Hexakis(2-amino­pyridinium) di-μ6-oxido-tetra-μ3-oxido-tetra­deca-μ2-oxido-octa­oxidodeca­vanadium(V) dihydrate

Yuan, C.; Lu, L.; Zhu, M.; Ma, Q.; Wu, Y.

doi:10.1107/S1600536809004334

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 3| March 2009| Pages m267-m268

doi:10.1107/S1600536809004334

Open

access

Hexakis(2-aminopyridinium) di-μ₆-oxido-tetra-μ₃-oxido-tetradeca-μ₂-oxido-octaoxidodecavanadium(V) dihydrate

Caixia Yuan,^a Liping Lu,^a Miaoli Zhu,^a ^* Qi Ma ^a and Yanbo Wu ^a

^aInstitute of Molecular Science, Key Laboratory of Chemical Biology and Molecular Engineering of the Education Ministry, Shanxi University, Taiyuan, Shanxi 030006, People's Republic of China
^*Correspondence e-mail: miaoli@sxu.edu.cn

(Received 12 January 2009; accepted 6 February 2009; online 13 February 2009)

In the title compound, (C₅H₇N₂)₆[V₁₀O₂₈]·2H₂O, the [V₁₀O₂₈]⁶⁻ anion is generated by crystallographic inversion symmetry and each of the five vanadium centres adopts a distorted VO₆ octahedral geometry. In the crystal structure, a network of N—H⋯O, N—H⋯(O,O) and O—H⋯O hydrogen bonds helps to establish the packing.

Related literature

For a related structure, see: Gong et al. (2006 ). For background to the biological activity of oxovanadates and peroxovanadium compounds, see: Pacigová et al. (2007 ).

Experimental

Crystal data

(C₅H₇N₂)₆[V₁₀O₂₈]·2H₂O
M_r = 1564.19
Monoclinic, P 2₁ /c
a = 9.840 (3) Å
b = 18.180 (6) Å
c = 14.299 (5) Å
β = 97.416 (4)°
V = 2536.6 (14) Å³
Z = 2
Mo Kα radiation
μ = 1.86 mm⁻¹
T = 298 (2) K
0.40 × 0.20 × 0.20 mm

Data collection

Bruker SMART 1K CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.523, T_max = 0.707
9858 measured reflections
4341 independent reflections
3949 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.074
wR(F²) = 0.128
S = 1.29
4341 reflections
370 parameters
H-atom parameters constrained
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Selected bond lengths (Å)

V1—O7	1.616 (4)
V1—O3	1.767 (4)
V1—O8	1.842 (4)
V1—O2	1.991 (4)
V1—O12	2.038 (4)
V1—O1	2.250 (4)
V2—O9	1.608 (4)
V2—O6	1.794 (4)
V2—O10	1.823 (4)
V2—O12ⁱ	2.015 (4)
V2—O2ⁱ	2.017 (4)
V2—O1	2.243 (4)
V3—O11	1.594 (4)
V3—O14	1.827 (4)
V3—O8	1.871 (4)
V3—O6	1.891 (4)
V3—O5	2.045 (4)
V3—O1	2.305 (4)
V4—O4	1.676 (4)
V4—O5ⁱ	1.680 (4)
V4—O12ⁱ	1.921 (4)
V4—O2	1.953 (4)
V4—O1ⁱ	2.097 (4)
V4—O1	2.111 (4)
V5—O13	1.590 (5)
V5—O14	1.835 (4)
V5—O10	1.864 (4)
V5—O3	1.881 (4)
V5—O4	2.045 (4)
V5—O1	2.318 (4)
Symmetry code: (i) -x+2, -y+2, -z+2.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O4ⁱⁱ	0.86	2.44	3.217 (9)	150
N1—H1A⋯O5ⁱⁱⁱ	0.86	2.55	3.286 (8)	144
N1—H1B⋯O10^iv	0.86	2.21	3.058 (8)	169
N2—H2A⋯O2ⁱⁱ	0.86	1.85	2.697 (7)	168
N3—H3A⋯O9^iv	0.86	2.17	2.969 (7)	155
N3—H3A⋯O7^v	0.86	2.48	3.017 (7)	122
N3—H3B⋯O14	0.86	2.09	2.908 (7)	158
N4—H4A⋯O12^v	0.86	1.84	2.698 (6)	174
N5—H5A⋯O7^v	0.86	2.23	3.085 (8)	175
N5—H5B⋯O9	0.86	2.22	3.057 (8)	164
N6—H6⋯O8^v	0.86	1.87	2.709 (7)	166
O15—H15A⋯O6^vi	0.85	2.09	2.926 (8)	166
O15—H15B⋯O7ⁱⁱ	0.85	2.13	2.977 (8)	180
Symmetry codes: (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[x-1, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iv) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (v) $[-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (vi) x-1, y, z.

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXTL/PC.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809004334/hb2897sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809004334/hb2897Isup2.hkl

checkCIF report

Comment top

Oxovanadates and peroxovanadium compounds are of great interest in biochemistry and medicine because of their diverse biological activites (Pacigová et al., 2007). Of them, decavanadates have showm high affinity for selected kinases and phosphorylase and has been used to facilitate crystallization of proteins. Herein, we report the structure of the title compound, (I), containing decavanadate anions, 2-aminopyridinium cations and water molecules (Fig. 1).

Compound (I) consists of a centrosymmetric [V₁₀O₂₈]^6- polyanion, two distinct 2-aminopyridium cations and a water molecule (Fig. 1). The [V₁₀O₂₈]^6- unit is constructed by ten VO₆ octahedra connected with each other via edge-sharing oxygen atoms. The different coordination of the oxygen atoms in the molecule results in different V—O bond distances (Table 1). The V—O (one coordinated oxygen) double bond distances range from 1.590 (5) to 1.616 (4) Å; the V—O (two coordinated oxygen) single bond distances range from 1.676 (4) to 2.045 (4) Å; the V—O (three coordinated oxygen) single bond distances range from 1.921 (4) to 2.038 (4)Å and the V—O (six coordinated oxygen) single bond distances are even longer (2.097 (4) to 2.318 (4) Å). These V—O bond types are similar to those in related compounds (Gong et al., 2006).

A three-dimensional supramolecular hydrogen-bonding network is observed in the crystal structure of (I); details are given in Table 2. All the (C₅H₇N₂)⁺ cations and water molecules are involved in hydrogen bonds with either terminal or bridging O atoms in the [V₁₀O₂₈]^6- anion (Fig. 2).

Related literature top

For a related structure, see: Gong et al. (2006). For background to the biological activity of oxovanadates and peroxovanadium compounds, see: Pacigová et al. (2007).

Experimental top

A hot aqueous VOSO₄ solution (1 mmol) was added dropwise to a stirred solution of 2-aminopyridine (1 mmol), which was dissolved in 20 ml of ethanol and refluxed for 4 h. Then the filtrate was kept open to slowly evaporate for a few days, depositiong yellow blocks of (I).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXTL/PC (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the structure of (I) with displacement ellipsoids drawn at the 30% probability level; H atoms and the water molecule are omitted for clarity.
	Fig. 2. The packing in (I), with hydrogen bonds indicated by dashed lines.

Hexakis(2-aminopyridinium) di-µ₆-oxido-tetra-µ₃-oxido- tetradeca-µ₂-oxido-octaoxidodecavanadium(V) dihydrate top

Crystal data top

(C₅H₇N₂)₆[V₁₀O₂₈]·2H₂O	F(000) = 1560
M_r = 1564.19	D_x = 2.048 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3889 reflections
a = 9.840 (3) Å	θ = 2.2–27.0°
b = 18.180 (6) Å	µ = 1.86 mm⁻¹
c = 14.299 (5) Å	T = 298 K
β = 97.416 (4)°	Block, yellow
V = 2536.6 (14) Å³	0.40 × 0.20 × 0.20 mm
Z = 2

Data collection top

Bruker SMART 1K CCD diffractometer	4341 independent reflections
Radiation source: fine-focus sealed tube	3949 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
ω scans	θ_max = 25.0°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −11→11
T_min = 0.523, T_max = 0.707	k = −21→18
9858 measured reflections	l = −16→12

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.074	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.128	H-atom parameters constrained
S = 1.29	w = 1/[σ²(F_o²) + (0.0095P)² + 8.6635P] where P = (F_o² + 2F_c²)/3
4341 reflections	(Δ/σ)_max = 0.002
370 parameters	Δρ_max = 0.53 e Å⁻³
0 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

(C₅H₇N₂)₆[V₁₀O₂₈]·2H₂O	V = 2536.6 (14) Å³
M_r = 1564.19	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.840 (3) Å	µ = 1.86 mm⁻¹
b = 18.180 (6) Å	T = 298 K
c = 14.299 (5) Å	0.40 × 0.20 × 0.20 mm
β = 97.416 (4)°

Data collection top

Bruker SMART 1K CCD diffractometer	4341 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	3949 reflections with I > 2σ(I)
T_min = 0.523, T_max = 0.707	R_int = 0.042
9858 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.074	0 restraints
wR(F²) = 0.128	H-atom parameters constrained
S = 1.29	Δρ_max = 0.53 e Å⁻³
4341 reflections	Δρ_min = −0.45 e Å⁻³
370 parameters

Special details top

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
V1	0.92911 (10)	1.06195 (6)	0.82727 (7)	0.0219 (3)
V2	0.93856 (11)	0.85376 (6)	0.99424 (7)	0.0223 (3)
V3	1.01726 (11)	0.90023 (6)	0.79935 (8)	0.0261 (3)
V4	0.84711 (10)	1.01767 (6)	1.02703 (7)	0.0207 (3)
V5	0.72947 (11)	0.93367 (6)	0.84923 (8)	0.0248 (3)
O1	0.9456 (4)	0.9637 (2)	0.9237 (3)	0.0187 (9)
O2	0.8818 (4)	1.1018 (2)	0.9486 (3)	0.0200 (9)
O3	0.7620 (4)	1.0262 (2)	0.7977 (3)	0.0260 (10)
O4	0.6972 (4)	0.9938 (2)	0.9652 (3)	0.0257 (10)
O5	1.1928 (4)	0.9330 (2)	0.8810 (3)	0.0262 (10)
O6	1.0166 (4)	0.8267 (2)	0.8929 (3)	0.0258 (10)
O7	0.9299 (4)	1.1366 (2)	0.7659 (3)	0.0302 (10)
O8	1.0138 (4)	0.9970 (2)	0.7546 (3)	0.0244 (10)
O9	0.9418 (5)	0.7791 (2)	1.0547 (3)	0.0307 (11)
O10	0.7627 (4)	0.8570 (2)	0.9357 (3)	0.0263 (10)
O11	1.0796 (5)	0.8564 (3)	0.7182 (3)	0.0357 (11)
O12	1.1132 (4)	1.0743 (2)	0.9091 (3)	0.0196 (9)
O13	0.5753 (5)	0.9180 (3)	0.8055 (3)	0.0356 (11)
O14	0.8326 (4)	0.8887 (2)	0.7676 (3)	0.0257 (10)
N1	0.4744 (8)	0.6382 (4)	0.4937 (6)	0.075 (3)
H1A	0.4151	0.6036	0.4825	0.090*
H1B	0.5513	0.6357	0.4713	0.090*
N2	0.3280 (5)	0.6980 (3)	0.5806 (4)	0.0319 (13)
H2A	0.2685	0.6638	0.5665	0.038*
N3	0.8180 (6)	0.7312 (3)	0.7329 (4)	0.0397 (15)
H3A	0.8710	0.7189	0.6922	0.048*
H3B	0.8259	0.7738	0.7591	0.048*
N4	0.7146 (5)	0.6182 (3)	0.7122 (4)	0.0301 (13)
H4A	0.7710	0.6077	0.6730	0.036*
C1	0.4480 (7)	0.6944 (4)	0.5460 (5)	0.0361 (17)
C2	0.5431 (7)	0.7514 (4)	0.5687 (5)	0.0387 (18)
H2	0.6274	0.7507	0.5459	0.046*
C3	0.5103 (8)	0.8073 (4)	0.6245 (6)	0.0442 (19)
H3	0.5722	0.8456	0.6388	0.053*
C4	0.3861 (7)	0.8082 (4)	0.6606 (6)	0.0424 (19)
H4	0.3651	0.8458	0.7003	0.051*
C5	0.2971 (7)	0.7535 (4)	0.6369 (5)	0.0355 (17)
H5	0.2127	0.7538	0.6597	0.043*
C6	0.7244 (7)	0.6848 (4)	0.7549 (5)	0.0291 (15)
C7	0.6326 (7)	0.7000 (4)	0.8184 (5)	0.0418 (19)
H7	0.6362	0.7453	0.8489	0.050*
C8	0.5373 (7)	0.6501 (5)	0.8361 (5)	0.045 (2)
H8	0.4777	0.6604	0.8798	0.054*
C9	0.5284 (8)	0.5829 (5)	0.7885 (6)	0.048 (2)
H9	0.4607	0.5490	0.7979	0.057*
C10	0.6201 (7)	0.5680 (4)	0.7286 (5)	0.0387 (18)
H10	0.6179	0.5226	0.6983	0.046*
N5	0.9609 (7)	0.6459 (4)	0.9265 (5)	0.0518 (18)
H5A	0.9958	0.6421	0.8746	0.062*
H5B	0.9708	0.6859	0.9587	0.062*
N6	0.8778 (6)	0.5280 (3)	0.9057 (4)	0.0324 (13)
H6	0.9138	0.5261	0.8540	0.039*
C11	0.8923 (7)	0.5903 (4)	0.9568 (5)	0.0301 (15)
C12	0.8313 (8)	0.5922 (4)	1.0402 (5)	0.0388 (18)
H12	0.8382	0.6344	1.0773	0.047*
C13	0.7629 (8)	0.5333 (5)	1.0668 (5)	0.049 (2)
H13	0.7232	0.5351	1.1224	0.058*
C14	0.7509 (9)	0.4700 (5)	1.0124 (6)	0.052 (2)
H14	0.7034	0.4293	1.0305	0.062*
C15	0.8107 (8)	0.4690 (4)	0.9313 (6)	0.046 (2)
H15	0.8048	0.4270	0.8939	0.055*
O15	0.2400 (7)	0.7219 (4)	0.8838 (5)	0.083 (2)
H15A	0.1820	0.7567	0.8795	0.125*
H15B	0.1917	0.6976	0.8409	0.125*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
V1	0.0254 (6)	0.0199 (6)	0.0200 (6)	−0.0005 (4)	0.0013 (4)	0.0038 (4)
V2	0.0268 (6)	0.0164 (5)	0.0237 (6)	−0.0012 (4)	0.0038 (5)	0.0001 (4)
V3	0.0308 (6)	0.0240 (6)	0.0242 (6)	−0.0007 (5)	0.0068 (5)	−0.0047 (5)
V4	0.0211 (5)	0.0193 (5)	0.0223 (6)	0.0022 (4)	0.0047 (4)	0.0013 (4)
V5	0.0229 (6)	0.0272 (6)	0.0238 (6)	−0.0033 (5)	0.0008 (5)	−0.0018 (5)
O1	0.019 (2)	0.018 (2)	0.020 (2)	−0.0005 (16)	0.0022 (17)	0.0005 (17)
O2	0.022 (2)	0.018 (2)	0.021 (2)	0.0030 (17)	0.0057 (17)	0.0021 (17)
O3	0.025 (2)	0.028 (2)	0.024 (2)	0.0028 (18)	−0.0015 (19)	0.0031 (19)
O4	0.019 (2)	0.028 (2)	0.031 (3)	0.0003 (18)	0.0050 (18)	0.0031 (19)
O5	0.023 (2)	0.027 (2)	0.030 (3)	0.0042 (18)	0.0085 (19)	−0.0017 (19)
O6	0.034 (2)	0.016 (2)	0.029 (3)	0.0033 (18)	0.008 (2)	−0.0041 (18)
O7	0.032 (2)	0.029 (3)	0.030 (3)	−0.001 (2)	0.003 (2)	0.008 (2)
O8	0.032 (2)	0.024 (2)	0.018 (2)	−0.0013 (19)	0.0040 (18)	−0.0012 (18)
O9	0.044 (3)	0.022 (2)	0.027 (3)	−0.005 (2)	0.006 (2)	0.0011 (19)
O10	0.030 (2)	0.022 (2)	0.028 (3)	−0.0047 (19)	0.0069 (19)	−0.0013 (19)
O11	0.048 (3)	0.033 (3)	0.028 (3)	−0.001 (2)	0.014 (2)	−0.005 (2)
O12	0.024 (2)	0.017 (2)	0.019 (2)	−0.0020 (17)	0.0035 (17)	0.0010 (17)
O13	0.031 (3)	0.040 (3)	0.033 (3)	0.000 (2)	−0.006 (2)	−0.003 (2)
O14	0.032 (2)	0.021 (2)	0.023 (2)	−0.0006 (19)	0.0014 (19)	−0.0029 (18)
N1	0.053 (4)	0.072 (6)	0.109 (7)	−0.026 (4)	0.043 (4)	−0.056 (5)
N2	0.026 (3)	0.032 (3)	0.038 (4)	−0.011 (2)	0.005 (3)	−0.013 (3)
N3	0.040 (3)	0.034 (3)	0.047 (4)	−0.002 (3)	0.013 (3)	−0.013 (3)
N4	0.025 (3)	0.036 (3)	0.032 (3)	0.002 (2)	0.011 (2)	−0.002 (3)
C1	0.033 (4)	0.040 (4)	0.037 (4)	−0.005 (3)	0.008 (3)	−0.009 (3)
C2	0.032 (4)	0.049 (5)	0.036 (4)	−0.018 (3)	0.008 (3)	0.002 (4)
C3	0.039 (4)	0.033 (4)	0.058 (5)	−0.017 (3)	−0.003 (4)	−0.001 (4)
C4	0.037 (4)	0.031 (4)	0.057 (5)	0.001 (3)	0.000 (4)	−0.012 (4)
C5	0.035 (4)	0.031 (4)	0.041 (4)	−0.002 (3)	0.006 (3)	−0.002 (3)
C6	0.027 (3)	0.033 (4)	0.027 (4)	0.005 (3)	−0.001 (3)	0.000 (3)
C7	0.036 (4)	0.048 (5)	0.042 (5)	0.012 (4)	0.010 (4)	−0.014 (4)
C8	0.030 (4)	0.067 (6)	0.042 (5)	0.001 (4)	0.019 (3)	−0.010 (4)
C9	0.040 (4)	0.049 (5)	0.057 (5)	−0.013 (4)	0.015 (4)	−0.010 (4)
C10	0.045 (4)	0.032 (4)	0.038 (4)	−0.008 (3)	0.003 (4)	−0.014 (3)
N5	0.068 (5)	0.035 (4)	0.054 (5)	−0.001 (3)	0.016 (4)	−0.005 (3)
N6	0.039 (3)	0.037 (3)	0.022 (3)	0.008 (3)	0.008 (3)	−0.008 (3)
C11	0.027 (3)	0.037 (4)	0.024 (4)	0.011 (3)	−0.008 (3)	−0.005 (3)
C12	0.049 (5)	0.044 (5)	0.024 (4)	0.016 (4)	0.008 (3)	−0.006 (3)
C13	0.051 (5)	0.066 (6)	0.033 (5)	0.007 (4)	0.019 (4)	−0.001 (4)
C14	0.056 (5)	0.051 (5)	0.052 (5)	−0.009 (4)	0.021 (4)	0.003 (4)
C15	0.056 (5)	0.036 (4)	0.047 (5)	−0.004 (4)	0.009 (4)	−0.014 (4)
O15	0.062 (4)	0.098 (6)	0.086 (5)	0.022 (4)	−0.004 (4)	−0.013 (4)

Geometric parameters (Å, º) top

V1—O7	1.616 (4)	N2—H2A	0.8600
V1—O3	1.767 (4)	N3—C6	1.316 (9)
V1—O8	1.842 (4)	N3—H3A	0.8600
V1—O2	1.991 (4)	N3—H3B	0.8599
V1—O12	2.038 (4)	N4—C10	1.345 (9)
V1—O1	2.250 (4)	N4—C6	1.353 (8)
V2—O9	1.608 (4)	N4—H4A	0.8599
V2—O6	1.794 (4)	C1—C2	1.405 (9)
V2—O10	1.823 (4)	C2—C3	1.357 (11)
V2—O12ⁱ	2.015 (4)	C2—H2	0.9299
V2—O2ⁱ	2.017 (4)	C3—C4	1.387 (11)
V2—O1	2.243 (4)	C3—H3	0.9300
V3—O11	1.594 (4)	C4—C5	1.339 (10)
V3—O14	1.827 (4)	C4—H4	0.9300
V3—O8	1.871 (4)	C5—H5	0.9300
V3—O6	1.891 (4)	C6—C7	1.389 (9)
V3—O5	2.045 (4)	C7—C8	1.352 (11)
V3—O1	2.305 (4)	C7—H7	0.9300
V4—O4	1.676 (4)	C8—C9	1.396 (11)
V4—O5ⁱ	1.680 (4)	C8—H8	0.9300
V4—O12ⁱ	1.921 (4)	C9—C10	1.349 (10)
V4—O2	1.953 (4)	C9—H9	0.9300
V4—O1ⁱ	2.097 (4)	C10—H10	0.9300
V4—O1	2.111 (4)	N5—C11	1.319 (9)
V5—O13	1.590 (5)	N5—H5A	0.8600
V5—O14	1.835 (4)	N5—H5B	0.8601
V5—O10	1.864 (4)	N6—C15	1.335 (9)
V5—O3	1.881 (4)	N6—C11	1.346 (8)
V5—O4	2.045 (4)	N6—H6	0.8600
V5—O1	2.318 (4)	C11—C12	1.403 (9)
O1—V4ⁱ	2.097 (4)	C12—C13	1.346 (11)
O2—V2ⁱ	2.017 (4)	C12—H12	0.9300
O5—V4ⁱ	1.680 (4)	C13—C14	1.386 (11)
O12—V4ⁱ	1.921 (4)	C13—H13	0.9300
O12—V2ⁱ	2.015 (4)	C14—C15	1.366 (11)
N1—C1	1.312 (9)	C14—H14	0.9300
N1—H1A	0.8599	C15—H15	0.9300
N1—H1B	0.8600	O15—H15A	0.8499
N2—C1	1.339 (8)	O15—H15B	0.8496
N2—C5	1.350 (8)

O7—V1—O3	104.4 (2)	V1—O1—V3	85.95 (14)
O7—V1—O8	101.4 (2)	V4ⁱ—O1—V5	170.8 (2)
O3—V1—O8	95.96 (19)	V4—O1—V5	87.36 (14)
O7—V1—O2	100.7 (2)	V2—O1—V5	85.25 (13)
O3—V1—O2	91.58 (18)	V1—O1—V5	85.16 (14)
O8—V1—O2	154.05 (18)	V3—O1—V5	83.19 (13)
O7—V1—O12	98.8 (2)	V4—O2—V1	107.04 (19)
O3—V1—O12	155.27 (18)	V4—O2—V2ⁱ	106.87 (19)
O8—V1—O12	87.81 (17)	V1—O2—V2ⁱ	101.98 (17)
O2—V1—O12	75.49 (16)	V1—O3—V5	115.8 (2)
O7—V1—O1	173.8 (2)	V4—O4—V5	110.3 (2)
O3—V1—O1	81.16 (17)	V4ⁱ—O5—V3	109.7 (2)
O8—V1—O1	80.48 (16)	V2—O6—V3	114.8 (2)
O2—V1—O1	76.19 (15)	V1—O8—V3	113.5 (2)
O12—V1—O1	75.36 (15)	V2—O10—V5	113.8 (2)
O9—V2—O6	102.8 (2)	V4ⁱ—O12—V2ⁱ	107.03 (18)
O9—V2—O10	103.1 (2)	V4ⁱ—O12—V1	106.72 (18)
O6—V2—O10	96.7 (2)	V2ⁱ—O12—V1	100.42 (17)
O9—V2—O12ⁱ	99.71 (19)	V3—O14—V5	113.9 (2)
O6—V2—O12ⁱ	154.72 (18)	C1—N1—H1A	119.8
O10—V2—O12ⁱ	89.15 (18)	C1—N1—H1B	120.1
O9—V2—O2ⁱ	99.5 (2)	H1A—N1—H1B	120.0
O6—V2—O2ⁱ	89.59 (18)	C1—N2—C5	122.3 (6)
O10—V2—O2ⁱ	154.54 (18)	C1—N2—H2A	119.0
O12ⁱ—V2—O2ⁱ	75.43 (16)	C5—N2—H2A	118.7
O9—V2—O1	173.9 (2)	C6—N3—H3A	120.0
O6—V2—O1	80.77 (17)	C6—N3—H3B	120.0
O10—V2—O1	81.23 (16)	H3A—N3—H3B	120.0
O12ⁱ—V2—O1	75.85 (15)	C10—N4—C6	122.6 (6)
O2ⁱ—V2—O1	75.47 (15)	C10—N4—H4A	118.8
O11—V3—O14	103.0 (2)	C6—N4—H4A	118.6
O11—V3—O8	102.3 (2)	N1—C1—N2	119.8 (7)
O14—V3—O8	92.79 (19)	N1—C1—C2	122.0 (7)
O11—V3—O6	101.5 (2)	N2—C1—C2	118.1 (6)
O14—V3—O6	90.05 (19)	C3—C2—C1	119.1 (7)
O8—V3—O6	154.81 (18)	C3—C2—H2	120.5
O11—V3—O5	100.7 (2)	C1—C2—H2	120.4
O14—V3—O5	156.20 (18)	C2—C3—C4	121.0 (7)
O8—V3—O5	84.18 (18)	C2—C3—H3	119.4
O6—V3—O5	83.21 (18)	C4—C3—H3	119.6
O11—V3—O1	175.1 (2)	C5—C4—C3	118.5 (7)
O14—V3—O1	81.71 (16)	C5—C4—H4	120.8
O8—V3—O1	78.46 (16)	C3—C4—H4	120.8
O6—V3—O1	77.20 (16)	C4—C5—N2	121.0 (7)
O5—V3—O1	74.55 (15)	C4—C5—H5	119.5
O4—V4—O5ⁱ	105.8 (2)	N2—C5—H5	119.5
O4—V4—O12ⁱ	97.83 (19)	N3—C6—N4	118.4 (6)
O5ⁱ—V4—O12ⁱ	98.45 (19)	N3—C6—C7	124.3 (7)
O4—V4—O2	96.17 (19)	N4—C6—C7	117.3 (6)
O5ⁱ—V4—O2	96.12 (19)	C8—C7—C6	120.9 (7)
O12ⁱ—V4—O2	156.20 (17)	C8—C7—H7	119.4
O4—V4—O1ⁱ	166.03 (18)	C6—C7—H7	119.7
O5ⁱ—V4—O1ⁱ	88.08 (18)	C7—C8—C9	119.9 (7)
O12ⁱ—V4—O1ⁱ	81.50 (16)	C7—C8—H8	120.3
O2—V4—O1ⁱ	80.29 (16)	C9—C8—H8	119.9
O4—V4—O1	87.89 (18)	C10—C9—C8	118.7 (7)
O5ⁱ—V4—O1	166.22 (19)	C10—C9—H9	120.7
O12ⁱ—V4—O1	81.02 (16)	C8—C9—H9	120.6
O2—V4—O1	80.36 (16)	N4—C10—C9	120.5 (7)
O1ⁱ—V4—O1	78.21 (17)	N4—C10—H10	119.7
O13—V5—O14	104.4 (2)	C9—C10—H10	119.7
O13—V5—O10	101.8 (2)	C11—N5—H5A	120.0
O14—V5—O10	91.43 (19)	C11—N5—H5B	120.0
O13—V5—O3	102.0 (2)	H5A—N5—H5B	120.0
O14—V5—O3	90.73 (19)	C15—N6—C11	123.3 (6)
O10—V5—O3	154.79 (19)	C15—N6—H6	118.4
O13—V5—O4	100.0 (2)	C11—N6—H6	118.3
O14—V5—O4	155.60 (18)	N5—C11—N6	119.3 (6)
O10—V5—O4	83.94 (18)	N5—C11—C12	123.6 (7)
O3—V5—O4	83.79 (18)	N6—C11—C12	117.1 (7)
O13—V5—O1	174.4 (2)	C13—C12—C11	120.4 (7)
O14—V5—O1	81.21 (17)	C13—C12—H12	119.8
O10—V5—O1	78.41 (16)	C11—C12—H12	119.8
O3—V5—O1	77.12 (16)	C12—C13—C14	120.8 (7)
O4—V5—O1	74.39 (15)	C12—C13—H13	119.6
V4ⁱ—O1—V4	101.79 (16)	C14—C13—H13	119.6
V4ⁱ—O1—V2	94.50 (15)	C15—C14—C13	118.2 (8)
V4—O1—V2	93.22 (15)	C15—C14—H14	120.9
V4ⁱ—O1—V1	93.87 (15)	C13—C14—H14	120.9
V4—O1—V1	93.23 (15)	N6—C15—C14	120.3 (7)
V2—O1—V1	168.2 (2)	N6—C15—H15	119.9
V4ⁱ—O1—V3	87.65 (14)	C14—C15—H15	119.9
V4—O1—V3	170.6 (2)	H15A—O15—H15B	91.4
V2—O1—V3	86.07 (14)

Symmetry code: (i) −x+2, −y+2, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4ⁱⁱ	0.86	2.44	3.217 (9)	150
N1—H1A···O5ⁱⁱⁱ	0.86	2.55	3.286 (8)	144
N1—H1B···O10^iv	0.86	2.21	3.058 (8)	169
N2—H2A···O2ⁱⁱ	0.86	1.85	2.697 (7)	168
N3—H3A···O9^iv	0.86	2.17	2.969 (7)	155
N3—H3A···O7^v	0.86	2.48	3.017 (7)	122
N3—H3B···O14	0.86	2.09	2.908 (7)	158
N4—H4A···O12^v	0.86	1.84	2.698 (6)	174
N5—H5A···O7^v	0.86	2.23	3.085 (8)	175
N5—H5B···O9	0.86	2.22	3.057 (8)	164
N6—H6···O8^v	0.86	1.87	2.709 (7)	166
O15—H15A···O6^vi	0.85	2.09	2.926 (8)	166
O15—H15B···O7ⁱⁱ	0.85	2.13	2.977 (8)	180

Symmetry codes: (ii) −x+1, y−1/2, −z+3/2; (iii) x−1, −y+3/2, z−1/2; (iv) x, −y+3/2, z−1/2; (v) −x+2, y−1/2, −z+3/2; (vi) x−1, y, z.

Experimental details

Crystal data
Chemical formula	(C₅H₇N₂)₆[V₁₀O₂₈]·2H₂O
M_r	1564.19
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	9.840 (3), 18.180 (6), 14.299 (5)
β (°)	97.416 (4)
V (Å³)	2536.6 (14)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.86
Crystal size (mm)	0.40 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART 1K CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.523, 0.707
No. of measured, independent and observed [I > 2σ(I)] reflections	9858, 4341, 3949
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.074, 0.128, 1.29
No. of reflections	4341
No. of parameters	370
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.45

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL/PC (Sheldrick, 2008).

Selected bond lengths (Å) top

V1—O7	1.616 (4)	V3—O6	1.891 (4)
V1—O3	1.767 (4)	V3—O5	2.045 (4)
V1—O8	1.842 (4)	V3—O1	2.305 (4)
V1—O2	1.991 (4)	V4—O4	1.676 (4)
V1—O12	2.038 (4)	V4—O5ⁱ	1.680 (4)
V1—O1	2.250 (4)	V4—O12ⁱ	1.921 (4)
V2—O9	1.608 (4)	V4—O2	1.953 (4)
V2—O6	1.794 (4)	V4—O1ⁱ	2.097 (4)
V2—O10	1.823 (4)	V4—O1	2.111 (4)
V2—O12ⁱ	2.015 (4)	V5—O13	1.590 (5)
V2—O2ⁱ	2.017 (4)	V5—O14	1.835 (4)
V2—O1	2.243 (4)	V5—O10	1.864 (4)
V3—O11	1.594 (4)	V5—O3	1.881 (4)
V3—O14	1.827 (4)	V5—O4	2.045 (4)
V3—O8	1.871 (4)	V5—O1	2.318 (4)

Symmetry code: (i) −x+2, −y+2, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4ⁱⁱ	0.86	2.44	3.217 (9)	150
N1—H1A···O5ⁱⁱⁱ	0.86	2.55	3.286 (8)	144
N1—H1B···O10^iv	0.86	2.21	3.058 (8)	169
N2—H2A···O2ⁱⁱ	0.86	1.85	2.697 (7)	168
N3—H3A···O9^iv	0.86	2.17	2.969 (7)	155
N3—H3A···O7^v	0.86	2.48	3.017 (7)	122
N3—H3B···O14	0.86	2.09	2.908 (7)	158
N4—H4A···O12^v	0.86	1.84	2.698 (6)	174
N5—H5A···O7^v	0.86	2.23	3.085 (8)	175
N5—H5B···O9	0.86	2.22	3.057 (8)	164
N6—H6···O8^v	0.86	1.87	2.709 (7)	166
O15—H15A···O6^vi	0.85	2.09	2.926 (8)	166
O15—H15B···O7ⁱⁱ	0.85	2.13	2.977 (8)	180

Symmetry codes: (ii) −x+1, y−1/2, −z+3/2; (iii) x−1, −y+3/2, z−1/2; (iv) x, −y+3/2, z−1/2; (v) −x+2, y−1/2, −z+3/2; (vi) x−1, y, z.

Acknowledgements

The authors acknowledge financial support from the National Natural Science Foundation of China (grant No. 20471033), the Provincial Natural Science Foundation of Shanxi Province of China (grant No. 20051013) and the Overseas Returned Scholar Foundation of Shanxi Province of China in 2008.

References

Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Gong, Y., Hu, C., Li, H., Tang, W., Huang, K. & Hou, W. B. (2006). J. Mol. Struct. 784, 228–238. Web of Science CSD CrossRef CAS Google Scholar
Pacigová, S., Rakovský, E., Sivák, M. & Žák, Z. (2007). Acta Cryst. C63, m419–m422. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.