Poly[4,4′-imino­dipyridinium [tetra-μ3-oxido-tetra­oxido-di-μ4-phosphato-κ4O:O′:O′′:O′′′-tetra­vanadium(V)]]

Farnum, G.A.; LaDuca, R.L.

doi:10.1107/S1600536808038348

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page m1602

doi:10.1107/S1600536808038348

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Poly[4,4′-iminodipyridinium [tetra-μ₃-oxido-tetraoxido-di-μ₄-phosphato-κ⁴O:O′:O′′:O′′′-tetravanadium(V)]]

Gregory A. Farnum ^a and Robert L. LaDuca ^a ^*

^aLyman Briggs College, Department of Chemistry, Michigan State University, East Lansing, MI 48825, USA
^*Correspondence e-mail: laduca@msu.edu

(Received 7 November 2008; accepted 17 November 2008; online 22 November 2008)

In the title salt, {(C₁₀H₁₁N₃)[V₄O₈(PO₄)₂]}_n, cubane-like [V₄O₈]⁴⁺ clusters are connected by phosphate anions into anionic [V₄P₂O₁₆]_n²ⁿ⁻ layers. These aggregate into the three-dimensional structure via N—H⋯O hydrogen-bonding mechanisms imparted by 4,4′-iminodipyridinium dications situated between the layers.

Related literature

For a nickel vanadate phase incorporating 4,4′-dipyridylamine, see: LaDuca et al. (2001 ). For a related layered vanadium phosphate solid containing doubly protonated 4,4′-bipyridine cations, see: Shi et al. (2004 ).

Experimental

Crystal data

(C₁₀H₁₁N₃)[V₄O₈(PO₄)₂]
M_r = 694.92
Monoclinic, P 2₁ /n
a = 7.4431 (10) Å
b = 14.524 (2) Å
c = 18.825 (3) Å
β = 94.363 (2)°
V = 2029.1 (5) Å³
Z = 4
Mo Kα radiation
μ = 2.04 mm⁻¹
T = 173 (2) K
0.20 × 0.20 × 0.04 mm

Data collection

Bruker SMART 1K diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.786, T_max = 0.922
21687 measured reflections
4652 independent reflections
3678 reflections with I > 2σ(I)
R_int = 0.047

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.101
S = 1.09
4652 reflections
325 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.03 e Å⁻³
Δρ_min = −0.76 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O10	0.93 (4)	2.14 (4)	2.885 (4)	136 (4)
N1—H1N⋯O9ⁱ	0.93 (4)	2.45 (4)	3.018 (5)	119 (4)
N2—H2N⋯O2ⁱⁱ	0.862 (19)	2.35 (2)	3.195 (4)	166 (4)
N3—H3N⋯O8ⁱⁱⁱ	0.90 (5)	2.02 (5)	2.902 (4)	164 (4)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x+2, -y+1, -z; (iii) $[x+{\script{3\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2003 ); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalMaker (Palmer, 2007 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808038348/tk2326sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808038348/tk2326Isup2.hkl

checkCIF report

Comment top

The kinked and hydrogen-bonding capable imine 4,4'-dipyridylamine has proven useful in the construction of novel mixed metal oxide phases (LaDuca et al., 2001). In an attempt to extend this chemistry into a metal phosphate oxide system, yellow plate-like crystals of the title compound (I) were obtained.

The asymmetric unit of (I) comprises a cluster of four pentavalent V atoms, four terminal O atoms, four triply bridging O atoms, two phosphate anions and an unligated 4,4'-iminodipyridinium dication (Fig. 1). Each V atom is octahedrally coordinated, with three µ₃O atom donors, two O atoms from two different phosphate anions, and one terminal O atom with a formal V=O double bond. The four V=O groups and four µ₃ O atoms form a cubane-type [V₄O₈]⁴⁺ cluster.

Quadruply bridging phosphate anions bridge these cationic clusters into anionic [V₄O₈(PO₄)₂]_n^2n- layers that are situated parallel to the bc-planes (Fig. 2). The phosphate groups bracket rhomboid apertures within the layers, with through-space P···P contact distances of 7.2685 (2) and 7.4431 (2) Å. Adjacent [V₄O₈(PO₄)₂]_n^2n- layers stack in an AB pattern into the 3-D structure by N—H···O hydrogen bonding mediated by the protonated pyridyl-N atoms and the central amine groups of the 4,4'-iminodipyridinium cations situated in the interlamellar regions (Fig. 3).

The overall structure of (I) is very similar to a related phase incorporating doubly protonated 4,4'-bipyridine cations (Shi et al., 2004).

Related literature top

For a nickel vanadate phase incorporating 4,4'-dipyridylamine, see: LaDuca et al. (2001). For a related layered vanadium phosphate solid containing doubly protonated 4,4'-bipyridine cations, see: Shi et al. (2004).

Experimental top

All chemicals were obtained commercially. Vanadium(V) oxide (140 mg, 0.77 mmol) and 4,4'-dipyridylamine (132 mg, 0.77 mmol) and phosphoric acid (526 mg of an 85.5% aqueous solution, 4.56 mmol) were placed into H₂O (10 ml ) in a 23 ml Teflon-lined Parr acid digestion bomb. The bomb was heated at 393 K for 72 h and was then allowed to cool to room temperature. Yellow plates of (I) were obtained along with a reddish-brown amorphous solid.

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalMaker (Palmer, 2007); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Asymmetric unit of (I), showing 50% probability ellipsoids and atom numbering scheme. Most H atom positions are shown as gray sticks. Color code: dark blue V, violet P, light blue N, red O, black C, pink H.
	Fig. 2. A single [V₄P₂O₁₆]_n^2n- layer in (I).
	Fig. 3. Packing diagram illustrating the ABAB layer stacking pattern, which forms the 3-D crystal structure of (I) through hydrogen bonding between the inorganic layers and 4,4'-iminodipyridinium cations.

Poly[4,4'-iminodipyridinium [tetra-µ₃-oxido-tetraoxidodi-µ₄-phosphato- κ⁴O:O':O'':O'''-tetravanadium(V)]] top

Crystal data top

(C₁₀H₁₁N₃)[V₄O₈(PO₄)₂]	F(000) = 1368
M_r = 694.92	D_x = 2.275 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 21687 reflections
a = 7.4431 (10) Å	θ = 1.8–28.2°
b = 14.524 (2) Å	µ = 2.04 mm⁻¹
c = 18.825 (3) Å	T = 173 K
β = 94.363 (2)°	Plate, yellow
V = 2029.1 (5) Å³	0.20 × 0.20 × 0.04 mm
Z = 4

Data collection top

Bruker SMART 1K diffractometer	4652 independent reflections
Radiation source: fine-focus sealed tube	3678 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
ω scans	θ_max = 28.2°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.786, T_max = 0.922	k = −19→19
21687 measured reflections	l = −24→24

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.0382P)² + 6.7132P] where P = (F_o² + 2F_c²)/3
4652 reflections	(Δ/σ)_max = 0.001
325 parameters	Δρ_max = 1.03 e Å⁻³
3 restraints	Δρ_min = −0.76 e Å⁻³

Crystal data top

(C₁₀H₁₁N₃)[V₄O₈(PO₄)₂]	V = 2029.1 (5) Å³
M_r = 694.92	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.4431 (10) Å	µ = 2.04 mm⁻¹
b = 14.524 (2) Å	T = 173 K
c = 18.825 (3) Å	0.20 × 0.20 × 0.04 mm
β = 94.363 (2)°

Data collection top

Bruker SMART 1K diffractometer	4652 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3678 reflections with I > 2σ(I)
T_min = 0.786, T_max = 0.922	R_int = 0.047
21687 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	3 restraints
wR(F²) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 1.03 e Å⁻³
4652 reflections	Δρ_min = −0.76 e Å⁻³
325 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	0.62200 (8)	0.45521 (4)	0.16868 (3)	0.00774 (14)
V2	0.65671 (8)	0.54528 (4)	0.33252 (3)	0.00778 (14)
V3	0.91535 (8)	0.41272 (4)	0.30933 (3)	0.00822 (14)
V4	0.89067 (8)	0.58608 (4)	0.19276 (3)	0.00808 (14)
P1	0.27074 (12)	0.50073 (6)	0.25058 (5)	0.00875 (19)
P2	0.74459 (12)	0.25121 (6)	0.21337 (5)	0.00750 (19)
O1	0.6496 (4)	0.53003 (17)	0.41627 (14)	0.0146 (6)
O2	0.5880 (3)	0.47775 (17)	0.08568 (14)	0.0141 (6)
O3	0.9438 (4)	0.38002 (18)	0.38988 (14)	0.0157 (6)
O4	0.3769 (3)	0.45212 (17)	0.19477 (14)	0.0117 (5)
O5	0.8869 (3)	0.62016 (17)	0.11231 (14)	0.0144 (5)
O6	0.6464 (3)	0.57326 (16)	0.20696 (13)	0.0093 (5)
O7	0.6413 (3)	0.32294 (16)	0.16610 (13)	0.0095 (5)
O8	0.6626 (3)	0.42384 (16)	0.29886 (13)	0.0093 (5)
O9	0.3989 (3)	0.54901 (17)	0.30680 (14)	0.0115 (5)
O10	0.8333 (3)	0.18063 (16)	0.16577 (13)	0.0093 (5)
O11	0.8977 (3)	0.29677 (16)	0.26015 (14)	0.0101 (5)
O12	0.6105 (3)	0.20382 (16)	0.25905 (14)	0.0104 (5)
O13	0.8962 (3)	0.54013 (16)	0.31834 (14)	0.0095 (5)
O14	0.1453 (3)	0.57446 (16)	0.21577 (14)	0.0114 (5)
O15	0.1609 (3)	0.42794 (16)	0.28734 (14)	0.0121 (5)
O16	0.8712 (3)	0.46004 (16)	0.18407 (13)	0.0096 (5)
N1	1.1851 (5)	0.2291 (3)	0.1230 (2)	0.0247 (8)
H1N	1.113 (5)	0.212 (3)	0.1588 (19)	0.030*
N2	1.5138 (4)	0.3207 (2)	−0.02781 (18)	0.0157 (7)
H2N	1.481 (6)	0.370 (2)	−0.050 (2)	0.019*
N3	1.9274 (4)	0.1840 (2)	−0.11738 (19)	0.0161 (7)
H3N	2.016 (6)	0.152 (3)	−0.136 (2)	0.019*
C1	1.1673 (5)	0.3154 (3)	0.0975 (2)	0.0215 (9)
H1	1.0813	0.3544	0.1146	0.026*
C2	1.2741 (5)	0.3461 (3)	0.0469 (2)	0.0174 (8)
H2	1.2593	0.4054	0.0287	0.021*
C3	1.4072 (5)	0.2878 (3)	0.0223 (2)	0.0128 (7)
C4	1.4197 (5)	0.1975 (3)	0.0485 (2)	0.0180 (8)
H4	1.5027	0.1566	0.0317	0.022*
C5	1.3089 (6)	0.1704 (3)	0.0990 (2)	0.0223 (9)
H5	1.3182	0.1110	0.1172	0.027*
C6	1.9152 (5)	0.1759 (3)	−0.0472 (2)	0.0183 (8)
H6	1.9969	0.1389	−0.0205	0.022*
C7	1.7833 (5)	0.2217 (3)	−0.0142 (2)	0.0159 (8)
H7	1.7759	0.2167	0.0347	0.019*
C8	1.6598 (5)	0.2760 (2)	−0.0557 (2)	0.0133 (7)
C9	1.6813 (5)	0.2865 (2)	−0.1276 (2)	0.0128 (7)
H9	1.6058	0.3257	−0.1553	0.015*
C10	1.8149 (5)	0.2386 (2)	−0.1577 (2)	0.0142 (8)
H10	1.8279	0.2440	−0.2063	0.017*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
V1	0.0072 (3)	0.0038 (3)	0.0120 (3)	0.0000 (2)	−0.0006 (2)	−0.0003 (2)
V2	0.0073 (3)	0.0036 (3)	0.0125 (3)	−0.0003 (2)	0.0011 (2)	−0.0002 (2)
V3	0.0071 (3)	0.0039 (3)	0.0134 (3)	0.0005 (2)	−0.0003 (2)	0.0008 (2)
V4	0.0074 (3)	0.0041 (3)	0.0128 (3)	−0.0002 (2)	0.0014 (2)	0.0002 (2)
P1	0.0057 (4)	0.0041 (4)	0.0165 (5)	0.0002 (3)	0.0008 (3)	−0.0012 (3)
P2	0.0070 (4)	0.0027 (4)	0.0130 (4)	0.0005 (3)	0.0012 (3)	−0.0002 (3)
O1	0.0196 (14)	0.0111 (13)	0.0135 (14)	−0.0002 (10)	0.0040 (11)	−0.0003 (10)
O2	0.0155 (13)	0.0113 (13)	0.0151 (14)	0.0003 (10)	−0.0013 (10)	0.0011 (10)
O3	0.0179 (14)	0.0113 (13)	0.0174 (15)	0.0027 (10)	−0.0014 (11)	0.0018 (10)
O4	0.0079 (12)	0.0092 (12)	0.0181 (14)	−0.0003 (10)	0.0007 (10)	−0.0043 (10)
O5	0.0172 (13)	0.0104 (13)	0.0160 (14)	−0.0013 (10)	0.0033 (11)	0.0007 (10)
O6	0.0069 (11)	0.0049 (11)	0.0159 (13)	0.0026 (9)	0.0003 (9)	−0.0015 (9)
O7	0.0102 (12)	0.0027 (11)	0.0155 (14)	0.0013 (9)	−0.0006 (10)	−0.0007 (9)
O8	0.0090 (12)	0.0044 (11)	0.0147 (13)	−0.0019 (9)	0.0021 (10)	−0.0006 (9)
O9	0.0069 (12)	0.0094 (12)	0.0183 (14)	−0.0010 (9)	0.0019 (10)	−0.0049 (10)
O10	0.0094 (12)	0.0039 (11)	0.0148 (14)	0.0007 (9)	0.0020 (10)	0.0005 (9)
O11	0.0084 (11)	0.0036 (11)	0.0180 (14)	0.0005 (9)	−0.0012 (10)	0.0002 (10)
O12	0.0095 (12)	0.0052 (11)	0.0171 (14)	0.0000 (9)	0.0046 (10)	0.0012 (10)
O13	0.0081 (12)	0.0030 (11)	0.0175 (14)	−0.0002 (9)	0.0005 (10)	−0.0013 (10)
O14	0.0076 (11)	0.0043 (11)	0.0229 (15)	−0.0003 (9)	0.0050 (10)	0.0035 (10)
O15	0.0080 (12)	0.0054 (12)	0.0227 (15)	0.0000 (9)	0.0004 (10)	0.0023 (10)
O16	0.0090 (12)	0.0043 (11)	0.0157 (13)	0.0016 (9)	0.0014 (10)	−0.0007 (10)
N1	0.0218 (19)	0.033 (2)	0.0203 (19)	−0.0092 (16)	0.0068 (15)	−0.0002 (16)
N2	0.0182 (16)	0.0098 (15)	0.0197 (18)	0.0021 (13)	0.0064 (13)	0.0039 (13)
N3	0.0143 (16)	0.0121 (16)	0.0224 (19)	−0.0020 (13)	0.0040 (14)	−0.0034 (13)
C1	0.0154 (19)	0.029 (2)	0.021 (2)	−0.0051 (17)	0.0042 (16)	−0.0103 (17)
C2	0.0147 (19)	0.017 (2)	0.021 (2)	−0.0027 (15)	0.0012 (15)	−0.0053 (16)
C3	0.0111 (17)	0.0165 (18)	0.0107 (18)	−0.0032 (15)	0.0006 (13)	−0.0017 (14)
C4	0.0168 (19)	0.018 (2)	0.019 (2)	−0.0013 (15)	0.0033 (16)	0.0012 (16)
C5	0.021 (2)	0.023 (2)	0.023 (2)	−0.0058 (17)	0.0041 (17)	0.0069 (17)
C6	0.0160 (19)	0.0130 (19)	0.025 (2)	−0.0007 (15)	−0.0037 (16)	0.0032 (16)
C7	0.0170 (19)	0.0152 (19)	0.015 (2)	−0.0017 (15)	0.0013 (15)	0.0018 (15)
C8	0.0133 (17)	0.0080 (17)	0.018 (2)	−0.0048 (14)	−0.0003 (15)	−0.0016 (14)
C9	0.0157 (18)	0.0069 (16)	0.0155 (19)	−0.0057 (14)	0.0001 (14)	0.0002 (14)
C10	0.0185 (19)	0.0073 (17)	0.0171 (19)	−0.0077 (14)	0.0030 (15)	−0.0013 (14)

Geometric parameters (Å, º) top

V1—O2	1.598 (3)	P2—O11	1.536 (2)
V1—O16	1.857 (2)	P2—O7	1.538 (2)
V1—O6	1.863 (2)	P2—O10	1.543 (3)
V1—O4	1.925 (3)	N1—C1	1.345 (6)
V1—O7	1.927 (2)	N1—C5	1.357 (6)
V1—O8	2.488 (3)	N1—H1N	0.93 (4)
V2—O1	1.597 (3)	N2—C3	1.364 (5)
V2—O13	1.824 (2)	N2—C8	1.401 (5)
V2—O8	1.876 (2)	N2—H2N	0.862 (19)
V2—O9	1.944 (2)	N3—C6	1.336 (5)
V2—O10ⁱ	1.967 (2)	N3—C10	1.346 (5)
V2—O6	2.394 (3)	N3—H3N	0.90 (5)
V3—O3	1.588 (3)	C1—C2	1.362 (6)
V3—O13	1.865 (2)	C1—H1	0.9300
V3—O8	1.883 (2)	C2—C3	1.408 (5)
V3—O15ⁱⁱ	1.917 (3)	C2—H2	0.9300
V3—O11	1.921 (2)	C3—C4	1.402 (5)
V3—O16	2.454 (3)	C4—C5	1.363 (6)
V4—O5	1.592 (3)	C4—H4	0.9300
V4—O16	1.843 (2)	C5—H5	0.9300
V4—O6	1.867 (2)	C6—C7	1.373 (6)
V4—O14ⁱⁱ	1.919 (2)	C6—H6	0.9300
V4—O12ⁱ	1.936 (2)	C7—C8	1.404 (5)
V4—O13	2.454 (3)	C7—H7	0.9300
P1—O15	1.533 (3)	C8—C9	1.384 (5)
P1—O4	1.534 (3)	C9—C10	1.371 (5)
P1—O14	1.535 (3)	C9—H9	0.9300
P1—O9	1.539 (3)	C10—H10	0.9300
P2—O12	1.529 (3)

O2—V1—O16	103.13 (13)	O12—P2—O11	111.02 (15)
O2—V1—O6	101.14 (12)	O12—P2—O7	108.15 (14)
O16—V1—O6	80.68 (10)	O11—P2—O7	110.88 (13)
O2—V1—O4	99.88 (13)	O12—P2—O10	110.73 (14)
O16—V1—O4	156.29 (11)	O11—P2—O10	106.72 (14)
O6—V1—O4	89.38 (11)	O7—P2—O10	109.35 (14)
O2—V1—O7	100.73 (12)	P1—O4—V1	135.36 (15)
O16—V1—O7	88.06 (10)	V1—O6—V4	95.95 (11)
O6—V1—O7	157.17 (11)	V1—O6—V2	102.74 (11)
O4—V1—O7	93.27 (11)	V4—O6—V2	101.53 (10)
O2—V1—O8	177.48 (11)	P2—O7—V1	134.08 (15)
O16—V1—O8	78.94 (10)	V2—O8—V3	95.40 (11)
O6—V1—O8	77.68 (10)	V2—O8—V1	98.99 (10)
O4—V1—O8	77.93 (10)	V3—O8—V1	99.46 (10)
O7—V1—O8	80.71 (9)	P1—O9—V2	135.01 (16)
O1—V2—O13	104.17 (13)	P2—O10—V2ⁱⁱⁱ	132.20 (15)
O1—V2—O8	101.92 (12)	P2—O11—V3	132.42 (15)
O13—V2—O8	82.17 (10)	P2—O12—V4ⁱⁱⁱ	133.42 (15)
O1—V2—O9	98.26 (13)	V2—O13—V3	97.83 (11)
O13—V2—O9	157.22 (12)	V2—O13—V4	100.65 (10)
O8—V2—O9	89.43 (10)	V3—O13—V4	100.26 (11)
O1—V2—O10ⁱ	97.26 (12)	P1—O14—V4^iv	135.73 (15)
O13—V2—O10ⁱ	90.42 (10)	P1—O15—V3^iv	136.61 (15)
O8—V2—O10ⁱ	160.60 (11)	V4—O16—V1	97.02 (11)
O9—V2—O10ⁱ	90.66 (10)	V4—O16—V3	100.90 (11)
O1—V2—O6	175.87 (11)	V1—O16—V3	101.46 (11)
O13—V2—O6	79.67 (10)	C1—N1—C5	121.2 (4)
O8—V2—O6	79.97 (10)	C1—N1—H1N	118 (3)
O9—V2—O6	78.02 (10)	C5—N1—H1N	121 (3)
O10ⁱ—V2—O6	81.07 (9)	C3—N2—C8	127.3 (3)
O3—V3—O13	102.45 (13)	C3—N2—H2N	118 (3)
O3—V3—O8	100.68 (13)	C8—N2—H2N	114 (3)
O13—V3—O8	80.90 (10)	C6—N3—C10	121.6 (3)
O3—V3—O15ⁱⁱ	100.40 (13)	C6—N3—H3N	117 (3)
O13—V3—O15ⁱⁱ	89.19 (11)	C10—N3—H3N	122 (3)
O8—V3—O15ⁱⁱ	158.20 (11)	N1—C1—C2	120.5 (4)
O3—V3—O11	101.38 (12)	N1—C1—H1	119.7
O13—V3—O11	155.60 (11)	C2—C1—H1	119.7
O8—V3—O11	89.63 (10)	C1—C2—C3	119.7 (4)
O15ⁱⁱ—V3—O11	91.63 (11)	C1—C2—H2	120.1
O3—V3—O16	178.86 (12)	C3—C2—H2	120.1
O13—V3—O16	78.69 (10)	N2—C3—C4	123.0 (3)
O8—V3—O16	79.38 (10)	N2—C3—C2	118.5 (4)
O15ⁱⁱ—V3—O16	79.66 (10)	C4—C3—C2	118.4 (4)
O11—V3—O16	77.48 (10)	C5—C4—C3	119.2 (4)
O5—V4—O16	103.23 (13)	C5—C4—H4	120.4
O5—V4—O6	102.74 (13)	C3—C4—H4	120.4
O16—V4—O6	80.95 (10)	N1—C5—C4	120.8 (4)
O5—V4—O14ⁱⁱ	100.81 (13)	N1—C5—H5	119.6
O16—V4—O14ⁱⁱ	90.13 (10)	C4—C5—H5	119.6
O6—V4—O14ⁱⁱ	156.16 (12)	N3—C6—C7	120.6 (4)
O5—V4—O12ⁱ	99.84 (12)	N3—C6—H6	119.7
O16—V4—O12ⁱ	156.34 (11)	C7—C6—H6	119.7
O6—V4—O12ⁱ	88.95 (10)	C6—C7—C8	118.8 (4)
O14ⁱⁱ—V4—O12ⁱ	90.67 (11)	C6—C7—H7	120.6
O5—V4—O13	177.67 (11)	C8—C7—H7	120.6
O16—V4—O13	79.09 (10)	C9—C8—N2	117.8 (3)
O6—V4—O13	77.30 (10)	C9—C8—C7	119.1 (4)
O14ⁱⁱ—V4—O13	79.32 (10)	N2—C8—C7	123.1 (4)
O12ⁱ—V4—O13	77.83 (10)	C10—C9—C8	119.3 (4)
O15—P1—O4	108.18 (14)	C10—C9—H9	120.3
O15—P1—O14	110.24 (14)	C8—C9—H9	120.3
O4—P1—O14	110.92 (15)	N3—C10—C9	120.4 (4)
O15—P1—O9	109.13 (15)	N3—C10—H10	119.8
O4—P1—O9	110.85 (14)	C9—C10—H10	119.8
O14—P1—O9	107.51 (14)

O15—P1—O4—V1	−133.2 (2)	O8—V3—O11—P2	15.9 (2)
O14—P1—O4—V1	105.7 (2)	O15ⁱⁱ—V3—O11—P2	−142.4 (2)
O2—V1—O4—P1	−125.5 (2)	O16—V3—O11—P2	−63.3 (2)
O16—V1—O4—P1	40.4 (4)	O11—P2—O12—V4ⁱⁱⁱ	−81.1 (2)
O6—V1—O4—P1	−24.3 (2)	O7—P2—O12—V4ⁱⁱⁱ	157.06 (19)
O7—V1—O4—P1	133.0 (2)	O10—P2—O12—V4ⁱⁱⁱ	37.3 (3)
O8—V1—O4—P1	53.2 (2)	O1—V2—O13—V3	85.66 (14)
O2—V1—O6—V4	−84.30 (13)	O8—V2—O13—V3	−14.73 (11)
O16—V1—O6—V4	17.36 (11)	O9—V2—O13—V3	−84.0 (3)
O4—V1—O6—V4	175.75 (12)	O10ⁱ—V2—O13—V3	−176.74 (12)
O7—V1—O6—V4	78.8 (3)	O6—V2—O13—V3	−95.89 (11)
O8—V1—O6—V4	97.97 (11)	O1—V2—O13—V4	−172.29 (11)
O2—V1—O6—V2	172.42 (11)	O8—V2—O13—V4	87.33 (11)
O16—V1—O6—V2	−85.91 (11)	O9—V2—O13—V4	18.0 (3)
O4—V1—O6—V2	72.48 (11)	O10ⁱ—V2—O13—V4	−74.69 (10)
O7—V1—O6—V2	−24.5 (3)	O6—V2—O13—V4	6.16 (8)
O8—V1—O6—V2	−5.31 (8)	O3—V3—O13—V2	−84.30 (14)
O5—V4—O6—V1	84.15 (13)	O8—V3—O13—V2	14.72 (11)
O16—V4—O6—V1	−17.49 (11)	O15ⁱⁱ—V3—O13—V2	175.22 (12)
O14ⁱⁱ—V4—O6—V1	−86.7 (3)	O11—V3—O13—V2	83.1 (3)
O12ⁱ—V4—O6—V1	−176.00 (12)	O16—V3—O13—V2	95.61 (11)
O13—V4—O6—V1	−98.25 (11)	O3—V3—O13—V4	173.31 (11)
O5—V4—O6—V2	−171.52 (11)	O8—V3—O13—V4	−87.67 (10)
O16—V4—O6—V2	86.85 (11)	O15ⁱⁱ—V3—O13—V4	72.83 (11)
O14ⁱⁱ—V4—O6—V2	17.6 (3)	O11—V3—O13—V4	−19.3 (3)
O12ⁱ—V4—O6—V2	−71.67 (11)	O16—V3—O13—V4	−6.78 (8)
O13—V4—O6—V2	6.09 (8)	O16—V4—O13—V2	−91.04 (12)
O1—V2—O6—V1	−110.6 (16)	O6—V4—O13—V2	−7.98 (11)
O13—V2—O6—V1	90.76 (11)	O14ⁱⁱ—V4—O13—V2	176.74 (12)
O8—V2—O6—V1	6.99 (11)	O12ⁱ—V4—O13—V2	83.71 (11)
O9—V2—O6—V1	−84.57 (11)	O16—V4—O13—V3	9.03 (11)
O10ⁱ—V2—O6—V1	−177.17 (12)	O6—V4—O13—V3	92.09 (11)
O13—V2—O6—V4	−8.13 (11)	O14ⁱⁱ—V4—O13—V3	−83.19 (11)
O8—V2—O6—V4	−91.91 (11)	O12ⁱ—V4—O13—V3	−176.22 (12)
O9—V2—O6—V4	176.53 (12)	O15—P1—O14—V4^iv	−13.6 (3)
O10ⁱ—V2—O6—V4	83.94 (11)	O4—P1—O14—V4^iv	106.2 (2)
O12—P2—O7—V1	104.0 (2)	O9—P1—O14—V4^iv	−132.5 (2)
O11—P2—O7—V1	−18.0 (3)	O4—P1—O15—V3^iv	−129.8 (2)
O10—P2—O7—V1	−135.4 (2)	O14—P1—O15—V3^iv	−8.3 (3)
O2—V1—O7—P2	149.9 (2)	O9—P1—O15—V3^iv	109.6 (2)
O16—V1—O7—P2	46.9 (2)	O5—V4—O16—V1	−83.47 (14)
O6—V1—O7—P2	−13.3 (4)	O6—V4—O16—V1	17.59 (11)
O4—V1—O7—P2	−109.4 (2)	O14ⁱⁱ—V4—O16—V1	175.38 (12)
O8—V1—O7—P2	−32.2 (2)	O12ⁱ—V4—O16—V1	83.4 (3)
O1—V2—O8—V3	−88.41 (13)	O13—V4—O16—V1	96.29 (11)
O13—V2—O8—V3	14.51 (11)	O5—V4—O16—V3	173.38 (11)
O9—V2—O8—V3	173.26 (12)	O6—V4—O16—V3	−85.56 (11)
O10ⁱ—V2—O8—V3	82.9 (3)	O14ⁱⁱ—V4—O16—V3	72.23 (11)
O6—V2—O8—V3	95.33 (10)	O12ⁱ—V4—O16—V3	−19.7 (3)
O1—V2—O8—V1	171.10 (11)	O13—V4—O16—V3	−6.86 (8)
O13—V2—O8—V1	−85.99 (11)	O2—V1—O16—V4	81.73 (13)
O9—V2—O8—V1	72.77 (10)	O6—V1—O16—V4	−17.64 (11)
O10ⁱ—V2—O8—V1	−17.6 (4)	O4—V1—O16—V4	−84.0 (3)
O6—V2—O8—V1	−5.16 (8)	O7—V1—O16—V4	−177.70 (12)
O3—V3—O8—V2	86.84 (13)	O8—V1—O16—V4	−96.79 (11)
O13—V3—O8—V2	−14.23 (11)	O2—V1—O16—V3	−175.60 (11)
O15ⁱⁱ—V3—O8—V2	−78.2 (3)	O6—V1—O16—V3	85.03 (11)
O11—V3—O8—V2	−171.65 (11)	O4—V1—O16—V3	18.7 (3)
O16—V3—O8—V2	−94.32 (10)	O7—V1—O16—V3	−75.03 (11)
O3—V3—O8—V1	−173.09 (11)	O8—V1—O16—V3	5.88 (8)
O13—V3—O8—V1	85.84 (10)	O13—V3—O16—V4	9.06 (11)
O15ⁱⁱ—V3—O8—V1	21.9 (3)	O8—V3—O16—V4	91.79 (11)
O11—V3—O8—V1	−71.58 (10)	O15ⁱⁱ—V3—O16—V4	−82.19 (11)
O16—V3—O8—V1	5.75 (8)	O11—V3—O16—V4	−176.21 (12)
O16—V1—O8—V2	89.44 (11)	O13—V3—O16—V1	−90.50 (12)
O6—V1—O8—V2	6.69 (10)	O8—V3—O16—V1	−7.77 (11)
O4—V1—O8—V2	−85.33 (11)	O15ⁱⁱ—V3—O16—V1	178.25 (12)
O7—V1—O8—V2	179.27 (12)	O11—V3—O16—V1	84.23 (11)
O16—V1—O8—V3	−7.62 (10)	C5—N1—C1—C2	−0.2 (6)
O6—V1—O8—V3	−90.37 (11)	N1—C1—C2—C3	−1.5 (6)
O4—V1—O8—V3	177.60 (12)	C8—N2—C3—C4	−6.6 (6)
O7—V1—O8—V3	82.21 (11)	C8—N2—C3—C2	175.7 (4)
O15—P1—O9—V2	106.2 (2)	C1—C2—C3—N2	−179.2 (4)
O4—P1—O9—V2	−12.8 (3)	C1—C2—C3—C4	3.0 (5)
O14—P1—O9—V2	−134.2 (2)	N2—C3—C4—C5	179.5 (4)
O1—V2—O9—P1	−129.9 (2)	C2—C3—C4—C5	−2.8 (6)
O13—V2—O9—P1	40.0 (4)	C1—N1—C5—C4	0.3 (6)
O8—V2—O9—P1	−27.9 (2)	C3—C4—C5—N1	1.2 (6)
O10ⁱ—V2—O9—P1	132.7 (2)	C10—N3—C6—C7	1.8 (6)
O6—V2—O9—P1	51.9 (2)	N3—C6—C7—C8	0.9 (6)
O12—P2—O10—V2ⁱⁱⁱ	−14.4 (2)	C3—N2—C8—C9	141.3 (4)
O11—P2—O10—V2ⁱⁱⁱ	106.6 (2)	C3—N2—C8—C7	−38.6 (6)
O7—P2—O10—V2ⁱⁱⁱ	−133.43 (19)	C6—C7—C8—C9	−4.0 (5)
O12—P2—O11—V3	−82.1 (2)	C6—C7—C8—N2	175.9 (3)
O7—P2—O11—V3	38.1 (3)	N2—C8—C9—C10	−175.4 (3)
O10—P2—O11—V3	157.15 (19)	C7—C8—C9—C10	4.5 (5)
O3—V3—O11—P2	116.7 (2)	C6—N3—C10—C9	−1.3 (5)
O13—V3—O11—P2	−50.7 (4)	C8—C9—C10—N3	−1.9 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O10	0.93 (4)	2.14 (4)	2.885 (4)	136 (4)
N1—H1N···O9ⁱⁱⁱ	0.93 (4)	2.45 (4)	3.018 (5)	119 (4)
N2—H2N···O2^v	0.86 (2)	2.35 (2)	3.195 (4)	166 (4)
N3—H3N···O8^vi	0.90 (5)	2.02 (5)	2.902 (4)	164 (4)

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

Experimental details

Crystal data
Chemical formula	(C₁₀H₁₁N₃)[V₄O₈(PO₄)₂]
M_r	694.92
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	173
a, b, c (Å)	7.4431 (10), 14.524 (2), 18.825 (3)
β (°)	94.363 (2)
V (Å³)	2029.1 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.04
Crystal size (mm)	0.20 × 0.20 × 0.04

Data collection
Diffractometer	Bruker SMART 1K diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.786, 0.922
No. of measured, independent and observed [I > 2σ(I)] reflections	21687, 4652, 3678
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.665

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.101, 1.09
No. of reflections	4652
No. of parameters	325
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)	1.03, −0.76

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), CrystalMaker (Palmer, 2007).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O10	0.93 (4)	2.14 (4)	2.885 (4)	136 (4)
N1—H1N···O9ⁱ	0.93 (4)	2.45 (4)	3.018 (5)	119 (4)
N2—H2N···O2ⁱⁱ	0.862 (19)	2.35 (2)	3.195 (4)	166 (4)
N3—H3N···O8ⁱⁱⁱ	0.90 (5)	2.02 (5)	2.902 (4)	164 (4)

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

Acknowledgements

We gratefully acknowledge the donors of the American Chemical Society Petroleum Research Fund for funding this work.

References

Bruker (2003). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
LaDuca, R. L., Rarig, R. S. & Zubieta, J. (2001). Inorg. Chem. 40, 607–612. Web of Science CSD CrossRef PubMed CAS Google Scholar
Palmer, D. (2007). CrystalMaker. CrystalMaker Software Ltd, Bicester, Oxfordshire, England. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shi, F.-N., Paz, F. A. A., Rocha, J., Klinowski, Ja. & Trindade, T. (2004). Eur. J. Inorg. Chem. pp.3031–3037. CrossRef Google Scholar

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