Two nickel-added poly(polyoxometalate)s built of Keggin-type {Ni<sub>6</sub>PW<sub>9</sub>} and Anderson-type NiW<sub>6</sub>O<sub>24</sub><i>via</i> WO<sub>4</sub>/Sb<sub>2</sub>O bridges and Ni-O-W linkages with efficient hydrogen evolution activity.
Zhang, Peng-Yun; Lian, Chen; Wang, Zhen-Wen; Chen, Juan; Lv, Hongjin; Yang, Guo-Yu; Dalton transactions (Cambridge, England : 2003) 53 (2024) 13409–13415; doi:10.1039/d4dt00928b

data_7716781
_publ_section_title
;
 Two nickel-added poly(polyoxometalate)s built of Keggin-type
 {Ni<sub>6</sub>PW<sub>9</sub>} and Anderson-type
 NiW<sub>6</sub>O<sub>24</sub><i>via</i> WO<sub>4</sub>/Sb<sub>2</sub>O
 bridges and Ni-O-W linkages with efficient hydrogen evolution activity.
;
_journal_issue                   32
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              13409
_journal_page_last               13415
_journal_paper_doi               10.1039/d4dt00928b
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety
'C15 N10 Na2 Ni13 O101 P2 Sb2 W23, 8(O), 8[H2O], 0.5[H2O]'
_chemical_formula_sum            'C15 H103 N10 Na2 Ni13 O117.5 P2 Sb2 W23'
_chemical_formula_weight         7647.27
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-05-26
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2024-07-10 deposited with the CCDC.	2024-07-25 downloaded from the CCDC.
;
_cell_angle_alpha                90.1970(10)
_cell_angle_beta                 106.1290(10)
_cell_angle_gamma                98.5440(10)
_cell_formula_units_Z            2
_cell_length_a                   14.1447(7)
_cell_length_b                   19.4035(9)
_cell_length_c                   22.8651(10)
_cell_measurement_reflns_used    9116
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      25.152
_cell_measurement_theta_min      2.369
_cell_volume                     5955.0(5)
_computing_data_collection       'Bruker SMART'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2013/4 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.972
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0476
_diffrn_reflns_av_unetI/netI     0.0382
_diffrn_reflns_Laue_measured_fraction_full 0.972
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            112550
_diffrn_reflns_point_group_measured_fraction_full 0.972
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         1.443
_exptl_absorpt_coefficient_mu    24.711
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.5401
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2012/1 (Bruker,2012) was used for absorption correction. wR2(int) was 0.1105 before and 0.0461 after correction. The Ratio of minimum to maximum transmission is 0.7248. The \l/2 correction factor is 0.0015.'
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    4.265
_exptl_crystal_description       needle
_exptl_crystal_F_000             6846
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.06
_refine_diff_density_max         5.956
_refine_diff_density_min         -4.522
_refine_diff_density_rms         0.379
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1586
_refine_ls_number_reflns         20912
_refine_ls_number_restraints     359
_refine_ls_restrained_S_all      1.256
_refine_ls_R_factor_all          0.0624
_refine_ls_R_factor_gt           0.0456
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0301P)^2^+391.8450P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0951
_refine_ls_wR_factor_ref         0.1009
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17081
_reflns_number_total             20912
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt00928b2.cif
_cod_data_source_block           z1
_cod_depositor_comments
'Adding full bibliography for 7716781--7716782.cif.'
_cod_original_formula_sum        'C15 H103 N10 Na2 Ni13 O117.50 P2 Sb2 W23'
_cod_database_code               7716781
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.319
_shelx_estimated_absorpt_t_min   0.110
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C5-C4 = C1-C2 = C1-C2A
 1.5 with sigma of 0.01
 N9-C13 = N6-C11 = N3-C5
 1.47 with sigma of 0.001
 N4-C4 = N2-C2A = N2-C2 = N1-C1
 1.48 with sigma of 0.001
 C14-C15 = C10-C12 = C3-C2 = C2A-C3 = C4-C6 = C14-C13
 1.52 with sigma of 0.01
 H4B-H12B_$2
 2.1 with sigma of 0.001
 C4-C6 = C8-C9
 1.52 with sigma of 0.01
 H12C-H12C_$3
 2.1 with sigma of 0.001
 C15-C14 = C6-C4 = C3-C2A = C3-C2
 1.54 with sigma of 0.001
 N2-C2 \\sim N2-C2A
 with sigma of 0.02
 N1-C2 \\sim N1-C2A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
N1 \\sim N2 \\sim C1 \\sim C2A \\sim C3 \\sim C2: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 2A
N3 \\sim N4 \\sim C5 \\sim C4 \\sim C6: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
C1 \\sim C2 \\sim C2A \\sim C3 \\sim C7 \\sim C8 \\sim C9 \\sim C10 \\sim C11
\\sim C12 \\sim C13 \\sim C14 \\sim C15: within 2A with sigma of 0.001 and
sigma for terminal atoms of 0.002 within 2A
N10 \\sim N9 \\sim C13 \\sim C14 \\sim C15: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
Uanis(C1) \\sim Ueq, Uanis(C2A) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C3) \\sim
Ueq, Uanis(C4) \\sim Ueq, Uanis(C5) \\sim Ueq: with sigma of 0.001 and sigma
for terminal atoms of 0.002
Uanis(O25) \\sim Ueq, Uanis(O48) \\sim Ueq, Uanis(O7) \\sim Ueq, Uanis(O29)
\\sim Ueq, Uanis(O61) \\sim Ueq, Uanis(O41) \\sim Ueq, Uanis(O50) \\sim Ueq,
Uanis(C7) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(O1) \\sim Ueq, Uanis(O3) \\sim Ueq, Uanis(O26) \\sim Ueq, Uanis(O27)
\\sim Ueq, Uanis(O42) \\sim Ueq, Uanis(O43) \\sim Ueq, Uanis(O95) \\sim Ueq,
Uanis(O2W) \\sim Ueq, Uanis(O3W) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(O6W) \\sim Ueq, Uanis(O7W) \\sim Ueq, Uanis(O10W) \\sim Ueq, Uanis(O11W)
\\sim Ueq, Uanis(O14W) \\sim Ueq, Uanis(O80) \\sim Ueq, Uanis(O45) \\sim Ueq:
with sigma of 0.001 and sigma for terminal atoms of 0.002
4. Others
 Fixed Sof: H1BC(0.4) H1BD(0.4) H1AA(0.6) H1AB(0.6) C2(0.4) H2(0.4) C2A(0.6)
 H2AA(0.6)
 Fixed X: C1(0.825341) C6(1.58193) C12(0.42068) C15(1.15435)
 Fixed Y: C1(0.84565) C6(0.651141) C12(0.50718) C15(0.323041)
 Fixed Z: C1(0.497419) C6(0.439899) C12(0.429569) C15(0.028361)
5.a Riding coordinates:
 N1(H1A,H1B), N2(H2A,H2B), N4(H4A,H4B), N5(H5A,H5B), C2(H2), C2A(H2AA), C3(H3C,
 H3D,H3E), C6(H6C,H6D,H6E), C12(H12A,H12B,H12C), C13(H13A,H13B), C15(H15A,H15B,
 H15C)
5.b Ternary CH refined with riding coordinates:
 C4(H4), C8(H8), C10(H10), C14(H14)
5.c Secondary CH2 refined with riding coordinates:
 N3(H3A,H3B), N6(H6A,H6B), N7(H7A,H7B), N8(H8A,H8B), N9(H9A,H9B), N10(H10A,
 H10B), C1(H1BC,H1BD), C1(H1AA,H1AB), C5(H5C,H5D), C7(H7C,H7D), C11(H11A,H11B)
5.d Idealised Me refined as rotating group:
 C9(H9C,H9D,H9E)
;
_smtbx_masks_special_details
;  
 a solvent mask was calculated and 187 electrons
 were found in a volume of 659\%A^3^ in 2 void 
per unit cell. This is consistent with the presence
 of 8[H2O], 0.5[H2O] per Formula Unit which 
account for 170 electrons per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              38771
_shelx_fab_checksum              88719
_olex2_submission_special_instructions 'No special instructions were received'