N1)+Sof(H1)]=1 with esd of 0.01
 1*[Sof(H1BD)+Sof(H1BE)+Sof(H1BF)+Sof(N1)+Sof(H1)]+1*[Sof(H1AA)+Sof(H1AB)+
 Sof(H1AC)+Sof(N2)+Sof(H2A)]=1 with esd of 0.01
 1*[Sof(Zn4)]+1*[Sof(Zn3)]=1 with esd of 0.01
 Sof(H13D)=Sof(H13E)=Sof(H13F)=Sof(N8)=FVAR(1)
 Sof(N7)=Sof(H13A)=Sof(H13B)=Sof(H13C)=FVAR(2)
 Sof(H7AA)=Sof(H7AB)=Sof(H7AC)=Sof(N4)=FVAR(3)
 Sof(N5)=Sof(H7BD)=Sof(H7BE)=Sof(H7BF)=FVAR(4)
 Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=Sof(N2)=Sof(H2A)=FVAR(5)
 Sof(H1BD)=Sof(H1BE)=Sof(H1BF)=Sof(N1)=Sof(H1)=FVAR(6)
6.a Me refined with riding coordinates:
 C7(H7BD,H7BE,H7BF), C7(H7AA,H7AB,H7AC), C13(H13A,H13B,H13C), C13(H13D,H13E,
 H13F), C1(H1BD,H1BE,H1BF), C1(H1AA,H1AB,H1AC)
6.b Aromatic/amide H refined with riding coordinates:
 N5(H5A), N7(H7), N9(H9A), C11(H11), N6(H6), C17(H17), C9(H9), C12(H12),
 C15(H15), C10(H10), C18(H18), C16(H16), N1(H1), C2(H2), C3(H3), C4(H4), C5(H5),
  N3(H3A), N2(H2A)
6.c Fitted hexagon refined as free rotating group:
 C2(C3,C4,C5,N3,C6)
;
_shelx_res_checksum              87484
_olex2_submission_special_instructions 'No special instructions were received'