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The title compound, [Zn(C7H8NO3S)2(H2O)4], has an octahedral coordination around the central Zn atom composed of two axial N atoms from the pyridine ligands and four equatorial O atoms of water mol­ecules, forming a monomeric centrosymmetric complex. The two Zn-N bond distances are 2.102 (3) Å, while the four Zn-O bond distances range from 2.114 (2) to 2.167 (2) Å. Packing is determined by hydrogen bonds formed by the water mol­ecules. The sulfonate group does not take part in coordination to the Zn atom.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100007964/na1464sup1.cif
Contains datablocks a01, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100007964/na1464Isup2.hkl
Contains datablock I

CCDC reference: 150316

Comment top

There has been considerable interest in pyridineethanesulfonic acid as a bifunctional ligand of new ternary radiopharmaceutical complexes (Costanzo et al., 1997; Edwards & Shuang, 1997; Shuang et al., 1998), but we have not found any report about the crystal structure of complexes it can form with metal ions. Recently, one of us has prepared a few complexes having two-dimensional square grids by hydrothermal synthesis method (Xiong et al., 1998; Lin et al., 1998; Owen, Wang et al., 1999; Owen, Xiong et al., 1999; Xiong et al., 1999), and tried to synthetize new complexes made by the 4-pyridineethanesulfonic acid (PES).

In this paper, we report on the crystal structure of the title compound, (I), which represents the first example of a metal complex with PES. The X-ray crystal structure determination shows that the N atom of the pyridine ring of PES coordinates to the zinc atom, but the sulfonate group of PES is not involved in coordination to metal, so a centrosymmetric monomer is formed with four water molecules equatorially coordinating in a plane while two N atoms occupy the axial positions, instead of constructing two- and three-dimensional supramolecular networks, as shown in Figure 1. The environment around the central Zn atom is an almost perfect octahedron with an N—Zn—N bond angle of 180° and an N—Zn—O bond angle near to 90°, similar to that of bis(N-isonicotinato) tetraaquazinc(II) (Biagini et al., 1971) in which two carboxylato ligands are not involved in coordination to zinc. The Zn—O bond distances Zn1—O2 and Zn1—O3 are 2.167 (2) and 2.114 (2) Å, respectively, while the Zn1—N1 bond distance is 2.102 (3) Å. The bond distances of C—C, CC, S—O and NC are unexceptional. \sch

The complex molecules are packed in the crystal by a hydrogen-bonding system involving the water molecules whose relevant geometric parameters are quoted in Table 1. The molecules of complexes are piled up in turn as layers through strong intermolecular O2W—H1—O2, O1W—H3—O1 and O1W—H4—O3 hydrogen bonds. These layers are linked through O2W—H2—O3 strong hydrogen bonds and weak C4—H4A—O2 ones to form three-dimensional network structure. Futher work will be focused on solvothermal synthesis to eliminate the coordinated water and have the sulfonate group connecting metal centres to construct one-, two- and three-dimensional supramolecular frameworks.

Experimental top

4-Pyridineethanesulfonic acid (0.1 g) and Zn(ClO4)2·2H2O (0.1 g) were added to water (10 ml) and pyridine (0.12 ml). The resulting solution was evaporated at room temperature for a few days. Colorless block-shaped crystals were obtained. The IR spectrum displayed a strong absorption band at 3350 cm−1.

Computing details top

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: SHELXTL (Sheldrick, 1997); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are shown at 35% probability levels.
Bis(4-Pyridineethanesulfonato-N) Tetraaquazinc top
Crystal data top
[Zn(C7H8NO3S)2(H2O)4]F(000) = 528
Mr = 509.84Dx = 1.691 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 9.0967 (14) ÅCell parameters from 45 reflections
b = 8.8122 (13) Åθ = 5.2–11.8°
c = 12.5396 (14) ŵ = 1.49 mm1
β = 94.91 (1)°T = 293 K
V = 1001.5 (2) Å3Block, colourless
Z = 20.60 × 0.40 × 0.15 mm
Data collection top
Bruker P4
diffractometer
1429 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.023
Graphite monochromatorθmax = 25.0°, θmin = 2.3°
2θ/ω scansh = 110
Absorption correction: empirical (using intensity measurements)
(North et al., 1968)
k = 110
Tmin = 0.618, Tmax = 0.800l = 1414
2411 measured reflections3 standard reflections every 97 reflections
1765 independent reflections intensity decay: 6.1%
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)] = 0.033H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.092 w = 1/[σ2(Fo2) + (0.0494P)2 + 1.0422P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
1765 reflectionsΔρmax = 0.76 e Å3
134 parametersΔρmin = 0.56 e Å3
6 restraintsExtinction correction: SHELXTL (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0129 (17)
Crystal data top
[Zn(C7H8NO3S)2(H2O)4]V = 1001.5 (2) Å3
Mr = 509.84Z = 2
Monoclinic, P21/cMo Kα radiation
a = 9.0967 (14) ŵ = 1.49 mm1
b = 8.8122 (13) ÅT = 293 K
c = 12.5396 (14) Å0.60 × 0.40 × 0.15 mm
β = 94.91 (1)°
Data collection top
Bruker P4
diffractometer
1429 reflections with I > 2σ(I)
Absorption correction: empirical (using intensity measurements)
(North et al., 1968)
Rint = 0.023
Tmin = 0.618, Tmax = 0.8003 standard reflections every 97 reflections
2411 measured reflections intensity decay: 6.1%
1765 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0336 restraints
wR(F2) = 0.092H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.76 e Å3
1765 reflectionsΔρmin = 0.56 e Å3
134 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
xyzUiso*/Ueq
Zn10.00000.00000.50000.0225 (2)
S10.75531 (10)0.05693 (10)0.90620 (6)0.0267 (3)
N10.1723 (3)0.0233 (3)0.6004 (2)0.0230 (6)
O10.8216 (4)0.0820 (3)0.9369 (2)0.0524 (8)
O20.6995 (3)0.1494 (3)0.99661 (18)0.0388 (7)
O30.8524 (3)0.1444 (3)0.82937 (17)0.0340 (6)
O1W0.0704 (3)0.2054 (3)0.42483 (18)0.0312 (6)
H30.10280.27460.46440.047*
H40.00530.24580.38840.047*
O2W0.1542 (3)0.1264 (3)0.60733 (17)0.0345 (6)
H10.19310.20430.58040.052*
H20.14910.14310.67390.052*
C10.3056 (4)0.0726 (4)0.5596 (3)0.0270 (8)
H1A0.32250.08230.48570.032*
C20.4177 (4)0.1094 (4)0.6214 (3)0.0292 (8)
H2A0.50780.14300.58930.035*
C30.3963 (4)0.0964 (4)0.7318 (3)0.0282 (8)
C40.2609 (4)0.0404 (4)0.7735 (3)0.0300 (8)
H4A0.24260.02630.84700.036*
C50.1534 (4)0.0057 (4)0.7065 (3)0.0266 (8)
H5A0.06360.03170.73640.032*
C60.5137 (4)0.1420 (4)0.8033 (3)0.0364 (9)
H6A0.58020.21420.76590.044*
H6B0.46790.19140.86680.044*
C70.6011 (4)0.0055 (4)0.8362 (3)0.0290 (8)
H7A0.53670.06010.88130.035*
H7B0.63540.05150.77270.035*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0216 (3)0.0265 (3)0.0207 (3)0.0009 (2)0.0092 (2)0.0007 (2)
S10.0275 (5)0.0297 (5)0.0250 (4)0.0024 (4)0.0138 (3)0.0023 (3)
N10.0205 (15)0.0282 (15)0.0210 (13)0.0000 (12)0.0069 (11)0.0015 (11)
O10.0546 (12)0.0493 (11)0.0569 (11)0.0025 (9)0.0247 (9)0.0042 (9)
O20.0363 (15)0.0558 (17)0.0247 (11)0.0112 (13)0.0046 (10)0.0077 (11)
O30.0285 (15)0.0479 (16)0.0265 (11)0.0077 (12)0.0073 (10)0.0024 (10)
O1W0.0324 (14)0.0287 (13)0.0346 (12)0.0028 (11)0.0150 (10)0.0046 (10)
O2W0.0403 (16)0.0416 (14)0.0226 (11)0.0130 (12)0.0079 (10)0.0030 (10)
C10.0245 (19)0.0338 (19)0.0229 (15)0.0009 (16)0.0038 (14)0.0003 (13)
C20.0196 (18)0.0317 (18)0.0369 (18)0.0006 (15)0.0057 (15)0.0007 (15)
C30.0284 (19)0.0221 (16)0.0368 (17)0.0057 (15)0.0173 (15)0.0035 (14)
C40.034 (2)0.0355 (18)0.0218 (16)0.0034 (17)0.0090 (15)0.0030 (14)
C50.0218 (19)0.0322 (18)0.0262 (16)0.0014 (14)0.0035 (14)0.0005 (13)
C60.035 (2)0.0319 (19)0.046 (2)0.0029 (17)0.0221 (17)0.0083 (16)
C70.030 (2)0.0265 (17)0.0334 (18)0.0057 (15)0.0161 (15)0.0009 (14)
Geometric parameters (Å, º) top
Zn1—N1i2.102 (3)S1—C71.776 (4)
Zn1—N12.102 (3)N1—C51.336 (4)
Zn1—O1W2.114 (2)N1—C11.347 (4)
Zn1—O1Wi2.114 (2)C1—C21.372 (5)
Zn1—O2Wi2.167 (2)C2—C31.386 (5)
Zn1—O2W2.167 (2)C3—C41.387 (5)
S1—O11.432 (3)C3—C61.506 (5)
S1—O21.452 (3)C4—C51.377 (5)
S1—O31.469 (3)C6—C71.518 (5)
N1i—Zn1—N1180.0O2—S1—O3111.58 (15)
N1i—Zn1—O1W91.68 (10)O1—S1—C7106.45 (17)
N1—Zn1—O1W88.32 (10)O2—S1—C7106.94 (17)
N1i—Zn1—O1Wi88.32 (10)O3—S1—C7105.40 (15)
N1—Zn1—O1Wi91.68 (10)C5—N1—C1116.7 (3)
O1W—Zn1—O1Wi180.0C5—N1—Zn1123.1 (2)
N1i—Zn1—O2Wi93.10 (10)C1—N1—Zn1119.8 (2)
N1—Zn1—O2Wi86.90 (10)N1—C1—C2123.4 (3)
O1W—Zn1—O2Wi90.46 (9)C1—C2—C3119.8 (3)
O1Wi—Zn1—O2Wi89.54 (9)C2—C3—C4116.7 (3)
N1i—Zn1—O2W86.90 (10)C2—C3—C6121.8 (3)
N1—Zn1—O2W93.10 (10)C4—C3—C6121.5 (3)
O1W—Zn1—O2W89.54 (9)C5—C4—C3120.2 (3)
O1Wi—Zn1—O2W90.46 (9)N1—C5—C4123.0 (3)
O2Wi—Zn1—O2W180.0C3—C6—C7111.4 (3)
O1—S1—O2113.39 (17)C6—C7—S1112.7 (2)
O1—S1—O3112.45 (18)
Symmetry code: (i) x, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2W—H1···O2ii0.85 (5)1.97 (4)2.814 (4)167 (2)
O2W—H2···O3iii0.85 (3)1.95 (1)2.795 (3)170 (1)
O1W—H3···O1iv0.85 (4)1.93 (6)2.788 (4)175 (1)
O1W—H4···O3ii0.85 (6)1.89 (6)2.743 (4)170 (1)
C4—H4A···O2v0.93 (1)2.58 (8)3.379 (4)143 (1)
Symmetry codes: (ii) x+1, y+1/2, z1/2; (iii) x+1, y, z; (iv) x1, y+1/2, z+3/2; (v) x1, y, z+2.

Experimental details

Crystal data
Chemical formula[Zn(C7H8NO3S)2(H2O)4]
Mr509.84
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)9.0967 (14), 8.8122 (13), 12.5396 (14)
β (°) 94.91 (1)
V3)1001.5 (2)
Z2
Radiation typeMo Kα
µ (mm1)1.49
Crystal size (mm)0.60 × 0.40 × 0.15
Data collection
DiffractometerBruker P4
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(North et al., 1968)
Tmin, Tmax0.618, 0.800
No. of measured, independent and
observed [I > 2σ(I)] reflections
2411, 1765, 1429
Rint0.023
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.033, 0.092, 1.04
No. of reflections1765
No. of parameters134
No. of restraints6
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.76, 0.56

Computer programs: XSCANS (Siemens, 1994), XSCANS, SHELXTL (Sheldrick, 1997), SHELXTL.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2W—H1···O2i0.85 (5)1.97 (4)2.814 (4)167 (2)
O2W—H2···O3ii0.85 (3)1.95 (1)2.795 (3)170 (1)
O1W—H3···O1iii0.85 (4)1.93 (6)2.788 (4)175 (1)
O1W—H4···O3i0.85 (6)1.89 (6)2.743 (4)170 (1)
C4—H4A···O2iv0.93 (1)2.58 (8)3.379 (4)143 (1)
Symmetry codes: (i) x+1, y+1/2, z1/2; (ii) x+1, y, z; (iii) x1, y+1/2, z+3/2; (iv) x1, y, z+2.
 

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