catena-Poly[[diaqua­(2,2′-bipyridine-κ²N,N′)zinc]-μ-2,2′-[1,4-phenylene­bis(sulfanedi­yl)]diacetato-κ²O:O′]

In the polymeric title complex, [Zn(C₁₀H₈O₄S₂)(C₁₀H₈N₂)(H₂O)₂]_n, the Zn²⁺ ion lies on a twofold rotation axis and exhibits an octa­hedral environment, in which it is coordinated by two trans O atoms from two symmetry-related 2,2′-[1,4-phenyl­enebis(sulfanedi­yl)]diacetate anions, two N atoms from one 2,2′-bipyridine ligand, and two cis O atoms from water mol­ecules. The dihedral angle between the two pyridine rings is 11.5 (1)°. Adjacent Zn²⁺ ions are bridged in a monodentate manner by the diacetate anions, forming a chain structure extending parallel to [101], and are further linked into the final three-dimensional structure by O—H...O hydrogen bonds between the coordinating water mol­ecules as donor and the non-coordinating carboxyl­ate O atoms as acceptor atoms.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.025
• wR factor = 0.070
• Data-to-parameter ratio = 16.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600          6

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          3
PLAT004_ALERT_5_G Info: Polymeric Structure Found with Dimension .          1
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Zn1    --  O1W     ..        5.8 su
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Zn1    --  N1      ..        7.3 su
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         15
            O1  -ZN1 -O1  -C6     14.13  0.13   2.655   1.555   1.555   1.555
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          2
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          3

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   8 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 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
   2 ALERT type 5 Informative message, check

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S1. Comment

1,4-Benzenebis(thioacetic acid), (C₁₀H₁₀O₄S₂), is a flexible aromatic multi-carboxylate ligand, which can be prepared from 1,4-benzenebisthiol (Yin & Feng, 2009). Compared with rigid ligands, these flexible aromatic carboxylate ligands contain more coordination sites (viz. S and O atoms) to construct various extended structures with different metal ions. Recently, some complexes derived from 1,4-benzenebis(thioacetic acid) with bipyridine ligands have been reported (Yin et al., 2009; Chen et al., 2010; Wang et al., 2011a,b; Jiang et al., 2012). Here we report the synthesis and structure of a new complex, [Zn(C₁₀H₈O₄S₂)(C₁₀H₈N₂)(H₂O)₂]_n, (I).

Complex (I) is isotypic with its Co(II) analogue (Jiang et al., 2012). A view on the molecular structure of (I), showing the coordination environment of the Zn²⁺ ion, is presented in Fig. 1. The asymmetric unit consists of one Zn²⁺ ion (situated on a twofold rotation axis), half of a [C₁₀H₈O₄S₂]^2- anion, half of a 2,2'-bipy molecule, and one coordinating water molecule. The Zn²⁺ ion is six-coordinated by two O atoms from two symmetry-related [C₁₀H₈O₄S₂]^2- anions (Zn—O 2.1529 (10) Å), two N atoms from one chelating 2,2'-bipy molecule (Zn—N 2.1477 (13) Å), and two water molecules (Zn—O 2.0896 (11) Å) to form a slightly distorted octahedral geometry. The two pyridine rings in the bipy ligand are almost parallel with a dihedral angle of 11.5 (1)°. As shown in Fig. 2, adjacent Zn²⁺ ions are monodentately linked by the [C₁₀H₈O₄S₂]^2- anions to form a chain structure running parallel to [101]. The chains are further linked by O—H···O hydrogen bonds to form the final three-dimensional supramolecular architecture (Fig. 3).

Related literature

For background to 1,4-benzenebis(thioacetic acid), including its synthesis and coordination behaviour, see: Yin & Feng (2009); Yin et al. (2009); Chen et al. (2010); Wang et al. (2011a,b); Jiang et al. (2012).

S2. Experimental

A mixture of 1,4-benzenebis(thioacetic acid) (0.103 g, 0.4 mmol), ZnCl₂.6H₂O (0.054 g, 0.4 mmol), 2,2'-bipy (0.031 g, 0.2 mmol), and Na₂CO₃ (0.042 g, 0.4 mmol) in H₂O (16 ml)/C₂H₅OH (2 ml) was placed in a 25 ml Teflon-lined stainless steel vessel and heated at 433 K for 72 h, then cooled to room temperature over 3 d. Colourless crystals suitable for X-ray analysis were obtained.

S3. Refinement

The carbon-bound H-atoms were positioned geometrically and included in the refinement using a riding model [aromatic C—H 0.93Å and aliphatic C—H 0.97 Å, U_iso(H) = 1.2U_eq(C)]. The oxygen-bound H-atoms were located in difference Fourier maps and refined with an O—H distance restrained to 0.85 Å and U_iso(H) = 1.2U_eq(O).

Computing details

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Crystal Impact, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) -x + 1,y,-z + 1/2.]
	Fig. 2. The chain structure of the title complex. All H atoms have been omitted for clarity.
	Fig. 3. The three-dimensional supramolecular structure built through O—H···O hydrogen bonds (dashed lines).

catena-Poly[[diaqua(2,2'-bipyridine-κ²N,N')zinc]- µ-2,2'-[1,4-phenylenebis(sulfanediyl)]diacetato-κ²O:O']

Crystal data

[Zn(C10H8O4S2)(C10H8N2)(H2O)2]	F(000) = 1056
Mr = 513.87	Dx = 1.626 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 7952 reflections
a = 20.4396 (8) Å	θ = 1.9–27.7°
b = 12.8695 (8) Å	µ = 1.41 mm^−1
c = 7.9798 (4) Å	T = 296 K
β = 90.765 (3)°	Block, colourless
V = 2098.88 (19) Å^3	0.22 × 0.16 × 0.11 mm
Z = 4

Data collection

Bruker APEXII CCD diffractometer	2448 independent reflections
Radiation source: fine-focus sealed tube	2237 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
ω scans	θmax = 27.7°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −26→26
Tmin = 0.761, Tmax = 0.853	k = −15→16
16253 measured reflections	l = −10→10

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) = 0.070	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.043P)^2 + 0.7442P] where P = (Fo^2 + 2Fc^2)/3
2448 reflections	(Δ/σ)max = 0.001
147 parameters	Δρmax = 0.31 e Å^−3
3 restraints	Δρmin = −0.31 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	0.5000	0.725191 (16)	0.2500	0.03569 (9)
S1	0.676748 (19)	0.62114 (4)	0.78141 (5)	0.04863 (12)
N1	0.44065 (7)	0.85617 (9)	0.31662 (16)	0.0391 (3)
O1W	0.57320 (6)	0.61941 (8)	0.18683 (14)	0.0435 (3)
H1WA	0.5703 (10)	0.5693 (13)	0.123 (2)	0.052*
H1WB	0.5785 (10)	0.5933 (15)	0.2793 (18)	0.052*
O1	0.54190 (6)	0.72445 (7)	0.49896 (13)	0.0398 (2)
O2	0.57240 (6)	0.55857 (8)	0.50514 (13)	0.0446 (3)
C1	0.38250 (9)	0.85086 (14)	0.3913 (2)	0.0484 (4)
H1A	0.3633	0.7861	0.4061	0.058*
C2	0.34980 (10)	0.93842 (17)	0.4477 (2)	0.0597 (5)
H2A	0.3089	0.9329	0.4966	0.072*
C3	0.37950 (11)	1.03389 (15)	0.4292 (3)	0.0618 (5)
H3A	0.3594	1.0937	0.4688	0.074*
C4	0.43876 (10)	1.03996 (13)	0.3523 (2)	0.0532 (4)
H4A	0.4592	1.1040	0.3391	0.064*
C5	0.46836 (8)	0.94978 (11)	0.29374 (19)	0.0403 (3)
C6	0.56711 (6)	0.64669 (10)	0.56961 (17)	0.0319 (3)
C7	0.59312 (7)	0.66315 (13)	0.74760 (18)	0.0395 (3)
H7A	0.5652	0.6258	0.8245	0.047*
H7B	0.5901	0.7365	0.7746	0.047*
C8	0.71752 (7)	0.69346 (13)	0.6228 (2)	0.0408 (3)
C9	0.71738 (8)	0.65950 (13)	0.4586 (2)	0.0479 (4)
H9A	0.6958	0.5983	0.4300	0.057*
C10	0.75080 (8)	0.78402 (14)	0.6640 (2)	0.0475 (4)
H10A	0.7518	0.8070	0.7745	0.057*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.04999 (16)	0.02228 (13)	0.03467 (14)	0.000	−0.00485 (10)	0.000
S1	0.0406 (2)	0.0562 (3)	0.0490 (2)	0.00141 (17)	−0.00659 (17)	0.01881 (18)
N1	0.0518 (7)	0.0284 (6)	0.0367 (6)	0.0019 (5)	−0.0129 (5)	−0.0020 (5)
O1W	0.0664 (7)	0.0291 (5)	0.0349 (5)	0.0064 (5)	−0.0039 (5)	−0.0045 (4)
O1	0.0540 (6)	0.0316 (5)	0.0336 (5)	0.0051 (4)	−0.0085 (5)	−0.0008 (4)
O2	0.0661 (7)	0.0290 (5)	0.0385 (5)	0.0007 (5)	−0.0048 (5)	0.0043 (4)
C1	0.0531 (9)	0.0449 (9)	0.0468 (9)	0.0033 (7)	−0.0084 (7)	−0.0017 (7)
C2	0.0590 (11)	0.0643 (12)	0.0555 (11)	0.0169 (9)	−0.0085 (8)	−0.0076 (9)
C3	0.0744 (13)	0.0478 (10)	0.0626 (11)	0.0254 (9)	−0.0234 (9)	−0.0171 (8)
C4	0.0680 (11)	0.0309 (8)	0.0600 (10)	0.0107 (7)	−0.0274 (9)	−0.0082 (7)
C5	0.0546 (8)	0.0258 (6)	0.0398 (7)	0.0028 (6)	−0.0231 (6)	−0.0023 (5)
C6	0.0324 (6)	0.0328 (7)	0.0304 (6)	−0.0034 (5)	0.0012 (5)	0.0042 (5)
C7	0.0400 (7)	0.0479 (8)	0.0307 (7)	0.0045 (6)	−0.0003 (6)	0.0028 (6)
C8	0.0310 (7)	0.0437 (8)	0.0475 (8)	0.0024 (6)	−0.0010 (6)	0.0051 (7)
C9	0.0418 (8)	0.0454 (9)	0.0564 (10)	−0.0066 (7)	0.0025 (7)	−0.0064 (7)
C10	0.0420 (8)	0.0553 (10)	0.0452 (9)	−0.0039 (7)	0.0003 (7)	−0.0075 (7)

Geometric parameters (Å, º)

Zn1—O1W^i	2.0896 (11)	C2—C3	1.379 (3)
Zn1—O1W	2.0896 (11)	C2—H2A	0.9300
Zn1—N1^i	2.1477 (13)	C3—C4	1.367 (3)
Zn1—N1	2.1477 (13)	C3—H3A	0.9300
Zn1—O1^i	2.1529 (10)	C4—C5	1.392 (2)
Zn1—O1	2.1529 (10)	C4—H4A	0.9300
S1—C8	1.7861 (16)	C5—C5^i	1.478 (4)
S1—C7	1.8095 (15)	C6—C7	1.5247 (19)
N1—C1	1.339 (2)	C7—H7A	0.9700
N1—C5	1.3447 (19)	C7—H7B	0.9700
O1W—H1WA	0.825 (14)	C8—C9	1.382 (2)
O1W—H1WB	0.817 (14)	C8—C10	1.387 (2)
O1—C6	1.2557 (16)	C9—C10^ii	1.388 (2)
O2—C6	1.2506 (17)	C9—H9A	0.9300
C1—C2	1.388 (3)	C10—C9^ii	1.388 (2)
C1—H1A	0.9300	C10—H10A	0.9300
O1W^i—Zn1—O1W	98.69 (7)	C1—C2—H2A	120.8
O1W^i—Zn1—N1^i	168.43 (5)	C4—C3—C2	119.51 (17)
O1W—Zn1—N1^i	92.47 (5)	C4—C3—H3A	120.2
O1W^i—Zn1—N1	92.47 (5)	C2—C3—H3A	120.2
O1W—Zn1—N1	168.43 (5)	C3—C4—C5	119.63 (17)
N1^i—Zn1—N1	76.59 (7)	C3—C4—H4A	120.2
O1W^i—Zn1—O1^i	86.70 (4)	C5—C4—H4A	120.2
O1W—Zn1—O1^i	92.97 (4)	N1—C5—C4	121.03 (16)
N1^i—Zn1—O1^i	89.66 (4)	N1—C5—C5^i	115.91 (9)
N1—Zn1—O1^i	90.74 (4)	C4—C5—C5^i	123.05 (11)
O1W^i—Zn1—O1	92.97 (4)	O2—C6—O1	125.11 (13)
O1W—Zn1—O1	86.70 (4)	O2—C6—C7	118.57 (12)
N1^i—Zn1—O1	90.74 (4)	O1—C6—C7	116.32 (12)
N1—Zn1—O1	89.66 (4)	C6—C7—S1	114.48 (10)
O1^i—Zn1—O1	179.49 (5)	C6—C7—H7A	108.6
C8—S1—C7	100.80 (7)	S1—C7—H7A	108.6
C1—N1—C5	118.97 (14)	C6—C7—H7B	108.6
C1—N1—Zn1	125.31 (11)	S1—C7—H7B	108.6
C5—N1—Zn1	115.42 (11)	H7A—C7—H7B	107.6
Zn1—O1W—H1WA	127.8 (14)	C9—C8—C10	119.04 (15)
Zn1—O1W—H1WB	97.9 (14)	C9—C8—S1	120.80 (13)
H1WA—O1W—H1WB	104.3 (17)	C10—C8—S1	120.15 (13)
C6—O1—Zn1	125.00 (9)	C8—C9—C10^ii	120.52 (16)
N1—C1—C2	122.49 (17)	C8—C9—H9A	119.7
N1—C1—H1A	118.8	C10^ii—C9—H9A	119.7
C2—C1—H1A	118.8	C8—C10—C9^ii	120.43 (16)
C3—C2—C1	118.3 (2)	C8—C10—H10A	119.8
C3—C2—H2A	120.8	C9^ii—C10—H10A	119.8
O1W^i—Zn1—N1—C1	7.41 (13)	C2—C3—C4—C5	0.0 (3)
O1W—Zn1—N1—C1	−157.1 (2)	C1—N1—C5—C4	2.5 (2)
N1^i—Zn1—N1—C1	−176.39 (15)	Zn1—N1—C5—C4	−171.45 (11)
O1^i—Zn1—N1—C1	94.13 (13)	C1—N1—C5—C5^i	−178.37 (15)
O1—Zn1—N1—C1	−85.55 (13)	Zn1—N1—C5—C5^i	7.63 (19)
O1W^i—Zn1—N1—C5	−179.03 (10)	C3—C4—C5—N1	−2.3 (2)
O1W—Zn1—N1—C5	16.4 (3)	C3—C4—C5—C5^i	178.72 (18)
N1^i—Zn1—N1—C5	−2.82 (7)	Zn1—O1—C6—O2	1.0 (2)
O1^i—Zn1—N1—C5	−92.30 (10)	Zn1—O1—C6—C7	−179.21 (9)
O1—Zn1—N1—C5	88.01 (10)	O2—C6—C7—S1	51.79 (17)
O1W^i—Zn1—O1—C6	63.39 (12)	O1—C6—C7—S1	−128.01 (12)
O1W—Zn1—O1—C6	−35.15 (12)	C8—S1—C7—C6	55.61 (13)
N1^i—Zn1—O1—C6	−127.58 (12)	C7—S1—C8—C9	−80.93 (14)
N1—Zn1—O1—C6	155.84 (12)	C7—S1—C8—C10	100.14 (14)
O1^i—Zn1—O1—C6	14.13 (13)	C10—C8—C9—C10^ii	−1.0 (3)
C5—N1—C1—C2	−0.6 (2)	S1—C8—C9—C10^ii	−179.94 (13)
Zn1—N1—C1—C2	172.80 (13)	C9—C8—C10—C9^ii	1.0 (3)
N1—C1—C2—C3	−1.7 (3)	S1—C8—C10—C9^ii	179.95 (13)
C1—C2—C3—C4	1.9 (3)

Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+3/2, −y+3/2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O2^iii	0.83 (1)	1.90 (2)	2.7107 (15)	170 (2)
O1W—H1WB···O2	0.82 (1)	1.86 (2)	2.6582 (16)	164 (2)

Symmetry code: (iii) x, −y+1, z−1/2.