Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680703471X/bg2076sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680703471X/bg2076Isup2.hkl |
CCDC reference: 657612
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C) = 0.004 Å
- R factor = 0.029
- wR factor = 0.078
- Data-to-parameter ratio = 14.3
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ? PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 2.00 Ratio PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for V PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C1 - C1_c ... 1.53 Ang.
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for V (5) 5.20
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
For related literature, see: Cheetham et al. (1999); Chirayil et al. (1998); Hagrman & Zubieta (2000); Hagrman et al. (2001); Khan et al. (2000); Liu et al. (2002); Nazar et al. (1996); Ojima & Nonoyama (1988); Zhang et al. (1996).
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.
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).
For related literature, see: Cheetham et al. (1999); Chirayil et al. (1998); Hagrman & Zubieta (2000); Hagrman et al. (2001); Khan et al. (2000); Liu et al. (2002); Nazar et al. (1996); Ojima & Nonoyama (1988); Zhang et al. (1996).
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.
(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 monochromator | 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 |
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.078 | H-atom parameters constrained |
S = 1.11 | Δρmax = 0.34 e Å−3 |
1300 reflections | Δρmin = −0.36 e Å−3 |
91 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. |
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. |
Experimental details
Crystal data | |
Chemical formula | (C6H16N4O2)[V2O6] |
Mr | 374.11 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 295 |
a, b, c (Å) | 6.7453 (3), 5.5087 (1), 18.1775 (2) |
β (°) | 100.114 (3) |
V (Å3) | 664.94 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.45 |
Crystal size (mm) | 0.20 × 0.12 × 0.08 |
Data collection | |
Diffractometer | Siemems SMART CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.760, 0.893 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4832, 1300, 1217 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.078, 1.11 |
No. of reflections | 1300 |
No. of parameters | 91 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.34, −0.36 |
Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1999), SHELXTL.
V—O1 | 1.6197 (18) | V—O3i | 1.8063 (17) |
V—O2 | 1.6322 (19) | V—O3 | 1.8127 (17) |
Symmetry code: (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) | 148.9 |
N2—H2C···O3iii | 0.89 | 2.01 | 2.799 (3) | 147.8 |
N2—H2E···O4iv | 0.89 | 1.96 | 2.833 (3) | 166.6 |
N2—H2D···O2 | 0.89 | 1.96 | 2.705 (3) | 140.0 |
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).