catena-Poly[bis­[bis­(1H-benzotriazole)zinc(II)]-μ₄-benzene-1,2,4,5-tetra­carboxyl­ato], a one-dimensional coordination polymer with double chains

In the title compound, [Zn₂(C₁₀H₂O₈)(C₆H₅N₃)₄]_n, the Zn^II atom has a distorted tetra­hedral coordination geometry, defined by two N atoms and two carboxyl O atoms from two benzotriazole ligands and a benzene-1,2,4,5-tetra­carboxyl­ate ligand. The structure exhibits one-dimensional double chains running along the [100] direction, which further extend into a three-dimensional supramolecular network by π–π stacking.

Key indicators

• Single-crystal X-ray study
• T = 283 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.037
• wR factor = 0.086
• Data-to-parameter ratio = 14.3

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   0 ALERT level B = Potentially serious problem
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   1 ALERT level G = General alerts; check

   5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
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S1. Comment

The rational design and synthesis of supramolecular complexes is of current interest in the field of supramolecular chemistry and crystal engineering. Benzotriazole (BTAH) is an attractive choice for multifunctional linking groups and has been inverstigated in the construction of metal-organic frameworks. Some structures of metal-organic polymers containing BTAH have been reported previously (Yuan & Zhou, 2004; Hu et al., 2005; Jones, Brechin, Collison, Raftery & Teat, 2002; Jones, Brecin, Collison, Harrison et al., 2002; Low et al., 2003; Meng et al., 2004). We present here the X-ray structure of the title compound, (I), which is a new example with a one-dimensional polymeric structure.

As shown in Fig. 1, the asymmetric unit of (I) contains one Zn^II atom, two benzotriazole (BTAH) ligands and one-half of a benzene-1,2,4,5-tetracarboxylate (BTC) ligand. The Zn^II atom is coordinated by two O atoms from two BTC ligands and two N atoms from two BTAH ligands, showing a distorted tetrahedral geometry. The Zn—O bond distances are 1.9469 (17) and 1.9572 (18) Å, while the Zn—N bond distances are 2.006 (2) and 2.038 (2) Å. Each BTC ligand is coordinated to four Zn^II atoms and each BTAH ligand is coordinated to one Zn^II atom. The dihedral angle between the planes of the two BTAH ligands is 61.739 (3)°.

The adjacent [Zn(BTAH)₂] units are linked by the BTC ligands to form one-dimensional double chains running along the (100) direction like a molecular ladder (Fig. 2). The two BTAH ligands coordinated to one Zn_II atom point out of the double chains. This orientation plays an important role in packing into a three-dimensional network through π–π stacking interactions between BTAH ligands. Firstly, the adjacent double chains are extended into a two-dimensional layer parallel to the [001] plane, and then a three-dimensional supramolecrlar network is formed by π–π stacking interactions. The face-to-face distances between neighboring parallel BTAH planes are 3.436 (3) and 3.571 (3) Å (Fig. 3).

S2. Experimental

Compound (I) was prepared by hydrothermal methods. A mixture of Zn(NO₃)₂·6H₂O (0.5 mmol), H₄BTC (0.6 mmol), benzotriazole (1.0 mmol) and water (12 ml) was stirred for 20 min in air. The mixture was then transferred to a 23 ml Teflon reactor and kept at 433 K for 72 h under autogenous pressure. Colorless single crystals of (I) suitable for X-ray analysis were obtained from the reaction mixture.

S3. Refinement

H atoms were placed in calculated positions, with C—H = 0.93 Å and N—H = 0.86 Å, and treated as riding atoms in the final cycles of refinement, with U_iso(H) = 1.2U_eq(carrier).

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecular structure of (I) with 50% probability displacement ellipsoids [symmetry code: (A) −x + 1, −y, −z + 1]. H atoms have been omitted.
	Fig. 2. A view of the one-dimensional double chains running along the [100] direction. H atoms have been omitted.
	Fig. 3. Packing model of the three-dimensional supramolecular network. H atoms have been omitted.

catena-Poly[bis[bis(1H-benzotriazole)zinc(II)]-µ₄-benzene- 1,2,4,5-trtracarboxylato]

Crystal data

[Zn2(C10H2O8)(C6H5N3)4]	F(000) = 868
Mr = 857.38	Dx = 1.797 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 15373 reflections
a = 7.7961 (16) Å	θ = 3.1–27.5°
b = 19.346 (4) Å	µ = 1.59 mm^−1
c = 10.732 (2) Å	T = 283 K
β = 101.78 (3)°	Block, colorless
V = 1584.6 (6) Å^3	0.26 × 0.22 × 0.17 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer	3628 independent reflections
Radiation source: fine-focus sealed tube	2924 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.049
Detector resolution: 0.01 pixels mm^-1	θmax = 27.5°, θmin = 3.1°
ϕ and ω scans	h = −10→8
Absorption correction: multi-scan (SADABS; Sheldrick, 1996; Blessing, 1995)	k = −25→25
Tmin = 0.668, Tmax = 0.764	l = −13→13
15373 measured reflections

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.086	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0405P)^2 + 0.7439P] where P = (Fo^2 + 2Fc^2)/3
3628 reflections	(Δ/σ)max = 0.001
253 parameters	Δρmax = 0.43 e Å^−3
0 restraints	Δρmin = −0.40 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. R-factors basedon 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	0.55321 (3)	0.171003 (14)	0.69136 (3)	0.02101 (10)
C1	0.6901 (3)	0.15219 (12)	0.9807 (2)	0.0228 (5)
C2	0.7874 (4)	0.09133 (14)	0.9873 (3)	0.0333 (6)
H2A	0.7980	0.0668	0.9147	0.040*
C3	0.8664 (4)	0.06966 (16)	1.1067 (3)	0.0421 (8)
H3A	0.9315	0.0290	1.1150	0.051*
C4	0.8528 (4)	0.10642 (17)	1.2169 (3)	0.0415 (7)
H4A	0.9110	0.0898	1.2956	0.050*
C5	0.7573 (4)	0.16556 (16)	1.2124 (3)	0.0367 (7)
H5A	0.7470	0.1897	1.2855	0.044*
C6	0.6758 (3)	0.18757 (13)	1.0907 (2)	0.0261 (5)
C7	0.7177 (3)	0.31540 (13)	0.6532 (2)	0.0232 (5)
C8	0.7323 (3)	0.35627 (13)	0.5496 (2)	0.0252 (5)
C9	0.8252 (4)	0.41858 (14)	0.5624 (3)	0.0332 (6)
H9A	0.8359	0.4453	0.4923	0.040*
C10	0.8993 (4)	0.43799 (15)	0.6840 (3)	0.0358 (6)
H10A	0.9611	0.4794	0.6973	0.043*
C11	0.8844 (4)	0.39678 (15)	0.7896 (3)	0.0355 (6)
H11A	0.9369	0.4119	0.8707	0.043*
C12	0.7956 (3)	0.33538 (14)	0.7771 (3)	0.0285 (6)
H12A	0.7875	0.3083	0.8473	0.034*
C13	0.1163 (3)	0.04787 (12)	0.5713 (2)	0.0183 (5)
C14	0.1753 (3)	−0.00192 (12)	0.4983 (2)	0.0205 (5)
H14A	0.2939	−0.0032	0.4963	0.025*
C15	0.0636 (3)	−0.05046 (12)	0.4271 (2)	0.0188 (5)
C16	0.2529 (3)	0.09310 (12)	0.6542 (2)	0.0207 (5)
C17	0.1404 (3)	−0.10511 (12)	0.3564 (2)	0.0206 (5)
N1	0.5948 (3)	0.18824 (11)	0.8794 (2)	0.0241 (4)
N2	0.5242 (3)	0.24233 (11)	0.9224 (2)	0.0281 (5)
N3	0.5714 (3)	0.24229 (11)	1.0477 (2)	0.0281 (5)
H3B	0.5400	0.2732	1.0961	0.034*
N4	0.6183 (3)	0.25884 (11)	0.6069 (2)	0.0248 (4)
N5	0.5729 (3)	0.26344 (12)	0.4822 (2)	0.0310 (5)
N6	0.6404 (3)	0.32113 (11)	0.4472 (2)	0.0304 (5)
H6A	0.6280	0.3348	0.3697	0.037*
O1	0.3295 (2)	0.13703 (10)	0.59607 (17)	0.0284 (4)
O2	0.2901 (3)	0.08211 (12)	0.76823 (19)	0.0499 (6)
O3	0.0518 (2)	−0.15673 (9)	0.31397 (18)	0.0276 (4)
O4	0.2980 (2)	−0.09541 (9)	0.3456 (2)	0.0327 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.01939 (14)	0.02260 (15)	0.02110 (15)	−0.00202 (11)	0.00430 (10)	−0.00557 (11)
C1	0.0233 (11)	0.0222 (12)	0.0230 (13)	−0.0044 (10)	0.0050 (10)	−0.0012 (9)
C2	0.0350 (14)	0.0279 (14)	0.0384 (16)	−0.0006 (12)	0.0105 (12)	−0.0024 (12)
C3	0.0341 (15)	0.0355 (16)	0.054 (2)	0.0041 (13)	0.0038 (14)	0.0149 (14)
C4	0.0369 (15)	0.0481 (18)	0.0353 (17)	−0.0087 (14)	−0.0023 (13)	0.0141 (14)
C5	0.0372 (15)	0.0467 (17)	0.0244 (14)	−0.0142 (14)	0.0019 (11)	−0.0025 (12)
C6	0.0262 (12)	0.0261 (13)	0.0258 (13)	−0.0074 (10)	0.0048 (10)	−0.0027 (10)
C7	0.0217 (11)	0.0236 (12)	0.0248 (13)	0.0023 (10)	0.0058 (9)	0.0009 (10)
C8	0.0290 (12)	0.0247 (12)	0.0225 (13)	0.0076 (11)	0.0064 (10)	0.0003 (10)
C9	0.0401 (15)	0.0262 (13)	0.0364 (16)	0.0040 (12)	0.0147 (12)	0.0054 (11)
C10	0.0375 (15)	0.0254 (14)	0.0456 (18)	−0.0049 (12)	0.0112 (13)	−0.0016 (12)
C11	0.0372 (15)	0.0372 (16)	0.0307 (15)	−0.0055 (13)	0.0036 (12)	−0.0078 (12)
C12	0.0285 (12)	0.0345 (14)	0.0219 (13)	−0.0030 (11)	0.0039 (10)	0.0011 (11)
C13	0.0199 (10)	0.0192 (11)	0.0161 (11)	−0.0007 (9)	0.0042 (9)	0.0008 (9)
C14	0.0160 (10)	0.0247 (12)	0.0213 (12)	−0.0029 (9)	0.0050 (9)	−0.0027 (9)
C15	0.0206 (10)	0.0173 (11)	0.0194 (11)	0.0009 (9)	0.0061 (9)	0.0001 (9)
C16	0.0186 (10)	0.0205 (11)	0.0221 (12)	0.0013 (9)	0.0019 (9)	−0.0039 (9)
C17	0.0248 (11)	0.0199 (11)	0.0177 (11)	−0.0007 (10)	0.0061 (9)	0.0002 (9)
N1	0.0253 (10)	0.0237 (10)	0.0231 (11)	−0.0027 (9)	0.0049 (8)	−0.0037 (8)
N2	0.0323 (11)	0.0272 (11)	0.0254 (11)	−0.0007 (9)	0.0072 (9)	−0.0026 (9)
N3	0.0339 (11)	0.0273 (11)	0.0244 (11)	−0.0040 (10)	0.0088 (9)	−0.0071 (9)
N4	0.0258 (10)	0.0259 (11)	0.0216 (11)	−0.0009 (9)	0.0021 (8)	0.0008 (8)
N5	0.0341 (11)	0.0327 (12)	0.0246 (12)	0.0001 (10)	0.0021 (9)	−0.0014 (9)
N6	0.0400 (12)	0.0320 (12)	0.0193 (11)	0.0057 (10)	0.0059 (9)	0.0037 (9)
O1	0.0241 (8)	0.0327 (10)	0.0269 (10)	−0.0108 (8)	0.0015 (7)	−0.0018 (8)
O2	0.0642 (14)	0.0554 (14)	0.0225 (11)	−0.0254 (12)	−0.0085 (10)	0.0031 (10)
O3	0.0344 (10)	0.0217 (9)	0.0286 (10)	−0.0053 (7)	0.0109 (8)	−0.0080 (7)
O4	0.0276 (9)	0.0270 (10)	0.0480 (12)	−0.0011 (8)	0.0183 (8)	−0.0125 (9)

Geometric parameters (Å, º)

Zn1—O1	1.9469 (17)	C10—C11	1.410 (4)
Zn1—O4^i	1.9572 (18)	C10—H10A	0.9300
Zn1—N1	2.006 (2)	C11—C12	1.368 (4)
Zn1—N4	2.038 (2)	C11—H11A	0.9300
C1—N1	1.375 (3)	C12—H12A	0.9300
C1—C6	1.389 (4)	C13—C14	1.378 (3)
C1—C2	1.394 (4)	C13—C15^ii	1.407 (3)
C2—C3	1.369 (4)	C13—C16	1.518 (3)
C2—H2A	0.9300	C14—C15	1.397 (3)
C3—C4	1.402 (5)	C14—H14A	0.9300
C3—H3A	0.9300	C15—C13^ii	1.407 (3)
C4—C5	1.361 (4)	C15—C17	1.496 (3)
C4—H4A	0.9300	C16—O2	1.217 (3)
C5—C6	1.398 (4)	C16—O1	1.273 (3)
C5—H5A	0.9300	C17—O3	1.247 (3)
C6—N3	1.357 (3)	C17—O4	1.271 (3)
C7—N4	1.374 (3)	N1—N2	1.310 (3)
C7—C8	1.388 (4)	N2—N3	1.319 (3)
C7—C12	1.399 (4)	N3—H3B	0.8600
C8—N6	1.364 (3)	N4—N5	1.316 (3)
C8—C9	1.398 (4)	N5—N6	1.320 (3)
C9—C10	1.367 (4)	N6—H6A	0.8600
C9—H9A	0.9300	O4—Zn1^i	1.9572 (18)
O1—Zn1—O4^i	98.38 (8)	C12—C11—H11A	118.8
O1—Zn1—N1	121.89 (9)	C10—C11—H11A	118.8
O4^i—Zn1—N1	110.33 (9)	C11—C12—C7	116.5 (2)
O1—Zn1—N4	108.98 (8)	C11—C12—H12A	121.8
O4^i—Zn1—N4	108.73 (9)	C7—C12—H12A	121.8
N1—Zn1—N4	107.77 (8)	C14—C13—C15^ii	118.7 (2)
N1—C1—C6	107.3 (2)	C14—C13—C16	117.4 (2)
N1—C1—C2	132.0 (2)	C15^ii—C13—C16	123.7 (2)
C6—C1—C2	120.7 (2)	C13—C14—C15	122.5 (2)
C3—C2—C1	116.3 (3)	C13—C14—H14A	118.7
C3—C2—H2A	121.9	C15—C14—H14A	118.7
C1—C2—H2A	121.9	C14—C15—C13^ii	118.7 (2)
C2—C3—C4	122.5 (3)	C14—C15—C17	118.9 (2)
C2—C3—H3A	118.8	C13^ii—C15—C17	122.3 (2)
C4—C3—H3A	118.8	O2—C16—O1	124.8 (2)
C5—C4—C3	122.1 (3)	O2—C16—C13	118.9 (2)
C5—C4—H4A	118.9	O1—C16—C13	116.2 (2)
C3—C4—H4A	118.9	O3—C17—O4	124.0 (2)
C4—C5—C6	115.5 (3)	O3—C17—C15	120.2 (2)
C4—C5—H5A	122.3	O4—C17—C15	115.9 (2)
C6—C5—H5A	122.3	N2—N1—C1	109.0 (2)
N3—C6—C1	104.0 (2)	N2—N1—Zn1	119.61 (16)
N3—C6—C5	133.0 (3)	C1—N1—Zn1	131.41 (17)
C1—C6—C5	123.0 (3)	N1—N2—N3	108.0 (2)
N4—C7—C8	107.2 (2)	N2—N3—C6	111.8 (2)
N4—C7—C12	131.9 (2)	N2—N3—H3B	124.1
C8—C7—C12	120.9 (2)	C6—N3—H3B	124.1
N6—C8—C7	104.2 (2)	N5—N4—C7	109.2 (2)
N6—C8—C9	133.2 (2)	N5—N4—Zn1	117.99 (16)
C7—C8—C9	122.5 (2)	C7—N4—Zn1	132.52 (17)
C10—C9—C8	116.1 (3)	N4—N5—N6	107.8 (2)
C10—C9—H9A	122.0	N5—N6—C8	111.5 (2)
C8—C9—H9A	122.0	N5—N6—H6A	124.2
C9—C10—C11	121.6 (3)	C8—N6—H6A	124.2
C9—C10—H10A	119.2	C16—O1—Zn1	115.31 (15)
C11—C10—H10A	119.2	C17—O4—Zn1^i	122.15 (16)
C12—C11—C10	122.4 (3)

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