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

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

doi:10.1107/S1600536809007521

organic compounds

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Volume 65| Part 4| April 2009| Page o690

doi:10.1107/S1600536809007521

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

Ai-E Shi,^a Yan-Jun Hou,^a Yi-Ming Zhang,^a Guang-Feng Hou ^a and Jin-Sheng Gao ^a ^*

^aCollege of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, People's Republic of China
^*Correspondence e-mail: hgf1000@163.com

(Received 19 February 2009; accepted 2 March 2009; online 6 March 2009)

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.

Related literature

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

Experimental

Crystal data

C₁₄H₁₄N₄·2H₂O
M_r = 274.32
Monoclinic, P 2₁ /c
a = 4.680 (2) Å
b = 18.640 (8) Å
c = 16.974 (10) Å
β = 91.15 (2)°
V = 1480.6 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 291 K
0.29 × 0.27 × 0.19 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.956, T_max = 0.984
14065 measured reflections
3361 independent reflections
1735 reflections with I > 2σ(I)
R_int = 0.050

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.123
S = 1.00
3361 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H15⋯N4	0.85	2.08	2.929 (3)	178
O1—H16⋯O2ⁱ	0.85	1.87	2.717 (2)	177
O2—H17⋯N2ⁱⁱ	0.85	2.08	2.923 (2)	170
O2—H18⋯O1	0.85	1.89	2.733 (2)	172
Symmetry codes: (i) x-1, y, z; (ii) -x+2, -y+1, -z+1.

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809007521/fl2236sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809007521/fl2236Isup2.hkl

checkCIF report

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.

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

	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]
	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

C₁₄H₁₄N₄·2H₂O	F(000) = 584
M_r = 274.32	D_x = 1.231 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8012 reflections
a = 4.680 (2) Å	θ = 6.5–54.9°
b = 18.640 (8) Å	µ = 0.09 mm⁻¹
c = 16.974 (10) Å	T = 291 K
β = 91.15 (2)°	Block, colorless
V = 1480.6 (13) Å³	0.29 × 0.27 × 0.19 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	3361 independent reflections
Radiation source: fine-focus sealed tube	1735 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.050
ω scan	θ_max = 27.5°, θ_min = 3.3°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −6→5
T_min = 0.956, T_max = 0.984	k = −23→24
14065 measured reflections	l = −22→22

Refinement top

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.123	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0547P)²] where P = (F_o² + 2F_c²)/3
3361 reflections	(Δ/σ)_max < 0.001
181 parameters	Δρ_max = 0.14 e Å⁻³
0 restraints	Δρ_min = −0.13 e Å⁻³

Crystal data top

C₁₄H₁₄N₄·2H₂O	V = 1480.6 (13) Å³
M_r = 274.32	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.680 (2) Å	µ = 0.09 mm⁻¹
b = 18.640 (8) Å	T = 291 K
c = 16.974 (10) Å	0.29 × 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)
T_min = 0.956, T_max = 0.984	R_int = 0.050
14065 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.123	H-atom parameters constrained
S = 1.00	Δρ_max = 0.14 e Å⁻³
3361 reflections	Δρ_min = −0.13 e Å⁻³
181 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

	x	y	z	U_iso*/U_eq
C1	0.8625 (5)	0.35411 (10)	0.69781 (13)	0.0727 (6)
H1	0.7584	0.3209	0.6680	0.087*
C2	1.0682 (5)	0.33893 (11)	0.75233 (13)	0.0784 (6)
H2	1.1345	0.2939	0.7677	0.094*
C3	1.1572 (4)	0.40427 (12)	0.77993 (12)	0.0737 (6)
H3	1.2983	0.4104	0.8187	0.088*
C4	0.6675 (4)	0.46818 (11)	0.63845 (12)	0.0709 (6)
H4	0.6093	0.5124	0.6635	0.085*
H5	0.4963	0.4419	0.6231	0.085*
C5	0.8366 (3)	0.48549 (9)	0.56601 (11)	0.0551 (4)
C6	0.8351 (4)	0.43987 (10)	0.50232 (12)	0.0642 (5)
H6	0.7232	0.3987	0.5034	0.077*
C7	1.0049 (4)	0.54625 (9)	0.56293 (11)	0.0622 (5)
H7	1.0099	0.5779	0.6053	0.075*
C8	0.5827 (4)	0.27680 (10)	−0.07594 (13)	0.0724 (6)
H8	0.6642	0.2909	−0.1230	0.087*
C9	0.3835 (5)	0.22438 (10)	−0.06711 (15)	0.0776 (6)
H9	0.3016	0.1955	−0.1061	0.093*
C10	0.3302 (4)	0.22347 (9)	0.01191 (14)	0.0706 (6)
H10	0.2015	0.1925	0.0354	0.085*
C11	0.8187 (4)	0.36625 (9)	0.01523 (13)	0.0663 (5)
H11	0.9808	0.3674	−0.0195	0.080*
H12	0.8916	0.3612	0.0688	0.080*
C12	0.6550 (3)	0.43624 (8)	0.00771 (11)	0.0527 (4)
C13	0.6725 (4)	0.47764 (9)	−0.05894 (11)	0.0616 (5)
H13	0.7898	0.4630	−0.0995	0.074*
C14	0.4809 (4)	0.45945 (9)	0.06678 (11)	0.0624 (5)
H14	0.4663	0.4324	0.1126	0.075*
N1	0.8358 (3)	0.42535 (8)	0.69450 (8)	0.0559 (4)
N2	1.0191 (3)	0.45779 (8)	0.74505 (9)	0.0660 (4)
N3	0.6401 (3)	0.30445 (7)	−0.00459 (10)	0.0579 (4)
N4	0.4843 (3)	0.27223 (7)	0.05120 (10)	0.0638 (4)
O1	0.4928 (3)	0.31462 (7)	0.21740 (9)	0.0847 (4)
H15	0.4939	0.3031	0.1690	0.127*
H16	0.3374	0.3373	0.2238	0.127*
O2	0.9966 (3)	0.38581 (8)	0.24291 (10)	0.1062 (6)
H17	0.9746	0.4311	0.2421	0.159*
H18	0.8329	0.3663	0.2386	0.159*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0920 (14)	0.0568 (11)	0.0693 (14)	−0.0064 (10)	0.0027 (12)	0.0032 (10)
C2	0.0967 (15)	0.0713 (13)	0.0674 (14)	0.0235 (12)	0.0093 (12)	0.0138 (11)
C3	0.0689 (12)	0.0959 (16)	0.0562 (12)	0.0135 (12)	−0.0021 (10)	0.0092 (11)
C4	0.0529 (10)	0.0895 (13)	0.0704 (14)	0.0117 (9)	0.0054 (10)	0.0187 (11)
C5	0.0413 (9)	0.0633 (10)	0.0605 (12)	0.0094 (8)	−0.0013 (8)	0.0145 (9)
C6	0.0646 (11)	0.0599 (10)	0.0679 (13)	−0.0089 (9)	−0.0060 (10)	0.0122 (10)
C7	0.0708 (11)	0.0571 (10)	0.0587 (12)	0.0052 (9)	−0.0026 (10)	0.0019 (9)
C8	0.0854 (14)	0.0656 (12)	0.0664 (15)	0.0127 (11)	0.0027 (11)	0.0025 (10)
C9	0.0921 (15)	0.0559 (11)	0.0839 (18)	0.0042 (11)	−0.0177 (13)	−0.0075 (11)
C10	0.0695 (12)	0.0487 (10)	0.0935 (18)	−0.0009 (9)	0.0001 (12)	0.0009 (10)
C11	0.0505 (10)	0.0544 (10)	0.0936 (16)	0.0012 (8)	−0.0073 (10)	0.0040 (10)
C12	0.0423 (8)	0.0491 (9)	0.0665 (12)	−0.0049 (7)	−0.0047 (8)	0.0034 (8)
C13	0.0599 (10)	0.0607 (11)	0.0646 (13)	0.0022 (8)	0.0130 (9)	0.0007 (9)
C14	0.0708 (11)	0.0570 (10)	0.0596 (12)	0.0019 (9)	0.0029 (10)	0.0135 (9)
N1	0.0495 (8)	0.0641 (9)	0.0543 (9)	0.0008 (7)	0.0061 (7)	0.0091 (7)
N2	0.0680 (9)	0.0699 (9)	0.0601 (10)	−0.0009 (8)	0.0042 (8)	−0.0023 (8)
N3	0.0561 (8)	0.0491 (7)	0.0682 (11)	0.0080 (7)	−0.0015 (8)	0.0022 (8)
N4	0.0669 (9)	0.0537 (8)	0.0709 (11)	0.0047 (8)	0.0043 (8)	0.0025 (8)
O1	0.0878 (9)	0.0774 (9)	0.0887 (11)	−0.0004 (7)	−0.0012 (8)	0.0027 (8)
O2	0.0867 (10)	0.0885 (10)	0.1433 (16)	0.0021 (8)	0.0031 (10)	−0.0361 (10)

Geometric parameters (Å, º) top

C1—N1	1.335 (2)	C9—C10	1.369 (3)
C1—C2	1.352 (3)	C9—H9	0.9300
C1—H1	0.9300	C10—N4	1.331 (2)
C2—C3	1.367 (3)	C10—H10	0.9300
C2—H2	0.9300	C11—N3	1.459 (2)
C3—N2	1.322 (2)	C11—C12	1.517 (2)
C3—H3	0.9300	C11—H11	0.9700
C4—N1	1.460 (2)	C11—H12	0.9700
C4—C5	1.510 (2)	C12—C13	1.373 (2)
C4—H4	0.9700	C12—C14	1.375 (2)
C4—H5	0.9700	C13—C14ⁱⁱ	1.380 (2)
C5—C6	1.375 (3)	C13—H13	0.9300
C5—C7	1.381 (2)	C14—C13ⁱⁱ	1.380 (2)
C6—C7ⁱ	1.374 (3)	C14—H14	0.9300
C6—H6	0.9300	N1—N2	1.345 (2)
C7—C6ⁱ	1.374 (3)	N3—N4	1.348 (2)
C7—H7	0.9300	O1—H15	0.8500
C8—N3	1.339 (2)	O1—H16	0.8500
C8—C9	1.361 (3)	O2—H17	0.8500
C8—H8	0.9300	O2—H18	0.8500

N1—C1—C2	107.56 (18)	C10—C9—H9	127.6
N1—C1—H1	126.2	N4—C10—C9	112.01 (18)
C2—C1—H1	126.2	N4—C10—H10	124.0
C1—C2—C3	104.84 (18)	C9—C10—H10	124.0
C1—C2—H2	127.6	N3—C11—C12	111.94 (14)
C3—C2—H2	127.6	N3—C11—H11	109.2
N2—C3—C2	112.08 (19)	C12—C11—H11	109.2
N2—C3—H3	124.0	N3—C11—H12	109.2
C2—C3—H3	124.0	C12—C11—H12	109.2
N1—C4—C5	111.25 (14)	H11—C11—H12	107.9
N1—C4—H4	109.4	C13—C12—C14	118.04 (16)
C5—C4—H4	109.4	C13—C12—C11	120.95 (17)
N1—C4—H5	109.4	C14—C12—C11	121.00 (16)
C5—C4—H5	109.4	C12—C13—C14ⁱⁱ	121.16 (16)
H4—C4—H5	108.0	C12—C13—H13	119.4
C6—C5—C7	118.11 (16)	C14ⁱⁱ—C13—H13	119.4
C6—C5—C4	120.89 (17)	C12—C14—C13ⁱⁱ	120.80 (16)
C7—C5—C4	120.97 (18)	C12—C14—H14	119.6
C7ⁱ—C6—C5	121.54 (17)	C13ⁱⁱ—C14—H14	119.6
C7ⁱ—C6—H6	119.2	C1—N1—N2	111.26 (16)
C5—C6—H6	119.2	C1—N1—C4	128.31 (17)
C6ⁱ—C7—C5	120.36 (17)	N2—N1—C4	119.92 (15)
C6ⁱ—C7—H7	119.8	C3—N2—N1	104.26 (16)
C5—C7—H7	119.8	C8—N3—N4	111.25 (16)
N3—C8—C9	107.6 (2)	C8—N3—C11	128.06 (17)
N3—C8—H8	126.2	N4—N3—C11	120.37 (16)
C9—C8—H8	126.2	C10—N4—N3	104.34 (16)
C8—C9—C10	104.80 (19)	H15—O1—H16	105.7
C8—C9—H9	127.6	H17—O2—H18	108.3

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H15···N4	0.85	2.08	2.929 (3)	178
O1—H16···O2ⁱⁱⁱ	0.85	1.87	2.717 (2)	177
O2—H17···N2ⁱ	0.85	2.08	2.923 (2)	170
O2—H18···O1	0.85	1.89	2.733 (2)	172

Symmetry codes: (i) −x+2, −y+1, −z+1; (iii) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₄N₄·2H₂O
M_r	274.32
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	291
a, b, c (Å)	4.680 (2), 18.640 (8), 16.974 (10)
β (°)	91.15 (2)
V (Å³)	1480.6 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.29 × 0.27 × 0.19

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.956, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	14065, 3361, 1735
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.123, 1.00
No. of reflections	3361
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.13

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H15···N4	0.85	2.08	2.929 (3)	177.9
O1—H16···O2ⁱ	0.85	1.87	2.717 (2)	177.3
O2—H17···N2ⁱⁱ	0.85	2.08	2.923 (2)	169.7
O2—H18···O1	0.85	1.89	2.733 (2)	171.6

Symmetry codes: (i) x−1, y, z; (ii) −x+2, −y+1, −z+1.

Acknowledgements

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

Bourne, S. A., De Villiers, K. & Egan, T. J. (2006). Acta Cryst. C62, o53–o57. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
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