Supra­molecular inter­action-induced assemblies of polyanions and 2-amino­pyridinium in two polyoxometalate-based hybrids

Organic–inorganic hybrids consisting of organic cations and polyanions are promising functional materials due to their various compositions and structures. An important aspect of these materials is the inter­actions between the organic and inorganic components, which not only produce the final structures, but also influence the properties. Here, we investigated the inter­actions between organic cations and polyanions using protonated 2-amino­pyridinium (Hap) as the cation, and successfully obtained two polyoxometalate-based hybrids, namely (C₅H₇N₂)₄[Mo₈O₂₆], (I), and (C₅H₇N₂)₂[NiMo₆O₁₆(OH)₂{CH₃C(CH₂O)₃}₂]·4H₂O, (II). In the crystal structure of (I), every Hap cation links with two polyanions by donating one or two N—H...O hydrogen bonds, and every polyanion is surrounded by eight Hap cations via terminal or bridging O atoms. Conversely, in compound (II), every Hap cation only links with one polyanion decorated by a triol ligand; this organic–inorganic component further assembles via uncoordinated water mol­ecules. In the extended structures, Hap plays a key role, not only providing a counter charge, but also acting as `glue' linking polyanions in the role of hydrogen-bond donors. In both compounds, as the nodes of the supra­molecular network, the polyanions exhibit an ordered two-dimensional arrangement due to strong hydrogen bonds and electrostatic inter­actions between the organic and inorganic parts. The electrochemistry of compound (I) shows that redox sourcing from polyanions is a surface-controlled process. Conversely, the magnetic behaviour of compound (II) indicates dominant anti­ferromagnetic properties.

Computing details

For both structures, data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

(compound_I)

Crystal data

(C5H7N2)4[Mo8O26]	Z = 1
Mr = 1564.02	F(000) = 748
Triclinic, P1	Dx = 2.630 Mg m^−3
a = 10.4179 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.5225 (4) Å	Cell parameters from 9786 reflections
c = 10.5988 (4) Å	θ = 3.1–27.5°
α = 65.356 (1)°	µ = 2.56 mm^−1
β = 69.658 (1)°	T = 293 K
γ = 77.922 (1)°	Block, light-yellow
V = 987.36 (6) Å^3	0.14 × 0.12 × 0.11 mm

Data collection

D8 VENTURE PHOTON II diffractometer	4143 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.021
phi and ω scans	θmax = 27.5°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2013)	h = −13→13
Tmin = 0.716, Tmax = 0.766	k = −13→13
31614 measured reflections	l = −13→13
4525 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.021	H-atom parameters constrained
wR(F^2) = 0.067	w = 1/[σ^2(Fo^2) + (0.0365P)^2 + 2.4139P] where P = (Fo^2 + 2Fc^2)/3
S = 0.97	(Δ/σ)max = 0.001
4525 reflections	Δρmax = 0.80 e Å^−3
280 parameters	Δρmin = −0.59 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.1495 (4)	0.0301 (3)	0.2388 (4)	0.0353 (7)
C2	0.0459 (4)	0.1337 (4)	0.2597 (4)	0.0420 (8)
H2	0.0665	0.2269	0.2204	0.050*
C3	−0.0834 (4)	0.0995 (5)	0.3364 (5)	0.0483 (9)
H3	−0.1515	0.1691	0.3512	0.058*
C4	−0.1171 (4)	−0.0394 (5)	0.3941 (4)	0.0481 (9)
H4	−0.2068	−0.0632	0.4469	0.058*
C5	−0.0166 (4)	−0.1376 (4)	0.3714 (4)	0.0445 (8)
H5	−0.0371	−0.2305	0.4077	0.053*
C6	0.7648 (3)	0.2843 (3)	0.0519 (3)	0.0316 (6)
C7	0.8356 (4)	0.1617 (4)	0.0282 (5)	0.0469 (9)
H7	0.9269	0.1630	−0.0283	0.056*
C8	0.7699 (5)	0.0428 (4)	0.0881 (5)	0.0533 (11)
H8	0.8173	−0.0379	0.0742	0.064*
C9	0.6324 (5)	0.0393 (4)	0.1701 (5)	0.0552 (11)
H9	0.5878	−0.0428	0.2116	0.066*
C10	0.5652 (5)	0.1582 (4)	0.1877 (4)	0.0483 (9)
H10	0.4729	0.1587	0.2409	0.058*
Mo1	0.46694 (2)	0.67220 (2)	0.50056 (2)	0.01890 (7)
Mo2	0.53042 (3)	0.64048 (2)	0.19652 (2)	0.02202 (7)
Mo3	0.27049 (3)	0.45022 (3)	0.33927 (3)	0.02597 (7)
Mo4	0.20801 (2)	0.47828 (3)	0.65014 (3)	0.02462 (7)
N1	0.1137 (3)	−0.1034 (3)	0.2966 (4)	0.0407 (7)
H1	0.1802	−0.1788	0.2936	0.049*
N2	0.2779 (4)	0.0567 (4)	0.1671 (4)	0.0569 (10)
H2A	0.3537	−0.0081	0.1557	0.068*
H2B	0.2906	0.1542	0.1072	0.068*
N3	0.6321 (3)	0.2766 (3)	0.1282 (3)	0.0364 (6)
H3A	0.5865	0.3510	0.1402	0.044*
N4	0.8255 (3)	0.4014 (3)	0.0050 (3)	0.0420 (7)
H4A	0.7682	0.4869	0.0247	0.050*
H4B	0.9106	0.3985	−0.0559	0.050*
O1	0.3642 (2)	0.8181 (2)	0.4445 (2)	0.0311 (5)
O2	0.5682 (2)	0.7174 (2)	0.5748 (2)	0.0261 (4)
O3	0.3449 (2)	0.5595 (2)	0.6846 (2)	0.0227 (4)
O4	0.6085 (2)	0.68828 (19)	0.3161 (2)	0.0221 (4)
O5	0.3982 (2)	0.5418 (2)	0.4318 (2)	0.0220 (4)
O6	0.4239 (3)	0.7885 (2)	0.1543 (3)	0.0359 (5)
O7	0.6672 (3)	0.6623 (2)	0.0436 (2)	0.0354 (5)
O8	0.4421 (2)	0.5072 (2)	0.1854 (2)	0.0271 (4)
O9	0.2213 (3)	0.3414 (3)	0.2861 (3)	0.0421 (6)
O10	0.1749 (3)	0.6046 (3)	0.2891 (3)	0.0397 (5)
O11	0.1854 (2)	0.3819 (2)	0.5446 (2)	0.0301 (5)
O12	0.1156 (3)	0.6308 (3)	0.5894 (3)	0.0411 (6)
O13	0.1120 (2)	0.3904 (3)	0.8224 (3)	0.0411 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0393 (17)	0.0298 (16)	0.0365 (17)	−0.0053 (13)	−0.0138 (14)	−0.0086 (13)
C2	0.049 (2)	0.0293 (16)	0.056 (2)	−0.0012 (14)	−0.0201 (18)	−0.0216 (16)
C3	0.044 (2)	0.053 (2)	0.056 (2)	0.0060 (17)	−0.0145 (18)	−0.033 (2)
C4	0.0359 (19)	0.062 (3)	0.041 (2)	−0.0100 (17)	−0.0109 (16)	−0.0116 (18)
C5	0.047 (2)	0.0348 (18)	0.047 (2)	−0.0135 (15)	−0.0167 (17)	−0.0038 (16)
C6	0.0369 (16)	0.0312 (15)	0.0249 (15)	0.0011 (13)	−0.0082 (12)	−0.0112 (12)
C7	0.045 (2)	0.046 (2)	0.051 (2)	0.0110 (17)	−0.0138 (17)	−0.0271 (18)
C8	0.081 (3)	0.0318 (18)	0.052 (2)	0.0124 (19)	−0.030 (2)	−0.0188 (17)
C9	0.086 (3)	0.037 (2)	0.045 (2)	−0.017 (2)	−0.017 (2)	−0.0128 (17)
C10	0.055 (2)	0.052 (2)	0.039 (2)	−0.0182 (18)	−0.0002 (17)	−0.0218 (18)
Mo1	0.02045 (12)	0.01403 (11)	0.01832 (12)	−0.00128 (8)	−0.00153 (9)	−0.00576 (8)
Mo2	0.02766 (13)	0.01659 (12)	0.01735 (12)	−0.00261 (9)	−0.00371 (9)	−0.00405 (9)
Mo3	0.02477 (13)	0.02705 (13)	0.02726 (14)	−0.00377 (9)	−0.00695 (10)	−0.01100 (10)
Mo4	0.01784 (12)	0.02699 (13)	0.02699 (13)	−0.00287 (9)	−0.00024 (9)	−0.01276 (10)
N1	0.0440 (17)	0.0228 (13)	0.0490 (18)	−0.0023 (12)	−0.0146 (14)	−0.0069 (12)
N2	0.0444 (19)	0.0344 (17)	0.070 (2)	−0.0044 (14)	−0.0093 (17)	−0.0044 (16)
N3	0.0392 (15)	0.0343 (14)	0.0357 (15)	−0.0035 (12)	−0.0018 (12)	−0.0204 (12)
N4	0.0348 (15)	0.0452 (17)	0.0405 (17)	−0.0080 (13)	0.0041 (13)	−0.0208 (14)
O1	0.0324 (11)	0.0220 (10)	0.0311 (11)	0.0038 (8)	−0.0051 (9)	−0.0088 (9)
O2	0.0282 (10)	0.0220 (10)	0.0262 (10)	−0.0056 (8)	−0.0034 (8)	−0.0094 (8)
O3	0.0229 (9)	0.0212 (9)	0.0191 (9)	−0.0029 (7)	−0.0001 (7)	−0.0071 (8)
O4	0.0232 (9)	0.0176 (9)	0.0195 (9)	−0.0054 (7)	−0.0003 (7)	−0.0043 (7)
O5	0.0222 (9)	0.0187 (9)	0.0226 (10)	−0.0018 (7)	−0.0033 (7)	−0.0077 (8)
O6	0.0479 (14)	0.0231 (11)	0.0362 (13)	0.0053 (10)	−0.0186 (11)	−0.0092 (9)
O7	0.0444 (13)	0.0304 (11)	0.0225 (11)	−0.0080 (10)	0.0002 (9)	−0.0072 (9)
O8	0.0337 (11)	0.0255 (10)	0.0234 (10)	−0.0049 (8)	−0.0062 (8)	−0.0110 (8)
O9	0.0468 (14)	0.0461 (14)	0.0438 (14)	−0.0122 (11)	−0.0148 (12)	−0.0213 (12)
O10	0.0363 (13)	0.0407 (13)	0.0416 (14)	0.0050 (10)	−0.0149 (11)	−0.0158 (11)
O11	0.0264 (10)	0.0315 (11)	0.0310 (11)	−0.0103 (9)	−0.0007 (9)	−0.0128 (9)
O12	0.0331 (12)	0.0388 (13)	0.0559 (16)	0.0075 (10)	−0.0159 (12)	−0.0245 (12)
O13	0.0297 (12)	0.0527 (15)	0.0323 (13)	−0.0134 (11)	0.0073 (10)	−0.0161 (11)

Geometric parameters (Å, º)

C1—N2	1.311 (5)	Mo2—O6	1.702 (2)
C1—N1	1.353 (4)	Mo2—O7	1.712 (2)
C1—C2	1.395 (5)	Mo2—O8	1.893 (2)
C2—C3	1.343 (6)	Mo2—O4	1.986 (2)
C2—H2	0.9300	Mo2—O5	2.2902 (19)
C3—C4	1.398 (6)	Mo2—O3^i	2.342 (2)
C3—H3	0.9300	Mo3—O9	1.695 (2)
C4—C5	1.342 (6)	Mo3—O10	1.698 (2)
C4—H4	0.9300	Mo3—O11	1.913 (2)
C5—N1	1.349 (5)	Mo3—O8	1.955 (2)
C5—H5	0.9300	Mo3—O2^i	2.290 (2)
C6—N4	1.327 (4)	Mo3—O5	2.427 (2)
C6—N3	1.337 (4)	Mo4—O12	1.685 (2)
C6—C7	1.420 (5)	Mo4—O13	1.703 (2)
C7—C8	1.353 (6)	Mo4—O11	1.888 (2)
C7—H7	0.9300	Mo4—O3	2.008 (2)
C8—C9	1.393 (7)	Mo4—O4^i	2.324 (2)
C8—H8	0.9300	Mo4—O5	2.4094 (19)
C9—C10	1.351 (6)	N1—H1	0.9414
C9—H9	0.9300	N2—H2A	0.9383
C10—N3	1.356 (5)	N2—H2B	0.9627
C10—H10	0.9300	N3—H3A	0.8600
Mo1—O1	1.688 (2)	N4—H4A	1.0272
Mo1—O2	1.749 (2)	N4—H4B	0.8999
Mo1—O3	1.9509 (19)	O2—Mo3^i	2.290 (2)
Mo1—O4	1.9622 (19)	O3—Mo2^i	2.342 (2)
Mo1—O5	2.1296 (19)	O4—Mo4^i	2.324 (2)
Mo1—O5^i	2.3635 (19)	O5—Mo1^i	2.3635 (19)
Mo1—Mo2	3.2025 (3)
N2—C1—N1	119.5 (3)	O7—Mo2—Mo1	136.39 (9)
N2—C1—C2	123.0 (3)	O8—Mo2—Mo1	119.83 (7)
N1—C1—C2	117.5 (3)	O4—Mo2—Mo1	35.54 (5)
C3—C2—C1	120.2 (3)	O5—Mo2—Mo1	41.62 (5)
C3—C2—H2	119.9	O3^i—Mo2—Mo1	79.31 (5)
C1—C2—H2	119.9	O9—Mo3—O10	106.64 (13)
C2—C3—C4	120.8 (4)	O9—Mo3—O11	103.25 (11)
C2—C3—H3	119.6	O10—Mo3—O11	99.73 (11)
C4—C3—H3	119.6	O9—Mo3—O8	100.37 (11)
C5—C4—C3	118.2 (4)	O10—Mo3—O8	97.97 (11)
C5—C4—H4	120.9	O11—Mo3—O8	144.86 (9)
C3—C4—H4	120.9	O9—Mo3—O2^i	91.17 (11)
C4—C5—N1	120.9 (3)	O10—Mo3—O2^i	162.08 (10)
C4—C5—H5	119.6	O11—Mo3—O2^i	77.47 (9)
N1—C5—H5	119.6	O8—Mo3—O2^i	76.40 (8)
N4—C6—N3	120.3 (3)	O9—Mo3—O5	160.89 (11)
N4—C6—C7	122.9 (3)	O10—Mo3—O5	92.27 (10)
N3—C6—C7	116.8 (3)	O11—Mo3—O5	75.45 (8)
C8—C7—C6	119.7 (4)	O8—Mo3—O5	73.74 (8)
C8—C7—H7	120.1	O2^i—Mo3—O5	69.84 (7)
C6—C7—H7	120.1	O12—Mo4—O13	105.45 (13)
C7—C8—C9	121.1 (4)	O12—Mo4—O11	100.95 (12)
C7—C8—H8	119.4	O13—Mo4—O11	102.81 (11)
C9—C8—H8	119.4	O12—Mo4—O3	96.03 (11)
C10—C9—C8	118.4 (4)	O13—Mo4—O3	102.08 (11)
C10—C9—H9	120.8	O11—Mo4—O3	144.74 (9)
C8—C9—H9	120.8	O12—Mo4—O4^i	162.02 (10)
C9—C10—N3	120.1 (4)	O13—Mo4—O4^i	90.34 (10)
C9—C10—H10	119.9	O11—Mo4—O4^i	83.44 (9)
N3—C10—H10	119.9	O3—Mo4—O4^i	71.81 (7)
O1—Mo1—O2	104.89 (11)	O12—Mo4—O5	92.99 (10)
O1—Mo1—O3	101.95 (10)	O13—Mo4—O5	161.26 (10)
O2—Mo1—O3	96.61 (9)	O11—Mo4—O5	76.32 (8)
O1—Mo1—O4	100.30 (10)	O3—Mo4—O5	72.11 (7)
O2—Mo1—O4	96.07 (9)	O4^i—Mo4—O5	70.93 (7)
O3—Mo1—O4	150.54 (8)	C5—N1—C1	122.4 (3)
O1—Mo1—O5	98.63 (10)	C5—N1—H1	116.1
O2—Mo1—O5	156.43 (9)	C1—N1—H1	121.3
O3—Mo1—O5	79.76 (8)	C1—N2—H2A	127.5
O4—Mo1—O5	78.02 (8)	C1—N2—H2B	113.9
O1—Mo1—O5^i	174.39 (10)	H2A—N2—H2B	117.7
O2—Mo1—O5^i	80.68 (8)	C6—N3—C10	123.7 (3)
O3—Mo1—O5^i	77.71 (7)	C6—N3—H3A	118.1
O4—Mo1—O5^i	78.26 (7)	C10—N3—H3A	118.1
O5—Mo1—O5^i	75.78 (8)	C6—N4—H4A	119.0
O1—Mo1—Mo2	89.33 (8)	C6—N4—H4B	112.0
O2—Mo1—Mo2	132.10 (7)	H4A—N4—H4B	127.9
O3—Mo1—Mo2	125.33 (6)	Mo1—O2—Mo3^i	117.09 (10)
O4—Mo1—Mo2	36.03 (6)	Mo1—O3—Mo4	110.54 (9)
O5—Mo1—Mo2	45.58 (5)	Mo1—O3—Mo2^i	109.53 (9)
O5^i—Mo1—Mo2	86.38 (5)	Mo4—O3—Mo2^i	102.72 (8)
O6—Mo2—O7	105.51 (12)	Mo1—O4—Mo2	108.43 (9)
O6—Mo2—O8	102.75 (11)	Mo1—O4—Mo4^i	111.73 (9)
O7—Mo2—O8	99.00 (11)	Mo2—O4—Mo4^i	104.07 (8)
O6—Mo2—O4	97.22 (10)	Mo1—O5—Mo2	92.80 (7)
O7—Mo2—O4	100.85 (10)	Mo1—O5—Mo1^i	104.22 (8)
O8—Mo2—O4	146.81 (8)	Mo2—O5—Mo1^i	98.06 (7)
O6—Mo2—O5	95.13 (10)	Mo1—O5—Mo4	91.37 (7)
O7—Mo2—O5	159.24 (10)	Mo2—O5—Mo4	163.63 (10)
O8—Mo2—O5	78.21 (8)	Mo1^i—O5—Mo4	96.25 (7)
O4—Mo2—O5	73.80 (7)	Mo1—O5—Mo3	163.28 (10)
O6—Mo2—O3^i	164.83 (10)	Mo2—O5—Mo3	86.84 (7)
O7—Mo2—O3^i	87.19 (9)	Mo1^i—O5—Mo3	92.37 (7)
O8—Mo2—O3^i	82.97 (8)	Mo4—O5—Mo3	84.65 (6)
O4—Mo2—O3^i	71.78 (7)	Mo2—O8—Mo3	114.94 (10)
O5—Mo2—O3^i	72.07 (7)	Mo4—O11—Mo3	117.91 (11)
O6—Mo2—Mo1	85.70 (8)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O10^ii	0.94	2.31	3.033 (4)	133
N2—H2A···O6^ii	0.94	2.12	2.946 (4)	147
N2—H2B···O7^iii	0.96	1.94	2.893 (4)	169
N3—H3A···O8	0.86	2.08	2.925 (3)	168
N4—H4A···O7	1.03	1.97	2.999 (4)	175
N4—H4B···O13^iv	0.90	2.05	2.949 (4)	174

Symmetry codes: (ii) x, y−1, z; (iii) −x+1, −y+1, −z; (iv) x+1, y, z−1.

(compound_II)

Crystal data

(C5H7N2)2[NiMo6O16(C5H9O3)2(OH)2]·4H2O	Z = 1
Mr = 1420.92	F(000) = 694
Triclinic, P1	Dx = 2.410 Mg m^−3
a = 9.1173 (11) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.3631 (14) Å	Cell parameters from 9975 reflections
c = 10.7022 (15) Å	θ = 3.1–27.5°
α = 85.653 (5)°	µ = 2.43 mm^−1
β = 77.403 (5)°	T = 293 K
γ = 83.439 (5)°	Block, light-green
V = 979.0 (2) Å^3	0.13 × 0.12 × 0.10 mm

Data collection

D8 VENTURE PHOTON II diffractometer	3785 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.033
phi and ω scans	θmax = 27.5°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2013)	h = −11→11
Tmin = 0.743, Tmax = 0.793	k = −13→13
32003 measured reflections	l = −13→13
4483 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.021	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.053	w = 1/[σ^2(Fo^2) + (0.0225P)^2 + 0.9013P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
4483 reflections	Δρmax = 0.49 e Å^−3
275 parameters	Δρmin = −0.44 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.6192 (3)	0.7302 (2)	0.4470 (2)	0.0253 (5)
H1A	0.6843	0.7626	0.3696	0.030*
H1B	0.5989	0.6432	0.4326	0.030*
C2	0.6067 (3)	0.6671 (3)	0.6808 (3)	0.0339 (6)
H2A	0.5805	0.5826	0.6649	0.041*
H2B	0.6660	0.6545	0.7466	0.041*
C3	0.7598 (3)	0.8515 (3)	0.5794 (3)	0.0272 (5)
H3A	0.8225	0.8358	0.6425	0.033*
H3B	0.8225	0.8818	0.4997	0.033*
C4	0.7029 (3)	0.7225 (3)	0.5582 (3)	0.0294 (6)
C5	0.8445 (3)	0.6250 (3)	0.5203 (3)	0.0412 (7)
H5A	0.8984	0.6135	0.5887	0.062*
H5B	0.9087	0.6580	0.4440	0.062*
H5C	0.8143	0.5430	0.5047	0.062*
C6	0.2786 (3)	0.4296 (3)	−0.0230 (3)	0.0387 (7)
C7	0.2950 (4)	0.5625 (3)	−0.0208 (3)	0.0411 (7)
H7	0.3737	0.5991	−0.0776	0.049*
C8	0.1959 (4)	0.6372 (3)	0.0642 (3)	0.0455 (8)
H8	0.2079	0.7249	0.0659	0.055*
C9	0.0766 (4)	0.5849 (3)	0.1491 (3)	0.0483 (8)
H9	0.0084	0.6366	0.2071	0.058*
C10	0.0623 (4)	0.4584 (3)	0.1453 (3)	0.0421 (7)
H10	−0.0170	0.4217	0.2013	0.051*
Mo1	0.31899 (2)	0.84478 (2)	0.32832 (2)	0.02615 (6)
Mo2	0.28845 (2)	0.76624 (2)	0.63287 (2)	0.02672 (6)
Mo3	0.47735 (2)	0.92445 (2)	0.81124 (2)	0.02452 (6)
N1	0.1616 (3)	0.3827 (2)	0.0609 (2)	0.0370 (6)
H1	0.1445	0.2976	0.0577	0.044*
N2	0.3670 (4)	0.3507 (3)	−0.1036 (3)	0.0665 (9)
H2C	0.4677	0.3842	−0.1628	0.080*
H2D	0.3728	0.2609	−0.0982	0.080*
Ni1	0.5000	1.0000	0.5000	0.01728 (9)
O1	0.1818 (2)	0.9101 (2)	0.2499 (2)	0.0423 (5)
O2	0.3483 (2)	0.6843 (2)	0.2971 (2)	0.0403 (5)
O3	0.19537 (19)	0.83851 (19)	0.50058 (19)	0.0309 (4)
O4	0.47803 (18)	0.81319 (16)	0.47016 (16)	0.0213 (3)
O5	0.3224 (3)	0.6049 (2)	0.6067 (2)	0.0450 (5)
O6	0.1416 (2)	0.7776 (2)	0.7634 (2)	0.0434 (5)
O7	0.4679 (2)	0.75014 (17)	0.72839 (17)	0.0272 (4)
O8	0.34096 (18)	0.96137 (16)	0.66380 (16)	0.0223 (4)
H8A	0.2626	1.0182	0.6999	0.033*
O9	0.3207 (2)	0.9189 (2)	0.93029 (19)	0.0397 (5)
O10	0.6229 (2)	0.8549 (2)	0.87772 (19)	0.0398 (5)
O11	0.50207 (19)	1.10339 (17)	0.79288 (17)	0.0272 (4)
O12	0.64067 (17)	0.95215 (16)	0.62198 (16)	0.0208 (3)
O13	0.0902 (3)	0.1292 (2)	0.0396 (2)	0.0444 (6)
H13A	0.016 (5)	0.133 (4)	0.091 (4)	0.067*
H13B	0.144 (5)	0.078 (4)	0.060 (4)	0.067*
O14	0.1057 (2)	0.1187 (2)	0.7761 (2)	0.0460 (5)
H14A	0.0998	0.1131	0.8587	0.069*
H14B	0.0228	0.1010	0.7557	0.069*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0264 (13)	0.0200 (12)	0.0276 (14)	0.0039 (9)	−0.0027 (10)	−0.0063 (10)
C2	0.0411 (16)	0.0248 (14)	0.0328 (15)	0.0070 (11)	−0.0072 (12)	0.0003 (11)
C3	0.0218 (12)	0.0297 (14)	0.0293 (14)	0.0057 (10)	−0.0061 (10)	−0.0076 (11)
C4	0.0291 (13)	0.0269 (14)	0.0304 (14)	0.0065 (10)	−0.0059 (11)	−0.0049 (11)
C5	0.0392 (16)	0.0356 (17)	0.0465 (19)	0.0161 (13)	−0.0112 (14)	−0.0111 (14)
C6	0.0462 (17)	0.0382 (17)	0.0314 (16)	0.0009 (13)	−0.0109 (13)	−0.0007 (13)
C7	0.0465 (18)	0.0369 (17)	0.0384 (17)	−0.0100 (13)	−0.0059 (14)	0.0077 (13)
C8	0.065 (2)	0.0281 (16)	0.0467 (19)	−0.0087 (14)	−0.0168 (16)	−0.0014 (14)
C9	0.056 (2)	0.044 (2)	0.0412 (19)	0.0049 (15)	−0.0061 (15)	−0.0078 (15)
C10	0.0428 (18)	0.0449 (19)	0.0382 (18)	−0.0074 (14)	−0.0086 (14)	0.0062 (14)
Mo1	0.02597 (12)	0.02823 (13)	0.02708 (12)	−0.00498 (9)	−0.00854 (9)	−0.00742 (9)
Mo2	0.02805 (12)	0.02319 (12)	0.02790 (13)	−0.00898 (9)	−0.00046 (9)	−0.00115 (9)
Mo3	0.02998 (12)	0.02503 (12)	0.01748 (11)	−0.00012 (9)	−0.00397 (8)	−0.00140 (8)
N1	0.0484 (15)	0.0260 (12)	0.0402 (15)	−0.0076 (10)	−0.0172 (12)	0.0047 (11)
N2	0.081 (2)	0.0485 (19)	0.058 (2)	0.0134 (16)	0.0041 (17)	−0.0139 (16)
Ni1	0.0187 (2)	0.0156 (2)	0.0179 (2)	−0.00174 (15)	−0.00454 (16)	−0.00175 (16)
O1	0.0333 (11)	0.0565 (14)	0.0418 (13)	−0.0035 (9)	−0.0172 (9)	−0.0069 (10)
O2	0.0467 (12)	0.0337 (11)	0.0428 (13)	−0.0096 (9)	−0.0079 (10)	−0.0136 (9)
O3	0.0230 (9)	0.0365 (11)	0.0341 (11)	−0.0069 (8)	−0.0049 (8)	−0.0046 (8)
O4	0.0214 (8)	0.0180 (8)	0.0239 (9)	−0.0003 (6)	−0.0030 (7)	−0.0040 (7)
O5	0.0535 (13)	0.0260 (11)	0.0566 (15)	−0.0125 (9)	−0.0091 (11)	−0.0041 (10)
O6	0.0387 (11)	0.0480 (13)	0.0386 (12)	−0.0142 (10)	0.0069 (9)	−0.0006 (10)
O7	0.0322 (10)	0.0216 (9)	0.0256 (10)	−0.0007 (7)	−0.0029 (7)	0.0003 (7)
O8	0.0207 (8)	0.0222 (9)	0.0224 (9)	−0.0003 (6)	−0.0011 (7)	−0.0043 (7)
O9	0.0466 (12)	0.0406 (12)	0.0263 (11)	−0.0032 (9)	0.0039 (9)	−0.0017 (9)
O10	0.0491 (12)	0.0412 (12)	0.0303 (11)	0.0053 (9)	−0.0170 (9)	−0.0002 (9)
O11	0.0303 (9)	0.0276 (10)	0.0234 (9)	−0.0007 (7)	−0.0041 (7)	−0.0070 (7)
O12	0.0204 (8)	0.0200 (8)	0.0216 (9)	0.0015 (6)	−0.0047 (6)	−0.0040 (7)
O13	0.0369 (13)	0.0421 (14)	0.0499 (15)	0.0008 (10)	−0.0014 (10)	−0.0048 (11)
O14	0.0293 (11)	0.0574 (15)	0.0496 (14)	0.0012 (9)	−0.0042 (9)	−0.0129 (11)

Geometric parameters (Å, º)

C1—O4	1.448 (3)	Mo1—O12^i	2.2974 (17)
C1—C4	1.541 (4)	Mo1—O4	2.3001 (17)
C1—H1A	0.9700	Mo2—O5	1.699 (2)
C1—H1B	0.9700	Mo2—O6	1.712 (2)
C2—O7	1.463 (3)	Mo2—O3	1.8719 (19)
C2—C4	1.523 (4)	Mo2—O7	2.0953 (18)
C2—H2A	0.9700	Mo2—O8	2.1954 (17)
C2—H2B	0.9700	Mo2—O4	2.2378 (17)
C3—O12	1.440 (3)	Mo3—O9	1.697 (2)
C3—C4	1.536 (4)	Mo3—O10	1.7037 (19)
C3—H3A	0.9700	Mo3—O11	1.8839 (18)
C3—H3B	0.9700	Mo3—O7	2.0901 (18)
C4—C5	1.545 (3)	Mo3—O8	2.1996 (17)
C5—H5A	0.9600	Mo3—O12	2.2575 (17)
C5—H5B	0.9600	N1—H1	0.9178
C5—H5C	0.9600	N2—H2C	1.0728
C6—N2	1.310 (4)	N2—H2D	0.9237
C6—N1	1.346 (4)	Ni1—O12	2.0203 (16)
C6—C7	1.405 (4)	Ni1—O12^i	2.0203 (16)
C7—C8	1.353 (5)	Ni1—O4^i	2.0248 (17)
C7—H7	0.9300	Ni1—O4	2.0249 (17)
C8—C9	1.390 (5)	Ni1—O8	2.0624 (16)
C8—H8	0.9300	Ni1—O8^i	2.0624 (17)
C9—C10	1.337 (5)	O8—H8A	0.9078
C9—H9	0.9300	O11—Mo1^i	1.9505 (18)
C10—N1	1.356 (4)	O12—Mo1^i	2.2975 (17)
C10—H10	0.9300	O13—H13A	0.77 (4)
Mo1—O2	1.701 (2)	O13—H13B	0.74 (4)
Mo1—O1	1.704 (2)	O14—H14A	0.8719
Mo1—O3	1.9405 (19)	O14—H14B	0.8727
Mo1—O11^i	1.9505 (18)
O4—C1—C4	113.4 (2)	O3—Mo2—O8	88.92 (7)
O4—C1—H1A	108.9	O7—Mo2—O8	70.57 (6)
C4—C1—H1A	108.9	O5—Mo2—O4	91.76 (9)
O4—C1—H1B	108.9	O6—Mo2—O4	163.31 (9)
C4—C1—H1B	108.9	O3—Mo2—O4	74.76 (7)
H1A—C1—H1B	107.7	O7—Mo2—O4	79.58 (7)
O7—C2—C4	113.4 (2)	O8—Mo2—O4	74.06 (6)
O7—C2—H2A	108.9	O9—Mo3—O10	105.33 (10)
C4—C2—H2A	108.9	O9—Mo3—O11	102.27 (9)
O7—C2—H2B	108.9	O10—Mo3—O11	104.90 (9)
C4—C2—H2B	108.9	O9—Mo3—O7	98.52 (9)
H2A—C2—H2B	107.7	O10—Mo3—O7	90.48 (9)
O12—C3—C4	113.8 (2)	O11—Mo3—O7	149.63 (7)
O12—C3—H3A	108.8	O9—Mo3—O8	91.85 (9)
C4—C3—H3A	108.8	O10—Mo3—O8	156.30 (8)
O12—C3—H3B	108.8	O11—Mo3—O8	86.76 (7)
C4—C3—H3B	108.8	O7—Mo3—O8	70.58 (7)
H3A—C3—H3B	107.7	O9—Mo3—O12	164.91 (8)
C2—C4—C3	111.7 (2)	O10—Mo3—O12	89.70 (8)
C2—C4—C1	110.6 (2)	O11—Mo3—O12	74.50 (7)
C3—C4—C1	114.0 (2)	O7—Mo3—O12	79.66 (7)
C2—C4—C5	107.4 (2)	O8—Mo3—O12	73.35 (6)
C3—C4—C5	106.6 (2)	C6—N1—C10	122.6 (3)
C1—C4—C5	106.1 (2)	C6—N1—H1	119.0
C4—C5—H5A	109.5	C10—N1—H1	118.3
C4—C5—H5B	109.5	C6—N2—H2C	119.0
H5A—C5—H5B	109.5	C6—N2—H2D	126.5
C4—C5—H5C	109.5	H2C—N2—H2D	111.1
H5A—C5—H5C	109.5	O12—Ni1—O12^i	180.0
H5B—C5—H5C	109.5	O12—Ni1—O4^i	85.63 (7)
N2—C6—N1	118.7 (3)	O12^i—Ni1—O4^i	94.38 (7)
N2—C6—C7	124.0 (3)	O12—Ni1—O4	94.37 (7)
N1—C6—C7	117.3 (3)	O12^i—Ni1—O4	85.62 (7)
C8—C7—C6	119.8 (3)	O4^i—Ni1—O4	180.00 (9)
C8—C7—H7	120.1	O12—Ni1—O8	81.40 (7)
C6—C7—H7	120.1	O12^i—Ni1—O8	98.60 (7)
C7—C8—C9	121.1 (3)	O4^i—Ni1—O8	98.43 (7)
C7—C8—H8	119.4	O4—Ni1—O8	81.57 (7)
C9—C8—H8	119.4	O12—Ni1—O8^i	98.60 (7)
C10—C9—C8	118.3 (3)	O12^i—Ni1—O8^i	81.40 (7)
C10—C9—H9	120.8	O4^i—Ni1—O8^i	81.57 (7)
C8—C9—H9	120.8	O4—Ni1—O8^i	98.43 (7)
C9—C10—N1	120.9 (3)	O8—Ni1—O8^i	180.0
C9—C10—H10	119.5	Mo2—O3—Mo1	117.44 (9)
N1—C10—H10	119.5	C1—O4—Ni1	114.16 (14)
O2—Mo1—O1	105.80 (11)	C1—O4—Mo2	120.84 (14)
O2—Mo1—O3	101.15 (9)	Ni1—O4—Mo2	101.79 (7)
O1—Mo1—O3	97.95 (9)	C1—O4—Mo1	123.43 (14)
O2—Mo1—O11^i	96.26 (9)	Ni1—O4—Mo1	100.35 (7)
O1—Mo1—O11^i	100.13 (9)	Mo2—O4—Mo1	91.78 (6)
O3—Mo1—O11^i	150.37 (8)	C2—O7—Mo3	120.19 (16)
O2—Mo1—O12^i	161.29 (8)	C2—O7—Mo2	120.36 (16)
O1—Mo1—O12^i	91.08 (9)	Mo3—O7—Mo2	110.68 (8)
O3—Mo1—O12^i	84.02 (7)	Ni1—O8—Mo2	102.02 (7)
O11^i—Mo1—O12^i	72.40 (7)	Ni1—O8—Mo3	102.74 (7)
O2—Mo1—O4	90.90 (9)	Mo2—O8—Mo3	103.13 (7)
O1—Mo1—O4	162.13 (9)	Ni1—O8—H8A	125.4
O3—Mo1—O4	72.08 (7)	Mo2—O8—H8A	117.1
O11^i—Mo1—O4	83.95 (7)	Mo3—O8—H8A	103.6
O12^i—Mo1—O4	73.45 (6)	Mo3—O11—Mo1^i	116.75 (9)
O5—Mo2—O6	104.86 (11)	C3—O12—Ni1	114.28 (14)
O5—Mo2—O3	104.77 (10)	C3—O12—Mo3	119.92 (15)
O6—Mo2—O3	101.84 (10)	Ni1—O12—Mo3	102.12 (7)
O5—Mo2—O7	89.61 (9)	C3—O12—Mo1^i	123.94 (14)
O6—Mo2—O7	98.72 (9)	Ni1—O12—Mo1^i	100.58 (7)
O3—Mo2—O7	150.77 (7)	Mo3—O12—Mo1^i	91.58 (6)
O5—Mo2—O8	157.19 (9)	H13A—O13—H13B	109 (4)
O6—Mo2—O8	89.66 (9)	H14A—O14—H14B	112.4
O7—C2—C4—C3	63.4 (3)	O6—Mo2—O3—Mo1	−179.00 (11)
O7—C2—C4—C1	−64.8 (3)	O7—Mo2—O3—Mo1	47.2 (2)
O7—C2—C4—C5	179.9 (2)	O8—Mo2—O3—Mo1	91.58 (10)
O12—C3—C4—C2	−60.1 (3)	O4—Mo2—O3—Mo1	17.82 (9)
O12—C3—C4—C1	66.2 (3)	C4—C1—O4—Ni1	59.4 (2)
O12—C3—C4—C5	−177.0 (2)	C4—C1—O4—Mo2	−62.6 (2)
O4—C1—C4—C2	60.8 (3)	C4—C1—O4—Mo1	−178.49 (15)
O4—C1—C4—C3	−66.1 (3)	C4—C2—O7—Mo3	−72.1 (3)
O4—C1—C4—C5	176.9 (2)	C4—C2—O7—Mo2	72.4 (3)
N2—C6—C7—C8	178.5 (3)	O9—Mo3—O11—Mo1^i	175.78 (10)
N1—C6—C7—C8	0.6 (5)	O10—Mo3—O11—Mo1^i	66.03 (12)
C6—C7—C8—C9	−0.7 (5)	O7—Mo3—O11—Mo1^i	−52.08 (19)
C7—C8—C9—C10	0.3 (5)	O8—Mo3—O11—Mo1^i	−93.03 (10)
C8—C9—C10—N1	0.1 (5)	O12—Mo3—O11—Mo1^i	−19.41 (8)
N2—C6—N1—C10	−178.2 (3)	C4—C3—O12—Ni1	−59.5 (2)
C7—C6—N1—C10	−0.1 (4)	C4—C3—O12—Mo3	62.2 (2)
C9—C10—N1—C6	−0.2 (5)	C4—C3—O12—Mo1^i	177.39 (15)
O5—Mo2—O3—Mo1	−69.95 (13)

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2C···O2^ii	1.07	2.05	2.951 (4)	139
N2—H2D···O11^iii	0.92	2.16	2.902 (3)	137
N1—H1···O13	0.92	1.90	2.815 (4)	173
O13—H13A···O6^iv	0.77 (4)	2.08 (4)	2.783 (3)	153 (4)
O13—H13B···O9^iii	0.74 (4)	2.45 (4)	2.967 (3)	129 (4)
O13—H13B···O10^v	0.74 (4)	2.54 (4)	2.964 (3)	118 (4)
O14—H14A···O13^vi	0.87	1.94	2.803 (4)	171
O14—H14B···O1^iv	0.87	1.90	2.747 (3)	164
O8—H8A···O14^vii	0.91	1.75	2.660 (3)	176

Symmetry codes: (ii) −x+1, −y+1, −z; (iii) x, y−1, z−1; (iv) −x, −y+1, −z+1; (v) −x+1, −y+1, −z+1; (vi) x, y, z+1; (vii) x, y+1, z.