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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 68| Part 8| August 2012| Page o2394
https://doi.org/10.1107/S1600536812029273

1,4-Bis(4H-1,2,4-triazol-4-yl)benzene dihydrate

Xiu-Guang Wang,a Jian-Hui Li,b Bin Dinga* and Gui-Xiang Dua

aTianjin Key Laboratory of Structure and Performance for Functional Molecules, Tianjin Normal University, Tianjin 300071, People's Republic of China, and bPingdingshan Education Institute, Henan 467000, People's Republic of China
*Correspondence e-mail: qsdingbin@yahoo.com.cn

(Received 6 June 2012; accepted 27 June 2012; online 10 July 2012)

The asymmetric unit of the title compound, C10H8N6·2H2O, comprises half the organic species, the mol­ecule being completed by inversion symmetry, and one water mol­ecule. The dihedral angle between the 1,2,4-triazole ring and the central benzene ring is 32.2 (2)°. The water mol­ecules form O—H⋯N hydrogen bonds with N-atom acceptors of the triazole rings. C—H⋯N hydrogen bonds are also observed, giving a three-dimensional framework.

Related literature

For the synthesis of the title compound, see: Wiley & Hart (1953[Wiley, R. H. & Hart, A. J. (1953). J. Org. Chem. 18, 1368-1371.]). For a comprehensive review on 1,2,4-triazole and its derivatives, see: Haasnoot (2000[Haasnoot, J. G. (2000). Coord. Chem. Rev. 131-135, 200-248.]). For iron(II) compounds containing 1,2,4-triazole ligands, see: Kahn et al. (1998[Kahn, O. & Martinez, C. J. (1998). Science, 279, 44-48.]). For 1,2,4-triazole and its derivatives, see: Aromí et al. (2011[Aromí, G., Barrios, L. A., Roubeau, O. & Gamez, P. (2011). Coord. Chem. Rev. 255, 485-546.]). For C—N bond lengths, see: Heyrovska (2008[Heyrovska, R. (2008). Open Struct. Biol. J. 2,1-7.]); Schoknecht & Kempe (2004[Schoknecht, B. & Kempe, R. (2004). Z. Anorg. Allg. Chem. 630, 1377-1379.]).

[Scheme 1]

Experimental

Crystal data

  • C10H8N6·2H2O

  • Mr = 248.26

  • Monoclinic, P 21 /n

  • a = 3.7090 (7) Å

  • b = 15.680 (3) Å

  • c = 9.6054 (18) Å

  • β = 99.748 (3)°

  • V = 550.56 (18) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.11 mm−1

  • T = 173 K

  • 0.18 × 0.05 × 0.04 mm
Data collection

  • Bruker APEXII CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.993, Tmax = 0.996

  • 2717 measured reflections

  • 959 independent reflections

  • 838 reflections with I > 2σ(I)

  • Rint = 0.022
Refinement

  • R[F2 > 2σ(F2)] = 0.055

  • wR(F2) = 0.129

  • S = 1.18

  • 959 reflections

  • 88 parameters

  • 2 restraints

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.35 e Å−3

  • Δρmin = −0.43 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
C1—H1⋯N3i 0.95 2.39 3.307 (3) 163
O1—H134⋯N2 0.88 (2) 1.98 (4) 2.816 (5) 158 (10)
Symmetry code: (i) [x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}].

Data collection: APEX2 (Bruker, 2008[Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2008[Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]) and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812029273/rn2105sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812029273/rn2105Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812029273/rn2105Isup3.cml

checkCIF report


Comment top

Nowadays 1,2,4-triazole and its derivatives have attracted great interest because they combine the coordination modes of pyrazole and imidazole. Some iron(II) complexes containing 1,2,4-triazole ligands have spin-crossover properties, which could be used in molecular-based memory devices, displays and optical switches. (Kahn et al., 1998).

A comprehensive review about 1,2,4-triazole and its derivatives also has been made by Haasnoot (Haasnoot, 2000). One of the requirements for producing such macroscopic properties is to create interactions between the molecular units and the active sites within the crystal lattices. 1,2,4-Triazole and in particular its derivatives are very interesting as bridging ligands (Aromí et al., 2011).

Herein we report the synthesis and the crystal structure of the title compound, 1,4-bis(4H-1,2,4- triazol-4-yl)benzene dihydrate, (I), which is expected to act as a tetradentate ligand to form low and multi-dimensional polymers with metal atoms.

The molecular structure of (I) is shown in Fig. 1. The triazole ring is almost perfectly planar maximum deviation from the least-squares plane is 0.001 (2) Å]. The distribution of bond lengths in the triazole ring vary from 1.305 (1)-1.430 (3) Å, which all fall in the range between 1.47 Å for a C-N single bond and 1.29 Å for a C=N double bond. The dihedral angle between the substituted benzene ring and the 1,2,4-triazole ring is 32.2 (2)°. The C1-N2 bond distance is 1.305 (1) Å and the C3-N1 bond distance is 1.430 (3) Å (Schoknecht & Kempe, 2004; Heyrovska, 2008), indicating that they correspond to double and single bonds, respectively. The C1-N1 bond distance is 1.352 (3) Å, which is 0.078 Å shorter than C3-N1 and 0.047 Å longer than C1-N2, indicating that there is a electron delocalisation in the 1,2,4-triazole π system.

Examination of the crystal structure with PLATON (Spek, 2009) shows the water molecules form O-H···N hydrogen bonds with the N-atom acceptors of the triazole rings, O-H···N and C1-H···N3 hydrogen bonds assemble (I) into a three dimensional supramolecular structure (Table 1, Figure 2) .

Related literature top

For the synthesis of the title compound, see: Wiley & Hart (1953). For a comprehensive review on 1,2,4-triazole and its derivatives, see: Haasnoot (2000). For iron(II) compounds containing 1,2,4-triazole ligands, see: Kahn et al. (1998). For 1,2,4-triazole and its derivatives, see: Aromí et al. (2011). For C—N bond lengths, see: Heyrovska (2008); Schoknecht & Kempe (2004).

Experimental top

The title compound was obtained by the reaction of N,N'-diformylhydrazine (880 mg, 10 mmol) and p-pheneylenediamine (540 mg, 5 mmol) in the presence of ammonium sulfate (264 mg, 2 mmol) for 5 h at 413 K (Wiley & Hart,1953). The title compound were collected and recrystallized from methanol. After several recrystallizations from methanol, the air-dried product was obtained as colorless block crystals. Anal. Calcd for C10H12N6O2: C, 48.38; H, 4.87%. Found: C, 48.85; H, 4.95%..

Refinement top

The water H atoms were located in a Fourier difference map and refined subject to an O-H restraint 0.88 (1) Å and an H···H restraint of 1.42 (2) Å. Other H atoms were allowed to ride on their parent atoms with C-H distances of 0.93 Å and Uiso(H) = 1.2Ueq(C). All of the non-hydrogen atoms were refined anisotropically.

Structure description top

Nowadays 1,2,4-triazole and its derivatives have attracted great interest because they combine the coordination modes of pyrazole and imidazole. Some iron(II) complexes containing 1,2,4-triazole ligands have spin-crossover properties, which could be used in molecular-based memory devices, displays and optical switches. (Kahn et al., 1998).

A comprehensive review about 1,2,4-triazole and its derivatives also has been made by Haasnoot (Haasnoot, 2000). One of the requirements for producing such macroscopic properties is to create interactions between the molecular units and the active sites within the crystal lattices. 1,2,4-Triazole and in particular its derivatives are very interesting as bridging ligands (Aromí et al., 2011).

Herein we report the synthesis and the crystal structure of the title compound, 1,4-bis(4H-1,2,4- triazol-4-yl)benzene dihydrate, (I), which is expected to act as a tetradentate ligand to form low and multi-dimensional polymers with metal atoms.

The molecular structure of (I) is shown in Fig. 1. The triazole ring is almost perfectly planar maximum deviation from the least-squares plane is 0.001 (2) Å]. The distribution of bond lengths in the triazole ring vary from 1.305 (1)-1.430 (3) Å, which all fall in the range between 1.47 Å for a C-N single bond and 1.29 Å for a C=N double bond. The dihedral angle between the substituted benzene ring and the 1,2,4-triazole ring is 32.2 (2)°. The C1-N2 bond distance is 1.305 (1) Å and the C3-N1 bond distance is 1.430 (3) Å (Schoknecht & Kempe, 2004; Heyrovska, 2008), indicating that they correspond to double and single bonds, respectively. The C1-N1 bond distance is 1.352 (3) Å, which is 0.078 Å shorter than C3-N1 and 0.047 Å longer than C1-N2, indicating that there is a electron delocalisation in the 1,2,4-triazole π system.

Examination of the crystal structure with PLATON (Spek, 2009) shows the water molecules form O-H···N hydrogen bonds with the N-atom acceptors of the triazole rings, O-H···N and C1-H···N3 hydrogen bonds assemble (I) into a three dimensional supramolecular structure (Table 1, Figure 2) .

For the synthesis of the title compound, see: Wiley & Hart (1953). For a comprehensive review on 1,2,4-triazole and its derivatives, see: Haasnoot (2000). For iron(II) compounds containing 1,2,4-triazole ligands, see: Kahn et al. (1998). For 1,2,4-triazole and its derivatives, see: Aromí et al. (2011). For C—N bond lengths, see: Heyrovska (2008); Schoknecht & Kempe (2004).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids and the atom-numbering schemes. The superscript (I) on the atom labels corresponds to atoms generated by the symmetry operation: -x, -y, 1-z.
[Figure 2] Fig. 2. A three-dimensional supramolecular sheet structure of the title compound. The crystal packing for (I), with the H bond interactions shown as dashed lines.
1,4-Bis(4H-1,2,4-triazol-4-yl)benzene dihydrate top
Crystal data top
C10H8N6·2H2OF(000) = 260
Mr = 248.26Dx = 1.497 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2717 reflections
a = 3.7090 (7) Åθ = 4.3–25.0°
b = 15.680 (3) ŵ = 0.11 mm−1
c = 9.6054 (18) ÅT = 173 K
β = 99.748 (3)°Block, colorless
V = 550.56 (18) Å30.18 × 0.05 × 0.04 mm
Z = 2
Data collection top
Bruker APEXII CCD
diffractometer		959 independent reflections
Radiation source: fine-focus sealed tube838 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.022
φ and ω scansθmax = 25.0°, θmin = 4.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −2→4
Tmin = 0.993, Tmax = 0.996k = −18→18
2717 measured reflectionsl = −11→11
Refinement top
Refinement on F22 restraints
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.055 w = 1/[σ2(Fo2) + (0.0241P)2 + 0.9002P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.129(Δ/σ)max < 0.001
S = 1.18Δρmax = 0.35 e Å−3
959 reflectionsΔρmin = −0.43 e Å−3
88 parameters
Crystal data top
C10H8N6·2H2OV = 550.56 (18) Å3
Mr = 248.26Z = 2
Monoclinic, P21/nMo Kα radiation
a = 3.7090 (7) ŵ = 0.11 mm−1
b = 15.680 (3) ÅT = 173 K
c = 9.6054 (18) Å0.18 × 0.05 × 0.04 mm
β = 99.748 (3)°
Data collection top
Bruker APEXII CCD
diffractometer		959 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		838 reflections with I > 2σ(I)
Tmin = 0.993, Tmax = 0.996Rint = 0.022
2717 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0552 restraints
wR(F2) = 0.129H atoms treated by a mixture of independent and constrained refinement
S = 1.18Δρmax = 0.35 e Å−3
959 reflectionsΔρmin = −0.43 e Å−3
88 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
xyzUiso*/Ueq
N10.1379 (5)0.15524 (13)0.3739 (2)0.0198 (5)
N20.2094 (6)0.29226 (14)0.3416 (2)0.0262 (6)
N30.2767 (6)0.24992 (14)0.2222 (2)0.0251 (6)
C10.1282 (7)0.23438 (16)0.4290 (3)0.0232 (6)
H10.06990.24630.51950.028*
C20.2311 (7)0.16877 (17)0.2441 (3)0.0248 (6)
H20.25900.12490.17850.030*
C30.0687 (6)0.07598 (15)0.4383 (3)0.0194 (6)
C40.1572 (7)0.06740 (16)0.5842 (3)0.0207 (6)
H40.26420.11360.64070.025*
C50.0875 (7)−0.00908 (16)0.6460 (3)0.0210 (6)
H50.1460−0.01590.74550.025*
O10.229 (3)0.4543 (3)0.4689 (5)0.181 (3)
H1340.19 (3)0.411 (4)0.410 (8)0.235*
H130.448 (12)0.434 (6)0.498 (10)0.181*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0191 (11)0.0195 (11)0.0213 (11)−0.0001 (8)0.0050 (8)0.0013 (9)
N20.0275 (12)0.0236 (12)0.0276 (12)0.0004 (9)0.0048 (9)0.0008 (9)
N30.0255 (12)0.0253 (12)0.0249 (12)−0.0015 (9)0.0057 (9)0.0039 (9)
C10.0231 (14)0.0227 (13)0.0236 (13)0.0012 (10)0.0038 (10)−0.0021 (11)
C20.0241 (14)0.0266 (14)0.0240 (14)−0.0001 (11)0.0052 (10)0.0013 (11)
C30.0164 (12)0.0191 (12)0.0235 (13)0.0006 (10)0.0058 (10)0.0024 (10)
C40.0198 (13)0.0190 (12)0.0228 (13)0.0000 (10)0.0023 (10)−0.0029 (10)
C50.0216 (13)0.0233 (13)0.0181 (12)0.0007 (10)0.0031 (10)0.0007 (10)
O10.365 (10)0.067 (3)0.089 (3)0.028 (4)−0.023 (4)−0.036 (2)
Geometric parameters (Å, º) top
N1—C11.352 (3)C3—C41.391 (3)
N1—C21.366 (3)C4—C51.382 (4)
N1—C31.430 (3)C4—H40.9500
N2—C11.305 (3)C5—C3i1.390 (4)
N2—N31.385 (3)C5—H50.9500
N3—C21.305 (3)O1—H1340.88 (2)
C1—H10.9500O1—H1340.88 (2)
C2—H20.9500O1—H130.87 (2)
C3—C5i1.390 (4)
C1—N1—C2104.0 (2)C5i—C3—N1119.4 (2)
C1—N1—C3127.6 (2)C4—C3—N1119.4 (2)
C2—N1—C3128.4 (2)C5—C4—C3119.2 (2)
C1—N2—N3107.0 (2)C5—C4—H4120.4
C2—N3—N2106.7 (2)C3—C4—H4120.4
N2—C1—N1111.3 (2)C4—C5—C3i119.6 (2)
N2—C1—H1124.4C4—C5—H5120.2
N1—C1—H1124.4C3i—C5—H5120.2
N3—C2—N1111.0 (2)H134—O1—H1340 (10)
N3—C2—H2124.5H134—O1—H1388 (8)
N1—C2—H2124.5H134—O1—H1388 (8)
C5i—C3—C4121.2 (2)
C1—N2—N3—C20.2 (3)C1—N1—C3—C5i147.9 (3)
N3—N2—C1—N10.0 (3)C2—N1—C3—C5i−32.6 (4)
C2—N1—C1—N2−0.2 (3)C1—N1—C3—C4−31.8 (4)
C3—N1—C1—N2179.4 (2)C2—N1—C3—C4147.7 (3)
N2—N3—C2—N1−0.3 (3)C5i—C3—C4—C5−0.1 (4)
C1—N1—C2—N30.3 (3)N1—C3—C4—C5179.6 (2)
C3—N1—C2—N3−179.2 (2)C3—C4—C5—C3i0.1 (4)
Symmetry code: (i) −x, −y, −z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1···N3ii0.952.393.307 (3)163
O1—H134···N20.88 (2)1.98 (4)2.816 (5)158 (10)
Symmetry code: (ii) x−1/2, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC10H8N6·2H2O
Mr248.26
Crystal system, space groupMonoclinic, P21/n
Temperature (K)173
a, b, c (Å)3.7090 (7), 15.680 (3), 9.6054 (18)
β (°) 99.748 (3)
V (Å3)550.56 (18)
Z2
Radiation typeMo Kα
µ (mm−1)0.11
Crystal size (mm)0.18 × 0.05 × 0.04
Data collection
DiffractometerBruker APEXII CCD
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.993, 0.996
No. of measured, independent and
observed [I > 2σ(I)] reflections		2717, 959, 838
Rint0.022
(sin θ/λ)max (Å−1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.055, 0.129, 1.18
No. of reflections959
No. of parameters88
No. of restraints2
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)0.35, −0.43

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1···N3i0.952.393.307 (3)163.3
O1—H134···N20.88 (2)1.98 (4)2.816 (5)158 (10)
Symmetry code: (i) x−1/2, −y+1/2, z+1/2.
 

Acknowledgements

This present work was supported financially by Tianjin Educational Committee (20090504 and 20110311).

References

First citationAromí, G., Barrios, L. A., Roubeau, O. & Gamez, P. (2011). Coord. Chem. Rev. 255, 485–546.  Google Scholar
 First citationBruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationHaasnoot, J. G. (2000). Coord. Chem. Rev. 131–135, 200–248.  Google Scholar
 First citationHeyrovska, R. (2008). Open Struct. Biol. J. 2,1–7.  CrossRef CAS Google Scholar
 First citationKahn, O. & Martinez, C. J. (1998). Science, 279, 44–48.  Web of Science CrossRef CAS Google Scholar
 First citationSchoknecht, B. & Kempe, R. (2004). Z. Anorg. Allg. Chem. 630, 1377–1379.  Web of Science CSD CrossRef CAS Google Scholar
 First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.  Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationWiley, R. H. & Hart, A. J. (1953). J. Org. Chem. 18, 1368–1371.  CrossRef CAS Web of Science Google Scholar

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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 68| Part 8| August 2012| Page o2394
https://doi.org/10.1107/S1600536812029273
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