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organic compounds
4-(1H-Tetrazol-5-yl)benzoic acid monohydrate
aChemistry and Life Sciences School, Quanzhou Normal University, Quanzhou, Fujian 362000, People's Republic of China, and bState Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, People's Republic of China
*Correspondence e-mail: zfk@ms.fjirsm.ac.cn
The 8H6N4O2·H2O, consists of one 4-(1H-tetrazol-5-yl)benzoic acid molecule and one water molecule. Hydrogen-bonding and π–π stacking (centroid–centroid distance between tetrazole and benzene rings = 3.78 Å) interactions link the molecules into a three-dimensional network.
of the title compound, CRelated literature
For general background, see: James et al. (2003); Kitagawa & Matsuda (2007
); Maspoch et al. (2007
); Pan et al. (2006
); Li et al. (2007
). For related tetrazole ligands, see: Demko et al. (2001
).
Experimental
Crystal data
|
Data collection
Refinement
|
|
Data collection: WinAFC Diffractometer Control Software (Rigaku, 2002); cell WinAFC Diffractometer Control Software; data reduction: CrystalStructure (Rigaku/MSC, 2004
; program(s) used to solve structure: SHELXTL (Sheldrick, 2008
); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536808019053/sj2513sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808019053/sj2513Isup2.hkl
A mixture of zinc bromide (225 mg, 1.0 mmol), Na(4-cba) (4-Hcba = 4-cyanobenzoic acid) (65 mg, 1.0 mmol) and NaN3 (65 mg, 1.0 mmol) in 10 ml water were transferred into a Teflon-line stainless steel autoclave and heated to 413 K for 3 days, then cooled to room temperature at the rate of 1 K/h. The resulting solid powder was acidified with HCl (2M) to give the target product. Crystals were obtained by slow evaporation of the resulting solution.
The H atoms bound to O1W, O1 and N1 were located in a difference Fourier synthesis and refined with isotropic displacement parameters and the O(N)—H distances restrained to a target value of 0.86 (1) Å, and with Uiso(H) of O1W being 1.2Ueq(O1W). The remaining aromatic H atoms were positioned geometrically and refined using a riding model with d(C-H) = 0.93Å, Uiso=1.2Ueq (C).
Data collection: WinAFC Diffractometer Control Software (Rigaku, 2002); cell
WinAFC Diffractometer Control Software (Rigaku, 2002); data reduction: CrystalStructure (Rigaku/MSC, 2004; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C8H6N4O2·H2O | F(000) = 432 |
Mr = 208.18 | Dx = 1.553 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 20 reflections |
a = 4.914 (2) Å | θ = 12–30° |
b = 5.219 (2) Å | µ = 0.12 mm−1 |
c = 34.720 (13) Å | T = 293 K |
β = 91.00 (3)° | Block, colorless |
V = 890.4 (6) Å3 | 0.20 × 0.10 × 0.10 mm |
Z = 4 |
Rigaku AFC-7R diffractometer | 1270 reflections with I > 2σ(I) |
Radiation source: rotating-anode generator | Rint = 0.028 |
Graphite monochromator | θmax = 25.0°, θmin = 3.5° |
ω–2θ scans | h = −1→5 |
Absorption correction: ψ scan (Psi in WinAFC Diffractometer Control Software; Rigaku 2002) | k = −6→6 |
Tmin = 0.928, Tmax = 1.000 | l = −41→41 |
3386 measured reflections | 3 standard reflections every 200 reflections |
1576 independent reflections | intensity decay: 0.3% |
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) = 0.095 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0403P)2 + 0.366P] where P = (Fo2 + 2Fc2)/3 |
1576 reflections | (Δ/σ)max < 0.001 |
148 parameters | Δρmax = 0.17 e Å−3 |
4 restraints | Δρmin = −0.29 e Å−3 |
C8H6N4O2·H2O | V = 890.4 (6) Å3 |
Mr = 208.18 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 4.914 (2) Å | µ = 0.12 mm−1 |
b = 5.219 (2) Å | T = 293 K |
c = 34.720 (13) Å | 0.20 × 0.10 × 0.10 mm |
β = 91.00 (3)° |
Rigaku AFC-7R diffractometer | 1270 reflections with I > 2σ(I) |
Absorption correction: ψ scan (Psi in WinAFC Diffractometer Control Software; Rigaku 2002) | Rint = 0.028 |
Tmin = 0.928, Tmax = 1.000 | 3 standard reflections every 200 reflections |
3386 measured reflections | intensity decay: 0.3% |
1576 independent reflections |
R[F2 > 2σ(F2)] = 0.038 | 4 restraints |
wR(F2) = 0.095 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.17 e Å−3 |
1576 reflections | Δρmin = −0.29 e Å−3 |
148 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 | ||
O1W | 1.3075 (3) | 1.2115 (3) | 0.22404 (4) | 0.0510 (4) | |
H1WA | 1.400 (4) | 1.292 (4) | 0.2414 (5) | 0.061* | |
H1WB | 1.175 (3) | 1.304 (4) | 0.2153 (6) | 0.061* | |
O1 | 0.6331 (3) | 1.1354 (3) | 0.04240 (4) | 0.0456 (4) | |
H1 | 0.509 (4) | 1.157 (6) | 0.0242 (6) | 0.100* | |
O2 | 0.7482 (3) | 0.7840 (3) | 0.00986 (3) | 0.0453 (4) | |
N1 | 1.6033 (3) | 0.8366 (3) | 0.18939 (4) | 0.0363 (4) | |
H2 | 1.514 (4) | 0.965 (3) | 0.1990 (6) | 0.068* | |
N2 | 1.8032 (3) | 0.7255 (3) | 0.21010 (4) | 0.0429 (4) | |
N3 | 1.8788 (3) | 0.5272 (3) | 0.19041 (4) | 0.0439 (4) | |
N4 | 1.7318 (3) | 0.5062 (3) | 0.15713 (4) | 0.0396 (4) | |
C1 | 0.9801 (3) | 0.8752 (3) | 0.06869 (4) | 0.0301 (4) | |
C2 | 1.1494 (4) | 0.6629 (3) | 0.06537 (5) | 0.0345 (4) | |
H2A | 1.1350 | 0.5576 | 0.0438 | 0.041* | |
C3 | 1.3393 (4) | 0.6083 (3) | 0.09416 (5) | 0.0338 (4) | |
H3A | 1.4531 | 0.4669 | 0.0918 | 0.041* | |
C4 | 1.3602 (3) | 0.7647 (3) | 0.12651 (4) | 0.0289 (4) | |
C5 | 1.1923 (4) | 0.9778 (3) | 0.12961 (5) | 0.0340 (4) | |
H5A | 1.2076 | 1.0839 | 0.1511 | 0.041* | |
C6 | 1.0034 (3) | 1.0320 (3) | 0.10098 (5) | 0.0332 (4) | |
H6A | 0.8908 | 1.1742 | 0.1033 | 0.040* | |
C7 | 0.7755 (3) | 0.9317 (3) | 0.03801 (5) | 0.0319 (4) | |
C8 | 1.5608 (3) | 0.7022 (3) | 0.15704 (4) | 0.0297 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1W | 0.0586 (9) | 0.0478 (9) | 0.0459 (8) | 0.0216 (7) | −0.0217 (6) | −0.0168 (6) |
O1 | 0.0509 (8) | 0.0439 (8) | 0.0414 (7) | 0.0187 (7) | −0.0173 (6) | −0.0079 (6) |
O2 | 0.0510 (8) | 0.0496 (8) | 0.0348 (7) | 0.0147 (7) | −0.0156 (6) | −0.0130 (6) |
N1 | 0.0399 (9) | 0.0372 (9) | 0.0313 (8) | 0.0110 (7) | −0.0114 (6) | −0.0040 (6) |
N2 | 0.0458 (9) | 0.0444 (9) | 0.0380 (8) | 0.0125 (8) | −0.0152 (7) | −0.0023 (7) |
N3 | 0.0463 (9) | 0.0443 (9) | 0.0407 (8) | 0.0143 (8) | −0.0138 (7) | −0.0013 (7) |
N4 | 0.0430 (9) | 0.0381 (9) | 0.0374 (8) | 0.0117 (7) | −0.0102 (7) | −0.0024 (7) |
C1 | 0.0313 (9) | 0.0303 (9) | 0.0286 (8) | 0.0010 (7) | −0.0027 (7) | −0.0002 (7) |
C2 | 0.0396 (10) | 0.0334 (10) | 0.0302 (9) | 0.0043 (8) | −0.0055 (7) | −0.0071 (7) |
C3 | 0.0350 (9) | 0.0318 (9) | 0.0346 (9) | 0.0077 (8) | −0.0052 (7) | −0.0029 (7) |
C4 | 0.0289 (8) | 0.0300 (9) | 0.0277 (8) | 0.0008 (7) | −0.0035 (7) | 0.0016 (7) |
C5 | 0.0399 (10) | 0.0323 (9) | 0.0294 (9) | 0.0050 (8) | −0.0070 (7) | −0.0064 (7) |
C6 | 0.0360 (9) | 0.0297 (9) | 0.0337 (9) | 0.0080 (8) | −0.0052 (7) | −0.0027 (7) |
C7 | 0.0333 (9) | 0.0326 (9) | 0.0296 (9) | 0.0035 (8) | −0.0031 (7) | −0.0011 (7) |
C8 | 0.0322 (9) | 0.0285 (9) | 0.0284 (8) | 0.0020 (8) | −0.0029 (7) | 0.0010 (7) |
O1W—H1WA | 0.858 (10) | C1—C2 | 1.392 (2) |
O1W—H1WB | 0.859 (10) | C1—C7 | 1.482 (2) |
O1—C7 | 1.283 (2) | C2—C3 | 1.385 (2) |
O1—H1 | 0.877 (10) | C2—H2A | 0.9300 |
O2—C7 | 1.250 (2) | C3—C4 | 1.391 (2) |
N1—C8 | 1.337 (2) | C3—H3A | 0.9300 |
N1—N2 | 1.339 (2) | C4—C5 | 1.390 (2) |
N1—H2 | 0.872 (10) | C4—C8 | 1.471 (2) |
N2—N3 | 1.298 (2) | C5—C6 | 1.378 (2) |
N3—N4 | 1.356 (2) | C5—H5A | 0.9300 |
N4—C8 | 1.324 (2) | C6—H6A | 0.9300 |
C1—C6 | 1.391 (2) | ||
H1WA—O1W—H1WB | 111 (2) | C4—C3—H3A | 120.0 |
C7—O1—H1 | 113 (2) | C5—C4—C3 | 119.78 (15) |
C8—N1—N2 | 109.02 (14) | C5—C4—C8 | 120.84 (15) |
C8—N1—H2 | 130.9 (16) | C3—C4—C8 | 119.38 (15) |
N2—N1—H2 | 119.7 (15) | C6—C5—C4 | 120.14 (15) |
N3—N2—N1 | 106.08 (14) | C6—C5—H5A | 119.9 |
N2—N3—N4 | 111.08 (14) | C4—C5—H5A | 119.9 |
C8—N4—N3 | 105.55 (14) | C5—C6—C1 | 120.35 (16) |
C6—C1—C2 | 119.63 (15) | C5—C6—H6A | 119.8 |
C6—C1—C7 | 120.49 (15) | C1—C6—H6A | 119.8 |
C2—C1—C7 | 119.88 (15) | O2—C7—O1 | 123.55 (15) |
C3—C2—C1 | 120.02 (16) | O2—C7—C1 | 120.08 (15) |
C3—C2—H2A | 120.0 | O1—C7—C1 | 116.37 (14) |
C1—C2—H2A | 120.0 | N4—C8—N1 | 108.27 (14) |
C2—C3—C4 | 120.08 (16) | N4—C8—C4 | 126.17 (15) |
C2—C3—H3A | 120.0 | N1—C8—C4 | 125.55 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2i | 0.88 (1) | 1.74 (1) | 2.620 (2) | 176 (3) |
O1W—H1WA···N2ii | 0.86 (1) | 2.23 (2) | 2.957 (2) | 142 (2) |
O1W—H1WB···N3iii | 0.86 (1) | 2.05 (1) | 2.903 (2) | 175 (2) |
Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+7/2, y+1/2, −z+1/2; (iii) x−1, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | C8H6N4O2·H2O |
Mr | 208.18 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 4.914 (2), 5.219 (2), 34.720 (13) |
β (°) | 91.00 (3) |
V (Å3) | 890.4 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.20 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Rigaku AFC-7R diffractometer |
Absorption correction | ψ scan (Psi in WinAFC Diffractometer Control Software; Rigaku 2002) |
Tmin, Tmax | 0.928, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3386, 1576, 1270 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.095, 1.01 |
No. of reflections | 1576 |
No. of parameters | 148 |
No. of restraints | 4 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.17, −0.29 |
Computer programs: WinAFC Diffractometer Control Software (Rigaku, 2002), CrystalStructure (Rigaku/MSC, 2004, SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2i | 0.877 (10) | 1.744 (10) | 2.620 (2) | 176 (3) |
O1W—H1WA···N2ii | 0.858 (10) | 2.234 (16) | 2.957 (2) | 142 (2) |
O1W—H1WB···N3iii | 0.859 (10) | 2.046 (10) | 2.903 (2) | 175 (2) |
Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+7/2, y+1/2, −z+1/2; (iii) x−1, y+1, z. |
Acknowledgements
This work was supported by the Knowledge Innovation Program of the Chinese Academy of Sciences and the Natural Science Foundation of Fujian Province (A0420002 and E0510029).
References
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The current interest in crystal engineering of metal-organic coordination polymers (MOCPs) stems not only from their intriguing variety of architectures and topologies but also from their characteristic physical and/or chemical properties, including ferroelectricity, luminescence, magnetism, nonlinear optics, and gas storage, (James, et al. 2003; Kitagawa, et al. 2007; Maspoch, et al. 2007; Pan, et al. 2006; Li, et al. 2007). Multifunctional organic ligands are necessary for constructing such frameworks. Tetrazoles are versatile ligands due to their many potential donor atoms. They can be synthesized easily by the reaction of a cyano group with NaN3 in the presence of ZnBr2 (Lewis acid) as a catalyst and water under reflux or hydrothermal reaction conditions (Demko, et al. 2001). Here, we report the synthesis and crystal structure of a new tetrazole [C8H6N4O2].H2O (I).
The asymmetric unit of (I), consists of one crystallographically independent 4–5H-tetrazolyl-benzenecarboxylate molecule and one lattice water molecule (Figure 1). The molecular skeleton of I is essentially planar and the dihedral angle between the tetrazole and benzene rings is 0.16 °. Two adjacent 4–5H-tetrazolyl-benzenecarboxylate molecules are linked to form a centrosymmetric dimer through O1—H1···O2 hydrogen bonds. These dimers are bridged by lattice water molecules through O1W—H1WA···N2 and O1W—H1WB···N3 hydrogen bonds to form a two-dimensional layer along the [0 1 0] and [7 0 1] directions, (Figure 2). The layers are organized further by π-π stacking interactions between the tetrazole and benzene rings to form a three-dimensional framework. The two rings involved in the π-π stacking interactions are nearly parallel to each other, with a dihedral angle of 0.15 ° between them. The Cg1···Cg2i distance is 3.78 Å where Cg1 and Cg2 are the centroids of the C1···C6 and C8/N1···N4 rings respectively (i = x-1, y, z).