1,1′-(Butane-1,4-di­yl)diimidazole-3,3′-diium tetra­chloridozincate(II) dihydrate

Yu, Y.-H.; Shi, A.-E.; Su, Y.; Hou, G.-F.; Gao, J.-S.

doi:10.1107/S160053680800874X

metal-organic compounds

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1,1′-(Butane-1,4-diyl)diimidazole-3,3′-diium tetrachloridozincate(II) dihydrate

Ying-Hui Yu,^a Ai-E Shi,^a Yu Su,^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 28 March 2008; accepted 1 April 2008; online 4 April 2008)

In the title compound, (C₁₀H₁₆N₄)[ZnCl₄]·2H₂O, the cation lies abouton a center of inversion and the anion about a twofold rotation axis. The Zn^II atom is four-coordinate in a tetrahedral environment. The cations, anions and water molecules are linked by N—H⋯O, N—H⋯Cl and O—H⋯Cl hydrogen bonds into a two-dimensional network.

Related literature

For background and the synthesis of 1,1′-(1,4-butanediyl)diimidazole, see: Ma et al. (2003 )

Experimental

Crystal data

(C₁₀H₁₆N₄)[ZnCl₄]·2H₂O
M_r = 435.47
Monoclinic, P 2/n
a = 7.4010 (15) Å
b = 10.927 (2) Å
c = 11.058 (2) Å
β = 95.23 (3)°
V = 890.6 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.99 mm⁻¹
T = 291 (2) K
0.18 × 0.17 × 0.15 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.713, T_max = 0.751
8575 measured reflections
2042 independent reflections
1760 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.081
S = 1.07
2042 reflections
101 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H10⋯Cl3ⁱ	0.85	2.43	3.275 (2)	177
O1—H9⋯Cl2ⁱⁱ	0.85	2.52	3.337 (3)	161
N2—H3⋯Cl2ⁱ	0.85 (3)	2.82 (3)	3.350 (2)	122 (3)
N2—H3⋯O1	0.85 (3)	2.15 (3)	2.890 (3)	145 (3)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y, -z+{\script{1\over 2}}]$ ; (ii) x-1, y, z.

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/S160053680800874X/ng2438sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680800874X/ng2438Isup2.hkl

checkCIF report

Comment top

The 1,1'-(1,4-butanediyl)diimidazole can be used as a flexible ligand to construct coordination polymer materials(Ma et al.., 2003). In our attempt to synthesize the zinc complex with the 1,1'-(1,4-butanediyl)diimidazole, we unexpectedly obtained the title compound (I). Herein, we report its crystal structure.

The Zn^II atom lies on an inversion center and is coordinated by four chlorine anions in an tetrahedronal environment(Figure 1). The 1,1'-(1,4-butanediyl)diimidazole molecule also lies on an inversion center and its N atom is protonated.

In the crystal structure, the cations and anions are linked by N—H···Cl hydrogen bonds. In addition, the water molecules are both as acceptor and donor of hydrogen bond link these molecule into a two-dimensional supramolecular network via N—H···O, O—H···Cl hydrogen bonds (Table 1; Figure 2).

Related literature top

For background and the synthesis of 1,1'-(1,4-butanediyl)diimidazole, see: Ma et al. (2003)

Experimental top

1,1'-(1,4-Butanediyl)diimidazole was prepared of imidazole and 1,4-dibromobutane in dimethylsulfoxide solution (Ma et al.., 2003). ZnCl₂ (0.272 g, 2 mmol) and 1,1'-(1,4-butanediyl)diimidazole (0.380 g, 2 mmol) were dissolved in hot methanol solution (15 ml) and added two drops hydrochloric acid then a clear solution was obtained. The resulting solution was allowed to stand in a desiccator at room temperature for several days. Colroless crystals of (I) were obtained. Unexpectedly, the salt-type adducts of this ligands was crystallized from solution.

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 intramolecular hydrogen bonding interactions.
	Fig. 2. A partial packing view, showing the two-dimensional hydrogen-bonding network. Dashed lines indicate the hydrogen-bonding interactions. H atoms not involved in hydrogen bonds have been omitted for clarity.

1,1'-(Butane-1,4-diyl)diimidazole-3,3'-diium tetrachloridozincate(II) dihydrate top

Crystal data top

(C₁₀H₁₆N₄)[ZnCl₄]·2H₂O	F(000) = 444
M_r = 435.47	D_x = 1.624 Mg m⁻³
Monoclinic, P2/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yac	Cell parameters from 6883 reflections
a = 7.4010 (15) Å	θ = 3.2–27.5°
b = 10.927 (2) Å	µ = 1.99 mm⁻¹
c = 11.058 (2) Å	T = 291 K
β = 95.23 (3)°	Block, colorless
V = 890.6 (3) Å³	0.18 × 0.17 × 0.15 mm
Z = 2

Data collection top

Rigaku R-AXIS RAPID diffractometer	2042 independent reflections
Radiation source: fine-focus sealed tube	1760 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
ω scans	θ_max = 27.5°, θ_min = 3.2°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −9→9
T_min = 0.713, T_max = 0.751	k = −14→14
8575 measured reflections	l = −14→14

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.081	w = 1/[σ²(F_o²) + (0.0301P)² + 0.5173P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
2042 reflections	Δρ_max = 0.47 e Å⁻³
101 parameters	Δρ_min = −0.37 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.038 (3)

Crystal data top

(C₁₀H₁₆N₄)[ZnCl₄]·2H₂O	V = 890.6 (3) Å³
M_r = 435.47	Z = 2
Monoclinic, P2/n	Mo Kα radiation
a = 7.4010 (15) Å	µ = 1.99 mm⁻¹
b = 10.927 (2) Å	T = 291 K
c = 11.058 (2) Å	0.18 × 0.17 × 0.15 mm
β = 95.23 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	2042 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1760 reflections with I > 2σ(I)
T_min = 0.713, T_max = 0.751	R_int = 0.042
8575 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.47 e Å⁻³
2042 reflections	Δρ_min = −0.37 e Å⁻³
101 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
Zn1	0.7500	0.75494 (3)	0.2500	0.03710 (15)
C1	0.4713 (3)	0.1878 (2)	0.2017 (2)	0.0405 (5)
H1	0.4499	0.1104	0.1684	0.049*
C2	0.4320 (4)	0.2946 (2)	0.1464 (2)	0.0469 (6)
H2	0.3790	0.3056	0.0676	0.056*
C3	0.5555 (4)	0.3335 (2)	0.3300 (2)	0.0448 (6)
H4	0.6019	0.3752	0.3993	0.054*
C4	0.6136 (3)	0.1221 (2)	0.4085 (2)	0.0450 (6)
H5	0.6771	0.1641	0.4770	0.054*
H6	0.6995	0.0680	0.3742	0.054*
C5	0.4626 (3)	0.0464 (2)	0.4529 (2)	0.0376 (5)
H7	0.3985	0.0040	0.3849	0.045*
H8	0.3770	0.0997	0.4885	0.045*
Cl2	0.87983 (10)	0.63431 (6)	0.11389 (5)	0.0543 (2)
Cl3	0.96871 (9)	0.86758 (5)	0.35304 (6)	0.0529 (2)
H3	0.475 (4)	0.461 (3)	0.216 (3)	0.066 (9)*
N1	0.5489 (2)	0.21294 (16)	0.31649 (16)	0.0347 (4)
N2	0.4846 (3)	0.3841 (2)	0.2278 (2)	0.0499 (5)
O1	0.3280 (3)	0.6019 (2)	0.1132 (2)	0.0775 (7)
H9	0.2192	0.6042	0.1319	0.116*
H10	0.3814	0.6708	0.1191	0.116*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0465 (2)	0.0277 (2)	0.0365 (2)	0.000	0.00102 (15)	0.000
C1	0.0413 (12)	0.0380 (12)	0.0412 (12)	0.0001 (10)	−0.0009 (10)	−0.0065 (10)
C2	0.0495 (14)	0.0545 (14)	0.0359 (12)	0.0036 (12)	0.0001 (10)	0.0056 (11)
C3	0.0631 (16)	0.0326 (11)	0.0393 (12)	−0.0061 (10)	0.0085 (11)	−0.0020 (10)
C4	0.0403 (13)	0.0434 (13)	0.0499 (13)	−0.0007 (10)	−0.0029 (10)	0.0146 (11)
C5	0.0362 (11)	0.0354 (11)	0.0408 (12)	0.0017 (9)	0.0019 (9)	0.0055 (10)
Cl2	0.0739 (5)	0.0480 (4)	0.0405 (3)	0.0215 (3)	0.0029 (3)	−0.0024 (3)
Cl3	0.0563 (4)	0.0355 (3)	0.0639 (4)	−0.0094 (3)	−0.0101 (3)	0.0011 (3)
N1	0.0374 (10)	0.0297 (8)	0.0371 (9)	−0.0009 (7)	0.0030 (8)	0.0036 (7)
N2	0.0659 (15)	0.0330 (10)	0.0522 (12)	0.0040 (10)	0.0135 (10)	0.0086 (9)
O1	0.0740 (15)	0.0611 (13)	0.0940 (17)	−0.0160 (11)	−0.0113 (12)	0.0114 (12)

Geometric parameters (Å, º) top

Zn1—Cl3	2.2577 (8)	C3—H4	0.9300
Zn1—Cl3ⁱ	2.2577 (8)	C4—N1	1.470 (3)
Zn1—Cl2	2.2782 (8)	C4—C5	1.508 (3)
Zn1—Cl2ⁱ	2.2782 (7)	C4—H5	0.9700
C1—C2	1.337 (3)	C4—H6	0.9700
C1—N1	1.372 (3)	C5—C5ⁱⁱ	1.521 (4)
C1—H1	0.9300	C5—H7	0.9700
C2—N2	1.362 (3)	C5—H8	0.9700
C2—H2	0.9300	N2—H3	0.85 (3)
C3—N2	1.322 (3)	O1—H9	0.8500
C3—N1	1.326 (3)	O1—H10	0.8501

Cl3—Zn1—Cl3ⁱ	113.93 (4)	C5—C4—H5	109.0
Cl3—Zn1—Cl2	108.83 (3)	N1—C4—H6	109.0
Cl3ⁱ—Zn1—Cl2	107.95 (3)	C5—C4—H6	109.0
Cl3—Zn1—Cl2ⁱ	107.95 (3)	H5—C4—H6	107.8
Cl3ⁱ—Zn1—Cl2ⁱ	108.83 (3)	C4—C5—C5ⁱⁱ	110.7 (2)
Cl2—Zn1—Cl2ⁱ	109.29 (4)	C4—C5—H7	109.5
C2—C1—N1	107.7 (2)	C5ⁱⁱ—C5—H7	109.5
C2—C1—H1	126.2	C4—C5—H8	109.5
N1—C1—H1	126.2	C5ⁱⁱ—C5—H8	109.5
C1—C2—N2	106.7 (2)	H7—C5—H8	108.1
C1—C2—H2	126.7	C3—N1—C1	108.14 (19)
N2—C2—H2	126.7	C3—N1—C4	125.9 (2)
N2—C3—N1	108.1 (2)	C1—N1—C4	125.95 (19)
N2—C3—H4	125.9	C3—N2—C2	109.4 (2)
N1—C3—H4	125.9	C3—N2—H3	125 (2)
N1—C4—C5	113.02 (19)	C2—N2—H3	126 (2)
N1—C4—H5	109.0	H9—O1—H10	113.5

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H10···Cl3ⁱ	0.85	2.43	3.275 (2)	177
O1—H9···Cl2ⁱⁱⁱ	0.85	2.52	3.337 (3)	161
N2—H3···Cl2ⁱ	0.85 (3)	2.82 (3)	3.350 (2)	122 (3)
N2—H3···O1	0.85 (3)	2.15 (3)	2.890 (3)	145 (3)

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

Experimental details

Crystal data
Chemical formula	(C₁₀H₁₆N₄)[ZnCl₄]·2H₂O
M_r	435.47
Crystal system, space group	Monoclinic, P2/n
Temperature (K)	291
a, b, c (Å)	7.4010 (15), 10.927 (2), 11.058 (2)
β (°)	95.23 (3)
V (Å³)	890.6 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.99
Crystal size (mm)	0.18 × 0.17 × 0.15

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.713, 0.751
No. of measured, independent and observed [I > 2σ(I)] reflections	8575, 2042, 1760
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.081, 1.07
No. of reflections	2042
No. of parameters	101
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.37

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—H10···Cl3ⁱ	0.85	2.43	3.275 (2)	177.1
O1—H9···Cl2ⁱⁱ	0.85	2.52	3.337 (3)	160.6
N2—H3···Cl2ⁱ	0.85 (3)	2.82 (3)	3.350 (2)	122 (3)
N2—H3···O1	0.85 (3)	2.15 (3)	2.890 (3)	145 (3)

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

Acknowledgements

The authors thank Heilongjiang University for supporting this study.

References

Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Ma, J.-F., Yang, J., Zheng, G.-L. & Liu, J.-F. (2003). Inorg. Chem. 42, 7531–7534. Web of Science CSD CrossRef PubMed CAS Google Scholar
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 5| May 2008| Page m628

doi:10.1107/S160053680800874X

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

1,1′-(Butane-1,4-di­yl)di­imidazole-3,3′-diium tetra­chloridozincate(II) dihydrate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

1,1′-(Butane-1,4-diyl)diimidazole-3,3′-diium tetrachloridozincate(II) dihydrate