Bis[2-(3,4-disulfanylphen-yl)acetato]bis-(2-methyl-1H-imidazole-κN)zinc(II).

In the title mononuclear zinc(II) complex, [Zn(C(8)H(7)O(2)S(2))(2)(C(4)H(6)N(2))(2)], the Zn(II) atom, lying on a twofold axis, is coordinated by two O atoms from two 2-(3,4-disulfanylphen-yl)acetate anions and by two N atoms from 2-methyl-imidazole ligands in a distorted tetra-hdral coordination. The crystal structure is stabilized by inter-molecular C-H⋯O and N-H⋯O hydrogen bonds and π-π inter-actions with a centroid-centroid distance of 3.6136 (16) Å.

Related literature

For general background to organometallic complexes and their applications, see: Sommerfeldt et al. (2008 ▶); Huang et al. (2007 ▶); Neville et al. (2008 ▶). Zinc derivatives are of particular inter­est owing to their unique photosensitizing properties for photodynamic therapy, see: You et al. (2006 ▶); Shi et al. (2008 ▶); Xiao et al. (2008 ▶, 2009 ▶). For related structures, see: Yang et al. (2004 ▶); You et al. (2003 ▶, 2004 ▶); Qiu et al. (2004 ▶, 2007 ▶); Halcrow et al. (2000 ▶).

Experimental

Crystal data

[Zn(C8H7O2S2)2(C4n class="Species">H6N2)2]

M = 628.16

Monoclinic,

a = 12.9599 (9) Å

b = 9.3909 (6) Å

c = 21.5549 (12) Å

β = 91.579 (2)°

V = 2622.4 (3) Å3

Z = 4

Mo Kα radiation

μ = 1.30 mm−1

T = 298 K

0.30 × 0.20 × 0.20 mm

Data collection

Bruker APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.697, T max = 0.782

15712 measured reflections

3260 independent reflections

3102 reflections with I > 2σ(I)

R int = 0.020

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.125

S = 1.12

3260 reflections

175 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.70 e Å−3

Δρmin = −0.60 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAIn class="Chemical">NT; 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.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809033893/rk2159sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809033893/rk2159Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Zn(C8H7O2S2)2(C4H6N2)2]	F(000) = 1296
Mr = 628.16	Dx = 1.591 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3063 reflections
a = 12.9599 (9) Å	θ = 2.3–26.7°
b = 9.3909 (6) Å	µ = 1.30 mm−1
c = 21.5549 (12) Å	T = 298 K
β = 91.579 (2)°	Block, colourless
V = 2622.4 (3) Å3	0.30 × 0.20 × 0.20 mm
Z = 4

Bruker APEXII area-detector diffractometer	3260 independent reflections
Radiation source: fine-focus sealed tube	3102 reflections with I > 2σ(I)
graphite	Rint = 0.020
φ and ω scans	θmax = 28.3°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −17→17
Tmin = 0.697, Tmax = 0.782	k = −12→12
15712 measured reflections	l = −28→28

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.125	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ2(Fo2) + (0.0644P)2 + 4.9284P] where P = (Fo2 + 2Fc2)/3
3260 reflections	(Δ/σ)max = 0.001
175 parameters	Δρmax = 0.70 e Å−3
0 restraints	Δρmin = −0.60 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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.

	x	y	z	Uiso*/Ueq
C1	0.2396 (2)	0.5043 (3)	0.48533 (12)	0.0379 (5)
N1	−0.07005 (15)	−0.0094 (2)	0.29964 (10)	0.0336 (4)
O1	−0.05381 (13)	0.28914 (19)	0.30382 (8)	0.0365 (4)
S1	0.28934 (7)	0.42402 (10)	0.55206 (4)	0.0571 (2)
H3A	0.2872	0.2970	0.5459	0.086*
Zn1	0.0000	0.13605 (4)	0.2500	0.03067 (13)
C2	0.2944 (2)	0.6098 (3)	0.45584 (13)	0.0364 (5)
H2	−0.251 (3)	−0.178 (4)	0.3375 (18)	0.058 (10)*
N2	−0.18947 (19)	−0.1506 (2)	0.33454 (12)	0.0412 (5)
O2	0.10600 (13)	0.25971 (19)	0.33887 (9)	0.0366 (4)
S2	0.41436 (6)	0.66341 (9)	0.48428 (4)	0.0489 (2)
H3B	0.4310	0.7829	0.4676	0.073*
C3	0.2536 (2)	0.6715 (3)	0.40205 (13)	0.0403 (6)
H3	0.2896	0.7431	0.3821	0.048*
C4	0.1594 (2)	0.6260 (3)	0.37831 (13)	0.0415 (6)
H4	0.1317	0.6689	0.3427	0.050*
C5	0.10476 (19)	0.5171 (3)	0.40649 (12)	0.0361 (5)
C6	0.1456 (2)	0.4587 (3)	0.46066 (12)	0.0393 (5)
H6	0.1093	0.3877	0.4808	0.047*
C7	0.0069 (2)	0.4586 (3)	0.37719 (14)	0.0422 (6)
H7A	−0.0251	0.5320	0.3515	0.051*
H7B	−0.0406	0.4356	0.4097	0.051*
C8	0.02273 (18)	0.3261 (3)	0.33751 (11)	0.0312 (4)
C9	−0.0334 (2)	−0.0732 (3)	0.35314 (13)	0.0417 (6)
H9	0.0316	−0.0587	0.3714	0.050*
C10	−0.1071 (2)	−0.1607 (3)	0.37499 (15)	0.0449 (6)
H10	−0.1024	−0.2166	0.4106	0.054*
C11	−0.16510 (19)	−0.0582 (3)	0.28945 (12)	0.0370 (5)
C12	−0.2349 (2)	−0.0175 (4)	0.23679 (16)	0.0590 (9)
H12A	−0.2573	0.0791	0.2420	0.088*
H12B	−0.2938	−0.0795	0.2355	0.088*
H12C	−0.1987	−0.0257	0.1987	0.088*

	U11	U22	U33	U12	U13	U23
C1	0.0419 (13)	0.0362 (12)	0.0355 (12)	−0.0028 (10)	−0.0015 (10)	−0.0026 (10)
N1	0.0279 (9)	0.0342 (10)	0.0390 (10)	−0.0042 (8)	0.0047 (8)	−0.0016 (8)
O1	0.0281 (8)	0.0389 (9)	0.0421 (9)	0.0006 (7)	−0.0039 (7)	−0.0082 (7)
S1	0.0623 (5)	0.0593 (5)	0.0487 (4)	−0.0145 (4)	−0.0168 (4)	0.0159 (4)
Zn1	0.0238 (2)	0.0328 (2)	0.0354 (2)	0.000	0.00027 (14)	0.000
C2	0.0337 (12)	0.0335 (11)	0.0419 (13)	−0.0027 (9)	0.0013 (10)	−0.0070 (10)
N2	0.0345 (11)	0.0364 (11)	0.0533 (13)	−0.0079 (9)	0.0095 (10)	0.0012 (9)
O2	0.0286 (8)	0.0360 (9)	0.0449 (9)	0.0012 (7)	−0.0033 (7)	−0.0036 (7)
S2	0.0354 (4)	0.0513 (4)	0.0595 (4)	−0.0100 (3)	−0.0046 (3)	−0.0066 (3)
C3	0.0433 (14)	0.0345 (12)	0.0433 (14)	−0.0051 (10)	0.0040 (11)	0.0005 (10)
C4	0.0476 (15)	0.0379 (13)	0.0387 (13)	0.0003 (11)	−0.0022 (11)	−0.0006 (10)
C5	0.0334 (11)	0.0335 (12)	0.0413 (12)	−0.0001 (9)	0.0012 (10)	−0.0105 (10)
C6	0.0409 (13)	0.0356 (12)	0.0416 (13)	−0.0060 (10)	0.0032 (10)	−0.0028 (10)
C7	0.0337 (12)	0.0407 (13)	0.0519 (15)	0.0020 (10)	−0.0028 (11)	−0.0135 (12)
C8	0.0306 (11)	0.0303 (10)	0.0327 (11)	−0.0026 (9)	0.0011 (9)	−0.0005 (9)
C9	0.0318 (12)	0.0472 (15)	0.0461 (14)	0.0008 (10)	0.0006 (10)	0.0051 (12)
C10	0.0420 (14)	0.0423 (14)	0.0507 (15)	0.0018 (11)	0.0056 (12)	0.0103 (12)
C11	0.0317 (11)	0.0370 (12)	0.0424 (13)	−0.0046 (9)	0.0055 (10)	−0.0045 (10)
C12	0.0418 (16)	0.081 (2)	0.0540 (18)	−0.0166 (16)	−0.0088 (13)	0.0081 (17)

C1—C6	1.384 (4)	C3—C4	1.379 (4)
C1—C2	1.384 (4)	C3—H3	0.9300
C1—S1	1.732 (3)	C4—C5	1.392 (4)
N1—C11	1.327 (3)	C4—H4	0.9300
N1—C9	1.373 (3)	C5—C6	1.382 (4)
N1—Zn1	1.972 (2)	C5—C7	1.506 (3)
O1—C8	1.262 (3)	C6—H6	0.9300
O1—Zn1	1.9858 (18)	C7—C8	1.527 (3)
S1—H3A	1.2000	C7—H7A	0.9700
Zn1—N1i	1.972 (2)	C7—H7B	0.9700
Zn1—O1i	1.9858 (18)	C9—C10	1.354 (4)
C2—C3	1.388 (4)	C9—H9	0.9300
C2—S2	1.730 (3)	C10—H10	0.9300
N2—C11	1.347 (4)	C11—C12	1.482 (4)
N2—C10	1.363 (4)	C12—H12A	0.9600
N2—H2	0.85 (4)	C12—H12B	0.9600
O2—C8	1.246 (3)	C12—H12C	0.9600
S2—H3B	1.2000
C6—C1—C2	120.2 (2)	C4—C5—C7	121.2 (3)
C6—C1—S1	119.2 (2)	C5—C6—C1	121.0 (2)
C2—C1—S1	120.6 (2)	C5—C6—H6	119.5
C11—N1—C9	106.7 (2)	C1—C6—H6	119.5
C11—N1—Zn1	126.04 (18)	C5—C7—C8	114.0 (2)
C9—N1—Zn1	127.18 (17)	C5—C7—H7A	108.7
C8—O1—Zn1	104.61 (15)	C8—C7—H7A	108.7
C1—S1—H3A	109.5	C5—C7—H7B	108.7
N1—Zn1—N1i	92.29 (12)	C8—C7—H7B	108.7
N1—Zn1—O1	90.59 (8)	H7A—C7—H7B	107.6
N1i—Zn1—O1	173.13 (8)	O2—C8—O1	122.9 (2)
N1—Zn1—O1i	173.13 (8)	O2—C8—C7	121.6 (2)
N1i—Zn1—O1i	90.59 (8)	O1—C8—C7	115.5 (2)
O1—Zn1—O1i	87.23 (11)	C10—C9—N1	109.0 (2)
C1—C2—C3	119.6 (2)	C10—C9—H9	125.5
C1—C2—S2	120.9 (2)	N1—C9—H9	125.5
C3—C2—S2	119.5 (2)	C9—C10—N2	106.4 (3)
C11—N2—C10	108.1 (2)	C9—C10—H10	126.8
C11—N2—H2	120 (3)	N2—C10—H10	126.8
C10—N2—H2	131 (3)	N1—C11—N2	109.8 (2)
C2—S2—H3B	109.5	N1—C11—C12	125.6 (3)
C4—C3—C2	119.6 (2)	N2—C11—C12	124.6 (2)
C4—C3—H3	120.2	C11—C12—H12A	109.5
C2—C3—H3	120.2	C11—C12—H12B	109.5
C3—C4—C5	121.4 (3)	H12A—C12—H12B	109.5
C3—C4—H4	119.3	C11—C12—H12C	109.5
C5—C4—H4	119.3	H12A—C12—H12C	109.5
C6—C5—C4	118.2 (2)	H12B—C12—H12C	109.5
C6—C5—C7	120.5 (2)
C11—N1—Zn1—N1i	−96.2 (2)	C6—C5—C7—C8	−81.8 (3)
C9—N1—Zn1—N1i	88.2 (2)	C4—C5—C7—C8	94.8 (3)
C8—O1—Zn1—O1i	−82.04 (15)	Zn1—O1—C8—O2	−8.8 (3)
C6—C1—C2—C3	1.2 (4)	Zn1—O1—C8—C7	171.33 (18)
S1—C1—C2—C3	179.3 (2)	C5—C7—C8—O2	12.1 (4)
C6—C1—C2—S2	−177.5 (2)	C5—C7—C8—O1	−168.1 (2)
S1—C1—C2—S2	0.6 (3)	C11—N1—C9—C10	0.1 (3)
C1—C2—C3—C4	−0.6 (4)	Zn1—N1—C9—C10	176.3 (2)
S2—C2—C3—C4	178.1 (2)	N1—C9—C10—N2	0.1 (3)
C2—C3—C4—C5	−1.2 (4)	C11—N2—C10—C9	−0.2 (3)
C3—C4—C5—C6	2.4 (4)	C9—N1—C11—N2	−0.2 (3)
C3—C4—C5—C7	−174.3 (2)	Zn1—N1—C11—N2	−176.49 (17)
C4—C5—C6—C1	−1.8 (4)	C9—N1—C11—C12	179.6 (3)
C7—C5—C6—C1	174.9 (2)	Zn1—N1—C11—C12	3.3 (4)
C2—C1—C6—C5	0.0 (4)	C10—N2—C11—N1	0.2 (3)
S1—C1—C6—C5	−178.1 (2)	C10—N2—C11—C12	−179.6 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12B···O1ii	0.96	2.46	3.381 (4)	161
N2—H2···O2iii	0.85 (4)	1.94 (4)	2.785 (3)	176 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12B⋯O1i	0.96	2.46	3.381 (4)	161
N2—H2⋯O2ii	0.85 (4)	1.94 (4)	2.785 (3)	176 (4)

Symmetry codes: (i) ; (ii) .