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Acta Cryst. (2007). E63, m2101    [ doi:10.1107/S1600536807032692 ]

Di-[mu]-sulfito-[kappa]6O,O':O',O''-bis[(2,2'-bipyridine-[kappa]2N,N')zinc(II)]

E Yang, X.-C. Song, S.-Z. Shen and Y.-D. Lin

Abstract top

In the title compound, [Zn2(SO3)2(C10H8N2)2], Zn2+ and SO32- form a dinuclear unit, with an inversion center at the mid-point of the Zn...Zn vector. Each Zn atom has distorted octahedral geometry and is coordinated by four O atoms from two SO32- anions and two N atoms of the 2,2'-bipyridine ligand.

Comment top

Metal organic frameworks based on the SO32- unit are of current interest (Nguyen et al., 2006). We report here a new zinc sulfite structure, Zn2(SO3)2(2,2'-bipyridine)2.

In the title compound, Zn2+ and SO32- form an dinuclear unit, with an inversion center at the mid-point of the Zn···Zn vector (Fig.1). Each Zn atom has distorted octahedral geometry and is coordinated by four O atoms from two different SO32- anions and two N atoms from the 2,2'-bipyridine ligand. It is worth noting that Zn1 and Zn1a share two common oxygen sites from two SO32- anions. In the SO32- group, one oxygen site is linked to two Zn2+ and one S4+ sites; the other two oxygen sites are each linked to one Zn2+ and one S4+ sites. The 2,2'-bipyridine ligands chelate the Zn sites.

Related literature top

For related literature, see: Nguyen et al. (2006).

Experimental top

A mixture of ZnSO3 (0.145 g, 1 mmol), 2,2'-bipyridine (0.168 g, 1 mmol) and H2O (18 ml) was sealed in a 25 ml Teflon-lined stainless steel reactor and was heated at 373 K for 3 d. On completion of the reaction, the reactor was cooled slowly to room temperature and the mixture was filtered, giving colorless single crystals suitable for X-ray analysis.

Refinement top

All H atoms were placed at calculated positions, and refined using a riding model [C—H = 0.93Å and Uiso(H) = 1.2Ueq(C)].

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1996); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids [symmetry code: (a) -x,-y,-z].
Di-µ-sulfito-κ6O,O':O',O''-bis[(2,2'-bipyridine-κ2N,N')zinc(II)] top
Crystal data top
[Zn2(SO3)2(C10H8N2)2]Z = 2
Mr = 603.23F(000) = 608
Monoclinic, P21/nDx = 1.923 Mg m−3
Hall symbol: -P2ynMo Kα radiation, λ = 0.71073 Å
a = 8.1444 (1) Åθ = 2.6–25.0°
b = 13.2118 (2) ŵ = 2.55 mm−1
c = 10.3020 (1) ÅT = 273 K
β = 109.970 (1)°Prism, colorless
V = 1041.86 (2) Å30.21 × 0.13 × 0.10 mm
Data collection top
Siemens SMART 1K CCD area-detector
diffractometer		1756 independent reflections
Radiation source: fine-focus sealed tube1413 reflections with I > 2σ(I)
graphiteRint = 0.055
φ and ω scansθmax = 25.0°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −9→9
Tmin = 0.700, Tmax = 0.800k = −15→15
8021 measured reflectionsl = −12→12
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.025Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.054H-atom parameters constrained
S = 0.94 w = 1/[σ2(Fo2) + (0.0226P)2]
where P = (Fo2 + 2Fc2)/3
1756 reflections(Δ/σ)max < 0.001
154 parametersΔρmax = 0.34 e Å−3
0 restraintsΔρmin = −0.46 e Å−3
Crystal data top
[Zn2(SO3)2(C10H8N2)2]V = 1041.86 (2) Å3
Mr = 603.23Z = 2
Monoclinic, P21/nMo Kα radiation
a = 8.1444 (1) ŵ = 2.55 mm−1
b = 13.2118 (2) ÅT = 273 K
c = 10.3020 (1) Å0.21 × 0.13 × 0.10 mm
β = 109.970 (1)°
Data collection top
Siemens SMART 1K CCD area-detector
diffractometer		1756 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1413 reflections with I > 2σ(I)
Tmin = 0.700, Tmax = 0.800Rint = 0.055
8021 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.025H-atom parameters constrained
wR(F2) = 0.054Δρmax = 0.34 e Å−3
S = 0.94Δρmin = −0.46 e Å−3
1756 reflectionsAbsolute structure: ?
154 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
Zn10.07078 (4)0.00807 (2)0.16944 (3)0.01426 (11)
S10.27778 (9)−0.00925 (5)0.00581 (7)0.01588 (17)
O20.1343 (2)−0.08446 (12)0.01526 (18)0.0166 (4)
N20.0632 (3)0.11128 (15)0.3230 (2)0.0141 (5)
N10.2190 (3)−0.06780 (14)0.3510 (2)0.0135 (5)
O10.2832 (2)0.06485 (13)0.12097 (18)0.0188 (4)
C60.1471 (3)0.08117 (18)0.4537 (3)0.0127 (6)
C50.3016 (4)−0.15614 (19)0.3572 (3)0.0177 (6)
H5A0.2819−0.19220.27580.021*
C40.1365 (4)0.13747 (19)0.5649 (3)0.0179 (6)
H4A0.19360.11590.65500.021*
C3−0.0344 (4)0.19588 (18)0.3002 (3)0.0172 (6)
H3A−0.09530.21490.20960.021*
C20.4143 (4)−0.1964 (2)0.4782 (3)0.0202 (7)
H2A0.4680−0.25870.47930.024*
C10.2462 (3)−0.01508 (18)0.4696 (3)0.0131 (6)
O30.1804 (3)0.04415 (13)−0.13110 (18)0.0186 (4)
C100.4447 (4)−0.14091 (19)0.5983 (3)0.0201 (7)
H10A0.5227−0.16470.68150.024*
C9−0.0478 (4)0.25539 (19)0.4057 (3)0.0199 (7)
H9A−0.11450.31420.38700.024*
C80.0400 (4)0.22563 (19)0.5396 (3)0.0203 (7)
H8A0.03430.26490.61280.024*
C70.3591 (4)−0.05038 (19)0.5940 (3)0.0177 (6)
H7A0.3772−0.01330.67440.021*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.01481 (19)0.01848 (17)0.00850 (19)−0.00008 (14)0.00271 (16)−0.00131 (13)
S10.0132 (4)0.0205 (3)0.0136 (4)−0.0016 (3)0.0043 (3)0.0005 (3)
O20.0164 (11)0.0184 (9)0.0146 (11)−0.0031 (8)0.0046 (10)0.0002 (8)
N20.0130 (14)0.0178 (11)0.0102 (13)−0.0021 (9)0.0024 (12)−0.0007 (9)
N10.0133 (13)0.0173 (11)0.0102 (13)−0.0029 (9)0.0044 (11)−0.0037 (9)
O10.0209 (12)0.0238 (10)0.0104 (11)−0.0070 (8)0.0036 (10)−0.0026 (8)
C60.0116 (15)0.0152 (13)0.0112 (16)−0.0032 (11)0.0039 (14)−0.0008 (10)
C50.0193 (17)0.0200 (14)0.0144 (17)0.0009 (12)0.0067 (15)−0.0026 (11)
C40.0215 (17)0.0213 (14)0.0107 (16)−0.0026 (12)0.0054 (15)−0.0022 (11)
C30.0165 (17)0.0182 (13)0.0156 (17)0.0027 (11)0.0038 (15)0.0038 (11)
C20.0211 (18)0.0197 (14)0.0212 (18)0.0046 (12)0.0091 (16)0.0031 (12)
C10.0117 (15)0.0175 (13)0.0108 (15)−0.0040 (11)0.0047 (14)0.0007 (11)
O30.0195 (12)0.0257 (10)0.0094 (11)−0.0042 (8)0.0034 (10)0.0020 (8)
C100.0175 (18)0.0249 (15)0.0146 (17)−0.0003 (12)0.0013 (15)0.0069 (12)
C90.0212 (18)0.0154 (13)0.0254 (18)0.0011 (12)0.0108 (16)−0.0019 (12)
C80.0231 (19)0.0210 (14)0.0192 (18)−0.0045 (12)0.0101 (16)−0.0083 (12)
C70.0200 (18)0.0226 (14)0.0096 (16)−0.0034 (12)0.0040 (15)−0.0007 (11)
Geometric parameters (Å, °) top
Zn1—O3i2.0651 (19)C6—C11.485 (3)
Zn1—O12.0963 (17)C5—C21.378 (4)
Zn1—N12.102 (2)C5—H5A0.9300
Zn1—N22.105 (2)C4—C81.379 (4)
Zn1—O22.2016 (16)C4—H4A0.9300
Zn1—O2i2.2932 (19)C3—C91.375 (3)
Zn1—S12.7708 (6)C3—H3A0.9300
Zn1—S1i2.7961 (8)C2—C101.386 (4)
S1—O11.5271 (17)C2—H2A0.9300
S1—O31.5337 (19)C1—C71.378 (4)
S1—O21.5618 (18)O3—Zn1i2.0651 (19)
S1—Zn1i2.7961 (8)C10—C71.378 (4)
O2—Zn1i2.2932 (19)C10—H10A0.9300
N2—C61.345 (3)C9—C81.377 (4)
N2—C31.345 (3)C9—H9A0.9300
N1—C51.337 (3)C8—H8A0.9300
N1—C11.357 (3)C7—H7A0.9300
C6—C41.393 (3)
O3i—Zn1—O1156.65 (7)Zn1—O2—Zn1i94.02 (7)
O3i—Zn1—N1103.97 (7)C6—N2—C3119.2 (2)
O1—Zn1—N196.46 (7)C6—N2—Zn1115.17 (16)
O3i—Zn1—N294.52 (8)C3—N2—Zn1125.06 (19)
O1—Zn1—N2100.69 (7)C5—N1—C1118.7 (2)
N1—Zn1—N278.21 (8)C5—N1—Zn1125.85 (18)
O3i—Zn1—O297.94 (7)C1—N1—Zn1115.07 (16)
O1—Zn1—O267.07 (6)S1—O1—Zn198.54 (9)
N1—Zn1—O299.90 (7)N2—C6—C4120.8 (2)
N2—Zn1—O2167.47 (8)N2—C6—C1115.8 (2)
O3i—Zn1—O2i66.11 (6)C4—C6—C1123.4 (2)
O1—Zn1—O2i94.10 (7)N1—C5—C2123.3 (2)
N1—Zn1—O2i169.26 (7)N1—C5—H5A118.3
N2—Zn1—O2i97.96 (7)C2—C5—H5A118.3
O2—Zn1—O2i85.98 (7)C8—C4—C6119.1 (3)
O3i—Zn1—S1128.67 (5)C8—C4—H4A120.4
O1—Zn1—S133.03 (5)C6—C4—H4A120.4
N1—Zn1—S1102.59 (6)N2—C3—C9122.6 (3)
N2—Zn1—S1133.68 (6)N2—C3—H3A118.7
O2—Zn1—S134.25 (5)C9—C3—H3A118.7
O2i—Zn1—S187.35 (4)C5—C2—C10117.7 (2)
O3i—Zn1—S1i32.58 (5)C5—C2—H2A121.2
O1—Zn1—S1i125.64 (5)C10—C2—H2A121.2
N1—Zn1—S1i136.49 (6)N1—C1—C7121.0 (2)
N2—Zn1—S1i101.41 (6)N1—C1—C6115.1 (2)
O2—Zn1—S1i88.53 (5)C7—C1—C6123.8 (2)
O2i—Zn1—S1i33.95 (4)S1—O3—Zn1i100.93 (8)
S1—Zn1—S1i107.589 (18)C7—C10—C2119.7 (3)
O1—S1—O3106.75 (10)C7—C10—H10A120.1
O1—S1—O2100.56 (9)C2—C10—H10A120.1
O3—S1—O2100.78 (10)C3—C9—C8118.3 (2)
O1—S1—Zn148.44 (7)C3—C9—H9A120.9
O3—S1—Zn1106.88 (7)C8—C9—H9A120.9
O2—S1—Zn152.49 (6)C9—C8—C4119.9 (2)
O1—S1—Zn1i104.57 (8)C9—C8—H8A120.1
O3—S1—Zn1i46.48 (7)C4—C8—H8A120.1
O2—S1—Zn1i55.09 (7)C10—C7—C1119.6 (2)
Zn1—S1—Zn1i72.411 (18)C10—C7—H7A120.2
S1—O2—Zn193.26 (8)C1—C7—H7A120.2
S1—O2—Zn1i90.96 (8)
Symmetry codes: (i) −x, −y, −z.
Table 1
Selected geometric parameters (Å, °) top
Zn1—O3i2.0651 (19)Zn1—N22.105 (2)
Zn1—O12.0963 (17)Zn1—O22.2016 (16)
Zn1—N12.102 (2)Zn1—O2i2.2932 (19)
O3i—Zn1—O1156.65 (7)N1—Zn1—O299.90 (7)
O3i—Zn1—N1103.97 (7)N2—Zn1—O2167.47 (8)
O1—Zn1—N196.46 (7)O3i—Zn1—O2i66.11 (6)
O3i—Zn1—N294.52 (8)O1—Zn1—O2i94.10 (7)
O1—Zn1—N2100.69 (7)N1—Zn1—O2i169.26 (7)
N1—Zn1—N278.21 (8)N2—Zn1—O2i97.96 (7)
O3i—Zn1—O297.94 (7)O2—Zn1—O2i85.98 (7)
O1—Zn1—O267.07 (6)
Symmetry codes: (i) −x, −y, −z.
Acknowledgements top

The authors acknowledge financial support from the Natural Science Foundations of Fujian Province (2006 F3042 and JB06073).

references
References top

Nguyen, D.-T., Chew, E., Zhang, Q., Choi, A. & Bu, X. (2006). Inorg. Chem. 45, 10722–10727.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Siemens (1996). SMART and SAINT (Versions 4.0), and SHELXTL (Version 5.06). Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Are SMART and SAINT really both Version 4.0?