Nonapiperidinium monohydrogen deca­vanadate tetra­nitrate

Graia, M.; Ksiksi, R.; Driss, A.

doi:10.1107/S1600536809026555

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Pages m953-m954

doi:10.1107/S1600536809026555

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Nonapiperidinium monohydrogen decavanadate tetranitrate

Mohsen Graia,^a ^* Regaya Ksiksi ^a and Ahmed Driss ^a

^aLaboratoire de Matériaux et de Cristallochimie, Faculté des Sciences de Tunis, Université de Tunis–El Manar, 2092 El Manar II Tunis, Tunisia
^*Correspondence e-mail: mohseng2002@yahoo.fr

(Received 17 May 2009; accepted 7 July 2009; online 18 July 2009)

The title compound, (C₅H₁₂N)₉[HV₁₀O₂₈](NO₃)₄, contains a monoprotonated decavanadate polyanion which lies on an inversion center. All the piperidinium cations adopt chair conformations. In the crystal structure, intermolecular N—H⋯O hydrogen bonds form chains along [001]. As well as half of a polyanion, the asymmetric unit contains one full and two half-occupancy nitrate ions and four full occupancy and one half-occupancy piperidinium cations; the half-occupancy piperidinium cation is disordered over two general sites with occupancies of 0.32 and 0.18, and is, in turn, disordered over an inversion center.

Related literature

For the biological activity of vanadium, see: Crans (1994 ); Elvingson et al. (1996 ). For its interactions with nitrogen compounds such as proteins and amino acids and its role in enzymatic reactions, see: Correia et al. (2004 ). For related structures, see: Ferreira da Silva et al. (2003 ); Maciejewska et al. (2003 ); Arrieta (1992 ); Wang et al. (2008 ); Wery et al. (1996 ).

Experimental

Crystal data

(C₅H₁₂N)₉[HV₁₀O₂₈](NO₃)₄
M_r = 1981.85
Triclinic, $[P \overline 1]$
a = 11.593 (2) Å
b = 13.290 (2) Å
c = 14.676 (2) Å
α = 105.858 (2)°
β = 110.335 (2)°
γ = 92.457 (2)°
V = 2015.6 (5) Å³
Z = 1
Mo Kα radiation
μ = 1.20 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.14 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.72, T_max = 0.90 (expected range = 0.676–0.846)
9193 measured reflections
8755 independent reflections
6099 reflections with I > 2σ(I)
R_int = 0.047
2 standard reflections frequency: 120 min intensity decay: 2%

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.118
S = 1.04
8755 reflections
598 parameters
262 restraints
H-atom parameters constrained
Δρ_max = 0.71 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
NC1—HC1A⋯O8	0.90	1.80	2.693 (3)	174
NC1—HC1B⋯ON6Aⁱ	0.90	1.95	2.829 (8)	164
NC1—HC1B⋯ON6B	0.90	2.05	2.876 (9)	153
NC1—HC1B⋯ON5Aⁱ	0.90	2.48	3.214 (12)	139
NC1—HC1B⋯ON5B	0.90	2.54	3.355 (13)	151
NC2—HC2A⋯ON4A	0.90	1.95	2.824 (7)	164
NC2—HC2A⋯ON4Bⁱ	0.90	2.05	2.909 (8)	159
NC2—HC2A⋯ON5Bⁱ	0.90	2.50	3.280 (13)	145
NC2—HC2A⋯ON5A	0.90	2.56	3.251 (12)	134
NC2—HC2B⋯O4	0.90	1.85	2.746 (3)	174
NC3—HC3A⋯O5ⁱⁱ	0.90	1.85	2.749 (4)	175
NC3—HC3B⋯ON3	0.90	2.06	2.885 (5)	152
NC3—HC3B⋯ON2	0.90	2.31	3.095 (5)	145
NC4—HC4A⋯O7	0.90	1.82	2.716 (4)	172
NC4—HC4B⋯ON3	0.90	2.16	2.954 (6)	147
NC4—HC4B⋯ON1	0.90	2.26	3.060 (6)	148
NC5—HC5A⋯O6	0.90	2.40	3.248 (17)	158
NC6—HC6A⋯ON4B	0.90	2.12	2.92 (2)	147
NC6—HC6B⋯O6ⁱ	0.90	1.92	2.80 (2)	166
Symmetry codes: (i) -x+1, -y+1, -z; (ii) -x+1, -y+1, -z+1.

Data collection: CAD-4 EXPRESS (Duisenberg, 1992 ; Macíček & Yordanov, 1992 ); cell refinement: CAD-4 EXPRESS; data reduction: MolEN (Fair, 1990 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1998 ); software used to prepare material for publication: publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809026555/lh2828sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809026555/lh2828Isup2.hkl

checkCIF report

Comment top

Vanadium is a rare metal with exceptional properties. Both its cationic and anionic forms can interact with biomolecules, and its coordination chemistry plays a predominant role in these interactions. Among several biological functions of vanadium, many important therapeutic effects have been described, including hormonal, cardiovascular, anticarcinogenic, sugar lowering activities (Elvingson et al., 1996; Crans, 1994). Because of the physiological relevance of vanadium, a better understanding of its complexation behavior with organic ligands is of vital interest. The interactions of this metal with nitrogen compounds like proteins and amino acids and its role in enzymatic reactions have been studied extensively (Correia et al., 2004). Herein we present the crystal structure of the title compound (I).

The asymmetric unit of (I) contains one half of a monoprotonated decavanadate polyanion [HV₁₀O₂₈]^5-, 4.5 piperidinum cations (C₅H₁₂N⁺), and 2 NO₃^-anions. The formula unit is generated by a crystallographic inversion centre. The [HV₁₀O₂₈]^5- polyanion is composed of ten distorted VO₆ edge-sharing octahedra and is best described as cubic close-packing of oxygen ions, with the octahedral holes filled by vanadium ions. Each VO₆ octahedron is considerably distorted, with bond angles at the V atoms ranging from 1.602 (2) to 2.345 (2) Å. The V—O distance depends upon the type of oxo ligands: V=O_t bond lengths to the terminal oxo O atoms vary from 1.603 (3) to 1.608 (2) Å, V—O_2b bond lengths to the O atoms bridging two V atoms vary from 1.693 (3) to 2.059 (3) Å, V—O_3b bond lengths to the O atoms bridging three V atoms vary from 1.914 (2) to 2.067 (3) Å and V—O_6b bond lengths to the O atoms shared between six V atoms range 2.081 (3) to 2.345 (3) Å. The V—V distances are in the range 3.091 (4) to 3.286 (4) Å. The V—O bond and angles of the [HV₁₀O₂₈]^6- are in agreement with those reported in literature (Ferreira da Silva et al., 2003; Maciejewska et al., 2003; Arrieta, 1992).

The organic groups are present as cations, C₅H₁₂N⁺. These piperidinium rings adopt chair conformation (Fig. 2). The bond lengths of C–N and C–C are in the range of 1.468 (6) – 1.502 (7) Å and 1.469 (8) – 1.543 (7) Å, respectively. The C–C–C, C—C—N and C—N—C angles are in the range of 106 (1) – 113 (1) Å, 107 (2) – 111.7 (4) Å and 112.1 (4) – 114.1 (1) Å, respectively. These values are in agreement with those reported in literature (Wang et al., 2008). As a result, we found one of the piperidinium cations in special position; this cation is disordred with a ca 16:9 occupancy ratio for its (NC5, C₅H₁₂N⁺) and (NC6, C₅H₁₂N⁺) components.

Similarly, we identified one disordered nitrate group, with a similar occupancy ratio for components N2O₃A and N2O₃B. The central N atom of N1O₃, N2O₃A and of N2O₃B nitrate groups is close to coplanarity with the three attached O atoms. The largest deviation from the plane being 0.0004 Å, 0.0062 and 0.0064 respectively. The N–O bond distances and O–N–O angles are in agreement with in the nitrate unit.

The most important feature of this crystal is the presence of N–H···O, hydrogen bonds with D···A distances ranging from 2.693 (3) to 3.355 (13) Å. These interactions connect the various fragments into a supramolecular structure. In fact, it is noted that piperidinium C₅H₁₂N⁺cations are located around the [HV₁₀O₂₈] (Fig. 2). Each [HV₁₀O₂₈]^5- cluster is surrounded by ten C₅H₁₂N⁺ cations. The N atoms of the organic cations are directing towards the doubly bridging O atoms of the cluster anion there by forming strong H-bonding. The NO₃^-anions contribute to the cohesion of the structure by hydrogen bonds (Fig 2). In fact, as can be seen from the packing diagram (Fig. 2), there are intermolecular hydrogen bonds between the nitrato O atoms and the N–H group of the piperidinium C₅H₁₂N⁺ cations.

Related literature top

For the biological activity of vanadium, see: Crans (1994); Elvingson et al. (1996). For its interactions with nitrogen compounds such as proteins and amino acids and its role in enzymatic reactions, see: Correia et al. (2004). For related structures, see: Ferreira da Silva et al. (2003); Maciejewska et al. (2003); Arrieta (1992); Wang et al. (2008); Wery et al. (1996).

Experimental top

The title compound was prepared by the reaction of vanadium (V) oxide (0.68 g, 3.74 mmol, Fluka, 99,9%), piperidin (1.72 g, 20.23 mmol, Fluka, > 99%), zinc nitrate (1.12 g, 3.77 mmol,Fluka, > 99%) and oxalic acid (1.23 g, 9.77 mmol, Prolabo, > 98%), dissolved in 40 ml ofdistilled water. Orange single crystals were obtained after six days from by slow evaporation at room temperature.

Computing details top

Data collection: CAD-4 EXPRESS (Duisenberg, 1992; Macíček & Yordanov, 1992); cell refinement: CAD-4 EXPRESS (Duisenberg, 1992; Macíček & Yordanov, 1992); data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1998); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top

	Fig. 1. View of the decavanadate unit of the title compound. Thermal ellipsoids are drawn at 35% probability. The purple spheres are vanadium atoms and the red spheres are oxygen atoms.
	Fig. 2. Part of the crystal structure of the title compound. The purple spheres are vanadium atoms, the red spheres are oxygen atoms, the cyan spheres are nitrogen atoms, the green spheres are carbon atoms and the white spheres represent hydrogen atoms. Hydrogen bonds are shown as dashed lines.

Nonapiperidinium monohydrogen decavanadate tetranitrate top

Crystal data top

(C₅H₁₂N)₉[HV₁₀O₂₈](NO₃)₄	Z = 1
M_r = 1981.85	F(000) = 1020
Triclinic, P1	D_x = 1.633 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.593 (2) Å	Cell parameters from 25 reflections
b = 13.290 (2) Å	θ = 11.8–15.2°
c = 14.676 (2) Å	µ = 1.20 mm⁻¹
α = 105.858 (2)°	T = 293 K
β = 110.335 (2)°	Hexagone, orange
γ = 92.457 (2)°	0.30 × 0.25 × 0.14 mm
V = 2015.6 (5) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	6099 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.047
Graphite monochromator	θ_max = 27.0°, θ_min = 2.3°
ω/2θ scans	h = 0→14
Absorption correction: ψ scan (North et al., 1968)	k = −16→16
T_min = 0.72, T_max = 0.90	l = −18→17
9193 measured reflections	2 standard reflections every 120 min
8755 independent reflections	intensity decay: 2%

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.118	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0517P)² + 1.3683P] where P = (F_o² + 2F_c²)/3
8755 reflections	(Δ/σ)_max = 0.001
598 parameters	Δρ_max = 0.71 e Å⁻³
262 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

(C₅H₁₂N)₉[HV₁₀O₂₈](NO₃)₄	γ = 92.457 (2)°
M_r = 1981.85	V = 2015.6 (5) Å³
Triclinic, P1	Z = 1
a = 11.593 (2) Å	Mo Kα radiation
b = 13.290 (2) Å	µ = 1.20 mm⁻¹
c = 14.676 (2) Å	T = 293 K
α = 105.858 (2)°	0.30 × 0.25 × 0.14 mm
β = 110.335 (2)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	6099 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.047
T_min = 0.72, T_max = 0.90	2 standard reflections every 120 min
9193 measured reflections	intensity decay: 2%
8755 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	262 restraints
wR(F²) = 0.118	H-atom parameters constrained
S = 1.04	Δρ_max = 0.71 e Å⁻³
8755 reflections	Δρ_min = −0.32 e Å⁻³
598 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	Occ. (<1)
V1	0.55004 (5)	0.32924 (4)	0.57070 (4)	0.03398 (13)
V2	0.65119 (4)	0.53839 (4)	0.54702 (4)	0.03033 (12)
V3	0.53337 (5)	0.33546 (4)	0.35568 (4)	0.03371 (13)
V4	0.62554 (5)	0.54954 (4)	0.33350 (4)	0.03911 (14)
V5	0.34440 (5)	0.46252 (4)	0.24253 (4)	0.03735 (14)
O1	0.64328 (19)	0.38796 (15)	0.50197 (15)	0.0347 (5)
O2	0.75038 (19)	0.56505 (17)	0.66911 (15)	0.0381 (5)
O3	0.73307 (19)	0.56874 (17)	0.48006 (16)	0.0398 (5)
O4	0.63901 (19)	0.40224 (17)	0.31868 (16)	0.0402 (5)
O5	0.5792 (2)	0.67820 (17)	0.38378 (16)	0.0405 (5)
O6	0.4801 (2)	0.50774 (18)	0.21948 (15)	0.0442 (5)
O7	0.39219 (19)	0.33201 (16)	0.24371 (15)	0.0384 (5)
O8	0.33299 (19)	0.60716 (17)	0.30494 (15)	0.0388 (5)
O9	0.2324 (2)	0.4357 (2)	0.13345 (16)	0.0544 (6)
O10	0.7271 (2)	0.5810 (2)	0.29078 (19)	0.0591 (7)
O11	0.5568 (2)	0.21462 (17)	0.32664 (17)	0.0479 (6)
O12	0.5744 (2)	0.20838 (17)	0.54415 (18)	0.0493 (6)
O13	0.50819 (17)	0.49809 (15)	0.59153 (14)	0.0329 (4)
O14	0.41649 (19)	0.32453 (16)	0.43204 (15)	0.0377 (5)
NO1	0.0877 (6)	0.0576 (4)	0.2869 (3)	0.0928 (15)
ON1	0.0314 (4)	0.0356 (4)	0.1946 (3)	0.1313 (17)
ON2	0.0455 (4)	0.0246 (3)	0.3412 (3)	0.1027 (12)
ON3	0.1908 (5)	0.1153 (3)	0.3274 (3)	0.1214 (17)
NO2A	0.7294 (9)	0.2038 (8)	−0.0230 (6)	0.067 (4)	0.50
ON4A	0.6735 (8)	0.1750 (5)	0.0262 (5)	0.081 (2)	0.50
ON5A	0.8303 (11)	0.2627 (12)	0.0230 (8)	0.118 (6)	0.50
ON6A	0.6819 (10)	0.1762 (6)	−0.1164 (5)	0.095 (3)	0.50
NO2B	0.3155 (9)	0.7704 (8)	0.0289 (7)	0.069 (3)	0.50
ON4B	0.3787 (7)	0.7673 (7)	−0.0239 (5)	0.088 (2)	0.50
ON5B	0.2040 (8)	0.7800 (15)	−0.0057 (10)	0.111 (5)	0.50
ON6B	0.3636 (8)	0.7675 (8)	0.1167 (5)	0.097 (3)	0.50
NC1	0.1785 (3)	0.7091 (2)	0.1898 (2)	0.0501 (7)
HC1A	0.2326	0.6740	0.2251	0.060*
HC1B	0.2150	0.7357	0.1546	0.060*
C11	0.1520 (4)	0.7977 (3)	0.2628 (3)	0.0617 (10)
H11A	0.0981	0.8390	0.2259	0.074*
H11B	0.2291	0.8438	0.3095	0.074*
C12	0.0900 (4)	0.7552 (4)	0.3221 (4)	0.0780 (13)
H12A	0.0693	0.8134	0.3672	0.094*
H12B	0.1472	0.7196	0.3639	0.094*
C13	−0.0280 (4)	0.6778 (4)	0.2506 (5)	0.0964 (17)
H13A	−0.0632	0.6474	0.2899	0.116*
H13B	−0.0890	0.7150	0.2142	0.116*
C14	0.0021 (4)	0.5903 (4)	0.1746 (4)	0.0895 (16)
H14A	0.0558	0.5485	0.2109	0.107*
H14B	−0.0743	0.5440	0.1268	0.107*
C15	0.0651 (4)	0.6333 (3)	0.1166 (3)	0.0719 (12)
H15A	0.0878	0.5758	0.0723	0.086*
H15B	0.0087	0.6690	0.0743	0.086*
NC2	0.7900 (3)	0.2878 (2)	0.2361 (2)	0.0481 (7)
HC2A	0.7548	0.2636	0.1675	0.058*
HC2B	0.7356	0.3223	0.2592	0.058*
C21	0.8144 (4)	0.1962 (3)	0.2766 (3)	0.0592 (10)
H21A	0.8686	0.1558	0.2485	0.071*
H21B	0.7367	0.1501	0.2561	0.071*
C22	0.8749 (4)	0.2352 (3)	0.3914 (3)	0.0674 (11)
H22A	0.8949	0.1753	0.4166	0.081*
H22B	0.8167	0.2687	0.4193	0.081*
C23	0.9934 (4)	0.3139 (3)	0.4281 (4)	0.0705 (12)
H23A	1.0562	0.2785	0.4080	0.085*
H23B	1.0257	0.3423	0.5020	0.085*
C24	0.9644 (4)	0.4038 (3)	0.3813 (3)	0.0666 (11)
H24A	0.9089	0.4438	0.4079	0.080*
H24B	1.0409	0.4512	0.4010	0.080*
C25	0.9051 (4)	0.3631 (3)	0.2668 (3)	0.0665 (11)
H25A	0.8849	0.4217	0.2396	0.080*
H25B	0.9626	0.3277	0.2392	0.080*
NC3	0.2756 (3)	0.1265 (2)	0.5400 (2)	0.0582 (8)
HC3A	0.3266	0.1885	0.5636	0.070*
HC3B	0.2239	0.1196	0.4758	0.070*
C31	0.3514 (4)	0.0395 (3)	0.5372 (3)	0.0701 (12)
H31A	0.3995	0.0433	0.4955	0.084*
H31B	0.2971	−0.0282	0.5069	0.084*
C32	0.4371 (4)	0.0478 (4)	0.6429 (4)	0.0754 (13)
H32A	0.4980	0.1113	0.6696	0.091*
H32B	0.4814	−0.0126	0.6407	0.091*
C33	0.3668 (5)	0.0516 (4)	0.7133 (4)	0.0879 (15)
H33A	0.4257	0.0642	0.7825	0.105*
H33B	0.3151	−0.0162	0.6927	0.105*
C34	0.2857 (5)	0.1383 (4)	0.7110 (4)	0.0842 (14)
H34A	0.2358	0.1340	0.7512	0.101*
H34B	0.3385	0.2067	0.7418	0.101*
C35	0.2012 (4)	0.1296 (4)	0.6038 (4)	0.0799 (14)
H35A	0.1405	0.0658	0.5758	0.096*
H35B	0.1568	0.1898	0.6045	0.096*
NC4	0.2310 (4)	0.1475 (3)	0.1487 (3)	0.0796 (11)
HC4A	0.2795	0.2109	0.1827	0.096*
HC4B	0.1871	0.1355	0.1856	0.096*
C41	0.1427 (5)	0.1505 (4)	0.0468 (5)	0.111 (2)
H41A	0.0856	0.0843	0.0122	0.133*
H41B	0.0943	0.2073	0.0568	0.133*
C42	0.2114 (6)	0.1669 (5)	−0.0166 (5)	0.114 (2)
H42A	0.2619	0.2364	0.0150	0.137*
H42B	0.1526	0.1651	−0.0830	0.137*
C43	0.2948 (6)	0.0835 (5)	−0.0303 (4)	0.119 (2)
H43A	0.3442	0.1007	−0.0669	0.143*
H43B	0.2441	0.0150	−0.0701	0.143*
C44	0.3815 (5)	0.0786 (5)	0.0750 (4)	0.0982 (17)
H44A	0.4276	0.0200	0.0655	0.118*
H44B	0.4409	0.1434	0.1102	0.118*
C45	0.3101 (5)	0.0651 (4)	0.1384 (4)	0.0896 (16)
H45A	0.2585	−0.0038	0.1075	0.108*
H45B	0.3676	0.0678	0.2056	0.108*
NC5	0.4959	0.6247 (10)	0.0557 (12)	0.074 (4)	0.32
HC5A	0.4993	0.6110	0.1133	0.089*	0.32
HC5B	0.4890	0.6935	0.0644	0.089*	0.32
C51	0.3848	0.5597 (14)	−0.0301 (17)	0.070 (6)	0.32
H51A	0.3801	0.5738	−0.0926	0.084*	0.32
H51B	0.3104	0.5774	−0.0173	0.084*	0.32
C52	0.3927	0.4430 (15)	−0.0415 (18)	0.054 (5)	0.32
H52A	0.3941	0.4273	0.0196	0.065*	0.32
H52B	0.3219	0.3988	−0.0993	0.065*	0.32
C53	0.5118	0.4239 (9)	−0.0582 (11)	0.051 (3)	0.32
H53A	0.5073	0.4388	−0.1203	0.061*	0.32
H53B	0.5198	0.3497	−0.0678	0.061*	0.32
C54	0.6266	0.4906 (16)	0.0293 (16)	0.063 (5)	0.32
H54A	0.6338	0.4759	0.0920	0.075*	0.32
H54B	0.7008	0.4749	0.0151	0.075*	0.32
C55	0.6128	0.6047 (15)	0.0395 (16)	0.068 (5)	0.32
H55A	0.6830	0.6503	0.0968	0.081*	0.32
H55B	0.6108	0.6200	−0.0219	0.081*	0.32
NC6	0.493 (2)	0.5751 (14)	−0.0322 (17)	0.061 (5)	0.18
HC6A	0.4901	0.6450	−0.0147	0.073*	0.18
HC6B	0.4911	0.5541	−0.0964	0.073*	0.18
C61	0.383 (2)	0.519 (2)	−0.029 (3)	0.067 (8)	0.18
H61A	0.3071	0.5352	−0.0734	0.080*	0.18
H61B	0.3835	0.5401	0.0403	0.080*	0.18
C62	0.389 (3)	0.402 (2)	−0.064 (2)	0.055 (7)	0.18
H62A	0.3159	0.3613	−0.0652	0.066*	0.18
H62B	0.3897	0.3813	−0.1321	0.066*	0.18
C63	0.505 (3)	0.3777 (17)	0.0089 (19)	0.061 (5)	0.18
H63A	0.5076	0.3023	−0.0104	0.073*	0.18
H63B	0.5062	0.4006	0.0779	0.073*	0.18
C64	0.617 (3)	0.438 (2)	0.003 (3)	0.072 (8)	0.18
H64A	0.6942	0.4223	0.0473	0.087*	0.18
H64B	0.6150	0.4160	−0.0661	0.087*	0.18
C65	0.611 (2)	0.555 (2)	0.038 (3)	0.058 (9)	0.18
H65A	0.6132	0.5762	0.1071	0.070*	0.18
H65B	0.6811	0.5952	0.0359	0.070*	0.18

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
V1	0.0360 (3)	0.0331 (3)	0.0323 (3)	0.0080 (2)	0.0090 (2)	0.0139 (2)
V2	0.0313 (3)	0.0305 (3)	0.0285 (2)	0.0043 (2)	0.0100 (2)	0.0095 (2)
V3	0.0336 (3)	0.0355 (3)	0.0308 (3)	0.0096 (2)	0.0113 (2)	0.0085 (2)
V4	0.0404 (3)	0.0491 (3)	0.0362 (3)	0.0076 (2)	0.0195 (2)	0.0192 (2)
V5	0.0390 (3)	0.0440 (3)	0.0252 (2)	0.0100 (2)	0.0059 (2)	0.0120 (2)
O1	0.0392 (11)	0.0362 (11)	0.0318 (10)	0.0157 (9)	0.0136 (9)	0.0136 (9)
O2	0.0321 (11)	0.0453 (12)	0.0323 (11)	0.0086 (9)	0.0066 (9)	0.0113 (9)
O3	0.0334 (11)	0.0506 (13)	0.0406 (12)	0.0092 (10)	0.0163 (9)	0.0183 (10)
O4	0.0382 (12)	0.0498 (13)	0.0379 (11)	0.0129 (10)	0.0202 (10)	0.0131 (10)
O5	0.0437 (12)	0.0438 (12)	0.0401 (12)	0.0048 (10)	0.0172 (10)	0.0206 (10)
O6	0.0491 (13)	0.0581 (14)	0.0289 (11)	0.0119 (11)	0.0156 (10)	0.0171 (10)
O7	0.0400 (12)	0.0407 (12)	0.0281 (10)	0.0099 (9)	0.0086 (9)	0.0057 (9)
O8	0.0384 (12)	0.0450 (12)	0.0325 (11)	0.0125 (9)	0.0073 (9)	0.0180 (9)
O9	0.0534 (15)	0.0671 (16)	0.0293 (11)	0.0154 (12)	0.0007 (10)	0.0125 (11)
O10	0.0555 (15)	0.0805 (18)	0.0568 (15)	0.0059 (13)	0.0327 (13)	0.0307 (14)
O11	0.0520 (14)	0.0419 (13)	0.0459 (13)	0.0170 (11)	0.0162 (11)	0.0085 (10)
O12	0.0586 (15)	0.0373 (12)	0.0521 (14)	0.0147 (11)	0.0158 (12)	0.0196 (11)
O13	0.0334 (11)	0.0424 (11)	0.0284 (10)	0.0150 (9)	0.0135 (9)	0.0157 (9)
O14	0.0408 (12)	0.0439 (12)	0.0348 (11)	0.0174 (10)	0.0160 (9)	0.0180 (9)
NO1	0.134 (4)	0.092 (3)	0.064 (3)	0.068 (3)	0.041 (3)	0.030 (3)
ON1	0.117 (3)	0.198 (5)	0.060 (2)	0.044 (3)	0.014 (2)	0.033 (3)
ON2	0.116 (3)	0.110 (3)	0.095 (3)	0.043 (2)	0.049 (3)	0.035 (2)
ON3	0.186 (5)	0.098 (3)	0.058 (2)	−0.006 (3)	0.024 (3)	0.022 (2)
NO2A	0.110 (12)	0.045 (6)	0.053 (6)	0.020 (7)	0.033 (8)	0.019 (4)
ON4A	0.142 (7)	0.053 (4)	0.055 (4)	0.003 (4)	0.048 (4)	0.013 (3)
ON5A	0.111 (8)	0.157 (15)	0.083 (7)	−0.008 (7)	0.033 (6)	0.039 (8)
ON6A	0.178 (10)	0.057 (4)	0.051 (4)	0.002 (5)	0.045 (5)	0.017 (3)
NO2B	0.088 (7)	0.056 (7)	0.063 (6)	0.012 (5)	0.031 (5)	0.017 (4)
ON4B	0.111 (6)	0.091 (6)	0.073 (5)	0.003 (5)	0.051 (4)	0.023 (4)
ON5B	0.093 (10)	0.119 (13)	0.104 (10)	0.026 (9)	0.025 (8)	0.024 (8)
ON6B	0.116 (7)	0.116 (7)	0.060 (5)	−0.001 (6)	0.030 (4)	0.035 (5)
NC1	0.0494 (17)	0.0560 (18)	0.0535 (17)	0.0200 (14)	0.0160 (14)	0.0325 (15)
C11	0.057 (2)	0.055 (2)	0.066 (3)	0.0146 (18)	0.015 (2)	0.0149 (19)
C12	0.073 (3)	0.093 (3)	0.076 (3)	0.024 (3)	0.039 (3)	0.021 (3)
C13	0.057 (3)	0.110 (4)	0.133 (5)	0.014 (3)	0.049 (3)	0.037 (4)
C14	0.055 (3)	0.075 (3)	0.121 (4)	−0.004 (2)	0.022 (3)	0.019 (3)
C15	0.065 (3)	0.066 (3)	0.060 (3)	0.017 (2)	0.000 (2)	0.011 (2)
NC2	0.0444 (16)	0.0531 (17)	0.0442 (16)	0.0118 (13)	0.0191 (13)	0.0071 (13)
C21	0.051 (2)	0.047 (2)	0.073 (3)	0.0094 (17)	0.020 (2)	0.0117 (19)
C22	0.056 (2)	0.070 (3)	0.074 (3)	0.015 (2)	0.011 (2)	0.035 (2)
C23	0.045 (2)	0.065 (3)	0.082 (3)	0.0108 (19)	0.005 (2)	0.019 (2)
C24	0.043 (2)	0.053 (2)	0.085 (3)	0.0018 (17)	0.010 (2)	0.011 (2)
C25	0.063 (3)	0.066 (3)	0.084 (3)	0.013 (2)	0.041 (2)	0.026 (2)
NC3	0.0533 (19)	0.0462 (17)	0.0531 (18)	−0.0058 (14)	0.0070 (15)	−0.0004 (14)
C31	0.073 (3)	0.052 (2)	0.078 (3)	0.009 (2)	0.035 (2)	0.001 (2)
C32	0.080 (3)	0.066 (3)	0.093 (3)	0.027 (2)	0.037 (3)	0.036 (3)
C33	0.112 (4)	0.071 (3)	0.103 (4)	0.017 (3)	0.051 (3)	0.047 (3)
C34	0.105 (4)	0.086 (3)	0.083 (3)	0.023 (3)	0.056 (3)	0.030 (3)
C35	0.066 (3)	0.076 (3)	0.105 (4)	0.012 (2)	0.047 (3)	0.018 (3)
NC4	0.067 (2)	0.054 (2)	0.111 (3)	−0.0089 (18)	0.025 (2)	0.027 (2)
C41	0.063 (3)	0.074 (4)	0.149 (6)	−0.007 (3)	−0.009 (4)	0.028 (4)
C42	0.119 (5)	0.084 (4)	0.097 (4)	0.003 (4)	−0.013 (4)	0.032 (3)
C43	0.145 (6)	0.105 (5)	0.066 (3)	0.008 (4)	0.012 (4)	0.002 (3)
C44	0.095 (4)	0.091 (4)	0.088 (4)	0.022 (3)	0.020 (3)	0.012 (3)
C45	0.087 (4)	0.060 (3)	0.093 (4)	0.006 (3)	0.004 (3)	0.018 (3)
NC5	0.090 (8)	0.066 (8)	0.049 (7)	0.001 (6)	0.019 (6)	0.002 (8)
C51	0.069 (8)	0.056 (10)	0.072 (11)	0.005 (7)	0.024 (7)	0.002 (9)
C52	0.060 (7)	0.056 (9)	0.038 (11)	−0.016 (8)	0.014 (8)	0.009 (10)
C53	0.071 (7)	0.045 (7)	0.039 (6)	0.010 (5)	0.019 (5)	0.020 (6)
C54	0.051 (7)	0.083 (12)	0.048 (10)	0.000 (8)	0.015 (7)	0.017 (12)
C55	0.083 (8)	0.069 (9)	0.041 (9)	−0.022 (8)	0.020 (7)	0.010 (8)
NC6	0.084 (11)	0.044 (9)	0.061 (11)	0.015 (9)	0.037 (9)	0.012 (9)
C61	0.057 (10)	0.040 (13)	0.055 (16)	−0.019 (10)	−0.010 (12)	−0.015 (14)
C62	0.083 (11)	0.046 (12)	0.037 (13)	−0.008 (11)	0.033 (9)	0.003 (12)
C63	0.100 (14)	0.047 (11)	0.038 (11)	0.012 (10)	0.042 (9)	−0.005 (10)
C64	0.075 (11)	0.058 (14)	0.068 (17)	0.006 (12)	0.009 (12)	0.018 (13)
C65	0.061 (10)	0.059 (12)	0.041 (17)	−0.007 (12)	0.022 (12)	−0.006 (16)

Geometric parameters (Å, º) top

V1—O12	1.608 (2)	C23—C24	1.528 (6)
V1—O8ⁱ	1.795 (2)	C23—H23A	0.9700
V1—O5ⁱ	1.849 (2)	C23—H23B	0.9700
V1—O1	1.978 (2)	C24—C25	1.502 (6)
V1—O14	2.067 (2)	C24—H24A	0.9700
V1—O13	2.277 (2)	C24—H24B	0.9700
V1—V3	3.1180 (8)	C25—H25A	0.9700
V2—O2	1.687 (2)	C25—H25B	0.9700
V2—O3	1.692 (2)	NC3—C35	1.472 (5)
V2—O1	1.914 (2)	NC3—C31	1.482 (5)
V2—O14ⁱ	2.003 (2)	NC3—HC3A	0.9000
V2—O13	2.081 (2)	NC3—HC3B	0.9000
V2—O13ⁱ	2.1346 (19)	C31—C32	1.493 (6)
V2—V5ⁱ	3.0747 (8)	C31—H31A	0.9700
V2—V4	3.0887 (8)	C31—H31B	0.9700
V3—O11	1.606 (2)	C32—C33	1.515 (6)
V3—O4	1.793 (2)	C32—H32A	0.9700
V3—O7	1.861 (2)	C32—H32B	0.9700
V3—O1	1.981 (2)	C33—C34	1.519 (6)
V3—O14	2.059 (2)	C33—H33A	0.9700
V3—O13ⁱ	2.2672 (19)	C33—H33B	0.9700
V3—V5	3.1193 (8)	C34—C35	1.506 (7)
V4—O10	1.602 (2)	C34—H34A	0.9700
V4—O6	1.845 (2)	C34—H34B	0.9700
V4—O5	1.850 (2)	C35—H35A	0.9700
V4—O4	1.929 (2)	C35—H35B	0.9700
V4—O3	2.014 (2)	NC4—C45	1.468 (6)
V4—O13ⁱ	2.345 (2)	NC4—C41	1.502 (7)
V4—V5	3.0906 (9)	NC4—HC4A	0.9000
V5—O9	1.606 (2)	NC4—HC4B	0.9000
V5—O6	1.830 (2)	C41—C42	1.469 (8)
V5—O7	1.846 (2)	C41—H41A	0.9700
V5—O8	1.922 (2)	C41—H41B	0.9700
V5—O2ⁱ	2.059 (2)	C42—C43	1.521 (8)
V5—O13ⁱ	2.3366 (19)	C42—H42A	0.9700
V5—V2ⁱ	3.0747 (8)	C42—H42B	0.9700
O2—V5ⁱ	2.059 (2)	C43—C44	1.542 (7)
O5—V1ⁱ	1.849 (2)	C43—H43A	0.9700
O8—V1ⁱ	1.795 (2)	C43—H43B	0.9700
O13—V2ⁱ	2.1346 (19)	C44—C45	1.482 (7)
O13—V3ⁱ	2.2672 (19)	C44—H44A	0.9700
O13—V5ⁱ	2.3366 (19)	C44—H44B	0.9700
O13—V4ⁱ	2.345 (2)	C45—H45A	0.9700
O14—V2ⁱ	2.003 (2)	C45—H45B	0.9700
NO1—ON1	1.224 (5)	NC5—C51	1.475 (12)
NO1—ON2	1.229 (6)	NC5—C55	1.477 (11)
NO1—ON3	1.244 (6)	NC5—HC5A	0.9000
NO2A—ON6A	1.224 (8)	NC5—HC5B	0.9000
NO2A—ON5A	1.233 (8)	C51—C52	1.524 (14)
NO2A—ON4A	1.243 (8)	C51—H51A	0.9700
NO2B—ON6B	1.227 (8)	C51—H51B	0.9700
NO2B—ON4B	1.232 (8)	C52—C53	1.503 (12)
NO2B—ON5B	1.241 (8)	C52—H52A	0.9700
NC1—C11	1.484 (4)	C52—H52B	0.9700
NC1—C15	1.486 (5)	C53—C54	1.515 (12)
NC1—HC1A	0.9000	C53—H53A	0.9700
NC1—HC1B	0.9000	C53—H53B	0.9700
C11—C12	1.504 (6)	C54—C55	1.503 (15)
C11—H11A	0.9700	C54—H54A	0.9700
C11—H11B	0.9700	C54—H54B	0.9700
C12—C13	1.524 (6)	C55—H55A	0.9700
C12—H12A	0.9700	C55—H55B	0.9700
C12—H12B	0.9700	NC6—C61	1.474 (17)
C13—C14	1.521 (6)	NC6—C65	1.482 (16)
C13—H13A	0.9700	NC6—HC6A	0.9000
C13—H13B	0.9700	NC6—HC6B	0.9000
C14—C15	1.499 (6)	C61—C62	1.516 (17)
C14—H14A	0.9700	C61—H61A	0.9700
C14—H14B	0.9700	C61—H61B	0.9700
C15—H15A	0.9700	C62—C63	1.508 (17)
C15—H15B	0.9700	C62—H62A	0.9700
NC2—C25	1.485 (5)	C62—H62B	0.9700
NC2—C21	1.491 (5)	C63—C64	1.535 (17)
NC2—HC2A	0.9000	C63—H63A	0.9700
NC2—HC2B	0.9000	C63—H63B	0.9700
C21—C22	1.506 (6)	C64—C65	1.514 (17)
C21—H21A	0.9700	C64—H64A	0.9700
C21—H21B	0.9700	C64—H64B	0.9700
C22—C23	1.525 (6)	C65—H65A	0.9700
C22—H22A	0.9700	C65—H65B	0.9700
C22—H22B	0.9700

O12—V1—O8ⁱ	104.18 (11)	C14—C13—H13A	109.7
O12—V1—O5ⁱ	101.89 (11)	C12—C13—H13A	109.7
O8ⁱ—V1—O5ⁱ	95.28 (10)	C14—C13—H13B	109.7
O12—V1—O1	100.96 (11)	C12—C13—H13B	109.7
O8ⁱ—V1—O1	92.68 (9)	H13A—C13—H13B	108.2
O5ⁱ—V1—O1	153.11 (9)	C15—C14—C13	112.1 (4)
O12—V1—O14	99.69 (10)	C15—C14—H14A	109.2
O8ⁱ—V1—O14	155.02 (9)	C13—C14—H14A	109.2
O5ⁱ—V1—O14	86.82 (9)	C15—C14—H14B	109.2
O1—V1—O14	75.51 (8)	C13—C14—H14B	109.2
O12—V1—O13	174.38 (10)	H14A—C14—H14B	107.9
O8ⁱ—V1—O13	80.74 (8)	NC1—C15—C14	109.4 (4)
O5ⁱ—V1—O13	80.13 (8)	NC1—C15—H15A	109.8
O1—V1—O13	75.87 (7)	C14—C15—H15A	109.8
O14—V1—O13	75.10 (7)	NC1—C15—H15B	109.8
O12—V1—V3	90.74 (9)	C14—C15—H15B	109.8
O8ⁱ—V1—V3	130.72 (7)	H15A—C15—H15B	108.3
O5ⁱ—V1—V3	127.63 (7)	C25—NC2—C21	112.5 (3)
O1—V1—V3	38.07 (6)	C25—NC2—HC2A	109.1
O14—V1—V3	40.83 (6)	C21—NC2—HC2A	109.1
O13—V1—V3	83.92 (5)	C25—NC2—HC2B	109.1
O2—V2—O3	107.57 (11)	C21—NC2—HC2B	109.1
O2—V2—O1	99.52 (9)	HC2A—NC2—HC2B	107.8
O3—V2—O1	97.77 (10)	NC2—C21—C22	109.9 (3)
O2—V2—O14ⁱ	95.78 (9)	NC2—C21—H21A	109.7
O3—V2—O14ⁱ	94.86 (10)	C22—C21—H21A	109.7
O1—V2—O14ⁱ	156.18 (9)	NC2—C21—H21B	109.7
O2—V2—O13	88.43 (9)	C22—C21—H21B	109.7
O3—V2—O13	163.72 (9)	H21A—C21—H21B	108.2
O1—V2—O13	82.11 (8)	C21—C22—C23	111.9 (4)
O14ⁱ—V2—O13	80.16 (8)	C21—C22—H22A	109.2
O2—V2—O13ⁱ	165.82 (9)	C23—C22—H22A	109.2
O3—V2—O13ⁱ	86.29 (9)	C21—C22—H22B	109.2
O1—V2—O13ⁱ	81.06 (8)	C23—C22—H22B	109.2
O14ⁱ—V2—O13ⁱ	79.69 (8)	H22A—C22—H22B	107.9
O13—V2—O13ⁱ	77.59 (8)	C22—C23—C24	109.4 (3)
O2—V2—V5ⁱ	39.01 (7)	C22—C23—H23A	109.8
O3—V2—V5ⁱ	146.50 (8)	C24—C23—H23A	109.8
O1—V2—V5ⁱ	92.17 (6)	C22—C23—H23B	109.8
O14ⁱ—V2—V5ⁱ	88.30 (6)	C24—C23—H23B	109.8
O13—V2—V5ⁱ	49.42 (5)	H23A—C23—H23B	108.2
O13ⁱ—V2—V5ⁱ	126.97 (6)	C25—C24—C23	111.8 (3)
O2—V2—V4	144.46 (8)	C25—C24—H24A	109.3
O3—V2—V4	36.99 (7)	C23—C24—H24A	109.3
O1—V2—V4	90.73 (6)	C25—C24—H24B	109.3
O14ⁱ—V2—V4	87.29 (6)	C23—C24—H24B	109.3
O13—V2—V4	126.83 (5)	H24A—C24—H24B	107.9
O13ⁱ—V2—V4	49.30 (5)	NC2—C25—C24	109.4 (3)
V5ⁱ—V2—V4	174.76 (2)	NC2—C25—H25A	109.8
O11—V3—O4	103.86 (11)	C24—C25—H25A	109.8
O11—V3—O7	101.51 (11)	NC2—C25—H25B	109.8
O4—V3—O7	95.26 (10)	C24—C25—H25B	109.8
O11—V3—O1	100.88 (10)	H25A—C25—H25B	108.2
O4—V3—O1	92.61 (9)	C35—NC3—C31	114.1 (4)
O7—V3—O1	153.70 (9)	C35—NC3—HC3A	108.7
O11—V3—O14	99.32 (11)	C31—NC3—HC3A	108.7
O4—V3—O14	155.65 (9)	C35—NC3—HC3B	108.7
O7—V3—O14	87.27 (9)	C31—NC3—HC3B	108.7
O1—V3—O14	75.62 (8)	HC3A—NC3—HC3B	107.6
O11—V3—O13ⁱ	173.84 (10)	NC3—C31—C32	110.0 (3)
O4—V3—O13ⁱ	81.88 (8)	NC3—C31—H31A	109.7
O7—V3—O13ⁱ	79.94 (8)	C32—C31—H31A	109.7
O1—V3—O13ⁱ	76.38 (7)	NC3—C31—H31B	109.7
O14—V3—O13ⁱ	74.71 (8)	C32—C31—H31B	109.7
O11—V3—V1	90.45 (9)	H31A—C31—H31B	108.2
O4—V3—V1	130.59 (7)	C31—C32—C33	111.6 (4)
O7—V3—V1	128.29 (7)	C31—C32—H32A	109.3
O1—V3—V1	37.99 (6)	C33—C32—H32A	109.3
O14—V3—V1	41.02 (6)	C31—C32—H32B	109.3
O13ⁱ—V3—V1	84.03 (5)	C33—C32—H32B	109.3
O11—V3—V5	133.84 (8)	H32A—C32—H32B	108.0
O4—V3—V5	83.23 (7)	C32—C33—C34	111.2 (4)
O7—V3—V5	32.56 (6)	C32—C33—H33A	109.4
O1—V3—V5	124.61 (6)	C34—C33—H33A	109.4
O14—V3—V5	86.12 (6)	C32—C33—H33B	109.4
O13ⁱ—V3—V5	48.29 (5)	C34—C33—H33B	109.4
V1—V3—V5	119.61 (2)	H33A—C33—H33B	108.0
O10—V4—O6	103.65 (12)	C35—C34—C33	112.0 (4)
O10—V4—O5	103.03 (12)	C35—C34—H34A	109.2
O6—V4—O5	92.59 (10)	C33—C34—H34A	109.2
O10—V4—O4	100.98 (12)	C35—C34—H34B	109.2
O6—V4—O4	88.62 (10)	C33—C34—H34B	109.2
O5—V4—O4	154.94 (9)	H34A—C34—H34B	107.9
O10—V4—O3	101.07 (11)	NC3—C35—C34	109.5 (4)
O6—V4—O3	154.99 (9)	NC3—C35—H35A	109.8
O5—V4—O3	85.48 (9)	C34—C35—H35A	109.8
O4—V4—O3	82.99 (9)	NC3—C35—H35B	109.8
O10—V4—O13ⁱ	174.85 (11)	C34—C35—H35B	109.8
O6—V4—O13ⁱ	81.17 (8)	H35A—C35—H35B	108.2
O5—V4—O13ⁱ	78.32 (8)	C45—NC4—C41	112.1 (4)
O4—V4—O13ⁱ	77.15 (8)	C45—NC4—HC4A	109.2
O3—V4—O13ⁱ	74.01 (8)	C41—NC4—HC4A	109.2
O10—V4—V2	131.42 (10)	C45—NC4—HC4B	109.2
O6—V4—V2	124.76 (7)	C41—NC4—HC4B	109.2
O5—V4—V2	80.44 (7)	HC4A—NC4—HC4B	107.9
O4—V4—V2	78.37 (6)	C42—C41—NC4	110.5 (4)
O3—V4—V2	30.36 (6)	C42—C41—H41A	109.5
O13ⁱ—V4—V2	43.65 (5)	NC4—C41—H41A	109.5
O10—V4—V5	136.23 (10)	C42—C41—H41B	109.5
O6—V4—V5	32.60 (7)	NC4—C41—H41B	109.5
O5—V4—V5	85.55 (7)	H41A—C41—H41B	108.1
O4—V4—V5	82.07 (7)	C41—C42—C43	112.1 (5)
O3—V4—V5	122.51 (6)	C41—C42—H42A	109.2
O13ⁱ—V4—V5	48.57 (5)	C43—C42—H42A	109.2
V2—V4—V5	92.184 (19)	C41—C42—H42B	109.2
O9—V5—O6	103.89 (12)	C43—C42—H42B	109.2
O9—V5—O7	102.81 (11)	H42A—C42—H42B	107.9
O6—V5—O7	93.08 (10)	C42—C43—C44	109.9 (5)
O9—V5—O8	101.31 (11)	C42—C43—H43A	109.7
O6—V5—O8	89.64 (10)	C44—C43—H43A	109.7
O7—V5—O8	154.30 (9)	C42—C43—H43B	109.7
O9—V5—O2ⁱ	100.73 (11)	C44—C43—H43B	109.7
O6—V5—O2ⁱ	155.14 (9)	H43A—C43—H43B	108.2
O7—V5—O2ⁱ	84.73 (9)	C45—C44—C43	111.4 (5)
O8—V5—O2ⁱ	82.19 (9)	C45—C44—H44A	109.3
O9—V5—O13ⁱ	174.15 (11)	C43—C44—H44A	109.3
O6—V5—O13ⁱ	81.70 (8)	C45—C44—H44B	109.3
O7—V5—O13ⁱ	78.39 (8)	C43—C44—H44B	109.3
O8—V5—O13ⁱ	76.73 (8)	H44A—C44—H44B	108.0
O2ⁱ—V5—O13ⁱ	73.60 (7)	NC4—C45—C44	111.7 (4)
O9—V5—V2ⁱ	131.76 (10)	NC4—C45—H45A	109.3
O6—V5—V2ⁱ	124.20 (7)	C44—C45—H45A	109.3
O7—V5—V2ⁱ	80.10 (6)	NC4—C45—H45B	109.3
O8—V5—V2ⁱ	77.28 (6)	C44—C45—H45B	109.3
O2ⁱ—V5—V2ⁱ	31.04 (6)	H45A—C45—H45B	108.0
O13ⁱ—V5—V2ⁱ	42.56 (5)	C51—NC5—C55	112.7 (11)
O9—V5—V4	136.76 (10)	C51—NC5—HC5A	109.0
O6—V5—V4	32.90 (7)	C55—NC5—HC5A	109.0
O7—V5—V4	86.10 (7)	C51—NC5—HC5B	109.0
O8—V5—V4	82.40 (7)	C55—NC5—HC5B	109.0
O2ⁱ—V5—V4	122.33 (6)	HC5A—NC5—HC5B	107.8
O13ⁱ—V5—V4	48.80 (5)	NC5—C51—C52	109.3 (11)
V2ⁱ—V5—V4	91.317 (19)	NC5—C51—H51A	109.8
O9—V5—V3	135.45 (9)	C52—C51—H51A	109.8
O6—V5—V3	81.46 (7)	NC5—C51—H51B	109.8
O7—V5—V3	32.87 (6)	C52—C51—H51B	109.8
O8—V5—V3	123.11 (6)	H51A—C51—H51B	108.3
O2ⁱ—V5—V3	83.46 (6)	C53—C52—C51	105.9 (10)
O13ⁱ—V5—V3	46.42 (5)	C53—C52—H52A	110.6
V2ⁱ—V5—V3	63.252 (17)	C51—C52—H52A	110.6
V4—V5—V3	60.646 (19)	C53—C52—H52B	110.6
V2—O1—V1	106.75 (9)	C51—C52—H52B	110.6
V2—O1—V3	107.80 (9)	H52A—C52—H52B	108.7
V1—O1—V3	103.94 (10)	C52—C53—C54	113.5 (11)
V2—O2—V5ⁱ	109.95 (11)	C52—C53—H53A	108.9
V2—O3—V4	112.65 (11)	C54—C53—H53A	108.9
V3—O4—V4	114.73 (10)	C52—C53—H53B	108.9
V1ⁱ—O5—V4	115.14 (11)	C54—C53—H53B	108.9
V5—O6—V4	114.50 (11)	H53A—C53—H53B	107.7
V5—O7—V3	114.57 (11)	C55—C54—C53	107.3 (10)
V1ⁱ—O8—V5	115.62 (10)	C55—C54—H54A	110.3
V2—O13—V2ⁱ	102.41 (8)	C53—C54—H54A	110.3
V2—O13—V3ⁱ	96.58 (8)	C55—C54—H54B	110.3
V2ⁱ—O13—V3ⁱ	91.23 (7)	C53—C54—H54B	110.3
V2—O13—V1	91.44 (7)	H54A—C54—H54B	108.5
V2ⁱ—O13—V1	95.85 (8)	NC5—C55—C54	108.9 (11)
V3ⁱ—O13—V1	167.94 (9)	NC5—C55—H55A	109.9
V2—O13—V5ⁱ	88.02 (7)	C54—C55—H55A	109.9
V2ⁱ—O13—V5ⁱ	169.33 (10)	NC5—C55—H55B	109.9
V3ⁱ—O13—V5ⁱ	85.29 (7)	C54—C55—H55B	109.9
V1—O13—V5ⁱ	86.00 (6)	H55A—C55—H55B	108.3
V2—O13—V4ⁱ	170.19 (9)	C61—NC6—C65	112.0 (19)
V2ⁱ—O13—V4ⁱ	87.06 (7)	C61—NC6—HC6A	109.2
V3ⁱ—O13—V4ⁱ	85.64 (6)	C65—NC6—HC6A	109.2
V1—O13—V4ⁱ	84.98 (7)	C61—NC6—HC6B	109.2
V5ⁱ—O13—V4ⁱ	82.63 (6)	C65—NC6—HC6B	109.2
V2ⁱ—O14—V3	106.17 (9)	HC6A—NC6—HC6B	107.9
V2ⁱ—O14—V1	107.18 (9)	NC6—C61—C62	107.0 (18)
V3—O14—V1	98.15 (9)	NC6—C61—H61A	110.3
ON1—NO1—ON2	122.1 (7)	C62—C61—H61A	110.3
ON1—NO1—ON3	119.3 (6)	NC6—C61—H61B	110.3
ON2—NO1—ON3	118.7 (5)	C62—C61—H61B	110.3
ON6A—NO2A—ON5A	120.8 (8)	H61A—C61—H61B	108.6
ON6A—NO2A—ON4A	119.7 (7)	C63—C62—C61	109.3 (18)
ON5A—NO2A—ON4A	119.5 (7)	C63—C62—H62A	109.8
ON6B—NO2B—ON4B	120.1 (7)	C61—C62—H62A	109.8
ON6B—NO2B—ON5B	119.9 (8)	C63—C62—H62B	109.8
ON4B—NO2B—ON5B	120.0 (8)	C61—C62—H62B	109.8
C11—NC1—C15	113.1 (3)	H62A—C62—H62B	108.3
C11—NC1—HC1A	109.0	C62—C63—C64	107.7 (17)
C15—NC1—HC1A	109.0	C62—C63—H63A	110.2
C11—NC1—HC1B	109.0	C64—C63—H63A	110.2
C15—NC1—HC1B	109.0	C62—C63—H63B	110.2
HC1A—NC1—HC1B	107.8	C64—C63—H63B	110.2
NC1—C11—C12	110.0 (3)	H63A—C63—H63B	108.5
NC1—C11—H11A	109.7	C65—C64—C63	107.7 (18)
C12—C11—H11A	109.7	C65—C64—H64A	110.2
NC1—C11—H11B	109.7	C63—C64—H64A	110.2
C12—C11—H11B	109.7	C65—C64—H64B	110.2
H11A—C11—H11B	108.2	C63—C64—H64B	110.2
C11—C12—C13	110.9 (4)	H64A—C64—H64B	108.5
C11—C12—H12A	109.5	NC6—C65—C64	108.5 (18)
C13—C12—H12A	109.5	NC6—C65—H65A	110.0
C11—C12—H12B	109.5	C64—C65—H65A	110.0
C13—C12—H12B	109.5	NC6—C65—H65B	110.0
H12A—C12—H12B	108.0	C64—C65—H65B	110.0
C14—C13—C12	109.9 (4)	H65A—C65—H65B	108.4

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
NC1—HC1A···O8	0.90	1.80	2.693 (3)	174
NC1—HC1B···ON6Aⁱⁱ	0.90	1.95	2.829 (8)	164
NC1—HC1B···ON6B	0.90	2.05	2.876 (9)	153
NC1—HC1B···ON5Aⁱⁱ	0.90	2.48	3.214 (12)	139
NC1—HC1B···ON5B	0.90	2.54	3.355 (13)	151
NC2—HC2A···ON4A	0.90	1.95	2.824 (7)	164
NC2—HC2A···ON4Bⁱⁱ	0.90	2.05	2.909 (8)	159
NC2—HC2A···ON5Bⁱⁱ	0.90	2.50	3.280 (13)	145
NC2—HC2A···ON5A	0.90	2.56	3.251 (12)	134
NC2—HC2B···O4	0.90	1.85	2.746 (3)	174
NC3—HC3A···O5ⁱ	0.90	1.85	2.749 (4)	175
NC3—HC3B···ON3	0.90	2.06	2.885 (5)	152
NC3—HC3B···ON2	0.90	2.31	3.095 (5)	145
NC4—HC4A···O7	0.90	1.82	2.716 (4)	172
NC4—HC4B···ON3	0.90	2.16	2.954 (6)	147
NC4—HC4B···ON1	0.90	2.26	3.060 (6)	148
NC5—HC5A···O6	0.90	2.40	3.248 (17)	158
NC6—HC6A···ON4B	0.90	2.12	2.92 (2)	147
NC6—HC6B···O6ⁱⁱ	0.90	1.92	2.80 (2)	166

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

Experimental details

Crystal data
Chemical formula	(C₅H₁₂N)₉[HV₁₀O₂₈](NO₃)₄
M_r	1981.85
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	11.593 (2), 13.290 (2), 14.676 (2)
α, β, γ (°)	105.858 (2), 110.335 (2), 92.457 (2)
V (Å³)	2015.6 (5)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.20
Crystal size (mm)	0.30 × 0.25 × 0.14

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.72, 0.90
No. of measured, independent and observed [I > 2σ(I)] reflections	9193, 8755, 6099
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.638

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.118, 1.04
No. of reflections	8755
No. of parameters	598
No. of restraints	262
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.71, −0.32

Computer programs: CAD-4 EXPRESS (Duisenberg, 1992; Macíček & Yordanov, 1992), MolEN (Fair, 1990), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1998), publCIF (Westrip, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
NC1—HC1A···O8	0.90	1.80	2.693 (3)	174.1
NC1—HC1B···ON6Aⁱ	0.90	1.95	2.829 (8)	163.5
NC1—HC1B···ON6B	0.90	2.05	2.876 (9)	152.7
NC1—HC1B···ON5Aⁱ	0.90	2.48	3.214 (12)	139.0
NC1—HC1B···ON5B	0.90	2.54	3.355 (13)	150.7
NC2—HC2A···ON4A	0.90	1.95	2.824 (7)	164.4
NC2—HC2A···ON4Bⁱ	0.90	2.05	2.909 (8)	158.5
NC2—HC2A···ON5Bⁱ	0.90	2.50	3.280 (13)	144.9
NC2—HC2A···ON5A	0.90	2.56	3.251 (12)	134.4
NC2—HC2B···O4	0.90	1.85	2.746 (3)	173.6
NC3—HC3A···O5ⁱⁱ	0.90	1.85	2.749 (4)	174.8
NC3—HC3B···ON3	0.90	2.06	2.885 (5)	151.9
NC3—HC3B···ON2	0.90	2.31	3.095 (5)	145.3
NC4—HC4A···O7	0.90	1.82	2.716 (4)	172.3
NC4—HC4B···ON3	0.90	2.16	2.954 (6)	147.4
NC4—HC4B···ON1	0.90	2.26	3.060 (6)	148.2
NC5—HC5A···O6	0.90	2.40	3.248 (17)	157.8
NC6—HC6A···ON4B	0.90	2.12	2.92 (2)	147.2
NC6—HC6B···O6ⁱ	0.90	1.92	2.80 (2)	166.1

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

References

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Volume 65| Part 8| August 2009| Pages m953-m954

doi:10.1107/S1600536809026555

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