A novel sandwich Ni-added polyoxometalate with nonlinear optical properties and photothermal conversion performance
Wang, Zhen-Wen; Wang, Yue-Lin; Yang, Guo-Yu; CrystEngComm 27 (2025) 1650–1656; doi:10.1039/D5CE00036J

data_7249946
_publ_section_title
;
 A novel sandwich Ni-added polyoxometalate with nonlinear optical
 properties and photothermal conversion performance
;
_journal_issue                   11
_journal_name_full               CrystEngComm
_journal_page_first              1650
_journal_page_last               1656
_journal_paper_doi               10.1039/D5CE00036J
_journal_volume                  27
_journal_year                    2025
_chemical_formula_moiety         'Cl Cs7.5 H4 N Na0.5 Ni4 O74 P2 W17, 4[H2O]'
_chemical_formula_sum            'Cl Cs7.5 H12 N Na0.5 Ni4 O78 P2 W17'
_chemical_formula_weight         5740.11
_space_group_crystal_system      tetragonal
_space_group_IT_number           113
_space_group_name_Hall           'P -4 2ab'
_space_group_name_H-M_alt        'P -4 21 m'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     dual
_audit_creation_date             2024-12-25
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-12-31 deposited with the CCDC.	2025-02-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.5884(9)
_cell_length_b                   21.5884(9)
_cell_length_c                   17.7901(11)
_cell_measurement_reflns_used    6048
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      28.0850
_cell_measurement_theta_min      3.7510
_cell_volume                     8291.2(7)
_computing_cell_refinement       'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4159
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.945
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -73.00  -5.00   1.00   47.00    --  -12.12 -75.00 144.00   68
  2  \w    -45.00  39.00   1.00   47.00    --  -12.12  77.00  30.00   84
  3  \w    -69.00  16.00   1.00   47.00    --  -12.12 -57.00-150.00   85
  4  \w    -79.00 -52.00   1.00   47.00    --  -12.12-178.00  90.00   27
  5  \w    -94.00 -52.00   1.00   47.00    --  -12.12-178.00 -90.00   42
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0105467000
_diffrn_orient_matrix_UB_12      0.0238647000
_diffrn_orient_matrix_UB_13      -0.0242139000
_diffrn_orient_matrix_UB_21      -0.0303222000
_diffrn_orient_matrix_UB_22      0.0126259000
_diffrn_orient_matrix_UB_23      -0.0011195000
_diffrn_orient_matrix_UB_31      0.0070292000
_diffrn_orient_matrix_UB_32      0.0187097000
_diffrn_orient_matrix_UB_33      0.0316535000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1252
_diffrn_reflns_av_unetI/netI     0.1109
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.945
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            68072
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.913
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.701
_diffrn_reflns_theta_min         3.403
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    27.786
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.61411
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.122a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    4.598
_exptl_crystal_description       block
_exptl_crystal_F_000             9912
_refine_diff_density_max         3.704
_refine_diff_density_min         -4.175
_refine_diff_density_rms         0.645
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.080(19)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     530
_refine_ls_number_reflns         11129
_refine_ls_number_restraints     896
_refine_ls_restrained_S_all      0.996
_refine_ls_R_factor_all          0.0965
_refine_ls_R_factor_gt           0.0533
_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^)+(0.0370P)^2^+128.4376P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0935
_refine_ls_wR_factor_ref         0.1102
_reflns_Friedel_coverage         0.793
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.876
_reflns_number_gt                8094
_reflns_number_total             11129
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ce00036j2.cif
_cod_data_source_block           1
_cod_depositor_comments          'Adding full bibliography for 7249946.cif.'
_cod_original_cell_volume        8291.3(9)
_cod_original_formula_sum        'Cl Cs7.50 H12 N Na0.50 Ni4 O78 P2 W17'
_cod_database_code               7249946
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.920(19)
 0.080(19)
2. Fixed Uiso
 At 1.2 times of:
  All N(H,H,H) groups
3. Restrained distances
 N1-H1D
 0.89 with sigma of 0.0041
 O28-O40
 3 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
P1 \\sim O18 \\sim O19 \\sim O20 \\sim O20: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
O1 \\sim O2 \\sim O3 \\sim O4 \\sim O5 \\sim O6 \\sim O7 \\sim O8 \\sim O9
\\sim O10 \\sim O11 \\sim O12 \\sim O13 \\sim O14 \\sim O15 \\sim O16 \\sim O17
\\sim O18 \\sim O19 \\sim O20 \\sim O21 \\sim O22 \\sim O23 \\sim O24 \\sim O25
\\sim O26 \\sim O27 \\sim O28 \\sim O29 \\sim O30 \\sim O31 \\sim O32 \\sim O33
\\sim O34 \\sim O35 \\sim O36 \\sim O37 \\sim O38 \\sim N1 \\sim O40 \\sim O1W
\\sim O2W \\sim O3W \\sim O4W \\sim O5W: within 3.5A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 3.5A
Uanis(O4W) \\sim Ueq, Uanis(O4W) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(O20) \\sim Ueq, Uanis(P1) \\sim Ueq, Uanis(O20) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(P1) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(O29) \\sim Ueq, Uanis(O8) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(O35) \\sim Ueq, Uanis(O6) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
5. Others
 Fixed Sof: Cs4(0.125) Cs5(0.5) Cs6(0.125) H1B(0.5) H1C(0.5)
 Fixed X: H1D(0.83522)
 Fixed Y: H1D(0.33522)
 Fixed Z: H1D(-0.00963)
6.a Riding coordinates:
 N1(H1A,H1B,H1C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 178 electrons were 
found in a volume of 388\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
4[H2O] per formula unit 
which account for 160 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   2.0
_smtbx_masks_void_truncation_radius 2.0
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.463
_oxdiff_exptl_absorpt_empirical_full_min 0.732