Acta Cryst. (2007). E63, m2189 [ doi:10.1107/S160053680703471X ]
The structure of a new vanadium oxide compound, catena-poly[N,N'-bis(2-ammonioethyl)oxamide [dioxidovanadate-![[mu]](/logos/entities/mu_rmgif.gif)
-oxido-dioxidovanadate--oxido]], {(C6H16N4O2)[V2O6]}n, exhibits helical vanadate chains, constructed from corner-sharing VO4 tetrahedra. Adjacent chains are packed together by extensive hydrogen bonds involving the inorganic framework and the templating guest cations, which are centrosymmetric and occupy the free space between the stacks of chains.
The Cu(oxen) was prepared according to the method of Ojima & Nonoyama (1988). A mixture of NH4VO3 (0.117 g,1.0 mmol), Cu(oxen) (0.118 g,0.5 mmol), H2C2O4·2H2O (0.0257 g,0.2 mmol) and methanol (8 ml), was sealed in a 25 ml Teflon-lined steel autoclave and heated under autogenous pressure at 353 K for 6 h. Then, the filtrate was kept at room temperature and brown block-like crystals were obtained after a week.
All the H atoms were positioned geometrically, with C—H = 0.97 Å and with N—H = 0.86 (NH) or 0.89 (NH3) Å, and allowed to ride during refinement with Uiso(H) = 1.2Ueq(C,N) for the CH2 and NH groups or 1.5Ueq(N) for the NH3 groups.
Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL.
![[Figure 1]](./bg2076fig1thm.gif)
| Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids. [symmetry codes: (i) 1 − x, 2 − y, −z; (ii) 1.5 − x, −1/2 + y, 1/2 − z. (i) 1 − x, 2 − y, −z;(ii) 1.5 − x, −1/2 + y, 1/2 − z;(iii) 1.5 − x, 1/2 + y, 1/2 − z; (iv) x, −1 + y, z. |
![[Figure 2]](./bg2076fig2thm.gif)
| Fig. 2. View of the 1-D helical vanadate chain of 1. |
![[Figure 3]](./bg2076fig3thm.gif)
| Fig. 3. Packing diagram of the title compound. |
| (C6H16N4O2)[V2O6] | F(000) = 380 |
| Mr = 374.11 | Dx = 1.869 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 4832 reflections |
| a = 6.7453 (3) Å | θ = 3.1–26.0° |
| b = 5.5087 (1) Å | µ = 1.45 mm−1 |
| c = 18.1775 (2) Å | T = 295 K |
| β = 100.114 (3)° | Block, brown |
| V = 664.94 (3) Å3 | 0.20 × 0.12 × 0.08 mm |
| Z = 2 |
| Siemems SMART CCD diffractometer | 1300 independent reflections |
| Radiation source: fine-focus sealed tube | 1217 reflections with I > 2σ(I) |
| graphite | Rint = 0.025 |
| φ and ω scans | θmax = 26.0°, θmin = 3.1° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→8 |
| Tmin = 0.760, Tmax = 0.893 | k = −6→6 |
| 4832 measured reflections | l = −22→22 |
| 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)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.078 | H-atom parameters constrained |
| S = 1.11 | w = 1/[σ2(Fo2) + (0.0358P)2 + 0.6776P] where P = (Fo2 + 2Fc2)/3 |
| 1300 reflections | (Δ/σ)max < 0.001 |
| 91 parameters | Δρmax = 0.34 e Å−3 |
| 0 restraints | Δρmin = −0.36 e Å−3 |
| (C6H16N4O2)[V2O6] | V = 664.94 (3) Å3 |
| Mr = 374.11 | Z = 2 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 6.7453 (3) Å | µ = 1.45 mm−1 |
| b = 5.5087 (1) Å | T = 295 K |
| c = 18.1775 (2) Å | 0.20 × 0.12 × 0.08 mm |
| β = 100.114 (3)° |
| Siemems SMART CCD diffractometer | 1300 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1217 reflections with I > 2σ(I) |
| Tmin = 0.760, Tmax = 0.893 | Rint = 0.025 |
| 4832 measured reflections | θmax = 26.0° |
| R[F2 > 2σ(F2)] = 0.029 | H-atom parameters constrained |
| wR(F2) = 0.078 | Δρmax = 0.34 e Å−3 |
| S = 1.11 | Δρmin = −0.36 e Å−3 |
| 1300 reflections | Absolute structure: ? |
| 91 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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. |
| x | y | z | Uiso*/Ueq | ||
| V | 0.65928 (5) | 0.70817 (7) | 0.20100 (2) | 0.01778 (15) | |
| O1 | 0.7174 (3) | 0.6053 (4) | 0.12407 (10) | 0.0363 (5) | |
| O2 | 0.4226 (3) | 0.7879 (4) | 0.18675 (13) | 0.0411 (5) | |
| O3 | 0.8179 (3) | 0.9687 (3) | 0.23015 (10) | 0.0291 (4) | |
| O4 | 0.2428 (2) | 0.9303 (3) | −0.01377 (9) | 0.0256 (4) | |
| C1 | 0.3990 (3) | 1.0441 (4) | 0.00875 (12) | 0.0188 (5) | |
| C2 | 0.2333 (4) | 1.3726 (5) | 0.06245 (14) | 0.0263 (5) | |
| H2A | 0.1252 | 1.3422 | 0.0207 | 0.032* | |
| H2B | 0.2613 | 1.5454 | 0.0635 | 0.032* | |
| C3 | 0.1615 (4) | 1.3043 (5) | 0.13401 (15) | 0.0295 (6) | |
| H3A | 0.2711 | 1.3257 | 0.1758 | 0.035* | |
| H3B | 0.0530 | 1.4122 | 0.1413 | 0.035* | |
| N1 | 0.4117 (3) | 1.2438 (4) | 0.04932 (11) | 0.0217 (4) | |
| H1A | 0.5286 | 1.2992 | 0.0685 | 0.026* | |
| N2 | 0.0899 (3) | 1.0505 (4) | 0.13286 (11) | 0.0242 (4) | |
| H2C | 0.0491 | 1.0172 | 0.1757 | 0.036* | |
| H2D | 0.1898 | 0.9508 | 0.1271 | 0.036* | |
| H2E | −0.0123 | 1.0308 | 0.0951 | 0.036* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| V | 0.0180 (2) | 0.0148 (2) | 0.0203 (2) | 0.00000 (14) | 0.00284 (15) | 0.00046 (14) |
| O1 | 0.0497 (12) | 0.0343 (11) | 0.0263 (9) | −0.0053 (9) | 0.0105 (8) | −0.0082 (8) |
| O2 | 0.0227 (10) | 0.0353 (11) | 0.0626 (14) | 0.0066 (8) | 0.0002 (9) | 0.0068 (10) |
| O3 | 0.0342 (10) | 0.0222 (9) | 0.0330 (9) | −0.0085 (7) | 0.0114 (8) | −0.0084 (7) |
| O4 | 0.0181 (8) | 0.0257 (9) | 0.0326 (9) | −0.0039 (7) | 0.0033 (7) | −0.0019 (7) |
| C1 | 0.0182 (11) | 0.0218 (11) | 0.0165 (10) | −0.0002 (9) | 0.0033 (8) | 0.0035 (9) |
| C2 | 0.0281 (13) | 0.0201 (12) | 0.0318 (13) | 0.0038 (10) | 0.0084 (10) | 0.0004 (10) |
| C3 | 0.0307 (14) | 0.0276 (14) | 0.0329 (14) | 0.0015 (10) | 0.0131 (11) | −0.0058 (11) |
| N1 | 0.0183 (10) | 0.0224 (10) | 0.0248 (10) | −0.0021 (8) | 0.0052 (8) | −0.0030 (8) |
| N2 | 0.0178 (10) | 0.0311 (11) | 0.0244 (10) | 0.0023 (8) | 0.0056 (8) | 0.0028 (8) |
| V—O1 | 1.6197 (18) | C2—H2A | 0.9700 |
| V—O2 | 1.6322 (19) | C2—H2B | 0.9700 |
| V—O3i | 1.8063 (17) | C3—N2 | 1.478 (3) |
| V—O3 | 1.8127 (17) | C3—H3A | 0.9700 |
| O4—C1 | 1.232 (3) | C3—H3B | 0.9700 |
| C1—N1 | 1.319 (3) | N1—H1A | 0.8600 |
| C1—C1ii | 1.532 (4) | N2—H2C | 0.8900 |
| C2—N1 | 1.452 (3) | N2—H2D | 0.8900 |
| C2—C3 | 1.513 (3) | N2—H2E | 0.8900 |
| O1—V—O2 | 109.60 (11) | N2—C3—C2 | 112.1 (2) |
| O1—V—O3i | 109.79 (9) | N2—C3—H3A | 109.2 |
| O2—V—O3i | 105.57 (10) | C2—C3—H3A | 109.2 |
| O1—V—O3 | 108.03 (9) | N2—C3—H3B | 109.2 |
| O2—V—O3 | 110.13 (9) | C2—C3—H3B | 109.2 |
| O3i—V—O3 | 113.68 (3) | H3A—C3—H3B | 107.9 |
| Viii—O3—V | 139.01 (10) | C1—N1—C2 | 121.7 (2) |
| O4—C1—N1 | 125.3 (2) | C1—N1—H1A | 119.2 |
| O4—C1—C1ii | 120.6 (3) | C2—N1—H1A | 119.2 |
| N1—C1—C1ii | 114.1 (2) | C3—N2—H2C | 109.5 |
| N1—C2—C3 | 114.8 (2) | C3—N2—H2D | 109.5 |
| N1—C2—H2A | 108.6 | H2C—N2—H2D | 109.5 |
| C3—C2—H2A | 108.6 | C3—N2—H2E | 109.5 |
| N1—C2—H2B | 108.6 | H2C—N2—H2E | 109.5 |
| C3—C2—H2B | 108.6 | H2D—N2—H2E | 109.5 |
| H2A—C2—H2B | 107.5 |
| Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) −x+1, −y+2, −z; (iii) −x+3/2, y+1/2, −z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···O1iv | 0.86 | 2.24 | 3.013 (3) | 149 |
| N2—H2C···O3v | 0.89 | 2.01 | 2.799 (3) | 148 |
| N2—H2E···O4vi | 0.89 | 1.96 | 2.833 (3) | 167 |
| N2—H2D···O2 | 0.89 | 1.96 | 2.705 (3) | 140 |
| Symmetry codes: (iv) x, y+1, z; (v) x−1, y, z; (vi) −x, −y+2, −z. |
| V—O1 | 1.6197 (18) | V—O3i | 1.8063 (17) |
| V—O2 | 1.6322 (19) | V—O3 | 1.8127 (17) |
| Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···O1ii | 0.86 | 2.24 | 3.013 (3) | 149 |
| N2—H2C···O3iii | 0.89 | 2.01 | 2.799 (3) | 148 |
| N2—H2E···O4iv | 0.89 | 1.96 | 2.833 (3) | 167 |
| N2—H2D···O2 | 0.89 | 1.96 | 2.705 (3) | 140 |
| Symmetry codes: (ii) x, y+1, z; (iii) x−1, y, z; (iv) −x, −y+2, −z. |
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Microporous inorganic solids have attracted considerable attention in the past decades due to their structural diversity and potential applications in diverse areas (Cheetham et al., 1999; Hagrman et al., 2001). Among those, vanadium oxide family has proved a particularly rich source of new compounds. This is in part due to the flexible ability of vanadium to adopt tetrahedral, square-pyramidal, trigonal bipyramidal and octahedral coordination geometries, as well as their various oxidation states (III, IV and V). Besides, the utilizaion of hydrothermal technique in combination with cationic organic templates has also resulted in a huge number of new structures (Nazar et al., 1996; Zhang et al., 1996; Chirayil et al., 1998; Hagrman & Zubieta, 2000; Khan et al., 2000; Liu et al., 2002). One may expect that the rational design of crystalline solids with complex architectures may be realised through shrewd choice of organic species. The aim of our work is to explore the construction of such materials, and a new chain-like vanadate (I), has been described here.
As shown in Fig. 1, the asymmetric unit contains only one half of a [(H2oxen)2+ ion. The Vv atom possesses a distorted tetrahedal geometry and is coordinated by two symetry related images of a bridging oxo group (O3) and two terminal unshared oxygen atoms (O1 and O2) with short vanadyl V=O bond distances (Table 1). The VO4 tetrahedra are linked together through common vertices, leading to the formation of unusual helical –O—V—O—V—O– chains (Fig. 2). Adjacent chains are further stacked in an ABAB sequence along the c axis. The diprotonated templates H2oxen, adopting the transoid conformation with an inversion centre at the mid-point of the C1—C1i bond [symmetry code: (i) 1 − x, 2 − y, −z], fill the space of neighboring chains to compensate the negative charges and further extend the structure into 3-D supramolecular framework through hydrogen bonds with N···O distances in the range 2.705 (3)–3.013 (3) Å (Fig. 3).