Diaqua­bis(4-oxo-1,4-dihydro­pyridine-3-sulfonato-κ2O3,O4)zinc(II)

Zhu, Z.-B.; Gao, S.; Ng, S.W.

doi:10.1107/S1600536809044948

metal-organic compounds

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Volume 65| Part 11| November 2009| Page m1493

https://doi.org/10.1107/S1600536809044948

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Diaquabis(4-oxo-1,4-dihydropyridine-3-sulfonato-κ²O³,O⁴)zinc(II)

Zhi-Biao Zhu,^a 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 27 October 2009; accepted 27 October 2009; online 31 October 2009)

In the crystal structure of the title compound, [Zn(C₅H₄NO₄S)₂(H₂O)₂], the 4-oxo-1,4-dihydropyridine-3-sulfonate anion chelates to water-coordinated zinc centres through the carbonyl O atom and through one O atom of the sulfonate group. The Zn^II atom lies on a center of inversion, and adjacent molecules are linked by N—H⋯O and O—H⋯O hydrogen bonds, forming a three-dimensional network.

Related literature

For the structure of the 4-oxo-1,4-dihydropyridine-3-sulfonate anion, see: Zhu et al. (2009 ).

Experimental

Crystal data

[Zn(C₅H₄NO₄S)₂(H₂O)₂]
M_r = 449.71
Monoclinic, P 2₁ /c
a = 4.9263 (1) Å
b = 20.9529 (6) Å
c = 7.4437 (2) Å
β = 98.9371 (9)°
V = 759.01 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.95 mm⁻¹
T = 293 K
0.23 × 0.17 × 0.14 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.662, T_max = 0.772
7334 measured reflections
1738 independent reflections
1629 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.074
S = 1.10
1738 reflections
127 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1w—H1⋯O2ⁱ	0.84 (1)	2.05 (2)	2.797 (2)	147 (2)
O1w—H2⋯O4ⁱⁱ	0.84 (1)	1.92 (1)	2.744 (2)	171 (3)
N1—H3⋯O3ⁱⁱⁱ	0.85 (1)	1.91 (1)	2.754 (2)	175 (3)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x+1, y, z; (iii) $[x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809044948/bt5120sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809044948/bt5120Isup2.hkl

checkCIF report

Related literature top

For the structure of the 4-oxo-1,4-dihydropyridine-3-sulfonate anion, see: Zhu et al. (2009).

Experimental top

Zinc carbonate (0.25 g, 2 mmol) was added to a hot aqueous solution of 4-hydroxypyridine-3-sulfonic acid (0.35 g, 2 mmol); the pH value was adjusted to6 with 0.1 M sodium hydroxide. The solution was allowed to evaporate slowly at room temperature, and colorless prismatic crystals were isolated after about five days. CH&N elemental analysis. Calc. for C₁₀H₁₂N₂O₁₀S₂Zn:C 26.71, H 2.69, N 6.23%; found: C 26.73, H 2.73, N 6.21%.

Structure description top

For the structure of the 4-oxo-1,4-dihydropyridine-3-sulfonate anion, see: Zhu et al. (2009).

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, 2009).

Figures top

Fig. 1. Anisotropic displacement ellipsoid plot (Barbour, 2001) of Zn(H₂O)₂(C₅H₄NO₄S)₂ at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

Diaquabis(4-oxo-1,4-dihydropyridine-3-sulfonato- κ²O³,O⁴)zinc(II) top

Crystal data top

[Zn(C₅H₄NO₄S)₂(H₂O)₂]	F(000) = 456
M_r = 449.71	D_x = 1.968 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6865 reflections
a = 4.9263 (1) Å	θ = 3.4–27.5°
b = 20.9529 (6) Å	µ = 1.95 mm⁻¹
c = 7.4437 (2) Å	T = 293 K
β = 98.9371 (9)°	Prism, colorless
V = 759.01 (3) Å³	0.23 × 0.17 × 0.14 mm
Z = 2

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	1738 independent reflections
Radiation source: fine-focus sealed tube	1629 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ω scans	θ_max = 27.5°, θ_min = 3.4°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −6→5
T_min = 0.662, T_max = 0.772	k = −27→27
7334 measured reflections	l = −9→9

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.074	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ²(F_o²) + (0.0399P)² + 0.5207P] where P = (F_o² + 2F_c²)/3
1738 reflections	(Δ/σ)_max = 0.001
127 parameters	Δρ_max = 0.45 e Å⁻³
3 restraints	Δρ_min = −0.46 e Å⁻³

Crystal data top

[Zn(C₅H₄NO₄S)₂(H₂O)₂]	V = 759.01 (3) Å³
M_r = 449.71	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.9263 (1) Å	µ = 1.95 mm⁻¹
b = 20.9529 (6) Å	T = 293 K
c = 7.4437 (2) Å	0.23 × 0.17 × 0.14 mm
β = 98.9371 (9)°

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	1738 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1629 reflections with I > 2σ(I)
T_min = 0.662, T_max = 0.772	R_int = 0.021
7334 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	3 restraints
wR(F²) = 0.074	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	Δρ_max = 0.45 e Å⁻³
1738 reflections	Δρ_min = −0.46 e Å⁻³
127 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	0.01991 (11)
S1	0.54548 (9)	0.35166 (2)	0.43742 (6)	0.02251 (13)
O1	0.6943 (3)	0.41242 (6)	0.46588 (19)	0.0246 (3)
O2	0.4026 (3)	0.33653 (7)	0.5890 (2)	0.0327 (3)
O3	0.7182 (3)	0.30080 (7)	0.3867 (2)	0.0380 (4)
O4	0.1877 (3)	0.47222 (6)	0.29786 (18)	0.0238 (3)
O1W	0.7120 (3)	0.54012 (7)	0.3004 (2)	0.0279 (3)
N1	−0.0061 (4)	0.30854 (10)	0.0136 (2)	0.0361 (5)
C1	0.2078 (4)	0.30795 (10)	0.1490 (3)	0.0303 (4)
H1A	0.3053	0.2703	0.1764	0.036*
C2	0.2849 (4)	0.36189 (8)	0.2474 (3)	0.0221 (4)
C3	0.1359 (4)	0.42039 (8)	0.2098 (2)	0.0209 (4)
C4	−0.0876 (4)	0.41740 (10)	0.0613 (3)	0.0294 (4)
H4	−0.1897	0.4540	0.0274	0.035*
C5	−0.1522 (5)	0.36232 (11)	−0.0300 (3)	0.0353 (5)
H5A	−0.2998	0.3615	−0.1245	0.042*
H1	0.738 (5)	0.5794 (5)	0.318 (4)	0.035 (7)*
H2	0.866 (3)	0.5233 (13)	0.301 (4)	0.040 (7)*
H3	−0.081 (6)	0.2742 (9)	−0.028 (4)	0.051 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.01975 (17)	0.01417 (16)	0.02420 (18)	−0.00106 (10)	−0.00165 (12)	−0.00169 (10)
S1	0.0258 (2)	0.0128 (2)	0.0270 (2)	0.00172 (16)	−0.00212 (18)	0.00056 (16)
O1	0.0221 (6)	0.0168 (6)	0.0333 (7)	0.0005 (5)	−0.0006 (5)	−0.0015 (5)
O2	0.0433 (8)	0.0247 (7)	0.0286 (7)	−0.0061 (6)	0.0009 (6)	0.0042 (6)
O3	0.0398 (8)	0.0203 (7)	0.0503 (10)	0.0124 (6)	−0.0037 (7)	−0.0046 (6)
O4	0.0226 (6)	0.0168 (6)	0.0295 (7)	0.0010 (5)	−0.0042 (5)	−0.0031 (5)
O1W	0.0263 (7)	0.0244 (7)	0.0333 (8)	0.0020 (6)	0.0059 (6)	0.0008 (6)
N1	0.0443 (11)	0.0297 (10)	0.0324 (10)	−0.0131 (8)	0.0006 (8)	−0.0141 (7)
C1	0.0366 (11)	0.0203 (9)	0.0337 (10)	−0.0038 (8)	0.0046 (8)	−0.0065 (8)
C2	0.0253 (9)	0.0178 (8)	0.0224 (9)	−0.0022 (7)	0.0008 (7)	−0.0024 (6)
C3	0.0215 (8)	0.0189 (8)	0.0212 (8)	−0.0032 (7)	−0.0005 (7)	0.0008 (6)
C4	0.0300 (10)	0.0295 (10)	0.0256 (9)	−0.0034 (8)	−0.0061 (8)	0.0025 (8)
C5	0.0364 (11)	0.0414 (12)	0.0248 (10)	−0.0108 (9)	−0.0056 (8)	−0.0042 (8)

Geometric parameters (Å, º) top

Zn1—O4	2.0618 (12)	O1W—H2	0.835 (10)
Zn1—O4ⁱ	2.0618 (12)	N1—C1	1.340 (3)
Zn1—O1ⁱ	2.1031 (13)	N1—C5	1.349 (3)
Zn1—O1	2.1031 (13)	N1—H3	0.846 (10)
Zn1—O1Wⁱ	2.1183 (15)	C1—C2	1.368 (3)
Zn1—O1W	2.1183 (15)	C1—H1A	0.9300
S1—O3	1.4496 (15)	C2—C3	1.434 (2)
S1—O2	1.4547 (17)	C3—C4	1.435 (2)
S1—O1	1.4681 (13)	C4—C5	1.352 (3)
S1—C2	1.7694 (19)	C4—H4	0.9300
O4—C3	1.274 (2)	C5—H5A	0.9300
O1W—H1	0.841 (10)

O4—Zn1—O4ⁱ	180.00 (7)	C3—O4—Zn1	133.12 (12)
O4—Zn1—O1ⁱ	91.86 (5)	Zn1—O1W—H1	111.3 (18)
O4ⁱ—Zn1—O1ⁱ	88.14 (5)	Zn1—O1W—H2	112 (2)
O4—Zn1—O1	88.14 (5)	H1—O1W—H2	107 (3)
O4ⁱ—Zn1—O1	91.86 (5)	C1—N1—C5	121.09 (18)
O1ⁱ—Zn1—O1	180.0	C1—N1—H3	121 (2)
O4—Zn1—O1Wⁱ	90.38 (6)	C5—N1—H3	116 (2)
O4ⁱ—Zn1—O1Wⁱ	89.62 (6)	N1—C1—C2	121.0 (2)
O1ⁱ—Zn1—O1Wⁱ	88.76 (5)	N1—C1—H1A	119.5
O1—Zn1—O1Wⁱ	91.24 (5)	C2—C1—H1A	119.5
O4—Zn1—O1W	89.62 (6)	C1—C2—C3	120.70 (17)
O4ⁱ—Zn1—O1W	90.38 (6)	C1—C2—S1	115.75 (15)
O1ⁱ—Zn1—O1W	91.24 (5)	C3—C2—S1	123.06 (13)
O1—Zn1—O1W	88.76 (5)	O4—C3—C2	124.95 (16)
O1Wⁱ—Zn1—O1W	180.00 (7)	O4—C3—C4	120.14 (17)
O3—S1—O2	114.58 (10)	C2—C3—C4	114.91 (16)
O3—S1—O1	112.02 (9)	C5—C4—C3	121.1 (2)
O2—S1—O1	111.59 (9)	C5—C4—H4	119.4
O3—S1—C2	105.27 (9)	C3—C4—H4	119.4
O2—S1—C2	105.55 (9)	C4—C5—N1	121.12 (18)
O1—S1—C2	107.12 (8)	C4—C5—H5A	119.4
S1—O1—Zn1	123.21 (8)	N1—C5—H5A	119.4

O3—S1—O1—Zn1	170.03 (10)	O2—S1—C2—C1	−89.44 (17)
O2—S1—O1—Zn1	−59.98 (12)	O1—S1—C2—C1	151.53 (16)
C2—S1—O1—Zn1	55.08 (12)	O3—S1—C2—C3	−155.77 (16)
O4—Zn1—O1—S1	−40.93 (10)	O2—S1—C2—C3	82.66 (17)
O4ⁱ—Zn1—O1—S1	139.07 (10)	O1—S1—C2—C3	−36.38 (18)
O1Wⁱ—Zn1—O1—S1	49.40 (10)	Zn1—O4—C3—C2	6.9 (3)
O1W—Zn1—O1—S1	−130.60 (10)	Zn1—O4—C3—C4	−173.69 (14)
O1ⁱ—Zn1—O4—C3	−173.83 (17)	C1—C2—C3—O4	177.73 (19)
O1—Zn1—O4—C3	6.17 (17)	S1—C2—C3—O4	6.0 (3)
O1Wⁱ—Zn1—O4—C3	−85.06 (18)	C1—C2—C3—C4	−1.7 (3)
O1W—Zn1—O4—C3	94.94 (18)	S1—C2—C3—C4	−173.44 (15)
C5—N1—C1—C2	0.0 (3)	O4—C3—C4—C5	−177.7 (2)
N1—C1—C2—C3	0.9 (3)	C2—C3—C4—C5	1.8 (3)
N1—C1—C2—S1	173.18 (17)	C3—C4—C5—N1	−1.0 (4)
O3—S1—C2—C1	32.14 (19)	C1—N1—C5—C4	0.0 (3)

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—H1···O2ⁱ	0.84 (1)	2.05 (2)	2.797 (2)	147 (2)
O1w—H2···O4ⁱⁱ	0.84 (1)	1.92 (1)	2.744 (2)	171 (3)
N1—H3···O3ⁱⁱⁱ	0.85 (1)	1.91 (1)	2.754 (2)	175 (3)

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

Experimental details

Crystal data
Chemical formula	[Zn(C₅H₄NO₄S)₂(H₂O)₂]
M_r	449.71
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	4.9263 (1), 20.9529 (6), 7.4437 (2)
β (°)	98.9371 (9)
V (Å³)	759.01 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.95
Crystal size (mm)	0.23 × 0.17 × 0.14

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.662, 0.772
No. of measured, independent and observed [I > 2σ(I)] reflections	7334, 1738, 1629
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.074, 1.10
No. of reflections	1738
No. of parameters	127
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.46

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalClear (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H1···O2ⁱ	0.84 (1)	2.05 (2)	2.797 (2)	147 (2)
O1w—H2···O4ⁱⁱ	0.84 (1)	1.92 (1)	2.744 (2)	171 (3)
N1—H3···O3ⁱⁱⁱ	0.85 (1)	1.91 (1)	2.754 (2)	175 (3)

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

Acknowledgements

We thank the Natural Science Foundation of Heilongjiang Province (No. B200501), Heilongjiang University and the University of Malaya for supporting this study.

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
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. (2009). publCIF. In preparation. Google Scholar
Zhu, Z.-B., Gao, S. & Ng, S. W. (2009). Acta Cryst. E65, o2687. Web of Science CrossRef IUCr Journals Google Scholar