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_7716782
_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
'2(C32 N28 Ni27.5 O199 P4 Sb4 W46), 10(O), 80[H2O]'
_chemical_formula_sum            'C64 H490 N56 Ni55 O488 P8 Sb8 W92'
_chemical_formula_weight         31220.10
_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     iterative
_audit_creation_date             2024-06-20
_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
_cell_angle_beta                 105.4530(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   36.8164(10)
_cell_length_b                   29.8064(8)
_cell_length_c                   25.4292(7)
_cell_measurement_reflns_used    9236
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      24.966
_cell_measurement_theta_min      2.210
_cell_volume                     26896.3(13)
_computing_cell_refinement       'SAINT V8.30C (?, 2016)'
_computing_data_collection       'Bruker SMART'
_computing_data_reduction        'SAINT V8.30C (?, 2016)'
_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    'olex2.solve 1.3 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.972
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0587
_diffrn_reflns_av_unetI/netI     0.0771
_diffrn_reflns_Laue_measured_fraction_full 0.972
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       43
_diffrn_reflns_limit_h_min       -43
_diffrn_reflns_limit_k_max       35
_diffrn_reflns_limit_k_min       -35
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            130490
_diffrn_reflns_point_group_measured_fraction_full 0.972
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         1.662
_diffrn_source_current           35.0
_diffrn_source_power             1.575
_diffrn_source_voltage           45.0
_exptl_absorpt_coefficient_mu    21.987
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.3737
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1751 before and 0.0577 after correction.
The Ratio of minimum to maximum transmission is 0.5015.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    3.855
_exptl_crystal_description       block
_exptl_crystal_F_000             28092
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.1
_refine_diff_density_max         3.109
_refine_diff_density_min         -2.911
_refine_diff_density_rms         0.271
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.330(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     3120
_refine_ls_number_reflns         47315
_refine_ls_number_restraints     23129
_refine_ls_restrained_S_all      101.570
_refine_ls_R_factor_all          0.0638
_refine_ls_R_factor_gt           0.0463
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0483P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0978
_refine_ls_wR_factor_ref         0.1024
_reflns_Friedel_coverage         0.999
_reflns_Friedel_fraction_full    0.972
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                38529
_reflns_number_total             47315
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt00928b2.cif
_cod_data_source_block           z2
_cod_depositor_comments
'Adding full bibliography for 7716781--7716782.cif.'
_cod_database_code               7716782
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.217
_shelx_estimated_absorpt_t_min   0.137
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.670(7)
 0.330(7)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C1-C2 = C3-C4 = C5-C6 = C7-C8 = C9-C10 = C11-C12 = C13-C14 = C15-C16 = C17-C18
 1.52 with sigma of 0.01
 W35-O22 = W27-O99 = W45-O135 = W6-O174 = W6-O143 = W14-O188
 1.68 with sigma of 0.01
 W46-O159 = W43-O135 = W45-O81
 1.68 with sigma of 0.001
 W46-O183 = W46-O176
 1.78 with sigma of 0.01
 W46-O169
 1.8 with sigma of 0.01
 C19-C20 = C21-C22 = C23-C24 = C28-C19 = C30-C31 = C29-C32 = C15-C26 = C17-C27
 1.52 with sigma of 0.01
 W26-O56
 1.68 with sigma of 0.001
 C18-N18 = C19-N19 = C20-N20 = C21-N21 = C22-N22 = C23-N23 = C24-N24 = C29-N25
 1.47 with sigma of 0.01
 C1-N1 = C2-N2 = C3-N3 = C4-N4 = C5-N5 = C6-N6 = C7-N7 = C8-N8 = C9-N9 = C10-
 N10 = C30-N27
 1.47 with sigma of 0.01
 C11-N11 = C12-N12 = C13-N13 = C14-N14 = C15-N15 = C16-N16 = C17-N17 = N28-C31
 1.47 with sigma of 0.01
 W26-O56 = W14-O188
 1.68 with sigma of 0.01
 P4-O23 = P3-O3 = P3-O6 = P3-O132 = P2-O53 = P2-O51 = P1-O190
 1.52 with sigma of 0.01
 H31B_$2-H2C_$3
 2.1 with sigma of 0.001
 W45-O133 = W43-O190 = W39-O53 = W35-O132 = W37-O3 = W38-O115
 2.46 with sigma of 0.01
 W34-O23 = W36-O89 = W24-O86 = W31-O51 = W41-O61 = W44-O6 = W17-O6
 2.47 with sigma of 0.001
4. Rigid bond restraints
 N15, C15, Ni28, N25, Ni28, N26, Ni28, C32, N7, C7, N8, C8, N12, C12, N13, C13,
  N16, C16, N23, C23, N18, C18
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
5. Uiso/Uaniso restraints and constraints
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 O39 \\sim O40 \\sim O41
\\sim O42 \\sim O43 \\sim O44 \\sim O45 \\sim O46 \\sim O47 \\sim O48 \\sim O49
\\sim O50 \\sim O51 \\sim O52 \\sim O53 \\sim O54 \\sim O55 \\sim O56 \\sim O57
\\sim O58 \\sim O59 \\sim O60 \\sim O61 \\sim O62 \\sim O63 \\sim O64 \\sim O65
\\sim O66 \\sim O67 \\sim O68 \\sim O69 \\sim O70 \\sim O71 \\sim O72 \\sim O73
\\sim O74 \\sim O75 \\sim O76 \\sim O77 \\sim O78 \\sim O79 \\sim O80 \\sim O81
\\sim O82 \\sim O83 \\sim O84 \\sim O85 \\sim O86 \\sim O87 \\sim O88 \\sim O89
\\sim O90 \\sim O91 \\sim O92 \\sim O93 \\sim O94 \\sim O95 \\sim O96 \\sim O97
\\sim O98 \\sim O99 \\sim O100 \\sim O101 \\sim O102 \\sim O103 \\sim O104
\\sim O105 \\sim O106 \\sim O107 \\sim O108 \\sim O109 \\sim O110 \\sim O111
\\sim O112 \\sim O113 \\sim O114 \\sim O115 \\sim O116 \\sim O117 \\sim O118
\\sim O119 \\sim O120 \\sim O121 \\sim O122 \\sim O123 \\sim O124 \\sim O125
\\sim O126 \\sim O127 \\sim O128 \\sim O129 \\sim O130 \\sim O131 \\sim O132
\\sim O133 \\sim O134 \\sim O135 \\sim O136 \\sim O137 \\sim O138 \\sim O139
\\sim O140 \\sim O141 \\sim O142 \\sim O143 \\sim O144 \\sim O145 \\sim O146
\\sim O147 \\sim O148 \\sim O149 \\sim O150 \\sim O151 \\sim O152 \\sim O153
\\sim O154 \\sim O155 \\sim O156 \\sim O157 \\sim O158 \\sim O159 \\sim O160
\\sim O161 \\sim O162 \\sim O163 \\sim O164 \\sim O165 \\sim O166 \\sim O167
\\sim O168 \\sim O169 \\sim O170 \\sim O171 \\sim O172 \\sim O173 \\sim O174
\\sim O175 \\sim O176 \\sim O177 \\sim O178 \\sim O179 \\sim O180 \\sim O181
\\sim O182 \\sim O183 \\sim O184 \\sim O185 \\sim O186 \\sim O187 \\sim O188
\\sim O189 \\sim O190 \\sim O1W \\sim O2W \\sim O3W \\sim O4W \\sim O5W \\sim
O6W \\sim O7W \\sim O8W \\sim O9W \\sim O10W \\sim O11W \\sim O12W \\sim O13W
\\sim O14W: within 6.8A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 6.8A
W2 \\sim O161 \\sim W3 \\sim O28 \\sim W5 \\sim O141 \\sim W29 \\sim O45 \\sim
W29 \\sim O60 \\sim W30 \\sim O95 \\sim W39 \\sim O39 \\sim W39 \\sim O181
\\sim W41 \\sim O34 \\sim W41 \\sim O62 \\sim W43 \\sim O75 \\sim W43 \\sim
O167 \\sim W45 \\sim O120 \\sim W46 \\sim O183 \\sim W1 \\sim O136 \\sim W2
\\sim O161 \\sim W3 \\sim O146 \\sim W4 \\sim O140 \\sim W5 \\sim O141 \\sim W6
\\sim O162 \\sim Sb1 \\sim O144 \\sim Sb2 \\sim O145 \\sim Sb3 \\sim O145 \\sim
Sb4 \\sim O144: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9
\\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17
\\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25
\\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim C30 \\sim C31 \\sim C32: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
N1 \\sim N2 \\sim N3 \\sim N4 \\sim N5 \\sim N6 \\sim N7 \\sim N8 \\sim N9
\\sim N10 \\sim N11 \\sim N12 \\sim N13 \\sim N14 \\sim N15 \\sim N16 \\sim N17
\\sim N18 \\sim N19 \\sim N20 \\sim N21 \\sim N22 \\sim N23 \\sim N24 \\sim N25
\\sim N26 \\sim N27 \\sim N28: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C31 \\sim N28: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
Uanis(O95) \\sim Ueq, Uanis(O190) \\sim Ueq, Uanis(O157) \\sim Ueq, Uanis(O169)
\\sim Ueq, Uanis(O94) \\sim Ueq, Uanis(O158) \\sim Ueq, Uanis(O146) \\sim Ueq,
Uanis(O141) \\sim Ueq, Uanis(O143) \\sim Ueq, Uanis(O138) \\sim Ueq,
Uanis(O103) \\sim Ueq, Uanis(O102) \\sim Ueq, Uanis(O134) \\sim Ueq,
Uanis(O14W) \\sim Ueq, Uanis(O165) \\sim Ueq, Uanis(O135) \\sim Ueq, Uanis(O41)
\\sim Ueq, Uanis(O61) \\sim Ueq, Uanis(O44) \\sim Ueq, Uanis(O40) \\sim Ueq,
Uanis(O46) \\sim Ueq, Uanis(O149) \\sim Ueq, Uanis(O28) \\sim Ueq, Uanis(O14)
\\sim Ueq, Uanis(O7W) \\sim Ueq, Uanis(O33) \\sim Ueq, Uanis(O69) \\sim Ueq,
Uanis(O8) \\sim Ueq, Uanis(O123) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C5) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C9) \\sim
Ueq, Uanis(C10) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C17) \\sim Ueq,
Uanis(C27) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C16)
\\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C14) \\sim Ueq,
Uanis(C11) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C32)
\\sim Ueq, Uanis(C24) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(N28) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(N23) \\sim Ueq, Uanis(N25)
\\sim Ueq, Uanis(N26) \\sim Ueq, Uanis(N27) \\sim Ueq, Uanis(C30) \\sim Ueq,
Uanis(C31) \\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(O7W) \\sim Ueq, Uanis(O8W)
\\sim Ueq, Uanis(Ni28) \\sim Ueq, Uanis(N1) \\sim Ueq: with sigma of 0.001 and
sigma for terminal atoms of 0.002
6. Others
 Fixed Sof: Ni28(0.5)
7.a Ternary CH refined with riding coordinates:
 C9(H9), C15(H15), C17(H17), C19(H19)
7.b Secondary CH2 refined with riding coordinates:
 N1(H1A,H1B), N2(H2A,H2B), N3(H3A,H3B), N4(H4A,H4B), N5(H5A,H5B), N6(H6A,H6B),
 N7(H7A,H7B), N8(H8A,H8B), N9(H9A,H9B), N10(H10A,H10B), N11(H11A,H11B),
 N12(H12A,H12B), N13(H13A,H13B), N14(H14A,H14B), N15(H15A,H15B), N16(H16A,H16B),
  N17(H17A,H17B), N18(H18A,H18B), N19(H19A,H19B), N20(H20A,H20B), N21(H21A,
 H21B), N22(H22A,H22B), N23(H23A,H23B), N24(H24A,H24B), N25(H25A,H25B),
 N26(H26A,H26B), N27(H27A,H27B), N28(H28A,H28B), C1(H1C,H1D), C2(H2C,H2D),
 C3(H3C,H3D), C4(H4C,H4D), C5(H5C,H5D), C6(H6C,H6D), C7(H7C,H7D), C8(H8C,H8D),
 C10(H10C,H10D), C11(H11C,H11D), C12(H12C,H12D), C13(H13C,H13D), C14(H14C,H14D),
  C16(H16C,H16D), C18(H18C,H18D), C20(H20C,H20D), C21(H21C,H21D), C22(H22C,
 H22D), C23(H23C,H23D), C24(H24C,H24D), C29(H29A,H29B), C30(H30A,H30B),
 C31(H31A,H31B), C32(H32A,H32B)
7.c Idealised Me refined as rotating group:
 C25(H25C,H25D,H25E), C26(H26C,H26D,H26E), C27(H27C,H27D,H27E), C28(H28C,H28D,
 H28E)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 1852 electrons were 
found in a volume of 6398\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
80[H2O] per formula unit 
which account for 1600 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              17818
_shelx_fab_checksum              52472
_olex2_submission_special_instructions 'No special instructions were received'