Tetra­kis(2-amino-4-methyl­pyridinium) cyclo-tetra-μ2-oxido-tetra­kis­[dioxido­vanadate(V)] tetra­hydrate

Tabatabaee, M.; Ahadiat, G.; Molčanov, K.

doi:10.1107/S1600536811026912

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page m1090

doi:10.1107/S1600536811026912

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Tetrakis(2-amino-4-methylpyridinium) cyclo-tetra-μ₂-oxido-tetrakis[dioxidovanadate(V)] tetrahydrate

Masoumeh Tabatabaee,^a ^* Ghasem Ahadiat ^a and Krešimir Molčanov ^b

^aDepartment of Chemistry, Islamic Azad University, Yazd branch, Yazd, Iran, and ^bDepartment of Physical Chemistry, Rudjer Bošković Institute, Bijenička 54, HR-10000 Zagreb, Croatia
^*Correspondence e-mail: tabatabaee45m@yahoo.com

(Received 28 June 2011; accepted 5 July 2011; online 13 July 2011)

The asymmetric unit of the title compound, (C₆H₉N₂)₄[V₄O₁₂]·4H₂O, contains half of a [V₄O₁₂]⁴⁻ anion, two 2-amino-4-methylpyridinium, (2a4mpH)⁺, cations and two water molecules. One water molecule is disordered over two sets of sites with equal occupancies and the H atoms for this molecule were not included in the refinement. The cation lies on an inversion center with four tetrahedral VO₄ units each sharing two vertices, forming an eight-membered ring. In the crystal, the components are linked by intermolecular N—H⋯O hydrogen bonds, forming a one-dimensional network along [100]. Further stabilization is provided by weak intermolecular C—H⋯O hydrogen bonds. In addition, π–π stacking interactions with centroid–centroid distances of 3.5420 (18), 3.7577 (18) and 3.6311 (19) Å are observed.

Related literature

For related structures, see: Paredes-García et al. (2008); Nakano et al. (2002 ).

Experimental

Crystal data

(C₆H₉N₂)₄[V₄O₁₂]·4H₂O
M_r = 900.39
Triclinic, $[P \overline 1]$
a = 7.8739 (3) Å
b = 11.1880 (5) Å
c = 11.7618 (6) Å
α = 73.609 (4)°
β = 76.945 (4)°
γ = 79.342 (4)°
V = 960.15 (7) Å³
Z = 1
Cu Kα radiation
μ = 8.59 mm⁻¹
T = 293 K
0.15 × 0.15 × 0.10 mm

Data collection

Oxford Diffraction Xcalibur Nova R diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England.]$ ) T_min = 0.518, T_max = 1
8031 measured reflections
3932 independent reflections
3371 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.129
S = 1.05
3932 reflections
250 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.86	1.85	2.700 (3)	167
N2—H2A⋯O3ⁱ	0.86	2.00	2.861 (3)	178
N2—H2B⋯O2ⁱⁱ	0.86	2.13	2.959 (3)	161
N3—H3⋯O4ⁱⁱ	0.86	1.92	2.767 (3)	167
N4—H4A⋯O6ⁱⁱ	0.86	2.26	2.995 (4)	143
N4—H4B⋯O5ⁱ	0.86	2.04	2.883 (4)	165
C2—H2⋯O1ⁱⁱ	0.93	2.60	3.363 (4)	140
C2—H2⋯O2ⁱⁱ	0.93	2.64	3.371 (4)	136
C4—H4⋯O5	0.93	2.52	3.352 (4)	149
Symmetry codes: (i) x, y+1, z; (ii) x-1, y+1, z.

Data collection: CrysAlis PRO (Oxford Diffraction, 2007); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS86 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: WinGX (Farrugia, 1999).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811026912/lh5277sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811026912/lh5277Isup2.hkl

checkCIF report

Comment top

The chemistry of polyoxovanadate compounds are of great interest. Hybrid organo-inorganic compounds based on vanadium oxides present potential applications in catalysis, electron conductivity, magnetism and photochemistry (Paredes-García et al., 2008). The VO₄ group is an important building block of many polynuclear species. A well known example is the V₄O₁₂^4– ring which has an eight-membered ring structure formed by four VO₄ tetrahedra sharing vertices (Nakano et al., 2002). The complexing ability of the V₄O₁₂^4– ion with transition metal ions is of great interest and the ring takes part as a ligand (Paredes-García et al., 2008). Herein we report the crystal structure of the title compound obtained as a side product from a reaction of ammonium vanadate, cobalt nitrate, boric acid and 2-Amino-4-methylpyridine.

The asymmetric unit of the title compound, (2a4mpH)₄(V₄O₁₂).4H₂O, comprises a half of a V₄O₁₂^4– anion, two (2a4mpH)⁺ cations and two solvent molecules of water (Fig. 1). One molecule of water is disordered over two positions (O7 and O8) with equal occupancies.

The V₄O₁₂^4– ion is centrosymmetric with four tetrahedral VO₄units which share two vertices with each other to form an eight-membered ring. The 2-Amino-4-methylpyridine molecule is protonated via its endocyclic nitrogen atom. In the crystal, extensive intermolecular N—H···O hydrogen-bonding interactions (Table 1) between cations, anions and solvent water molecules form 1-D motive chains along [100] (Fig.2). The crystal packing is defined by a layered structure in which chains involving 2a4mpH⁺ and V₄O₁₂^4– ions are associated via π–π stacking interactions between the aromatic rings of (2a4mpH)⁺ cations into layers parallel to (110) (Fig. 3).

Related literature top

For related structures, see: Paredes-García et al. (2008); Nakano et al. (2002).

Experimental top

Ammonium vanadate, cobalt nitrate hexahydrate, boric acidand 2-amino-4-methylpyridine (in molar ratio 0.5:1:1:2) were dissolved in H₂O (50ml). The reaction mixture was placed in a Parr-Teflon lined stainless steel vessel. It was sealed and heated at 443K for 48 h. The reaction mixture was gradually cooled to room temperature. Pale yellow crystals were isolated from solution.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2007); cell refinement: CrysAlis PRO (Oxford Diffraction, 2007); data reduction: CrysAlis PRO (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2008); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. ORTEP-3 drawing of the asymmetric unit of the title compound with displacement ellipsoids drawn at the 50 % proabality leveland hydrogen atoms are depicted as spheres of arbitrary radii. Symmetry operator: (i) 2 - x, -y, 1 - z.
	Fig. 2. A hydrogen-bonded (dotted lines) chain consisting of anions and cations, extending in the direction [100]. The solvent water molecules are not shown.
	Fig. 3. Packing of the title compound viewed along [100] with π–π stacking interactions shown as dashed lines.

Tetrakis(2-amino-4-methylpyridinium) cyclo-tetra-µ₂-oxido-tetrakis[dioxidovanadate(V)] tetrahydrate top

Crystal data top

(C₆H₉N₂)₄[V₄O₁₂]·4H₂O	Z = 1
M_r = 900.39	F(000) = 332
Triclinic, P1	D_x = 1.557 Mg m⁻³
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54179 Å
a = 7.8739 (3) Å	Cell parameters from 4890 reflections
b = 11.1880 (5) Å	θ = 4.0–75.8°
c = 11.7618 (6) Å	µ = 8.59 mm⁻¹
α = 73.609 (4)°	T = 293 K
β = 76.945 (4)°	Prism, pale yellow
γ = 79.342 (4)°	0.15 × 0.15 × 0.10 mm
V = 960.15 (7) Å³

Data collection top

Oxford Diffraction Xcalibur Nova R diffractometer	3932 independent reflections
Graphite monochromator	3371 reflections with I > 2σ(I)
Detector resolution: 10.4323 pixels mm^-1	R_int = 0.033
ω scans	θ_max = 76.0°, θ_min = 4.0°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007)	h = −9→9
T_min = 0.518, T_max = 1	k = −13→13
8031 measured reflections	l = −14→11

Refinement top

Refinement on F²	3 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.044	w = 1/[σ²(F_o²) + (0.085P)² + 0.0501P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.129	(Δ/σ)_max = 0.001
S = 1.05	Δρ_max = 0.47 e Å⁻³
3932 reflections	Δρ_min = −0.33 e Å⁻³
250 parameters

Crystal data top

(C₆H₉N₂)₄[V₄O₁₂]·4H₂O	γ = 79.342 (4)°
M_r = 900.39	V = 960.15 (7) Å³
Triclinic, P1	Z = 1
a = 7.8739 (3) Å	Cu Kα radiation
b = 11.1880 (5) Å	µ = 8.59 mm⁻¹
c = 11.7618 (6) Å	T = 293 K
α = 73.609 (4)°	0.15 × 0.15 × 0.10 mm
β = 76.945 (4)°

Data collection top

Oxford Diffraction Xcalibur Nova R diffractometer	3932 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007)	3371 reflections with I > 2σ(I)
T_min = 0.518, T_max = 1	R_int = 0.033
8031 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	3 restraints
wR(F²) = 0.129	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.47 e Å⁻³
3932 reflections	Δρ_min = −0.33 e Å⁻³
250 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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
V2	0.96401 (5)	0.16480 (4)	0.30891 (4)	0.04115 (14)
V1	0.95947 (5)	−0.13283 (4)	0.42124 (4)	0.03986 (14)
O1	0.9714 (3)	−0.24965 (19)	0.3592 (2)	0.0530 (5)
O2	1.0932 (2)	−0.17853 (19)	0.53675 (18)	0.0498 (4)
O3	0.7553 (3)	−0.0950 (2)	0.4789 (2)	0.0589 (5)
O4	1.0430 (2)	0.00128 (17)	0.30665 (17)	0.0473 (4)
O5	0.7916 (3)	0.2148 (2)	0.2444 (2)	0.0575 (5)
O6	1.1255 (3)	0.2451 (2)	0.2325 (2)	0.0600 (5)
C1	0.5148 (3)	0.6860 (2)	0.4084 (2)	0.0446 (5)
C2	0.3830 (4)	0.6228 (3)	0.3964 (3)	0.0489 (6)
H2	0.2663	0.645	0.4292	0.059*
C3	0.4245 (5)	0.5298 (3)	0.3373 (3)	0.0577 (7)
C4	0.6019 (5)	0.4953 (3)	0.2905 (3)	0.0647 (8)
H4	0.6333	0.4311	0.2509	0.078*
C5	0.7261 (4)	0.5561 (3)	0.3034 (3)	0.0620 (7)
H5	0.8432	0.534	0.2714	0.074*
C6	0.2802 (6)	0.4652 (4)	0.3238 (4)	0.0836 (12)
H6C	0.3308	0.4022	0.2805	0.125*
H6A	0.1994	0.526	0.2801	0.125*
H6B	0.2188	0.4264	0.4021	0.125*
N1	0.6839 (3)	0.6492 (2)	0.3625 (2)	0.0497 (5)
H1	0.7662	0.6853	0.3708	0.06*
N2	0.4799 (3)	0.7794 (2)	0.4625 (2)	0.0547 (6)
H2A	0.5642	0.8155	0.4679	0.066*
H2B	0.3731	0.8038	0.4921	0.066*
C7	0.5200 (4)	1.0124 (3)	0.2050 (3)	0.0523 (6)
C8	0.6928 (4)	0.9673 (3)	0.1585 (3)	0.0521 (6)
H8	0.7863	1.0016	0.1677	0.062*
C9	0.7251 (4)	0.8738 (3)	0.1000 (3)	0.0563 (7)
C10	0.5819 (5)	0.8220 (3)	0.0874 (3)	0.0622 (7)
H10	0.6011	0.7592	0.0466	0.075*
C11	0.4163 (4)	0.8645 (3)	0.1352 (3)	0.0601 (7)
H11	0.3217	0.8295	0.1287	0.072*
C12	0.9095 (5)	0.8251 (4)	0.0517 (4)	0.0783 (10)
H12B	0.9078	0.7602	0.0133	0.117*
H12A	0.9734	0.7914	0.1167	0.117*
H12C	0.9656	0.8924	−0.0061	0.117*
N3	0.3879 (3)	0.9573 (3)	0.1922 (2)	0.0559 (6)
H3	0.2815	0.9827	0.2218	0.067*
N4	0.4820 (4)	1.1037 (3)	0.2601 (3)	0.0750 (8)
H4A	0.3743	1.1281	0.2878	0.09*
H4B	0.5649	1.1391	0.2686	0.09*
O9	0.3335 (12)	0.6497 (8)	−0.0146 (6)	0.186 (3)
O7	0.0661 (13)	0.4852 (7)	0.0806 (8)	0.121 (3)	0.5
O8	0.754 (2)	0.5676 (10)	−0.0400 (7)	0.191 (7)	0.5
H9A	0.255 (15)	0.616 (10)	−0.047 (11)	0.3*
H9B	0.385 (17)	0.573 (7)	0.037 (10)	0.3*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
V2	0.0395 (2)	0.0430 (2)	0.0433 (2)	−0.00904 (16)	−0.01011 (16)	−0.01024 (17)
V1	0.0361 (2)	0.0433 (2)	0.0449 (2)	−0.00975 (15)	−0.00796 (16)	−0.01537 (17)
O1	0.0542 (10)	0.0535 (10)	0.0622 (12)	−0.0098 (8)	−0.0159 (9)	−0.0259 (9)
O2	0.0471 (9)	0.0566 (10)	0.0500 (10)	−0.0079 (8)	−0.0129 (8)	−0.0164 (8)
O3	0.0415 (9)	0.0704 (13)	0.0701 (13)	−0.0124 (8)	−0.0044 (9)	−0.0273 (11)
O4	0.0453 (9)	0.0458 (9)	0.0518 (10)	−0.0089 (7)	−0.0060 (7)	−0.0141 (8)
O5	0.0538 (11)	0.0611 (12)	0.0635 (12)	−0.0017 (9)	−0.0250 (9)	−0.0175 (10)
O6	0.0578 (11)	0.0601 (12)	0.0615 (12)	−0.0238 (9)	−0.0071 (9)	−0.0069 (10)
C1	0.0447 (12)	0.0455 (12)	0.0445 (12)	−0.0119 (9)	−0.0129 (10)	−0.0050 (10)
C2	0.0446 (12)	0.0478 (13)	0.0556 (15)	−0.0120 (10)	−0.0164 (11)	−0.0057 (11)
C3	0.0701 (17)	0.0508 (14)	0.0603 (17)	−0.0165 (13)	−0.0298 (14)	−0.0074 (13)
C4	0.082 (2)	0.0559 (16)	0.0640 (18)	−0.0073 (15)	−0.0203 (16)	−0.0231 (14)
C5	0.0563 (16)	0.0669 (18)	0.0613 (18)	−0.0024 (13)	−0.0081 (13)	−0.0192 (15)
C6	0.103 (3)	0.071 (2)	0.098 (3)	−0.033 (2)	−0.049 (2)	−0.018 (2)
N1	0.0434 (11)	0.0548 (12)	0.0530 (13)	−0.0138 (9)	−0.0096 (9)	−0.0113 (10)
N2	0.0443 (11)	0.0592 (13)	0.0667 (15)	−0.0142 (9)	−0.0080 (10)	−0.0224 (12)
C7	0.0422 (13)	0.0661 (16)	0.0475 (14)	−0.0106 (11)	−0.0094 (10)	−0.0095 (12)
C8	0.0453 (13)	0.0668 (17)	0.0436 (13)	−0.0120 (11)	−0.0086 (10)	−0.0097 (12)
C9	0.0547 (15)	0.0694 (18)	0.0410 (13)	−0.0093 (13)	−0.0070 (11)	−0.0086 (12)
C10	0.0710 (19)	0.0665 (18)	0.0530 (16)	−0.0120 (15)	−0.0173 (14)	−0.0147 (14)
C11	0.0597 (16)	0.0683 (18)	0.0555 (16)	−0.0216 (14)	−0.0220 (13)	−0.0033 (14)
C12	0.066 (2)	0.097 (3)	0.069 (2)	−0.0061 (18)	0.0031 (17)	−0.032 (2)
N3	0.0404 (11)	0.0698 (15)	0.0544 (13)	−0.0123 (10)	−0.0082 (9)	−0.0077 (11)
N4	0.0472 (13)	0.090 (2)	0.097 (2)	−0.0088 (13)	−0.0057 (14)	−0.0436 (19)
O9	0.225 (8)	0.230 (8)	0.116 (4)	−0.091 (6)	−0.042 (4)	−0.016 (5)
O7	0.161 (8)	0.072 (4)	0.101 (6)	−0.012 (4)	−0.004 (5)	0.007 (4)
O8	0.38 (2)	0.118 (7)	0.071 (5)	−0.122 (11)	0.017 (8)	−0.006 (5)

Geometric parameters (Å, º) top

V2—O5	1.636 (2)	N2—H2A	0.86
V2—O6	1.637 (2)	N2—H2B	0.86
V2—O2ⁱ	1.812 (2)	C7—N4	1.314 (4)
V2—O4	1.8258 (18)	C7—N3	1.358 (4)
V1—O3	1.625 (2)	C7—C8	1.404 (4)
V1—O1	1.6467 (19)	C8—C9	1.364 (5)
V1—O2	1.809 (2)	C8—H8	0.93
V1—O4	1.8232 (19)	C9—C10	1.414 (5)
O2—V2ⁱ	1.812 (2)	C9—C12	1.495 (5)
C1—N2	1.328 (4)	C10—C11	1.353 (5)
C1—N1	1.353 (4)	C10—H10	0.93
C1—C2	1.411 (4)	C11—N3	1.349 (5)
C2—C3	1.361 (4)	C11—H11	0.93
C2—H2	0.93	C12—H12B	0.96
C3—C4	1.406 (5)	C12—H12A	0.96
C3—C6	1.513 (4)	C12—H12C	0.96
C4—C5	1.346 (5)	N3—H3	0.86
C4—H4	0.93	N4—H4A	0.86
C5—N1	1.362 (4)	N4—H4B	0.86
C5—H5	0.93	O9—H9A	0.97 (2)
C6—H6C	0.96	O9—H9B	0.98 (2)
C6—H6A	0.96	O7—O8ⁱⁱ	1.460 (18)
C6—H6B	0.96	O8—O7ⁱⁱ	1.460 (18)
N1—H1	0.86

O5—V2—O6	109.93 (12)	C1—N1—C5	121.2 (3)
O5—V2—O2ⁱ	109.51 (10)	C1—N1—H1	119.4
O6—V2—O2ⁱ	111.16 (11)	C5—N1—H1	119.4
O5—V2—O4	110.27 (10)	C1—N2—H2A	120
O6—V2—O4	106.15 (10)	C1—N2—H2B	120
O2ⁱ—V2—O4	109.79 (9)	H2A—N2—H2B	120
O3—V1—O1	108.79 (11)	N4—C7—N3	119.4 (3)
O3—V1—O2	110.32 (11)	N4—C7—C8	123.0 (3)
O1—V1—O2	110.20 (10)	N3—C7—C8	117.5 (3)
O3—V1—O4	110.02 (11)	C9—C8—C7	120.8 (3)
O1—V1—O4	109.41 (10)	C9—C8—H8	119.6
O2—V1—O4	108.10 (9)	C7—C8—H8	119.6
V1—O2—V2ⁱ	129.30 (11)	C8—C9—C10	119.0 (3)
V1—O4—V2	123.94 (10)	C8—C9—C12	120.7 (3)
N2—C1—N1	118.9 (2)	C10—C9—C12	120.3 (3)
N2—C1—C2	122.9 (3)	C11—C10—C9	119.4 (3)
N1—C1—C2	118.2 (3)	C11—C10—H10	120.3
C3—C2—C1	120.8 (3)	C9—C10—H10	120.3
C3—C2—H2	119.6	N3—C11—C10	120.4 (3)
C1—C2—H2	119.6	N3—C11—H11	119.8
C2—C3—C4	118.9 (3)	C10—C11—H11	119.8
C2—C3—C6	119.7 (3)	C9—C12—H12B	109.5
C4—C3—C6	121.4 (3)	C9—C12—H12A	109.5
C5—C4—C3	119.5 (3)	H12B—C12—H12A	109.5
C5—C4—H4	120.3	C9—C12—H12C	109.5
C3—C4—H4	120.3	H12B—C12—H12C	109.5
C4—C5—N1	121.4 (3)	H12A—C12—H12C	109.5
C4—C5—H5	119.3	C11—N3—C7	122.8 (3)
N1—C5—H5	119.3	C11—N3—H3	118.6
C3—C6—H6C	109.5	C7—N3—H3	118.6
C3—C6—H6A	109.5	C7—N4—H4A	120
H6C—C6—H6A	109.5	C7—N4—H4B	120
C3—C6—H6B	109.5	H4A—N4—H4B	120
H6C—C6—H6B	109.5	H9A—O9—H9B	102 (4)
H6A—C6—H6B	109.5

O3—V1—O2—V2ⁱ	−9.82 (19)	C3—C4—C5—N1	0.9 (5)
O1—V1—O2—V2ⁱ	−129.97 (15)	N2—C1—N1—C5	−178.3 (3)
O4—V1—O2—V2ⁱ	110.52 (14)	C2—C1—N1—C5	1.7 (4)
O3—V1—O4—V2	29.34 (16)	C4—C5—N1—C1	−1.3 (5)
O1—V1—O4—V2	148.80 (13)	N4—C7—C8—C9	−178.8 (3)
O2—V1—O4—V2	−91.18 (13)	N3—C7—C8—C9	1.7 (5)
O5—V2—O4—V1	−86.26 (15)	C7—C8—C9—C10	−0.5 (5)
O6—V2—O4—V1	154.71 (13)	C7—C8—C9—C12	−179.4 (3)
O2ⁱ—V2—O4—V1	34.48 (15)	C8—C9—C10—C11	−1.1 (5)
N2—C1—C2—C3	178.2 (3)	C12—C9—C10—C11	177.8 (3)
N1—C1—C2—C3	−1.8 (4)	C9—C10—C11—N3	1.4 (5)
C1—C2—C3—C4	1.4 (5)	C10—C11—N3—C7	0.0 (5)
C1—C2—C3—C6	−178.9 (3)	N4—C7—N3—C11	179.0 (3)
C2—C3—C4—C5	−1.0 (5)	C8—C7—N3—C11	−1.5 (4)
C6—C3—C4—C5	179.3 (4)

Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱⁱⁱ	0.86	1.85	2.700 (3)	167
N2—H2A···O3ⁱⁱⁱ	0.86	2.00	2.861 (3)	178
N2—H2B···O2^iv	0.86	2.13	2.959 (3)	161
N3—H3···O4^iv	0.86	1.92	2.767 (3)	167
N4—H4A···O6^iv	0.86	2.26	2.995 (4)	143
N4—H4B···O5ⁱⁱⁱ	0.86	2.04	2.883 (4)	165
C2—H2···O1^iv	0.93	2.60	3.363 (4)	140
C2—H2···O2^iv	0.93	2.64	3.371 (4)	136
C4—H4···O5	0.93	2.52	3.352 (4)	149

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

Experimental details

Crystal data
Chemical formula	(C₆H₉N₂)₄[V₄O₁₂]·4H₂O
M_r	900.39
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.8739 (3), 11.1880 (5), 11.7618 (6)
α, β, γ (°)	73.609 (4), 76.945 (4), 79.342 (4)
V (Å³)	960.15 (7)
Z	1
Radiation type	Cu Kα
µ (mm⁻¹)	8.59
Crystal size (mm)	0.15 × 0.15 × 0.10

Data collection
Diffractometer	Oxford Diffraction Xcalibur Nova R diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2007)
T_min, T_max	0.518, 1
No. of measured, independent and observed [I > 2σ(I)] reflections	8031, 3932, 3371
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.629

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.129, 1.05
No. of reflections	3932
No. of parameters	250
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.33

Computer programs: CrysAlis PRO (Oxford Diffraction, 2007), SHELXS86 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2008), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	1.85	2.700 (3)	167
N2—H2A···O3ⁱ	0.86	2.00	2.861 (3)	178
N2—H2B···O2ⁱⁱ	0.86	2.13	2.959 (3)	161
N3—H3···O4ⁱⁱ	0.86	1.92	2.767 (3)	167
N4—H4A···O6ⁱⁱ	0.86	2.26	2.995 (4)	143
N4—H4B···O5ⁱ	0.86	2.04	2.883 (4)	165
C2—H2···O1ⁱⁱ	0.93	2.60	3.363 (4)	140
C2—H2···O2ⁱⁱ	0.93	2.64	3.371 (4)	136
C4—H4···O5	0.93	2.52	3.352 (4)	149

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

Acknowledgements

This research was supported by the Islamic Azad University, Yazd Branch, and by the Ministry of Science, Education and Sports of Croatia, grant No. 098–1191344-2943.

References

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