Bis(2-amino­pyrazine-κN4)dichlorido­zinc

Gao, S.; Ng, S.W.

doi:10.1107/S1600536811026031

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 8| August 2011| Pages m1049-m1050

doi:10.1107/S1600536811026031

Open

access

Bis(2-aminopyrazine-κN⁴)dichloridozinc

Shan Gao ^a and Seik Weng Ng ^b,^c ^*

^aKey Laboratory of Functional Inorganic Material Chemistry, Ministry of Education, Heilongjiang University, Harbin 150080, People's Republic of China, ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^cChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 28 June 2011; accepted 1 July 2011; online 9 July 2011)

In the title adduct, [ZnCl₂(C₄H₅N₃)₂], the Zn^II atom lies on a twofold rotation axis that relates one Cl atom to the other as well as one 2-aminopyrazine ligand to the other; the coordination geometry is a distorted tetrahedron. In the crystal, adjacent molecules are linked by N—H⋯N hydrogen bonds across the center of inversion, generating a chain; neighboring chains are linked by N—H⋯Cl hydrogen bonds, forming a three-dimensional network.

Related literature

For a related compound, CoCl₂(C₄H₅N₃)₄, see: Kang et al. (2009 ).

Experimental

Crystal data

[ZnCl₂(C₄H₅N₃)₂]
M_r = 326.49
Monoclinic, C 2/c
a = 17.1445 (12) Å
b = 6.1660 (4) Å
c = 12.0198 (8) Å
β = 98.608 (2)°
V = 1256.34 (15) Å³
Z = 4
Mo Kα radiation
μ = 2.37 mm⁻¹
T = 293 K
0.35 × 0.30 × 0.15 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.491, T_max = 0.718
5769 measured reflections
1432 independent reflections
1350 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.066
S = 1.06
1432 reflections
84 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Selected bond lengths (Å)

Zn1—N3	2.0576 (12)
Zn1—Cl1	2.2403 (4)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N2ⁱ	0.87 (1)	2.27 (1)	3.141 (2)	176 (3)
N1—H2⋯Cl1ⁱⁱ	0.87 (1)	2.63 (2)	3.392 (2)	147 (2)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (ii) x, y+1, z.

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811026031/xu5256sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811026031/xu5256Isup2.hkl

checkCIF report

Comment top

We have reported the metal(II) dichloride adducts of 2-aminopyrazine. For example, cobalt(II) dichloride forms a tetrakis adduct (Kang et al., 2009). The corresponding zinc(II) dichloride is a bis adduct; in the adduct, ZnCl₂(C₄H₅N₃)₂ (Scheme I, Fig. 1), the Zn^II atom lies on a twofold axis and the geometry is a tetrahedron. Adjacent adduct molecules are linked by an N–H···N hydrogen across a center-of-inversion to generate a chain; neighboring chains are linked by an N–H···Cl hydrogen bond to form a layer (Table 1).

Related literature top

For a related compound, CoCl₂(C₄H₅N₃)₄, see: Kang et al. (2009).

Experimental top

Zinc dichloride hexahydrate (2 mmol) and 2-aminopyrazine (2 mmol) were dissolved in water (20 ml); the solution was filtered. Colorless crystals separated from solution after several days.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalClear (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of ZnCl₂(C₄H₅N₃)₂ at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. The Zn atom lies on a twofold axis and the unlabeled atoms are related to the labeled ones by 1 - x, y, 1/2 - z.

Bis(2-aminopyrazine-κN⁴)dichloridozinc top

Crystal data top

[ZnCl₂(C₄H₅N₃)₂]	F(000) = 656
M_r = 326.49	D_x = 1.726 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5413 reflections
a = 17.1445 (12) Å	θ = 3.4–27.5°
b = 6.1660 (4) Å	µ = 2.37 mm⁻¹
c = 12.0198 (8) Å	T = 293 K
β = 98.608 (2)°	Prism, colorless
V = 1256.34 (15) Å³	0.35 × 0.30 × 0.15 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	1432 independent reflections
Radiation source: fine-focus sealed tube	1350 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ω scans	θ_max = 27.5°, θ_min = 3.4°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −22→22
T_min = 0.491, T_max = 0.718	k = −7→7
5769 measured reflections	l = −15→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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.066	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0415P)² + 0.3611P] where P = (F_o² + 2F_c²)/3
1432 reflections	(Δ/σ)_max = 0.001
84 parameters	Δρ_max = 0.32 e Å⁻³
2 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

[ZnCl₂(C₄H₅N₃)₂]	V = 1256.34 (15) Å³
M_r = 326.49	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 17.1445 (12) Å	µ = 2.37 mm⁻¹
b = 6.1660 (4) Å	T = 293 K
c = 12.0198 (8) Å	0.35 × 0.30 × 0.15 mm
β = 98.608 (2)°

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	1432 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1350 reflections with I > 2σ(I)
T_min = 0.491, T_max = 0.718	R_int = 0.029
5769 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	2 restraints
wR(F²) = 0.066	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.32 e Å⁻³
1432 reflections	Δρ_min = −0.32 e Å⁻³
84 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Zn1	0.5000	0.04567 (4)	0.2500	0.03073 (11)
Cl1	0.44416 (2)	−0.15067 (7)	0.37370 (3)	0.04100 (13)
N1	0.63303 (10)	0.7312 (3)	0.48482 (17)	0.0590 (5)
H1	0.6731 (12)	0.808 (4)	0.516 (2)	0.088*
H2	0.5858 (9)	0.779 (5)	0.486 (2)	0.088*
N2	0.71831 (9)	0.4959 (3)	0.41464 (14)	0.0431 (3)
N3	0.59049 (7)	0.2453 (2)	0.31966 (11)	0.0330 (3)
C1	0.66520 (10)	0.1889 (3)	0.30962 (16)	0.0439 (4)
H1A	0.6746	0.0646	0.2698	0.053*
C2	0.72731 (10)	0.3139 (3)	0.35775 (17)	0.0456 (4)
H2A	0.7782	0.2698	0.3504	0.055*
C3	0.57962 (10)	0.4231 (3)	0.37660 (14)	0.0352 (3)
H3	0.5287	0.4646	0.3850	0.042*
C4	0.64450 (10)	0.5519 (2)	0.42521 (15)	0.0380 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.02308 (15)	0.02663 (16)	0.04198 (17)	0.000	0.00323 (10)	0.000
Cl1	0.0322 (2)	0.0426 (2)	0.0489 (2)	0.00146 (16)	0.00822 (16)	0.01054 (17)
N1	0.0411 (9)	0.0467 (9)	0.0853 (12)	−0.0010 (8)	−0.0031 (8)	−0.0283 (9)
N2	0.0292 (7)	0.0403 (7)	0.0577 (9)	−0.0066 (6)	−0.0007 (6)	−0.0060 (7)
N3	0.0265 (6)	0.0298 (6)	0.0422 (6)	−0.0028 (5)	0.0035 (5)	−0.0027 (5)
C1	0.0301 (8)	0.0404 (9)	0.0617 (10)	−0.0027 (7)	0.0086 (7)	−0.0139 (8)
C2	0.0257 (8)	0.0477 (9)	0.0636 (11)	−0.0030 (7)	0.0070 (7)	−0.0081 (8)
C3	0.0261 (8)	0.0330 (7)	0.0460 (8)	0.0003 (6)	0.0034 (6)	−0.0016 (6)
C4	0.0350 (9)	0.0320 (8)	0.0450 (9)	−0.0022 (6)	−0.0008 (7)	−0.0023 (6)

Geometric parameters (Å, º) top

Zn1—N3	2.0576 (12)	N2—C4	1.336 (2)
Zn1—N3ⁱ	2.0576 (12)	N3—C3	1.320 (2)
Zn1—Cl1	2.2403 (4)	N3—C1	1.350 (2)
Zn1—Cl1ⁱ	2.2403 (4)	C1—C2	1.371 (2)
N1—C4	1.348 (2)	C1—H1A	0.9300
N1—H1	0.87 (1)	C2—H2A	0.9300
N1—H2	0.87 (1)	C3—C4	1.419 (2)
N2—C2	1.335 (2)	C3—H3	0.9300

N3—Zn1—N3ⁱ	106.52 (7)	N3—C1—C2	120.33 (16)
N3—Zn1—Cl1	115.10 (4)	N3—C1—H1A	119.8
N3ⁱ—Zn1—Cl1	102.85 (4)	C2—C1—H1A	119.8
N3—Zn1—Cl1ⁱ	102.85 (4)	N2—C2—C1	123.16 (17)
N3ⁱ—Zn1—Cl1ⁱ	115.10 (4)	N2—C2—H2A	118.4
Cl1—Zn1—Cl1ⁱ	114.58 (2)	C1—C2—H2A	118.4
C4—N1—H1	120.5 (19)	N3—C3—C4	121.01 (15)
C4—N1—H2	120 (2)	N3—C3—H3	119.5
H1—N1—H2	119 (3)	C4—C3—H3	119.5
C2—N2—C4	116.72 (15)	N2—C4—N1	118.57 (16)
C3—N3—C1	118.01 (14)	N2—C4—C3	120.76 (15)
C3—N3—Zn1	123.46 (11)	N1—C4—C3	120.67 (17)
C1—N3—Zn1	118.50 (10)

N3ⁱ—Zn1—N3—C3	41.52 (11)	C4—N2—C2—C1	1.2 (3)
Cl1—Zn1—N3—C3	−71.75 (13)	N3—C1—C2—N2	−1.0 (3)
Cl1ⁱ—Zn1—N3—C3	162.95 (12)	C1—N3—C3—C4	0.4 (2)
N3ⁱ—Zn1—N3—C1	−140.45 (14)	Zn1—N3—C3—C4	178.43 (12)
Cl1—Zn1—N3—C1	106.28 (13)	C2—N2—C4—N1	178.12 (19)
Cl1ⁱ—Zn1—N3—C1	−19.02 (13)	C2—N2—C4—C3	−0.7 (3)
C3—N3—C1—C2	0.1 (3)	N3—C3—C4—N2	−0.1 (3)
Zn1—N3—C1—C2	−178.02 (15)	N3—C3—C4—N1	−178.88 (17)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2ⁱⁱ	0.87 (1)	2.27 (1)	3.141 (2)	176 (3)
N1—H2···Cl1ⁱⁱⁱ	0.87 (1)	2.63 (2)	3.392 (2)	147 (2)

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

Experimental details

Crystal data
Chemical formula	[ZnCl₂(C₄H₅N₃)₂]
M_r	326.49
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	17.1445 (12), 6.1660 (4), 12.0198 (8)
β (°)	98.608 (2)
V (Å³)	1256.34 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.37
Crystal size (mm)	0.35 × 0.30 × 0.15

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.491, 0.718
No. of measured, independent and observed [I > 2σ(I)] reflections	5769, 1432, 1350
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.066, 1.06
No. of reflections	1432
No. of parameters	84
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.32

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalClear (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Selected bond lengths (Å) top

Zn1—N3

2.0576 (12)

Zn1—Cl1

2.2403 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2ⁱ	0.87 (1)	2.27 (1)	3.141 (2)	176 (3)
N1—H2···Cl1ⁱⁱ	0.87 (1)	2.63 (2)	3.392 (2)	147 (2)

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

Acknowledgements

This work is supported by the Key Project of the Natural Science Foundation of Heilongjiang Province (No. ZD200903), the Innovation Team of the Education Bureau of Heilongjiang Province (No. 2010 t d03), the Key Project of the Education Bureau of Heilongjiang Province, China (No. 12511z023) and the University of Malaya.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Kang, W., Huo, L.-H., Gao, S. & Ng, S. W. (2009). Acta Cryst. E65, m1502. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalClear. 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
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar