Di-μ-sulfito-κ⁶O,O′:O′,O′′-bis­[(2,2′-bipyridine-κ²N,N′)zinc(II)]

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.

Key indicators

• Single-crystal X-ray study
• T = 273 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.025
• wR factor = 0.054
• Data-to-parameter ratio = 11.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.97
PLAT143_ALERT_4_C su on c - Axis Small or Missing (x 100000) .....         10 Ang.
PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 =          3
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Zn1    -   O2      ..       6.33 su
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) .       1.12 Ratio

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn1         (2)       2.20

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

Metal organic frameworks based on the SO₃^2- 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 SO₃^2- 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 SO₃^2- 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 SO₃^2- anions. In the SO₃^2- 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

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

S2. Experimental

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.

S3. Refinement

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

Computing details

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

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)]

Crystal data

[Zn2(SO3)2(C10H8N2)2]	Z = 2
Mr = 603.23	F(000) = 608
Monoclinic, P21/n	Dx = 1.923 Mg m^−3
Hall symbol: -P2yn	Mo Kα radiation, λ = 0.71073 Å
a = 8.1444 (1) Å	θ = 2.6–25.0°
b = 13.2118 (2) Å	µ = 2.55 mm^−1
c = 10.3020 (1) Å	T = 273 K
β = 109.970 (1)°	Prism, colorless
V = 1041.86 (2) Å^3	0.21 × 0.13 × 0.10 mm

Data collection

Siemens SMART 1K CCD area-detector diffractometer	1756 independent reflections
Radiation source: fine-focus sealed tube	1413 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.055
φ and ω scans	θmax = 25.0°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.700, Tmax = 0.800	k = −15→15
8021 measured reflections	l = −12→12

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.054	H-atom parameters constrained
S = 0.94	w = 1/[σ^2(Fo^2) + (0.0226P)^2] where P = (Fo^2 + 2Fc^2)/3
1756 reflections	(Δ/σ)max < 0.001
154 parameters	Δρmax = 0.34 e Å^−3
0 restraints	Δρmin = −0.46 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Zn1	0.07078 (4)	0.00807 (2)	0.16944 (3)	0.01426 (11)
S1	0.27778 (9)	−0.00925 (5)	0.00581 (7)	0.01588 (17)
O2	0.1343 (2)	−0.08446 (12)	0.01526 (18)	0.0166 (4)
N2	0.0632 (3)	0.11128 (15)	0.3230 (2)	0.0141 (5)
N1	0.2190 (3)	−0.06780 (14)	0.3510 (2)	0.0135 (5)
O1	0.2832 (2)	0.06485 (13)	0.12097 (18)	0.0188 (4)
C6	0.1471 (3)	0.08117 (18)	0.4537 (3)	0.0127 (6)
C5	0.3016 (4)	−0.15614 (19)	0.3572 (3)	0.0177 (6)
H5A	0.2819	−0.1922	0.2758	0.021*
C4	0.1365 (4)	0.13747 (19)	0.5649 (3)	0.0179 (6)
H4A	0.1936	0.1159	0.6550	0.021*
C3	−0.0344 (4)	0.19588 (18)	0.3002 (3)	0.0172 (6)
H3A	−0.0953	0.2149	0.2096	0.021*
C2	0.4143 (4)	−0.1964 (2)	0.4782 (3)	0.0202 (7)
H2A	0.4680	−0.2587	0.4793	0.024*
C1	0.2462 (3)	−0.01508 (18)	0.4696 (3)	0.0131 (6)
O3	0.1804 (3)	0.04415 (13)	−0.13110 (18)	0.0186 (4)
C10	0.4447 (4)	−0.14091 (19)	0.5983 (3)	0.0201 (7)
H10A	0.5227	−0.1647	0.6815	0.024*
C9	−0.0478 (4)	0.25539 (19)	0.4057 (3)	0.0199 (7)
H9A	−0.1145	0.3142	0.3870	0.024*
C8	0.0400 (4)	0.22563 (19)	0.5396 (3)	0.0203 (7)
H8A	0.0343	0.2649	0.6128	0.024*
C7	0.3591 (4)	−0.05038 (19)	0.5940 (3)	0.0177 (6)
H7A	0.3772	−0.0133	0.6744	0.021*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.01481 (19)	0.01848 (17)	0.00850 (19)	−0.00008 (14)	0.00271 (16)	−0.00131 (13)
S1	0.0132 (4)	0.0205 (3)	0.0136 (4)	−0.0016 (3)	0.0043 (3)	0.0005 (3)
O2	0.0164 (11)	0.0184 (9)	0.0146 (11)	−0.0031 (8)	0.0046 (10)	0.0002 (8)
N2	0.0130 (14)	0.0178 (11)	0.0102 (13)	−0.0021 (9)	0.0024 (12)	−0.0007 (9)
N1	0.0133 (13)	0.0173 (11)	0.0102 (13)	−0.0029 (9)	0.0044 (11)	−0.0037 (9)
O1	0.0209 (12)	0.0238 (10)	0.0104 (11)	−0.0070 (8)	0.0036 (10)	−0.0026 (8)
C6	0.0116 (15)	0.0152 (13)	0.0112 (16)	−0.0032 (11)	0.0039 (14)	−0.0008 (10)
C5	0.0193 (17)	0.0200 (14)	0.0144 (17)	0.0009 (12)	0.0067 (15)	−0.0026 (11)
C4	0.0215 (17)	0.0213 (14)	0.0107 (16)	−0.0026 (12)	0.0054 (15)	−0.0022 (11)
C3	0.0165 (17)	0.0182 (13)	0.0156 (17)	0.0027 (11)	0.0038 (15)	0.0038 (11)
C2	0.0211 (18)	0.0197 (14)	0.0212 (18)	0.0046 (12)	0.0091 (16)	0.0031 (12)
C1	0.0117 (15)	0.0175 (13)	0.0108 (15)	−0.0040 (11)	0.0047 (14)	0.0007 (11)
O3	0.0195 (12)	0.0257 (10)	0.0094 (11)	−0.0042 (8)	0.0034 (10)	0.0020 (8)
C10	0.0175 (18)	0.0249 (15)	0.0146 (17)	−0.0003 (12)	0.0013 (15)	0.0069 (12)
C9	0.0212 (18)	0.0154 (13)	0.0254 (18)	0.0011 (12)	0.0108 (16)	−0.0019 (12)
C8	0.0231 (19)	0.0210 (14)	0.0192 (18)	−0.0045 (12)	0.0101 (16)	−0.0083 (12)
C7	0.0200 (18)	0.0226 (14)	0.0096 (16)	−0.0034 (12)	0.0040 (15)	−0.0007 (11)

Geometric parameters (Å, º)

Zn1—O3^i	2.0651 (19)	C6—C1	1.485 (3)
Zn1—O1	2.0963 (17)	C5—C2	1.378 (4)
Zn1—N1	2.102 (2)	C5—H5A	0.9300
Zn1—N2	2.105 (2)	C4—C8	1.379 (4)
Zn1—O2	2.2016 (16)	C4—H4A	0.9300
Zn1—O2^i	2.2932 (19)	C3—C9	1.375 (3)
Zn1—S1	2.7708 (6)	C3—H3A	0.9300
Zn1—S1^i	2.7961 (8)	C2—C10	1.386 (4)
S1—O1	1.5271 (17)	C2—H2A	0.9300
S1—O3	1.5337 (19)	C1—C7	1.378 (4)
S1—O2	1.5618 (18)	O3—Zn1^i	2.0651 (19)
S1—Zn1^i	2.7961 (8)	C10—C7	1.378 (4)
O2—Zn1^i	2.2932 (19)	C10—H10A	0.9300
N2—C6	1.345 (3)	C9—C8	1.377 (4)
N2—C3	1.345 (3)	C9—H9A	0.9300
N1—C5	1.337 (3)	C8—H8A	0.9300
N1—C1	1.357 (3)	C7—H7A	0.9300
C6—C4	1.393 (3)
O3^i—Zn1—O1	156.65 (7)	Zn1—O2—Zn1^i	94.02 (7)
O3^i—Zn1—N1	103.97 (7)	C6—N2—C3	119.2 (2)
O1—Zn1—N1	96.46 (7)	C6—N2—Zn1	115.17 (16)
O3^i—Zn1—N2	94.52 (8)	C3—N2—Zn1	125.06 (19)
O1—Zn1—N2	100.69 (7)	C5—N1—C1	118.7 (2)
N1—Zn1—N2	78.21 (8)	C5—N1—Zn1	125.85 (18)
O3^i—Zn1—O2	97.94 (7)	C1—N1—Zn1	115.07 (16)
O1—Zn1—O2	67.07 (6)	S1—O1—Zn1	98.54 (9)
N1—Zn1—O2	99.90 (7)	N2—C6—C4	120.8 (2)
N2—Zn1—O2	167.47 (8)	N2—C6—C1	115.8 (2)
O3^i—Zn1—O2^i	66.11 (6)	C4—C6—C1	123.4 (2)
O1—Zn1—O2^i	94.10 (7)	N1—C5—C2	123.3 (2)
N1—Zn1—O2^i	169.26 (7)	N1—C5—H5A	118.3
N2—Zn1—O2^i	97.96 (7)	C2—C5—H5A	118.3
O2—Zn1—O2^i	85.98 (7)	C8—C4—C6	119.1 (3)
O3^i—Zn1—S1	128.67 (5)	C8—C4—H4A	120.4
O1—Zn1—S1	33.03 (5)	C6—C4—H4A	120.4
N1—Zn1—S1	102.59 (6)	N2—C3—C9	122.6 (3)
N2—Zn1—S1	133.68 (6)	N2—C3—H3A	118.7
O2—Zn1—S1	34.25 (5)	C9—C3—H3A	118.7
O2^i—Zn1—S1	87.35 (4)	C5—C2—C10	117.7 (2)
O3^i—Zn1—S1^i	32.58 (5)	C5—C2—H2A	121.2
O1—Zn1—S1^i	125.64 (5)	C10—C2—H2A	121.2
N1—Zn1—S1^i	136.49 (6)	N1—C1—C7	121.0 (2)
N2—Zn1—S1^i	101.41 (6)	N1—C1—C6	115.1 (2)
O2—Zn1—S1^i	88.53 (5)	C7—C1—C6	123.8 (2)
O2^i—Zn1—S1^i	33.95 (4)	S1—O3—Zn1^i	100.93 (8)
S1—Zn1—S1^i	107.589 (18)	C7—C10—C2	119.7 (3)
O1—S1—O3	106.75 (10)	C7—C10—H10A	120.1
O1—S1—O2	100.56 (9)	C2—C10—H10A	120.1
O3—S1—O2	100.78 (10)	C3—C9—C8	118.3 (2)
O1—S1—Zn1	48.44 (7)	C3—C9—H9A	120.9
O3—S1—Zn1	106.88 (7)	C8—C9—H9A	120.9
O2—S1—Zn1	52.49 (6)	C9—C8—C4	119.9 (2)
O1—S1—Zn1^i	104.57 (8)	C9—C8—H8A	120.1
O3—S1—Zn1^i	46.48 (7)	C4—C8—H8A	120.1
O2—S1—Zn1^i	55.09 (7)	C10—C7—C1	119.6 (2)
Zn1—S1—Zn1^i	72.411 (18)	C10—C7—H7A	120.2
S1—O2—Zn1	93.26 (8)	C1—C7—H7A	120.2
S1—O2—Zn1^i	90.96 (8)

Symmetry code: (i) −x, −y, −z.