(3-Amino­pyrazin-4-ium-2-carboxyl­ate-κ2N1,O)diaqua­zinc(II) dinitrate

Gao, S.; Ng, S.W.

doi:10.1107/S1600536810042509

metal-organic compounds

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Volume 66| Part 11| November 2010| Page m1466

https://doi.org/10.1107/S1600536810042509

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(3-Aminopyrazin-4-ium-2-carboxylate-κ²N¹,O)diaquazinc(II) dinitrate

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

^aCollege of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, People's Republic of China, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 6 October 2010; accepted 20 October 2010; online 30 October 2010)

The water-coordinated Zn^II atom in the title salt, [Zn(C₅H₅N₃O₂)₂(H₂O)₂](NO₃)₂, is N,O-chelated by a zwitterionic aminopyraziniocarboxylate unit; the metal atom, which lies on a center of inversion, shows an octahedral coordination. The nitrate ion interacts indirectly, through N—H⋯O hydrogen bonds. In the crystal, adjacent cations and anions are connected by O—H⋯O hydrogen bonds into a three-dimensional network motif. The crystal studied was a non-merohedral twin with two minor components of 15.1 (1) and 8.0 (1)%.

Related literature

For a related structure, see: Tayebee et al. (2008 ). For the treatment of non-merohedral twins, see: Spek (2003 ).

Experimental

Crystal data

[Zn(C₅H₅N₃O₂)₂(H₂O)₂](NO₃)₂
M_r = 503.66
Monoclinic, P 2₁ /c
a = 13.4676 (14) Å
b = 9.7059 (9) Å
c = 6.6682 (6) Å
β = 96.610 (3)°
V = 865.84 (14) Å³
Z = 2
Mo Kα radiation
μ = 1.51 mm⁻¹
T = 293 K
0.24 × 0.21 × 0.18 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.580, T_max = 1.000
8164 measured reflections
1983 independent reflections
1739 reflections with I > 2σ(I)
R_int = 0.053

Refinement

R[F² > 2σ(F²)] = 0.060
wR(F²) = 0.175
S = 1.15
1983 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 1.37 e Å⁻³
Δρ_min = −1.66 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1w—H1w1⋯O1ⁱ	0.82	2.17	2.895 (5)	148
O1w—H1w2⋯O2ⁱⁱ	0.82	1.99	2.752 (6)	154
N2—H2⋯O3	0.88	1.86	2.703 (6)	161
N3—H31⋯O4	0.88	2.14	2.981 (6)	161
N3—H32⋯O5ⁱⁱⁱ	0.88	2.33	2.994 (7)	133
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810042509/nk2064sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810042509/nk2064Isup2.hkl

checkCIF report

Comment top

3-Aminopyrazine-2-carboxylic acid forms a number of aqua complexes with divalent transition metals in which the metal atom is N,O-chelated by the monoanion. In an attempt at the solution synthesis of the zinc derivative, the sodium ion used as a reactant is incorporated into the crystal structure (Tayebee et al., 2008). In the present study, the attempt by a hydrothermal route yielded Zn(H₂O)₂(C₅H₅N₃O₂)₂ 2NO₃ (Scheme I, Fig. 1). The water-coordinated zinc atom in the salt is N,O-chelated by a zwitterionic aminopyraziniocarboxylate unit; the metal atom, which lies on a center of inversion, shows octahedral coordination. The nitrate ion interacts indirectly, through N–H···O hydrogen bonds. Adjacent cations and anions are connected by O–H···O hydrogen bonds into a three-dimensional network motif.

Related literature top

For a related structure, see: Tayebee et al. (2008). For the treatment of non-merohedral twins, see: Spek (2003).

Experimental top

Zinc nitrate hexahydrate (0.30 g, 1 mmol), 3-aminopyrazine-2-carboxylic acid (0.28 g, 2 mmol), and sodium hydroxide (0.08 g 2 mmol) were dissolved in a H₂O/DMF (12 ml, v/v = 2:1) solution. The mixture was sealed in a 25- ml Teflon-lined stainless steel bomb and held at 443 K for 3 d. The bomb was gradually cooled to room temperature, and yellow crystals were obtained after several days.

Structure description top

For a related structure, see: Tayebee et al. (2008). For the treatment of non-merohedral twins, see: Spek (2003).

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: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Displacement ellipsoid plot of Zn(H₂O)₂(C₅H₅N₃O₂)₂ 2NO₃ at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. Unlabeled atoms are related to labeled atoms by 1 - x, 1 - y, 1 - z.

(3-Aminopyrazin-4-ium-2-carboxylate-κ²N¹,O)diaquazinc(II) dinitrate top

Crystal data top

[Zn(C₅H₅N₃O₂)₂(H₂O)₂](NO₃)₂	F(000) = 512
M_r = 503.66	D_x = 1.932 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7197 reflections
a = 13.4676 (14) Å	θ = 3.1–27.5°
b = 9.7059 (9) Å	µ = 1.51 mm⁻¹
c = 6.6682 (6) Å	T = 293 K
β = 96.610 (3)°	Prism, yellow
V = 865.84 (14) Å³	0.24 × 0.21 × 0.18 mm
Z = 2

Data collection top

Rigaku R-AXIS RAPID diffractometer	1983 independent reflections
Radiation source: fine-focus sealed tube	1739 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
Detector resolution: 10.000 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −17→17
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −11→12
T_min = 0.580, T_max = 1.000	l = −8→8
8164 measured reflections

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.175	H-atom parameters constrained
S = 1.15	w = 1/[σ²(F_o²) + (0.0553P)² + 4.4842P] where P = (F_o² + 2F_c²)/3
1983 reflections	(Δ/σ)_max = 0.001
145 parameters	Δρ_max = 1.37 e Å⁻³
0 restraints	Δρ_min = −1.66 e Å⁻³

Crystal data top

[Zn(C₅H₅N₃O₂)₂(H₂O)₂](NO₃)₂	V = 865.84 (14) Å³
M_r = 503.66	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.4676 (14) Å	µ = 1.51 mm⁻¹
b = 9.7059 (9) Å	T = 293 K
c = 6.6682 (6) Å	0.24 × 0.21 × 0.18 mm
β = 96.610 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	1983 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1739 reflections with I > 2σ(I)
T_min = 0.580, T_max = 1.000	R_int = 0.053
8164 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.175	H-atom parameters constrained
S = 1.15	Δρ_max = 1.37 e Å⁻³
1983 reflections	Δρ_min = −1.66 e Å⁻³
145 parameters

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

	x	y	z	U_iso*/U_eq
Zn1	0.5000	0.5000	0.5000	0.0239 (3)
O1	0.5443 (3)	0.7058 (4)	0.5390 (6)	0.0286 (8)
O2	0.6686 (3)	0.8494 (4)	0.4874 (6)	0.0302 (8)
O3	1.0229 (3)	0.4552 (5)	0.2346 (9)	0.0472 (12)
O4	1.0421 (4)	0.6731 (5)	0.2591 (11)	0.0630 (17)
O5	1.1600 (3)	0.5475 (5)	0.1631 (8)	0.0452 (11)
O1W	0.5552 (3)	0.4400 (5)	0.8042 (6)	0.0388 (10)
H1W1	0.5111	0.3991	0.8552	0.058*
H1W2	0.5717	0.5089	0.8710	0.058*
N1	0.6477 (3)	0.4895 (4)	0.4259 (7)	0.0280 (10)
N2	0.8377 (3)	0.5065 (5)	0.3357 (8)	0.0288 (9)
H2	0.9001	0.5100	0.3091	0.035*
N3	0.8428 (3)	0.7410 (5)	0.3867 (8)	0.0331 (11)
H31	0.9044	0.7417	0.3544	0.040*
H32	0.8146	0.8183	0.4193	0.040*
N4	1.0755 (3)	0.5598 (5)	0.2176 (8)	0.0320 (10)
C1	0.6305 (4)	0.7331 (5)	0.4932 (8)	0.0235 (10)
C2	0.6923 (4)	0.6113 (5)	0.4370 (7)	0.0221 (9)
C3	0.7931 (4)	0.6243 (5)	0.3862 (8)	0.0245 (10)
C4	0.7906 (4)	0.3840 (6)	0.3245 (10)	0.0357 (12)
H4	0.8231	0.3057	0.2849	0.043*
C5	0.6951 (4)	0.3757 (6)	0.3717 (10)	0.0358 (13)
H5	0.6625	0.2910	0.3664	0.043*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0173 (4)	0.0251 (4)	0.0306 (5)	−0.0034 (3)	0.0077 (3)	0.0000 (3)
O1	0.0223 (17)	0.0259 (17)	0.039 (2)	0.0009 (14)	0.0117 (15)	−0.0037 (16)
O2	0.0281 (18)	0.0218 (17)	0.041 (2)	0.0008 (14)	0.0031 (16)	−0.0001 (15)
O3	0.031 (2)	0.026 (2)	0.089 (4)	−0.0043 (18)	0.024 (2)	−0.003 (2)
O4	0.048 (3)	0.025 (2)	0.124 (5)	0.001 (2)	0.045 (3)	−0.010 (3)
O5	0.023 (2)	0.040 (2)	0.075 (3)	−0.0003 (17)	0.020 (2)	−0.003 (2)
O1W	0.042 (2)	0.041 (2)	0.033 (2)	−0.0187 (19)	0.0033 (18)	0.0027 (18)
N1	0.023 (2)	0.024 (2)	0.039 (3)	−0.0002 (16)	0.0121 (18)	0.0015 (18)
N2	0.0153 (18)	0.037 (2)	0.035 (2)	0.0016 (17)	0.0058 (17)	0.0005 (19)
N3	0.023 (2)	0.031 (2)	0.046 (3)	−0.0061 (18)	0.011 (2)	0.000 (2)
N4	0.027 (2)	0.027 (2)	0.043 (3)	0.0000 (18)	0.0092 (19)	0.000 (2)
C1	0.022 (2)	0.025 (2)	0.023 (2)	0.0004 (18)	0.0022 (18)	−0.0004 (19)
C2	0.021 (2)	0.022 (2)	0.023 (2)	0.0012 (18)	0.0043 (18)	0.0022 (18)
C3	0.020 (2)	0.030 (3)	0.024 (2)	−0.0011 (18)	0.0035 (18)	0.000 (2)
C4	0.032 (3)	0.027 (3)	0.049 (3)	0.006 (2)	0.011 (3)	−0.003 (3)
C5	0.036 (3)	0.021 (2)	0.052 (4)	−0.001 (2)	0.013 (3)	−0.001 (2)

Geometric parameters (Å, º) top

Zn1—O1	2.092 (4)	N1—C2	1.324 (6)
Zn1—O1ⁱ	2.092 (4)	N1—C5	1.346 (7)
Zn1—N1ⁱ	2.107 (4)	N2—C4	1.345 (7)
Zn1—N1	2.107 (4)	N2—C3	1.353 (7)
Zn1—O1wⁱ	2.158 (4)	N2—H2	0.8800
Zn1—O1w	2.158 (4)	N3—C3	1.315 (7)
O1—C1	1.262 (6)	N3—H31	0.8800
O2—C1	1.242 (6)	N3—H32	0.8800
O3—N4	1.250 (6)	C1—C2	1.517 (7)
O4—N4	1.232 (7)	C2—C3	1.442 (7)
O5—N4	1.240 (6)	C4—C5	1.362 (8)
O1W—H1W1	0.8200	C4—H4	0.9300
O1W—H1W2	0.8200	C5—H5	0.9300

O1—Zn1—O1ⁱ	180.0	C4—N2—H2	118.6
O1—Zn1—N1ⁱ	100.84 (15)	C3—N2—H2	118.6
O1ⁱ—Zn1—N1ⁱ	79.16 (15)	C3—N3—H31	120.0
O1—Zn1—N1	79.16 (15)	C3—N3—H32	120.0
O1ⁱ—Zn1—N1	100.84 (15)	H31—N3—H32	120.0
N1ⁱ—Zn1—N1	180.0	O4—N4—O5	121.5 (5)
O1—Zn1—O1Wⁱ	85.51 (16)	O4—N4—O3	118.6 (5)
O1ⁱ—Zn1—O1Wⁱ	94.49 (16)	O5—N4—O3	119.9 (5)
N1ⁱ—Zn1—O1Wⁱ	88.56 (18)	O2—C1—O1	126.4 (5)
N1—Zn1—O1Wⁱ	91.44 (18)	O2—C1—C2	117.4 (4)
O1—Zn1—O1W	94.49 (16)	O1—C1—C2	116.2 (4)
O1ⁱ—Zn1—O1W	85.51 (16)	N1—C2—C3	119.9 (4)
N1ⁱ—Zn1—O1W	91.44 (18)	N1—C2—C1	116.8 (4)
N1—Zn1—O1W	88.56 (18)	C3—C2—C1	123.2 (4)
O1Wⁱ—Zn1—O1W	180.0	N3—C3—N2	119.2 (4)
C1—O1—Zn1	115.3 (3)	N3—C3—C2	124.6 (5)
Zn1—O1W—H1W1	109.5	N2—C3—C2	116.2 (5)
Zn1—O1W—H1W2	109.5	N2—C4—C5	119.4 (5)
H1W1—O1W—H1W2	109.5	N2—C4—H4	120.3
C2—N1—C5	121.5 (5)	C5—C4—H4	120.3
C2—N1—Zn1	112.2 (3)	N1—C5—C4	120.2 (5)
C5—N1—Zn1	126.3 (4)	N1—C5—H5	119.9
C4—N2—C3	122.8 (4)	C4—C5—H5	119.9

N1ⁱ—Zn1—O1—C1	−176.2 (4)	C5—N1—C2—C1	178.1 (5)
N1—Zn1—O1—C1	3.8 (4)	Zn1—N1—C2—C1	−1.6 (6)
O1Wⁱ—Zn1—O1—C1	−88.5 (4)	O2—C1—C2—N1	−174.0 (5)
O1W—Zn1—O1—C1	91.5 (4)	O1—C1—C2—N1	5.0 (7)
O1—Zn1—N1—C2	−0.9 (4)	O2—C1—C2—C3	2.6 (7)
O1ⁱ—Zn1—N1—C2	179.1 (4)	O1—C1—C2—C3	−178.3 (5)
O1Wⁱ—Zn1—N1—C2	84.2 (4)	C4—N2—C3—N3	−177.5 (6)
O1W—Zn1—N1—C2	−95.8 (4)	C4—N2—C3—C2	2.7 (8)
O1—Zn1—N1—C5	179.4 (5)	N1—C2—C3—N3	178.0 (5)
O1ⁱ—Zn1—N1—C5	−0.6 (5)	C1—C2—C3—N3	1.4 (8)
O1Wⁱ—Zn1—N1—C5	−95.5 (5)	N1—C2—C3—N2	−2.2 (7)
O1W—Zn1—N1—C5	84.5 (5)	C1—C2—C3—N2	−178.8 (5)
Zn1—O1—C1—O2	173.2 (4)	C3—N2—C4—C5	−2.2 (10)
Zn1—O1—C1—C2	−5.7 (6)	C2—N1—C5—C4	−0.7 (10)
C5—N1—C2—C3	1.3 (8)	Zn1—N1—C5—C4	179.0 (5)
Zn1—N1—C2—C3	−178.4 (4)	N2—C4—C5—N1	1.1 (10)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H1w1···O1ⁱⁱ	0.82	2.17	2.895 (5)	148
O1w—H1w2···O2ⁱⁱⁱ	0.82	1.99	2.752 (6)	154
N2—H2···O3	0.88	1.86	2.703 (6)	161
N3—H31···O4	0.88	2.14	2.981 (6)	161
N3—H32···O5^iv	0.88	2.33	2.994 (7)	133

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

Experimental details

Crystal data
Chemical formula	[Zn(C₅H₅N₃O₂)₂(H₂O)₂](NO₃)₂
M_r	503.66
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	13.4676 (14), 9.7059 (9), 6.6682 (6)
β (°)	96.610 (3)
V (Å³)	865.84 (14)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.51
Crystal size (mm)	0.24 × 0.21 × 0.18

Data collection
Diffractometer	Rigaku R-AXIS RAPID
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.580, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	8164, 1983, 1739
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.175, 1.15
No. of reflections	1983
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.37, −1.66

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H1w1···O1ⁱ	0.82	2.17	2.895 (5)	148
O1w—H1w2···O2ⁱⁱ	0.82	1.99	2.752 (6)	154
N2—H2···O3	0.88	1.86	2.703 (6)	161
N3—H31···O4	0.88	2.14	2.981 (6)	161
N3—H32···O5ⁱⁱⁱ	0.88	2.33	2.994 (7)	133

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

Acknowledgements

We thank 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), Heilongjiang University and the University of Malaya for supporting this study.

References

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