5,5′-(Butane-1,4-di­yl)bis­(1H-tetra­zole) dihydrate

Xin, J.-H.; Tong, X.-L.

doi:10.1107/S1600536810048993

organic compounds

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Volume 66| Part 12| December 2010| Page o3328

https://doi.org/10.1107/S1600536810048993

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5,5′-(Butane-1,4-diyl)bis(1H-tetrazole) dihydrate

Jian-Hua Xin ^a and Xiao-Lan Tong ^a ^*

^aCollege of Biology, Chemistry and Material Science, East China of Technology, 344000 Fuzhou, Jiangxi, People's Republic of China
^*Correspondence e-mail: tongxiaolan@163.com

(Received 22 November 2010; accepted 23 November 2010; online 27 November 2010)

The title compound, C₆H₁₀N₈·2H₂O, was prepared by the reaction of hexanedinitrile and sodium azide. The di-1H-tetrazole molecule lies on a crystallographic centre of inversion and is linked to the water molecules by N—H⋯O and O—H⋯N hydrogen bonds, forming a two-dimensional supramolecular structure in the crystal.

Related literature

For tetrazole derivatives, see: Demko & Sharpless (2001 ); Diop et al. (2002 ); Kitagawa et al. (2004 ); Li et al. (2007 ); Tamura et al. (1998 ); Tong et al. (2009 ); Zhao et al. (2008 ).

Experimental

Crystal data

C₆H₁₀N₈·2H₂O
M_r = 230.25
Monoclinic, C 2/c
a = 6.994 (3) Å
b = 11.590 (5) Å
c = 14.097 (6) Å
β = 100.716 (7)°
V = 1122.8 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 294 K
0.20 × 0.18 × 0.16 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.979, T_max = 0.983
2756 measured reflections
992 independent reflections
722 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.147
S = 1.04
992 reflections
73 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WB⋯N3ⁱ	0.85	2.02	2.851 (3)	165
O1W—H1WA⋯N4ⁱⁱ	0.85	1.99	2.822 (3)	167
N1—H1⋯O1W	0.86	1.80	2.662 (3)	175
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x, -y, z+{\script{1\over 2}}]$ .

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810048993/bt5418sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810048993/bt5418Isup2.hkl

checkCIF report

Comment top

The tetrazole derivatives are very important molecules in pharmacological and biochemical properties (Tamura et al., 1998). Since Sharpless et al. have introduced a simple and effective method to synthesize the tetrazole derivatives (Demko et al., 2001), they have been used extensively in areas as diverse as medicinal chemistry, coordination chemistry and material chemistry (Zhao et al., 2008; Kitagawa et al., 2004; Li et al., 2007). Among these, The flexible 5-substituted tetrazolate ligands have been less investigated (Diop et al., 2002), although we have studied the coordination of the bis(tetrazole) ligands separated by alkyl (CH₂)_n spacers (Tong et al., 2009). Here, as the additional of our work, we report the crystal structure of the title compound (Fig. 1).

1,2-Bis(tetrazol-5-yl)butpane lies on a crystallographic centre of inversion and is linked to the water molecules by N—H···O and O—H···N hydrogen bonds into a 2-D supramolecular structure (Fig. 2).

Related literature top

For tetrazole derivatives, see: Demko & Sharpless (2001); Diop et al. (2002); Kitagawa et al. (2004); Li et al. (2007); Tamura et al. (1998); Tong et al. (2009); Zhao et al. (2008).

Experimental top

1,2-Bis(tetrazol-5-yl)butane was prepared using a reported procedure (Tong et al., 2009) (Scheme I). 1,2-Bis(tetrazol-5-yl)butane and water (12 ml) was sealed in a 25 ml Teflon-lined stainless steel vessel and heated at 393 k for 72 hr., then cooled to room temperature. Colorless prism-shaped crystals of the title compound were isolated and washed with water and ethanol and dried in air.

Structure description top

For tetrazole derivatives, see: Demko & Sharpless (2001); Diop et al. (2002); Kitagawa et al. (2004); Li et al. (2007); Tamura et al. (1998); Tong et al. (2009); Zhao et al. (2008).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title compound, (I), with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. The packing diagram of the title compound. Hydrogen bonds are shown as dashed line.

5,5'-(Butane-1,4-diyl)bis(1H-tetrazole) dihydrate top

Crystal data top

C₆H₁₀N₈·2H₂O	F(000) = 488
M_r = 230.25	D_x = 1.362 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1178 reflections
a = 6.994 (3) Å	θ = 2.9–25.0°
b = 11.590 (5) Å	µ = 0.11 mm⁻¹
c = 14.097 (6) Å	T = 294 K
β = 100.716 (7)°	Block, colorless
V = 1122.8 (8) Å³	0.20 × 0.18 × 0.16 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	992 independent reflections
Radiation source: fine-focus sealed tube	722 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
φ and ω scans	θ_max = 25.0°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→8
T_min = 0.979, T_max = 0.983	k = −13→10
2756 measured reflections	l = −16→15

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.147	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0759P)² + 0.9248P] where P = (F_o² + 2F_c²)/3
992 reflections	(Δ/σ)_max < 0.001
73 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₆H₁₀N₈·2H₂O	V = 1122.8 (8) Å³
M_r = 230.25	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 6.994 (3) Å	µ = 0.11 mm⁻¹
b = 11.590 (5) Å	T = 294 K
c = 14.097 (6) Å	0.20 × 0.18 × 0.16 mm
β = 100.716 (7)°

Data collection top

Bruker SMART CCD area-detector diffractometer	992 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	722 reflections with I > 2σ(I)
T_min = 0.979, T_max = 0.983	R_int = 0.025
2756 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.147	H-atom parameters constrained
S = 1.04	Δρ_max = 0.16 e Å⁻³
992 reflections	Δρ_min = −0.21 e Å⁻³
73 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
O1W	0.2175 (3)	0.10913 (15)	0.88483 (13)	0.0697 (7)
H1WA	0.2503	0.0847	0.9424	0.105*
H1WB	0.2153	0.1823	0.8886	0.105*
N1	0.2521 (3)	−0.00531 (16)	0.72515 (14)	0.0487 (6)
H1	0.2430	0.0355	0.7751	0.058*
N2	0.2517 (4)	−0.11987 (17)	0.72219 (16)	0.0607 (7)
N3	0.2679 (4)	−0.14652 (18)	0.63566 (16)	0.0624 (7)
N4	0.2787 (4)	−0.05060 (17)	0.58246 (14)	0.0536 (7)
C1	0.2683 (4)	0.0365 (2)	0.63995 (16)	0.0422 (6)
C3	0.2750 (4)	0.1611 (2)	0.61690 (17)	0.0505 (7)
H3A	0.3991	0.1922	0.6488	0.061*
H3B	0.1737	0.2006	0.6428	0.061*
C4	0.2488 (4)	0.1863 (2)	0.50977 (17)	0.0463 (7)
H4A	0.3525	0.1493	0.4838	0.056*
H4B	0.1261	0.1541	0.4771	0.056*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1W	0.131 (2)	0.0449 (11)	0.0368 (11)	0.0010 (11)	0.0256 (11)	−0.0017 (8)
N1	0.0817 (16)	0.0361 (12)	0.0306 (11)	−0.0005 (10)	0.0162 (10)	0.0006 (9)
N2	0.101 (2)	0.0406 (13)	0.0419 (13)	−0.0030 (12)	0.0169 (12)	0.0072 (10)
N3	0.108 (2)	0.0365 (12)	0.0451 (14)	−0.0027 (12)	0.0196 (13)	0.0011 (10)
N4	0.0960 (18)	0.0327 (11)	0.0344 (11)	−0.0022 (11)	0.0181 (11)	0.0010 (9)
C1	0.0603 (16)	0.0364 (12)	0.0306 (12)	−0.0024 (11)	0.0103 (10)	0.0003 (10)
C3	0.082 (2)	0.0344 (13)	0.0373 (14)	−0.0022 (12)	0.0157 (12)	−0.0011 (11)
C4	0.0661 (16)	0.0366 (13)	0.0373 (13)	−0.0007 (12)	0.0120 (11)	0.0020 (10)

Geometric parameters (Å, º) top

O1W—H1WA	0.8500	C1—C3	1.482 (3)
O1W—H1WB	0.8500	C3—C4	1.516 (3)
N1—C1	1.320 (3)	C3—H3A	0.9700
N1—N2	1.328 (3)	C3—H3B	0.9700
N1—H1	0.8600	C4—C4ⁱ	1.503 (5)
N2—N3	1.284 (3)	C4—H4A	0.9700
N3—N4	1.351 (3)	C4—H4B	0.9700
N4—C1	1.305 (3)

H1WA—O1W—H1WB	106.1	C1—C3—H3A	108.8
C1—N1—N2	109.8 (2)	C4—C3—H3A	108.8
C1—N1—H1	125.1	C1—C3—H3B	108.8
N2—N1—H1	125.1	C4—C3—H3B	108.8
N3—N2—N1	105.69 (19)	H3A—C3—H3B	107.7
N2—N3—N4	110.7 (2)	C4ⁱ—C4—C3	111.7 (3)
C1—N4—N3	106.1 (2)	C4ⁱ—C4—H4A	109.3
N4—C1—N1	107.7 (2)	C3—C4—H4A	109.3
N4—C1—C3	127.6 (2)	C4ⁱ—C4—H4B	109.3
N1—C1—C3	124.7 (2)	C3—C4—H4B	109.3
C1—C3—C4	113.8 (2)	H4A—C4—H4B	108.0

C1—N1—N2—N3	0.1 (3)	N2—N1—C1—N4	−0.1 (3)
N1—N2—N3—N4	0.0 (3)	N2—N1—C1—C3	−179.6 (2)
N2—N3—N4—C1	0.0 (3)	N4—C1—C3—C4	13.6 (4)
N3—N4—C1—N1	0.1 (3)	N1—C1—C3—C4	−167.1 (3)
N3—N4—C1—C3	179.5 (2)	C1—C3—C4—C4ⁱ	178.4 (3)

Symmetry code: (i) −x+1/2, −y+1/2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WB···N3ⁱⁱ	0.85	2.02	2.851 (3)	165
O1W—H1WA···N4ⁱⁱⁱ	0.85	1.99	2.822 (3)	167
N1—H1···O1W	0.86	1.80	2.662 (3)	175

Symmetry codes: (ii) −x+1/2, y+1/2, −z+3/2; (iii) x, −y, z+1/2.

Experimental details

Crystal data
Chemical formula	C₆H₁₀N₈·2H₂O
M_r	230.25
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	294
a, b, c (Å)	6.994 (3), 11.590 (5), 14.097 (6)
β (°)	100.716 (7)
V (Å³)	1122.8 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.20 × 0.18 × 0.16

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.979, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	2756, 992, 722
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.147, 1.04
No. of reflections	992
No. of parameters	73
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.21

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WB···N3ⁱ	0.85	2.02	2.851 (3)	165.2
O1W—H1WA···N4ⁱⁱ	0.85	1.99	2.822 (3)	167.0
N1—H1···O1W	0.86	1.80	2.662 (3)	174.8

Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) x, −y, z+1/2.

Acknowledgements

This work was was supported by the Postgraduate Foundation of East China of Technology (No·Y09–11–02)

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