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Acta Cryst. (2008). E64, m1195    [ doi:10.1107/S1600536808026342 ]

Bis[2-(2-pyridylmethyleneamino)benzenesulfonato-[kappa]3N,N',O]zinc(II) dihydrate

C.-X. Cai, M. Ou-Yang, Z.-Y. Zhao and Y.-M. Jiang

Abstract top

In the title complex, [Zn(C12H9N2O3S)2]·2H2O, the ZnII ion lies on a crystallographic inversion center and is coordinated by four N atoms and two O atoms from two tridentate 2-(2-pyridylmethyleneamino)benzenesulfonate ligands in a slightly distorted octahedral environment. In the crystal structure, the complex forms a two-dimensional network through intermolecular O-H...O and C-H...O hydrogen bonds.

Comment top

The design and control of supermolecular coordination complex networks in which both coordination bonds and hydrogen bonds take part in the self-assembly chemistry (Zheng, et al., 2001; Zhou, et al., 2004) have recently garnered increasing interest. Schiff base complexes that contain both sulfur and amino acid functionalities have received much attention owing to their potential applications in pharmacy. (Casella & Gullotti, 1981, 1986; Wang et al., 1994; Li et al., 2006; Zhang et al., 2007, 2008).

Our group has focused on the exploration of the coordination chemistry of the sulfonate ligands for years (Zhang et al. 2004; Jiang et al. 2006; Li et al. 2007). We report here the synthesis and the structure of the mononuclear ZnII Paba complex (Fig. 1). The structure is composed of one ZnII, two deprotonated Paba- ligands and two guest water molecules. The six-coordinated ZnII atom has a distorted octahedral geometry, being coordinated by pyridine N, imine N and sulfonate O atoms from two deprotonated Paba- ligands in a tridentate facial arrangement. This structure is similar to those reported for complexes with N,N',O-tridentate donor ligands (Li et al., 2006; Correia et al., 2003).

There are extensive hydrogen bonds (O4-H2W···O2 and O4-H1W···O3), in which the donor is O-H of the guest water and S=O acts as acceptor, which forms a two-dimension sheet structure (Fig. 2).

Related literature top

For related literature, see: Casella & Gullotti (1981, 1986); Jiang et al. (2006); Li et al. (2006, 2007); Wang et al. (1994); Zhang et al. (2004, 2007, 2008); Correia et al. (2003); Zheng et al. (2001); Zhou et al. (2004).

Experimental top

The potassium salt of 2-(pyridylmethyl)imine-2-benzenesulfonic acid (PabaK) was synthesized according to the literature method (Casella & Gullotti, 1986).

To prepare the title complex, the ligand PabaK (1 mmol, 0.30 g) was dissolved in methanol (10 mL) at 333 K and an aqueous solution (10 mL) containing ZnCl2(0.5 mmol, 0.068 g) was added. The resulting solution was stirred at 333 K for 4 h, then cooled to room temperature and filtered. Yellow crystals suitable for X-ray diffraction were obtained by slow evaporation over several days, with a yield of 55%. Elemental analysis, found (%): C, 46.05; H, 3.55; N, 8.95; S, 10.42; calc (%): C, 46.16; H, 3.53; N, 8.98; S, 10.26.

Refinement top

H atoms bonded to C atoms were positioned geometrically with the C-H distance of 0.93 Å, and treated as riding atoms, with Uiso(H) = 1.2Ueq(C). Water hydrogens were placed in fixed positions and assigned Uiso values of 1.5Ueq of the water oxygen atom.

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. An ellipsoid plot (30% probability) showing the numbering scheme. Dashed lines indicate hydrogen bonds. Symmetry code: (a) -x+1, y, -z+1/2.
[Figure 2] Fig. 2. 2-D structure, as viewed down the a axis. Dashed lines indicate hydrogen bonds.
Bis[2-(2-pyridylmethyleneamino)benzenesulfonato- κ3N,N',O]zinc(II) dihydrate top
Crystal data top
[Zn(C12H9N2O3S1)2]·2H2OF000 = 1280
Mr = 623.95Dx = 1.594 Mg m−3
Orthorhombic, PbcnMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2n 2abCell parameters from 7323 reflections
a = 19.7090 (15) Åθ = 2.5–28.2º
b = 8.0722 (6) ŵ = 1.16 mm−1
c = 16.3390 (13) ÅT = 295 (2) K
V = 2599.5 (3) Å3Block, yellow
Z = 40.49 × 0.45 × 0.37 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		2412 independent reflections
Radiation source: fine-focus sealed tube2100 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.024
T = 295(2) Kθmax = 25.5º
φ and ω scansθmin = 2.5º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −23→23
Tmin = 0.600, Tmax = 0.673k = −9→9
17894 measured reflectionsl = −19→19
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.026H-atom parameters constrained
wR(F2) = 0.074  w = 1/[σ2(Fo2) + (0.0373P)2 + 1.7627P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
2412 reflectionsΔρmax = 0.46 e Å−3
177 parametersΔρmin = −0.42 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Zn(C12H9N2O3S1)2]·2H2OV = 2599.5 (3) Å3
Mr = 623.95Z = 4
Orthorhombic, PbcnMo Kα
a = 19.7090 (15) ŵ = 1.16 mm−1
b = 8.0722 (6) ÅT = 295 (2) K
c = 16.3390 (13) Å0.49 × 0.45 × 0.37 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		2412 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2100 reflections with I > 2σ(I)
Tmin = 0.600, Tmax = 0.673Rint = 0.024
17894 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.026177 parameters
wR(F2) = 0.074H-atom parameters constrained
S = 1.04Δρmax = 0.46 e Å−3
2412 reflectionsΔρmin = −0.42 e Å−3
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
xyzUiso*/Ueq
Zn10.50000.82446 (4)0.25000.02769 (11)
S10.37616 (2)0.67719 (6)0.34320 (3)0.03070 (14)
O10.45098 (7)0.67650 (18)0.33822 (8)0.0344 (3)
O20.34865 (8)0.84229 (19)0.33446 (10)0.0456 (4)
O30.35256 (7)0.5876 (2)0.41443 (8)0.0431 (4)
N10.49613 (8)1.0216 (2)0.16032 (10)0.0341 (4)
N20.40820 (8)0.7687 (2)0.17245 (9)0.0297 (4)
C10.44459 (10)1.0145 (3)0.10605 (12)0.0332 (4)
C20.43673 (13)1.1301 (3)0.04460 (14)0.0452 (6)
H20.40071.12230.00810.054*
C30.48322 (13)1.2579 (3)0.03809 (15)0.0506 (6)
H30.47861.3380−0.00250.061*
C40.53638 (13)1.2645 (3)0.09261 (15)0.0483 (6)
H40.56881.34800.08900.058*
C50.54084 (12)1.1447 (3)0.15295 (14)0.0420 (5)
H50.57661.15030.19000.050*
C60.39854 (10)0.8728 (3)0.11481 (12)0.0354 (5)
H60.36260.85900.07860.042*
C70.36755 (9)0.6238 (3)0.17777 (12)0.0313 (4)
C80.34696 (11)0.5353 (3)0.10925 (13)0.0437 (5)
H80.35790.57360.05720.052*
C90.31015 (12)0.3900 (3)0.11817 (15)0.0524 (6)
H90.29620.33200.07200.063*
C100.29391 (13)0.3306 (3)0.19512 (16)0.0516 (6)
H100.26980.23220.20050.062*
C110.31364 (11)0.4180 (3)0.26416 (13)0.0403 (5)
H110.30220.37920.31600.048*
C120.35039 (10)0.5632 (3)0.25581 (11)0.0300 (4)
O40.29845 (11)1.0939 (4)0.44343 (14)0.1079 (10)
H1W0.25721.11440.43940.162*
H2W0.30831.01050.41580.162*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.02732 (18)0.03263 (19)0.02311 (18)0.000−0.00389 (11)0.000
S10.0291 (3)0.0396 (3)0.0234 (2)−0.0001 (2)0.00018 (18)−0.0016 (2)
O10.0287 (7)0.0462 (9)0.0285 (7)−0.0028 (6)−0.0034 (6)0.0038 (6)
O20.0482 (9)0.0452 (9)0.0436 (9)0.0102 (7)−0.0018 (7)−0.0079 (7)
O30.0416 (8)0.0620 (10)0.0257 (7)−0.0062 (8)0.0039 (6)0.0035 (7)
N10.0400 (9)0.0346 (9)0.0278 (9)−0.0007 (7)−0.0057 (7)0.0011 (7)
N20.0278 (8)0.0375 (9)0.0238 (8)−0.0006 (7)0.0004 (6)0.0004 (7)
C10.0343 (10)0.0377 (11)0.0275 (10)0.0035 (9)−0.0036 (8)0.0023 (8)
C20.0519 (14)0.0471 (13)0.0367 (12)0.0017 (11)−0.0113 (10)0.0096 (10)
C30.0728 (17)0.0386 (13)0.0403 (13)−0.0023 (12)−0.0064 (12)0.0105 (11)
C40.0628 (15)0.0363 (12)0.0458 (13)−0.0117 (11)−0.0019 (11)0.0022 (10)
C50.0490 (13)0.0391 (12)0.0380 (12)−0.0084 (10)−0.0102 (10)0.0012 (9)
C60.0310 (11)0.0475 (12)0.0276 (10)0.0001 (9)−0.0057 (8)0.0034 (9)
C70.0245 (10)0.0410 (11)0.0284 (10)−0.0009 (8)−0.0004 (8)−0.0015 (9)
C80.0417 (12)0.0609 (15)0.0286 (11)−0.0085 (11)0.0014 (9)−0.0050 (10)
C90.0505 (14)0.0679 (16)0.0389 (13)−0.0180 (13)−0.0001 (11)−0.0169 (12)
C100.0464 (14)0.0552 (15)0.0530 (15)−0.0211 (12)0.0021 (11)−0.0085 (12)
C110.0363 (12)0.0495 (13)0.0351 (11)−0.0088 (10)0.0038 (9)0.0017 (10)
C120.0232 (9)0.0399 (11)0.0270 (10)−0.0007 (8)−0.0001 (7)−0.0023 (8)
O40.0592 (13)0.168 (3)0.0964 (18)0.0323 (15)−0.0209 (12)−0.0725 (19)
Geometric parameters (Å, °) top
Zn1—O12.1065 (14)C3—C41.376 (3)
Zn1—O1i2.1065 (14)C3—H30.9300
Zn1—N1i2.1643 (18)C4—C51.384 (3)
Zn1—N12.1643 (18)C4—H40.9300
Zn1—N22.2544 (16)C5—H50.9300
Zn1—N2i2.2544 (16)C6—H60.9300
S1—O21.4459 (16)C7—C81.389 (3)
S1—O31.4470 (15)C7—C121.407 (3)
S1—O11.4769 (14)C8—C91.387 (3)
S1—C121.7730 (19)C8—H80.9300
N1—C51.334 (3)C9—C101.383 (3)
N1—C11.350 (2)C9—H90.9300
N2—C61.277 (3)C10—C111.386 (3)
N2—C71.421 (3)C10—H100.9300
C1—C21.380 (3)C11—C121.384 (3)
C1—C61.467 (3)C11—H110.9300
C2—C31.384 (3)O4—H1W0.8332
C2—H20.9300O4—H2W0.8339
O1—Zn1—O1i110.92 (8)C3—C2—H2120.5
O1—Zn1—N1i88.27 (6)C4—C3—C2118.9 (2)
O1i—Zn1—N1i149.76 (6)C4—C3—H3120.6
O1—Zn1—N1149.76 (6)C2—C3—H3120.6
O1i—Zn1—N188.27 (6)C3—C4—C5118.9 (2)
N1i—Zn1—N185.36 (9)C3—C4—H4120.6
O1—Zn1—N284.45 (5)C5—C4—H4120.6
O1i—Zn1—N282.55 (5)N1—C5—C4122.9 (2)
N1i—Zn1—N2123.75 (6)N1—C5—H5118.5
N1—Zn1—N274.81 (6)C4—C5—H5118.5
O1—Zn1—N2i82.55 (5)N2—C6—C1119.53 (18)
O1i—Zn1—N2i84.45 (5)N2—C6—H6120.2
N1i—Zn1—N2i74.81 (6)C1—C6—H6120.2
N1—Zn1—N2i123.75 (6)C8—C7—C12118.80 (19)
N2—Zn1—N2i156.97 (9)C8—C7—N2122.62 (18)
O2—S1—O3114.81 (10)C12—C7—N2118.51 (17)
O2—S1—O1111.87 (9)C9—C8—C7120.2 (2)
O3—S1—O1111.31 (9)C9—C8—H8119.9
O2—S1—C12106.94 (9)C7—C8—H8119.9
O3—S1—C12107.23 (9)C10—C9—C8120.7 (2)
O1—S1—C12103.86 (9)C10—C9—H9119.7
S1—O1—Zn1119.57 (8)C8—C9—H9119.7
C5—N1—C1118.00 (18)C9—C10—C11119.9 (2)
C5—N1—Zn1125.86 (14)C9—C10—H10120.1
C1—N1—Zn1116.11 (14)C11—C10—H10120.1
C6—N2—C7120.22 (17)C12—C11—C10119.8 (2)
C6—N2—Zn1113.76 (14)C12—C11—H11120.1
C7—N2—Zn1125.63 (12)C10—C11—H11120.1
N1—C1—C2122.3 (2)C11—C12—C7120.62 (18)
N1—C1—C6115.76 (17)C11—C12—S1120.65 (15)
C2—C1—C6121.93 (19)C7—C12—S1118.73 (15)
C1—C2—C3119.1 (2)H1W—O4—H2W110.2
C1—C2—H2120.5
Symmetry codes: (i) −x+1, y, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O4—H1W···O3ii0.832.213.014 (3)162
O4—H2W···O20.832.062.877 (3)166
C4—H4···O3iii0.932.483.407 (3)175
C6—H6···O4iv0.932.573.436 (3)155
Symmetry codes: (ii) −x+1/2, y+1/2, z; (iii) −x+1, y+1, −z+1/2; (iv) x, −y+2, z−1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O4—H1W···O3i0.832.213.014 (3)162
O4—H2W···O20.832.062.877 (3)166
C4—H4···O3ii0.932.483.407 (3)175
C6—H6···O4iii0.932.573.436 (3)155
Symmetry codes: (i) −x+1/2, y+1/2, z; (ii) −x+1, y+1, −z+1/2; (iii) x, −y+2, z−1/2.
Acknowledgements top

This work was funded by Guangxi Science Foundation, Guangxi Zhuang Autonomous Region of the People's Republic of China (grant No. 0731053).

references
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