catena-Poly[[bis­(benzene-1,3-dicarboxyl­ato-κ²O,O′)zinc(II)]-μ-4,4′-bipyridine-κ²N:N′]

In the title compound, [Zn(C₈H₅O₄)₂(C₁₀H₈N₂)]_n, the Zn^II atom lies on a twofold rotation axis, and is coordinated by two N atoms of two 4,4′-bipyridine ligands and two carboxyl­ate groups, each in a chelating mode, from two isophthalate ligands. The 4,4′-bipyridine ligand, located on an inversion center, bridges the Zn^II atoms, forming a one-dimensional zigzag chain structure. O—H...O hydrogen bonds and π–π stacking inter­actions [with a shortest atom-to-atom distance of 3.41 (1) Å] are observed between the chains.

Key indicators

• Single-crystal X-ray study
• T = 292 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.033
• wR factor = 0.091
• Data-to-parameter ratio = 14.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C3
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C13

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn1         (2)       1.94

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 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
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

Metal-organic complexes with a variety of supramolecular architectures have attracted increasing interest because of their novel topologies and potential applications as functional materials (Eddaoudi et al., 2001). Recently, a successful strategy for preparing these materials has been the assembly reaction between transition metal ions and two types of ligands, one acts as a terminal ligand and the other acts as a bridging ligand. In this respect, diverse dicarboxylates with various oriented carboxyl groups have been utilized to build coordination polymers. These ligands are able to bridge metal centers in different modes and also produce either linear or zigzag polymeric chains (Chen & Liu, 2002; Groeneman et al., 1999; Li et al., 2006). In this work, we use isophthalic acid as a terminal ligand and 4,4'-bipyridine (bpy) as a bridging ligand, generating a new compound, (I), under hydrothermal condition.

Selected bond lengths and angles for (I) are given in Table 1. In compound (I), the Zn^II atom lying on a twofold rotation axis is six-coordinated by two N atoms from two bpy ligands, and two carboxylate groups, each in a chelating mode, from two isophthalate ligands (Fig. 1). The bpy ligand located on an inversion center bridges the Zn^II atoms, forming a one-dimensional zigzag chain structure. It is noteworthy that there exist π-π interactions, with the shortest atom-to-atom distance of 3.41 (1) Å, and O—H···O hydrogen bonds (Table 2, Fig. 2) between the isophthalate ligands in the neighboring chains, which lead to a three-dimensional supramolecular network.

Related literature

For general background, see: Eddaoudi et al. (2001). For related structures, see: Chen & Liu (2002); Groeneman et al. (1999); Li et al. (2006).

S2. Experimental

Compound (I) was prepared from a mixture of Zn(NO₃)₂.6H₂O (0.119 g, 0.4 mmol), isophthalic acid (0.134 g, 0.8 mmol), bpy (0.070 g, 0.4 mmol) and H₂O (18 ml) in a 30 ml Teflon-lined autoclave under autogenous pressure at 423 K for 7 d. After cooling to room temperature, colorless crystals suitable for X-ray structure analysis were obtained. Analysis, calculated for C₂₆H₁₈N₂O₈Zn: C 64.7, H 2.7, N 5.8%; found: C 64.5, H 2.6, N 5.7%.

S3. Refinement

All H atoms on C atoms were positioned geometrically and refined as riding atoms, with C—H= 0.93Å and U_iso(H) = 1.2U_eq(C) and with O—H = 0.82Å and U_iso(H) = 1.5U_eq(O).

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The asymmetric unit of (I), together with symmetry-related atoms to complete the Zn coordination. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) 1 - x, y, 3/2 - z, (ii) 1/2 - x, -1/2 - y, 1 - z.]
	Fig. 2. View of the chain structure in (I).

catena-Poly[[bis(benzene-1,3-dicarboxylato-κ²O,O')zinc(II)]- µ-4,4'-bipyridine-κ²N:N']

Crystal data

[Zn(C8H5O4)2(C10H8N2)]	F(000) = 1128
Mr = 551.79	Dx = 1.520 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2132 reflections
a = 20.940 (3) Å	θ = 2.4–26.1°
b = 9.6078 (12) Å	µ = 1.07 mm^−1
c = 14.7942 (19) Å	T = 292 K
β = 125.884 (2)°	Block, colorless
V = 2411.4 (6) Å^3	0.12 × 0.09 × 0.05 mm
Z = 4

Data collection

Bruker SMART APEX CCD area-detector diffractometer	2385 independent reflections
Radiation source: fine-focus sealed tube	2096 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
φ and ω scans	θmax = 26.1°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −25→24
Tmin = 0.890, Tmax = 0.951	k = −11→11
6569 measured reflections	l = −18→17

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.091	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0583P)^2] where P = (Fo^2 + 2Fc^2)/3
2385 reflections	(Δ/σ)max < 0.001
168 parameters	Δρmax = 0.39 e Å^−3
0 restraints	Δρmin = −0.40 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Zn1	0.5000	0.12559 (3)	0.7500	0.03382 (14)
C2	0.32554 (15)	−0.1920 (3)	0.64815 (19)	0.0543 (6)
H2A	0.3122	−0.2483	0.6859	0.065*
O2	0.39232 (9)	0.29538 (15)	0.71869 (12)	0.0433 (4)
O1	0.49428 (9)	0.19702 (15)	0.86982 (13)	0.0461 (4)
C5	0.36932 (14)	−0.0250 (2)	0.54810 (19)	0.0533 (6)
H5A	0.3839	0.0327	0.5125	0.064*
O4	0.25572 (10)	0.67575 (18)	0.91871 (14)	0.0606 (5)
H4	0.2165	0.7250	0.8809	0.091*
O3	0.22568 (15)	0.6223 (2)	0.75308 (18)	0.1004 (9)
N1	0.40947 (9)	−0.01606 (16)	0.65816 (14)	0.0362 (4)
C3	0.28368 (11)	−0.20154 (19)	0.53335 (16)	0.0338 (4)
C10	0.38715 (12)	0.5013 (2)	1.02708 (18)	0.0437 (5)
H10A	0.3772	0.5512	1.0714	0.052*
C13	0.26886 (15)	0.6106 (2)	0.8536 (2)	0.0487 (6)
C6	0.43472 (12)	0.27635 (19)	0.82190 (17)	0.0357 (4)
C12	0.46543 (13)	0.3362 (2)	1.00919 (18)	0.0423 (5)
H12A	0.5082	0.2756	1.0425	0.051*
C7	0.41740 (12)	0.35150 (19)	0.89450 (17)	0.0339 (4)
C8	0.35402 (12)	0.4413 (2)	0.84621 (17)	0.0381 (5)
H8A	0.3213	0.4514	0.7691	0.046*
C9	0.33852 (12)	0.5171 (2)	0.91158 (18)	0.0396 (5)
C11	0.44993 (14)	0.4114 (3)	1.07490 (19)	0.0494 (6)
H11A	0.4825	0.4005	1.1520	0.059*
C4	0.30732 (15)	−0.1149 (2)	0.4840 (2)	0.0531 (6)
H4A	0.2813	−0.1172	0.4071	0.064*
C1	0.38671 (15)	−0.0992 (3)	0.70599 (19)	0.0542 (6)
H1A	0.4137	−0.0944	0.7830	0.065*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0357 (2)	0.0348 (2)	0.0313 (2)	0.000	0.01984 (17)	0.000
C2	0.0657 (15)	0.0592 (14)	0.0373 (12)	−0.0254 (12)	0.0298 (12)	−0.0015 (11)
O2	0.0557 (9)	0.0459 (8)	0.0385 (8)	−0.0018 (7)	0.0334 (8)	−0.0011 (6)
O1	0.0466 (9)	0.0489 (8)	0.0476 (9)	0.0067 (7)	0.0303 (8)	−0.0040 (7)
C5	0.0570 (14)	0.0655 (15)	0.0377 (12)	−0.0221 (12)	0.0278 (12)	−0.0006 (11)
O4	0.0575 (10)	0.0744 (11)	0.0521 (11)	0.0161 (9)	0.0334 (9)	−0.0125 (9)
O3	0.126 (2)	0.138 (2)	0.0536 (13)	0.0874 (16)	0.0614 (14)	0.0386 (13)
N1	0.0377 (9)	0.0369 (8)	0.0344 (9)	−0.0025 (7)	0.0214 (8)	−0.0009 (7)
C3	0.0372 (10)	0.0340 (10)	0.0331 (10)	−0.0006 (8)	0.0223 (9)	−0.0016 (8)
C10	0.0488 (12)	0.0509 (12)	0.0411 (12)	−0.0074 (10)	0.0317 (11)	−0.0121 (10)
C13	0.0633 (16)	0.0489 (13)	0.0509 (15)	0.0122 (11)	0.0430 (14)	0.0060 (10)
C6	0.0414 (11)	0.0325 (9)	0.0422 (12)	−0.0063 (8)	0.0295 (10)	−0.0051 (8)
C12	0.0412 (12)	0.0483 (11)	0.0391 (12)	0.0013 (9)	0.0245 (11)	−0.0001 (10)
C7	0.0370 (11)	0.0344 (10)	0.0360 (11)	−0.0056 (8)	0.0246 (10)	−0.0030 (8)
C8	0.0442 (11)	0.0422 (11)	0.0341 (11)	−0.0004 (9)	0.0265 (10)	−0.0002 (9)
C9	0.0460 (12)	0.0400 (11)	0.0423 (12)	−0.0028 (9)	0.0312 (11)	−0.0027 (9)
C11	0.0483 (13)	0.0661 (14)	0.0313 (11)	−0.0030 (11)	0.0218 (11)	−0.0053 (10)
C4	0.0581 (15)	0.0672 (15)	0.0321 (12)	−0.0238 (12)	0.0253 (12)	−0.0059 (10)
C1	0.0599 (15)	0.0638 (15)	0.0282 (11)	−0.0242 (12)	0.0199 (11)	−0.0054 (10)

Geometric parameters (Å, º)

Zn1—O1^i	1.9689 (15)	C3—C4	1.377 (3)
Zn1—O1	1.9689 (15)	C3—C3^ii	1.483 (4)
Zn1—N1	2.0669 (16)	C10—C11	1.373 (3)
Zn1—N1^i	2.0669 (16)	C10—C9	1.393 (3)
Zn1—O2	2.5953 (15)	C10—H10A	0.9300
C2—C1	1.372 (3)	C13—C9	1.485 (3)
C2—C3	1.384 (3)	C6—C7	1.504 (3)
C2—H2A	0.9300	C12—C7	1.383 (3)
O2—C6	1.251 (2)	C12—C11	1.394 (3)
O1—C6	1.266 (2)	C12—H12A	0.9300
C5—N1	1.327 (3)	C7—C8	1.380 (3)
C5—C4	1.374 (3)	C8—C9	1.392 (3)
C5—H5A	0.9300	C8—H8A	0.9300
O4—C13	1.307 (3)	C11—H11A	0.9300
O4—H4	0.8200	C4—H4A	0.9300
O3—C13	1.210 (3)	C1—H1A	0.9300
N1—C1	1.327 (3)
O1^i—Zn1—O1	139.21 (9)	O3—C13—O4	122.2 (2)
O1^i—Zn1—N1	98.86 (6)	O3—C13—C9	122.7 (2)
O1—Zn1—N1	107.76 (6)	O4—C13—C9	115.1 (2)
O1^i—Zn1—N1^i	107.76 (6)	O2—C6—O1	122.22 (18)
O1—Zn1—N1^i	98.86 (6)	O2—C6—C7	120.39 (18)
N1—Zn1—N1^i	97.64 (9)	O1—C6—C7	117.37 (18)
O1—Zn1—O2	55.71 (5)	C7—C12—C11	120.1 (2)
O1^i—Zn1—O2	97.19 (5)	C7—C12—H12A	119.9
N1—Zn1—O2	86.01 (6)	C11—C12—H12A	119.9
N1^i—Zn1—O2	153.80 (6)	C8—C7—C12	119.26 (18)
O2^i—Zn1—O2	102.11 (6)	C8—C7—C6	119.45 (18)
C1—C2—C3	119.8 (2)	C12—C7—C6	121.25 (19)
C1—C2—H2A	120.1	C7—C8—C9	120.82 (19)
C3—C2—H2A	120.1	C7—C8—H8A	119.6
C6—O1—Zn1	105.40 (13)	C9—C8—H8A	119.6
N1—C5—C4	123.4 (2)	C8—C9—C10	119.66 (19)
N1—C5—H5A	118.3	C8—C9—C13	117.70 (19)
C4—C5—H5A	118.3	C10—C9—C13	122.63 (19)
C13—O4—H4	109.5	C10—C11—C12	120.7 (2)
C5—N1—C1	116.62 (18)	C10—C11—H11A	119.6
C5—N1—Zn1	121.76 (14)	C12—C11—H11A	119.6
C1—N1—Zn1	121.57 (14)	C5—C4—C3	120.1 (2)
C4—C3—C2	116.42 (19)	C5—C4—H4A	119.9
C4—C3—C3^ii	121.6 (2)	C3—C4—H4A	119.9
C2—C3—C3^ii	122.0 (2)	N1—C1—C2	123.7 (2)
C11—C10—C9	119.43 (19)	N1—C1—H1A	118.2
C11—C10—H10A	120.3	C2—C1—H1A	118.2
C9—C10—H10A	120.3

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O2^iii	0.82	1.97	2.771 (3)	165

Symmetry code: (iii) −x+1/2, y+1/2, −z+3/2.