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Acta Cryst. (2009). E65, o690    [ doi:10.1107/S1600536809007521 ]

1,4-Bis[(1H-pyrazol-1-yl)methyl]benzene dihydrate

A.-E. Shi, Y.-J. Hou, Y.-M. Zhang, G.-F. Hou and J.-S. Gao

Abstract top

The asymmetric unit of the title compound, C14H14N4·2H2O consists of two half-molecules of the main molecule, each situated on an inversion center, and two molecules of water. One-dimensional chains of water molecules are built up by O-H...O hydrogen bonds which are then linked with the main molecule via O-H...N hydrogen bonds, forming a two-dimensional supramolecular network in the ac plane.

Comment top

The title compound is not only an excellent flexible ligand, but also a hydrogen bonding acceptor that can be used to construct supramolecular structures (Chang et al. (1993). In this paper, we report a two-dimensional supramolecular network similar to that reported earlier (Bourne et al. 2006), composed of 1,4-bis((1H-pyrazol-1-yl)methyl)benzene and water.

In (I), all bond lengths and angles are normal. The flexible ligand molecules display a 'Z' shape, with the pyrazole rings on opposite sides of the plane of the phenyl ring (Fig. 1).

In the crystal, one-dimensional water chains are built up by O—H···O hydrogen bonding interactions. The chains are then linked to the ligands (I),via O—H···N hydrogen bonds, forming a two-dimensional supramolecular network along the ac plane (Fig. 2, Table 1).

Related literature top

For background and the synthesis, see: Chang et al. (1993). For similar structures, see: Bourne et al. (2006).

Experimental top

The title compound was prepared from pyrazole (6.8 g, 100 mmol), Na2CO3 (16 g, 100 mmol) and 1,4-bis(bromomethyl)benzene (21.3 g, 50 mmol)in benzene. The solution was refluxed for 3 h. The title compound (4.7 g, 20 mmol) was then dissolved in hot water (30 ml) to give a clear solution and allowed to stand in a desiccator at room temperature for several days after which colorless crystals of (I) were obtained.

Refinement top

H atoms bound to C atoms were placed in calculated positions and treated as riding on their parent atoms, with C—H = 0.93 Å (aromatic), C—H = 0.97 Å (methylene), and with Uiso(H) = 1.2Ueq(C). Water H atoms were initially located in a difference Fourier map, but they were treated as riding on their parent atoms with O—H = 0.85 Å and with with Uiso(H) = 1.5Ueq(O).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); 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: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing displacement ellipsoids at the 30% probability level for non-H atoms. Dashed lines indicate the hydrogen-bonding interactions [Symmetry codes; (I) -x + 2, -y + 1, -z + 1]
[Figure 2] Fig. 2. A partial packing view, showing the two-dimensional network. Dashed lines indicate the hydrogen-bonding interactions. Only H atoms involved in hydrogren bonds are shown.
1,4-Bis[(1H-pyrazol-1-yl)methyl]benzene dihydrate top
Crystal data top
C14H14N4·2H2OF(000) = 584
Mr = 274.32Dx = 1.231 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 8012 reflections
a = 4.680 (2) Åθ = 6.5–54.9°
b = 18.640 (8) ŵ = 0.09 mm−1
c = 16.974 (10) ÅT = 291 K
β = 91.15 (2)°Block, colorless
V = 1480.6 (13) Å30.29 × 0.27 × 0.19 mm
Z = 4
Data collection top
Rigaku R-AXIS RAPID
diffractometer		3361 independent reflections
Radiation source: fine-focus sealed tube1735 reflections with I > 2σ(I)
graphiteRint = 0.050
ω scanθmax = 27.5°, θmin = 3.3°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		h = −6→5
Tmin = 0.956, Tmax = 0.984k = −23→24
14065 measured reflectionsl = −22→22
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.123H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.0547P)2]
where P = (Fo2 + 2Fc2)/3
3361 reflections(Δ/σ)max < 0.001
181 parametersΔρmax = 0.14 e Å−3
0 restraintsΔρmin = −0.13 e Å−3
Crystal data top
C14H14N4·2H2OV = 1480.6 (13) Å3
Mr = 274.32Z = 4
Monoclinic, P21/cMo Kα radiation
a = 4.680 (2) ŵ = 0.09 mm−1
b = 18.640 (8) ÅT = 291 K
c = 16.974 (10) Å0.29 × 0.27 × 0.19 mm
β = 91.15 (2)°
Data collection top
Rigaku R-AXIS RAPID
diffractometer		3361 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		1735 reflections with I > 2σ(I)
Tmin = 0.956, Tmax = 0.984Rint = 0.050
14065 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.048H-atom parameters constrained
wR(F2) = 0.123Δρmax = 0.14 e Å−3
S = 1.00Δρmin = −0.13 e Å−3
3361 reflectionsAbsolute structure: ?
181 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
C10.8625 (5)0.35411 (10)0.69781 (13)0.0727 (6)
H10.75840.32090.66800.087*
C21.0682 (5)0.33893 (11)0.75233 (13)0.0784 (6)
H21.13450.29390.76770.094*
C31.1572 (4)0.40427 (12)0.77993 (12)0.0737 (6)
H31.29830.41040.81870.088*
C40.6675 (4)0.46818 (11)0.63845 (12)0.0709 (6)
H40.60930.51240.66350.085*
H50.49630.44190.62310.085*
C50.8366 (3)0.48549 (9)0.56601 (11)0.0551 (4)
C60.8351 (4)0.43987 (10)0.50232 (12)0.0642 (5)
H60.72320.39870.50340.077*
C71.0049 (4)0.54625 (9)0.56293 (11)0.0622 (5)
H71.00990.57790.60530.075*
C80.5827 (4)0.27680 (10)−0.07594 (13)0.0724 (6)
H80.66420.2909−0.12300.087*
C90.3835 (5)0.22438 (10)−0.06711 (15)0.0776 (6)
H90.30160.1955−0.10610.093*
C100.3302 (4)0.22347 (9)0.01191 (14)0.0706 (6)
H100.20150.19250.03540.085*
C110.8187 (4)0.36625 (9)0.01523 (13)0.0663 (5)
H110.98080.3674−0.01950.080*
H120.89160.36120.06880.080*
C120.6550 (3)0.43624 (8)0.00771 (11)0.0527 (4)
C130.6725 (4)0.47764 (9)−0.05894 (11)0.0616 (5)
H130.78980.4630−0.09950.074*
C140.4809 (4)0.45945 (9)0.06678 (11)0.0624 (5)
H140.46630.43240.11260.075*
N10.8358 (3)0.42535 (8)0.69450 (8)0.0559 (4)
N21.0191 (3)0.45779 (8)0.74505 (9)0.0660 (4)
N30.6401 (3)0.30445 (7)−0.00459 (10)0.0579 (4)
N40.4843 (3)0.27223 (7)0.05120 (10)0.0638 (4)
O10.4928 (3)0.31462 (7)0.21740 (9)0.0847 (4)
H150.49390.30310.16900.127*
H160.33740.33730.22380.127*
O20.9966 (3)0.38581 (8)0.24291 (10)0.1062 (6)
H170.97460.43110.24210.159*
H180.83290.36630.23860.159*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0920 (14)0.0568 (11)0.0693 (14)−0.0064 (10)0.0027 (12)0.0032 (10)
C20.0967 (15)0.0713 (13)0.0674 (14)0.0235 (12)0.0093 (12)0.0138 (11)
C30.0689 (12)0.0959 (16)0.0562 (12)0.0135 (12)−0.0021 (10)0.0092 (11)
C40.0529 (10)0.0895 (13)0.0704 (14)0.0117 (9)0.0054 (10)0.0187 (11)
C50.0413 (9)0.0633 (10)0.0605 (12)0.0094 (8)−0.0013 (8)0.0145 (9)
C60.0646 (11)0.0599 (10)0.0679 (13)−0.0089 (9)−0.0060 (10)0.0122 (10)
C70.0708 (11)0.0571 (10)0.0587 (12)0.0052 (9)−0.0026 (10)0.0019 (9)
C80.0854 (14)0.0656 (12)0.0664 (15)0.0127 (11)0.0027 (11)0.0025 (10)
C90.0921 (15)0.0559 (11)0.0839 (18)0.0042 (11)−0.0177 (13)−0.0075 (11)
C100.0695 (12)0.0487 (10)0.0935 (18)−0.0009 (9)0.0001 (12)0.0009 (10)
C110.0505 (10)0.0544 (10)0.0936 (16)0.0012 (8)−0.0073 (10)0.0040 (10)
C120.0423 (8)0.0491 (9)0.0665 (12)−0.0049 (7)−0.0047 (8)0.0034 (8)
C130.0599 (10)0.0607 (11)0.0646 (13)0.0022 (8)0.0130 (9)0.0007 (9)
C140.0708 (11)0.0570 (10)0.0596 (12)0.0019 (9)0.0029 (10)0.0135 (9)
N10.0495 (8)0.0641 (9)0.0543 (9)0.0008 (7)0.0061 (7)0.0091 (7)
N20.0680 (9)0.0699 (9)0.0601 (10)−0.0009 (8)0.0042 (8)−0.0023 (8)
N30.0561 (8)0.0491 (7)0.0682 (11)0.0080 (7)−0.0015 (8)0.0022 (8)
N40.0669 (9)0.0537 (8)0.0709 (11)0.0047 (8)0.0043 (8)0.0025 (8)
O10.0878 (9)0.0774 (9)0.0887 (11)−0.0004 (7)−0.0012 (8)0.0027 (8)
O20.0867 (10)0.0885 (10)0.1433 (16)0.0021 (8)0.0031 (10)−0.0361 (10)
Geometric parameters (Å, °) top
C1—N11.335 (2)C9—C101.369 (3)
C1—C21.352 (3)C9—H90.9300
C1—H10.9300C10—N41.331 (2)
C2—C31.367 (3)C10—H100.9300
C2—H20.9300C11—N31.459 (2)
C3—N21.322 (2)C11—C121.517 (2)
C3—H30.9300C11—H110.9700
C4—N11.460 (2)C11—H120.9700
C4—C51.510 (2)C12—C131.373 (2)
C4—H40.9700C12—C141.375 (2)
C4—H50.9700C13—C14ii1.380 (2)
C5—C61.375 (3)C13—H130.9300
C5—C71.381 (2)C14—C13ii1.380 (2)
C6—C7i1.374 (3)C14—H140.9300
C6—H60.9300N1—N21.345 (2)
C7—C6i1.374 (3)N3—N41.348 (2)
C7—H70.9300O1—H150.8500
C8—N31.339 (2)O1—H160.8500
C8—C91.361 (3)O2—H170.8500
C8—H80.9300O2—H180.8500
N1—C1—C2107.56 (18)C10—C9—H9127.6
N1—C1—H1126.2N4—C10—C9112.01 (18)
C2—C1—H1126.2N4—C10—H10124.0
C1—C2—C3104.84 (18)C9—C10—H10124.0
C1—C2—H2127.6N3—C11—C12111.94 (14)
C3—C2—H2127.6N3—C11—H11109.2
N2—C3—C2112.08 (19)C12—C11—H11109.2
N2—C3—H3124.0N3—C11—H12109.2
C2—C3—H3124.0C12—C11—H12109.2
N1—C4—C5111.25 (14)H11—C11—H12107.9
N1—C4—H4109.4C13—C12—C14118.04 (16)
C5—C4—H4109.4C13—C12—C11120.95 (17)
N1—C4—H5109.4C14—C12—C11121.00 (16)
C5—C4—H5109.4C12—C13—C14ii121.16 (16)
H4—C4—H5108.0C12—C13—H13119.4
C6—C5—C7118.11 (16)C14ii—C13—H13119.4
C6—C5—C4120.89 (17)C12—C14—C13ii120.80 (16)
C7—C5—C4120.97 (18)C12—C14—H14119.6
C7i—C6—C5121.54 (17)C13ii—C14—H14119.6
C7i—C6—H6119.2C1—N1—N2111.26 (16)
C5—C6—H6119.2C1—N1—C4128.31 (17)
C6i—C7—C5120.36 (17)N2—N1—C4119.92 (15)
C6i—C7—H7119.8C3—N2—N1104.26 (16)
C5—C7—H7119.8C8—N3—N4111.25 (16)
N3—C8—C9107.6 (2)C8—N3—C11128.06 (17)
N3—C8—H8126.2N4—N3—C11120.37 (16)
C9—C8—H8126.2C10—N4—N3104.34 (16)
C8—C9—C10104.80 (19)H15—O1—H16105.7
C8—C9—H9127.6H17—O2—H18108.3
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+1, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H15···N40.852.082.929 (3)178
O1—H16···O2iii0.851.872.717 (2)177
O2—H17···N2i0.852.082.923 (2)170
O2—H18···O10.851.892.733 (2)172
Symmetry codes: (iii) x−1, y, z; (i) −x+2, −y+1, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H15···N40.852.082.929 (3)178
O1—H16···O2i0.851.872.717 (2)177
O2—H17···N2ii0.852.082.923 (2)170
O2—H18···O10.851.892.733 (2)172
Symmetry codes: (i) x−1, y, z; (ii) −x+2, −y+1, −z+1.
Acknowledgements top

The authors acknowledge financial support from the National Natural Science Foundation of China (grant No. 20872030), the Research Foundation of Heilongjiang Provincial Education Department (grant No. 11513073), the Project of the Special Fund of the Science and Technology Innovation People of Harbin (grant No. RC2006QN018001) and Heilongjiang University.

references
References top

Bourne, S. A., De Villiers, K. & Egan, T. J. (2006). Acta Cryst. C62, o53–o57.

Chang, W.-K., Sheu, S.-C., Lee, G.-H., Wang, Y., Ho, T.-I. & Lin, Y.-C. (1993). Dalton Trans. pp. 687–694.

Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.

Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.

Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.