Tetra-kis(2-amino-4-methyl-pyridinium) cyclo-tetra-μ(2)-oxido-tetra-kis-[dioxido-vanadate(V)] tetra-hydrate.

The asymmetric unit of the title compound, (C(6)H(9)N(2))(4)[V(4)O(12)]·4H(2)O, contains half of a [V(4)O(12)](4-) anion, two 2-amino-4-methyl-pyridinium, (2a4mpH)(+), cations and two water mol-ecules. One water mol-ecule is disordered over two sets of sites with equal occupancies and the H atoms for this mol-ecule were not included in the refinement. The cation lies on an inversion center with four tetra-hedral VO(4) units each sharing two vertices, forming an eight-membered ring. In the crystal, the components are linked by inter-molecular N-H⋯O hydrogen bonds, forming a one-dimensional network along [100]. Further stabilization is provided by weak inter-molecular C-H⋯O hydrogen bonds. In addition, π-π stacking inter-actions 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 = 900.39

Triclinic,

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 ▶) 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[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.129

S = 1.05

3932 reflections

250 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.47 e Å−3

Δρmin = −0.33 e Å−3

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) ▶.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811026912/lh5277sup1.cif

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

(C6H9N2)4[V4O12]·4H2O	Z = 1
Mr = 900.39	F(000) = 332
Triclinic, P1	Dx = 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

Oxford Diffraction Xcalibur Nova R diffractometer	3932 independent reflections
graphite	3371 reflections with I > 2σ(I)
Detector resolution: 10.4323 pixels mm-1	Rint = 0.033
ω scans	θmax = 76.0°, θmin = 4.0°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007)	h = −9→9
Tmin = 0.518, Tmax = 1	k = −13→13
8031 measured reflections	l = −14→11

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(Fo2) + (0.085P)2 + 0.0501P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.129	(Δ/σ)max = 0.001
S = 1.05	Δρmax = 0.47 e Å−3
3932 reflections	Δρmin = −0.33 e Å−3
250 parameters

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.

	x	y	z	Uiso*/Ueq	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*

	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)

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)

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···O2iv	0.86	2.13	2.959 (3)	161
N3—H3···O4iv	0.86	1.92	2.767 (3)	167
N4—H4A···O6iv	0.86	2.26	2.995 (4)	143
N4—H4B···O5iii	0.86	2.04	2.883 (4)	165
C2—H2···O1iv	0.93	2.60	3.363 (4)	140
C2—H2···O2iv	0.93	2.64	3.371 (4)	136
C4—H4···O5	0.93	2.52	3.352 (4)	149

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) ; (ii) .