Tris(μ-1,4-benzene­di­carboxyl­ate)­tetrakis­(di­methyl sulfoxide)­di-μ₃-hydroxo-tetrazinc dihydrate

The title compound, [Zn₄(OH)₂(C₈H₄O₄)₃(C₂H₆OS)₄]·2H₂O, has been prepared from the self-assembly reaction of Zn(ClO₄)₂, NaOMe and H₂bdc in di­methyl sulfoxide. The polymer exhibits a zeotype structure with microporous layers of ca 10.22 × 12.29 Å.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.009 Å
• R factor = 0.052
• wR factor = 0.127
• Data-to-parameter ratio = 14.4

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level B:



PLAT_420  Alert B D-H Without Acceptor       O      -   H1O               ?


 Alert Level C:



PLAT_213  Alert C Atom  C1     has ADP max/min Ratio ...........       3.20


 0 Alert Level A = Potentially serious problem

 1 Alert Level B = Potential problem

 1 Alert Level C = Please check

---

S1. Comment

Microporous material based on metal-organic polymers is a new field of great current interest in inorganic and new material chemistry. A current goal in this sense is to build a genuinely stable and useful metal–organic zeotype by selecting appropriate building blocks and organic ligands (Schnebeck et al., 1999; Scherer et al., 1999; Gardner et al., 1995; Hennigar et al., 1997). In the last few years, much effort has been devoted to the use of transition metal ions with exo-bidentate ligands, such as polypyridyl or pyrazines and 1,4-benzenedicarboxylate, to generate polymeric metal–organic coordination polymers with two- or three-dimensional networks. Very recently, Goodgame and Williams reported a new type of metal–organic large-pore zeotype [Zn(dimto)₂]_n(dmf)_n [dimto is 2,4,6-tri(1-imidazolyl)-1,3,5-triazine-2-one and dmf is N,N-dimethylformamide], which was generated from zinc bromide and 2,4,6-tri(1-imidazolyl)-1,3,5-triazine (timt) (Goodgame et al., 1999). Li reported a porous polymer [{Zn₄O(bdc)₃}(dmf)₈(C₆H₅Cl)]_n, which could absorb and deabsorb nitrogen gas (Li et al., 1999).

Herein we report a coordination polymer with a porous zeotype structure [{Zn₄(OH)₂(bdc)₃(dmso)₄}2H₂O]_n, (I), which is built from [Zn₄(OH)₂]⁶⁺ rhombic cluster unit and 1,4-benzenedicarboxylate. The crystallographic analysis reveals that the title compound constitutes the basic building blocks. The four Zn atoms are connected by two hydroxide groups forming a tetranuclear [Zn₄(OH)₂] cluster unit (Fig. 1). Such cluster units are linked by bdc ligand through µ and µ₄ bridges to form a two-dimensional microporous layers with the dimensions of 10.22 × 12.29 Å. Four dimethyl sulfoxide (DMSO) solvent molecules are each weekly coordinated to each zinc(II) center.

Bdc ligands link metal–hydroxide cluster of Zn₄(OH)₂ forming a three-dimensional network with microporous structure. Such three-demensional coordination polymer with metal cluster and hydroxide bridges is quite rare in metal–organic polymers (Li et al., 1999). As shown in Fig. 1, Zn^II atoms adopt two different coordination environments. One is tetracoordinated in a distorted tetrahedral fashion of ZnO₄, with three O atoms from different bdc ligands and one O atom from hydroxyl. The other is hexacoordinated in a distorted octahedral fashion of ZnO₆ of six O atoms, two from different hydroxyls, two from bdc ligands and the others from two DMSO molecules. Zn—O bonds fall in the range of 2.079 (4)–2.107 (4) Å. There are two different kinds of coordination modes of the bdc ligand, one acts as a µ₄-bridge linking four Zn atoms, the other acts as a µ bridge linking two Zn atoms.

S2. Experimental

A mixture of 1,4-benzene dicarboxylic acid (H₂bdc) (0.166 g, 1 mmol) and NaOMe (0.055 g, 1 mmol) in 25 ml of DMSO was stirred for 30 min. To the reaction mixture, solid Zn(ClO₄)₂·6H₂O (0.372 g, 1 mmol) was added. After stirrinf for 8 h at 323 K, the reaction mixture was filtered to give a colorless solution. Slow diffusing with diethyl ether containing triethylamine (0.025 ml) into the filtrate, natural evaporation of the filtrate in air yielded a large amount of colorless block crystals of the title compound.

S3. Refinement

The positions of the H atoms were generated geometrically (C—H bond fixed at 0.96 Å) and treated by a mixture of independent and constrained refinement, assigned isotropic displacement parameters, and allowed to ride on their respective parent C atoms before the final cycle of least-squares refinement. Hydroxo and water H atoms were placed in calculated positions (Nardelli, 1995, 1999).

Computing details

Data collection: SMART (Siemens, 1994); cell refinement: SMART; data reduction: SMART; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The structure of (I). Displacement ellipsoids are plotted at the 40% probability level.
	Fig. 2. Packing diagram of (I).

Tris(µ-1,4-benzenedicarboxylate)tetrakis(dimethyl sulfoxide)di-µ₃-hydroxo-tetrazinc dihydrate

Crystal data

[Zn4(OH)2(C8H4O4)3(C2H6OS)4]·2H2O	Dx = 1.671 Mg m^−3
Mr = 1136.38	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 145 reflections
a = 14.4988 (2) Å	θ = 2.2–25.0°
b = 17.1659 (1) Å	µ = 2.36 mm^−1
c = 18.1536 (5) Å	T = 293 K
V = 4518.16 (14) Å^3	Plate, colorless
Z = 4	0.36 × 0.32 × 0.26 mm
F(000) = 2312

Data collection

Smart CCD diffractometer	3986 independent reflections
Radiation source: fine-focus sealed tube	2600 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.058
ω scans	θmax = 25.0°, θmin = 2.2°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −10→17
Tmin = 0.445, Tmax = 0.542	k = −20→8
12140 measured reflections	l = −21→18

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.128	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0691P)^2 + 17.1727P] where P = (Fo^2 + 2Fc^2)/3
3986 reflections	(Δ/σ)max = 0.001
276 parameters	Δρmax = 1.88 e Å^−3
3 restraints	Δρmin = −0.62 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	0.55551 (5)	0.06052 (4)	0.54823 (4)	0.0276 (2)
Zn2	0.34708 (5)	0.05295 (4)	0.60236 (4)	0.0270 (2)
S1	0.62938 (15)	0.20725 (11)	0.46236 (11)	0.0530 (6)
S2	0.73751 (15)	0.04497 (14)	0.64932 (12)	0.0646 (6)
O	0.4193 (3)	0.0397 (2)	0.5129 (2)	0.0260 (9)
H1O	0.3903 (7)	0.0724 (7)	0.4789 (8)	0.047*
O1	0.5771 (4)	0.1320 (3)	0.4588 (2)	0.0492 (13)
O2	0.6927 (3)	0.0796 (3)	0.5822 (2)	0.0496 (13)
O11	0.5409 (3)	−0.0143 (2)	0.6402 (2)	0.0359 (11)
O12	0.3956 (3)	−0.0159 (3)	0.6800 (2)	0.0380 (11)
O13	0.4844 (3)	−0.3425 (3)	0.8885 (2)	0.0436 (12)
O14	0.6315 (3)	−0.3431 (3)	0.8528 (2)	0.0402 (11)
O21	0.2186 (3)	0.0194 (3)	0.5967 (3)	0.0512 (14)
O22	0.2152 (4)	0.1107 (3)	0.5125 (4)	0.0736 (18)
C1	0.7294 (9)	0.1879 (8)	0.4128 (8)	0.167 (7)
H1A	0.7689	0.1546	0.4412	0.250*
H1B	0.7608	0.2359	0.4024	0.250*
H1C	0.7137	0.1625	0.3673	0.250*
C2	0.5754 (11)	0.2669 (6)	0.3958 (7)	0.167 (8)
H2A	0.5168	0.2842	0.4142	0.251*
H2B	0.5664	0.2378	0.3513	0.251*
H2C	0.6137	0.3113	0.3858	0.251*
C3	0.6908 (6)	0.0934 (7)	0.7263 (4)	0.087 (3)
H3A	0.6279	0.0775	0.7332	0.130*
H3B	0.6931	0.1486	0.7184	0.130*
H3C	0.7260	0.0804	0.7694	0.130*
C4	0.8496 (5)	0.0862 (6)	0.6520 (5)	0.079 (3)
H4A	0.8859	0.0654	0.6124	0.118*
H4B	0.8784	0.0738	0.6982	0.118*
H4C	0.8453	0.1418	0.6470	0.118*
C11	0.4772 (5)	−0.0409 (3)	0.6793 (3)	0.0299 (15)
C12	0.4993 (4)	−0.1076 (4)	0.7296 (3)	0.0306 (15)
C13	0.5848 (5)	−0.1421 (4)	0.7274 (4)	0.0403 (17)
H13A	0.6309	−0.1208	0.6980	0.048*
C14	0.6032 (5)	−0.2086 (4)	0.7686 (4)	0.0410 (17)
H14A	0.6612	−0.2318	0.7666	0.049*
C15	0.5346 (4)	−0.2402 (4)	0.8127 (3)	0.0311 (15)
C16	0.4494 (5)	−0.2048 (4)	0.8163 (4)	0.0385 (16)
H16A	0.4040	−0.2252	0.8469	0.046*
C17	0.4314 (4)	−0.1391 (4)	0.7749 (3)	0.0337 (15)
H17A	0.3735	−0.1158	0.7773	0.040*
C18	0.5507 (5)	−0.3142 (3)	0.8553 (3)	0.0299 (14)
C21	0.1803 (4)	0.0549 (5)	0.5457 (4)	0.0426 (17)
C22	0.0858 (4)	0.0265 (4)	0.5231 (4)	0.0396 (17)
C23	0.0384 (5)	0.0649 (5)	0.4680 (4)	0.0490 (19)
H23A	0.0642	0.1089	0.4463	0.059*
C24	−0.0471 (5)	0.0388 (5)	0.4447 (4)	0.051 (2)
H24A	−0.0784	0.0651	0.4075	0.061*
O1W	0.3082 (15)	0.2097 (12)	0.4212 (10)	0.429 (16)
H2OW	0.2861 (15)	0.2497 (13)	0.4523 (11)	0.772*
H1OW	0.2817 (15)	0.1618 (14)	0.4409 (10)	0.772*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0319 (4)	0.0251 (4)	0.0258 (4)	−0.0042 (3)	−0.0006 (3)	−0.0033 (3)
Zn2	0.0280 (4)	0.0240 (4)	0.0291 (4)	−0.0010 (3)	−0.0030 (3)	−0.0011 (3)
S1	0.0799 (15)	0.0353 (10)	0.0439 (11)	−0.0202 (10)	0.0025 (10)	0.0008 (9)
S2	0.0618 (14)	0.0663 (15)	0.0657 (14)	−0.0012 (12)	−0.0192 (11)	0.0018 (11)
O	0.028 (2)	0.022 (2)	0.028 (2)	0.0044 (18)	−0.0016 (17)	0.0001 (17)
O1	0.069 (3)	0.038 (3)	0.040 (3)	−0.020 (3)	0.000 (2)	0.004 (2)
O2	0.044 (3)	0.067 (4)	0.038 (3)	−0.009 (3)	−0.008 (2)	0.002 (3)
O11	0.044 (3)	0.028 (2)	0.036 (2)	−0.007 (2)	−0.008 (2)	0.006 (2)
O12	0.048 (3)	0.032 (3)	0.034 (3)	0.012 (2)	0.000 (2)	0.007 (2)
O13	0.050 (3)	0.033 (3)	0.048 (3)	0.005 (2)	0.006 (2)	0.018 (2)
O14	0.041 (3)	0.030 (3)	0.049 (3)	0.001 (2)	−0.003 (2)	0.009 (2)
O21	0.034 (3)	0.078 (4)	0.042 (3)	−0.012 (3)	−0.002 (2)	−0.005 (3)
O22	0.048 (3)	0.050 (4)	0.122 (5)	−0.016 (3)	−0.021 (3)	0.015 (4)
C1	0.147 (12)	0.126 (12)	0.227 (16)	−0.069 (10)	0.135 (12)	−0.044 (11)
C2	0.32 (2)	0.059 (7)	0.120 (10)	−0.037 (10)	−0.126 (12)	0.029 (7)
C3	0.073 (6)	0.145 (10)	0.043 (5)	−0.009 (7)	−0.003 (4)	−0.019 (6)
C4	0.047 (5)	0.115 (8)	0.074 (6)	0.005 (5)	−0.014 (4)	−0.018 (6)
C11	0.041 (4)	0.022 (3)	0.027 (3)	0.003 (3)	−0.007 (3)	0.002 (3)
C12	0.037 (4)	0.022 (3)	0.033 (4)	0.003 (3)	−0.003 (3)	0.003 (3)
C13	0.046 (4)	0.032 (4)	0.043 (4)	−0.002 (3)	−0.002 (3)	0.012 (3)
C14	0.037 (4)	0.033 (4)	0.052 (4)	0.004 (3)	−0.007 (3)	0.013 (3)
C15	0.042 (4)	0.021 (3)	0.030 (3)	0.001 (3)	−0.001 (3)	0.002 (3)
C16	0.045 (4)	0.032 (4)	0.038 (4)	−0.001 (3)	0.008 (3)	0.010 (3)
C17	0.037 (4)	0.029 (3)	0.036 (4)	0.008 (3)	0.001 (3)	0.003 (3)
C18	0.045 (4)	0.016 (3)	0.028 (3)	0.000 (3)	−0.004 (3)	−0.003 (3)
C21	0.029 (4)	0.049 (5)	0.049 (4)	0.003 (4)	−0.001 (3)	−0.020 (4)
C22	0.025 (3)	0.048 (4)	0.045 (4)	0.002 (3)	−0.004 (3)	−0.007 (3)
C23	0.037 (4)	0.049 (5)	0.061 (5)	−0.010 (4)	−0.003 (3)	0.004 (4)
C24	0.034 (4)	0.062 (5)	0.058 (5)	0.001 (4)	−0.011 (4)	0.001 (4)
O1W	0.57 (3)	0.35 (3)	0.36 (2)	−0.02 (2)	0.37 (2)	−0.015 (19)

Geometric parameters (Å, º)

Zn1—O1	2.058 (4)	C2—H2A	0.9600
Zn1—O^i	2.079 (4)	C2—H2B	0.9600
Zn1—O13^ii	2.104 (4)	C2—H2C	0.9600
Zn1—O	2.107 (4)	C3—H3A	0.9600
Zn1—O2	2.108 (5)	C3—H3B	0.9600
Zn1—O11	2.117 (4)	C3—H3C	0.9600
Zn1—Zn1^i	3.1582 (13)	C4—H4A	0.9600
Zn2—O	1.947 (4)	C4—H4B	0.9600
Zn2—O21	1.953 (4)	C4—H4C	0.9600
Zn2—O12	1.969 (4)	C11—C12	1.498 (8)
Zn2—O14^ii	1.986 (4)	C12—C13	1.375 (9)
S1—O1	1.500 (5)	C12—C17	1.394 (9)
S1—C1	1.739 (11)	C13—C14	1.390 (9)
S1—C2	1.767 (10)	C13—H13A	0.9300
S2—O2	1.503 (5)	C14—C15	1.387 (9)
S2—C3	1.762 (9)	C14—H14A	0.9300
S2—C4	1.774 (8)	C15—C16	1.377 (9)
O—Zn1^i	2.079 (4)	C15—C18	1.507 (8)
O—H1O	0.9343	C16—C17	1.380 (9)
O11—C11	1.252 (7)	C16—H16A	0.9300
O12—C11	1.258 (7)	C17—H17A	0.9300
O13—C18	1.234 (7)	C21—C22	1.510 (9)
O13—Zn1^iii	2.104 (4)	C22—C23	1.382 (9)
O14—C18	1.273 (7)	C22—C24^iv	1.384 (10)
O14—Zn2^iii	1.986 (4)	C23—C24	1.384 (9)
O21—C21	1.240 (8)	C23—H23A	0.9300
O22—C21	1.239 (9)	C24—C22^iv	1.384 (10)
C1—H1A	0.9600	C24—H24A	0.9300
C1—H1B	0.9600	O1W—H2OW	0.9448
C1—H1C	0.9600	O1W—H1OW	0.9752
O1—Zn1—O^i	92.62 (17)	H2A—C2—H2B	109.5
O1—Zn1—O13^ii	90.02 (19)	S1—C2—H2C	109.5
O^i—Zn1—O13^ii	173.89 (17)	H2A—C2—H2C	109.5
O1—Zn1—O	90.18 (17)	H2B—C2—H2C	109.5
O^i—Zn1—O	82.04 (15)	S2—C3—H3A	109.5
O13^ii—Zn1—O	92.45 (16)	S2—C3—H3B	109.5
O1—Zn1—O2	89.72 (19)	H3A—C3—H3B	109.5
O^i—Zn1—O2	96.83 (18)	S2—C3—H3C	109.5
O13^ii—Zn1—O2	88.69 (19)	H3A—C3—H3C	109.5
O—Zn1—O2	178.86 (18)	H3B—C3—H3C	109.5
O1—Zn1—O11	176.95 (19)	S2—C4—H4A	109.5
O^i—Zn1—O11	86.34 (16)	S2—C4—H4B	109.5
O13^ii—Zn1—O11	91.30 (18)	H4A—C4—H4B	109.5
O—Zn1—O11	92.51 (16)	S2—C4—H4C	109.5
O2—Zn1—O11	87.56 (17)	H4A—C4—H4C	109.5
O1—Zn1—Zn1^i	91.84 (13)	H4B—C4—H4C	109.5
O^i—Zn1—Zn1^i	41.35 (10)	O11—C11—O12	125.1 (6)
O13^ii—Zn1—Zn1^i	133.08 (13)	O11—C11—C12	117.8 (6)
O—Zn1—Zn1^i	40.69 (10)	O12—C11—C12	117.1 (6)
O2—Zn1—Zn1^i	138.18 (15)	C13—C12—C17	119.1 (6)
O11—Zn1—Zn1^i	89.26 (12)	C13—C12—C11	120.3 (6)
O—Zn2—O21	115.80 (18)	C17—C12—C11	120.4 (6)
O—Zn2—O12	109.58 (17)	C12—C13—C14	120.8 (6)
O21—Zn2—O12	101.6 (2)	C12—C13—H13A	119.6
O—Zn2—O14^ii	111.29 (18)	C14—C13—H13A	119.6
O21—Zn2—O14^ii	115.8 (2)	C15—C14—C13	119.5 (6)
O12—Zn2—O14^ii	100.96 (19)	C15—C14—H14A	120.2
O1—S1—C1	103.6 (5)	C13—C14—H14A	120.2
O1—S1—C2	104.3 (4)	C16—C15—C14	119.9 (6)
C1—S1—C2	97.3 (8)	C16—C15—C18	119.1 (6)
O2—S2—C3	106.9 (4)	C14—C15—C18	121.0 (6)
O2—S2—C4	105.2 (4)	C15—C16—C17	120.3 (6)
C3—S2—C4	98.1 (4)	C15—C16—H16A	119.9
Zn2—O—Zn1^i	129.5 (2)	C17—C16—H16A	119.9
Zn2—O—Zn1	103.31 (17)	C16—C17—C12	120.4 (6)
Zn1^i—O—Zn1	97.96 (15)	C16—C17—H17A	119.8
Zn2—O—H1O	103.7	C12—C17—H17A	119.8
Zn1^i—O—H1O	103.0	O13—C18—O14	125.6 (6)
Zn1—O—H1O	121.5	O13—C18—C15	117.5 (6)
S1—O1—Zn1	123.8 (3)	O14—C18—C15	116.9 (6)
S2—O2—Zn1	125.7 (3)	O22—C21—O21	124.0 (7)
C11—O11—Zn1	137.9 (4)	O22—C21—C22	119.2 (7)
C11—O12—Zn2	122.2 (4)	O21—C21—C22	116.8 (7)
C18—O13—Zn1^iii	142.4 (4)	C23—C22—C24^iv	119.4 (6)
C18—O14—Zn2^iii	118.6 (4)	C23—C22—C21	119.6 (7)
C21—O21—Zn2	108.8 (5)	C24^iv—C22—C21	121.0 (7)
S1—C1—H1A	109.5	C22—C23—C24	120.8 (7)
S1—C1—H1B	109.5	C22—C23—H23A	119.6
H1A—C1—H1B	109.5	C24—C23—H23A	119.6
S1—C1—H1C	109.5	C23—C24—C22^iv	119.8 (7)
H1A—C1—H1C	109.5	C23—C24—H24A	120.1
H1B—C1—H1C	109.5	C22^iv—C24—H24A	120.1
S1—C2—H2A	109.5	H2OW—O1W—H1OW	105.1
S1—C2—H2B	109.5

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1OW···O22	0.98	1.84	2.731 (16)	150
O1W—H2OW···S1^v	0.94	2.85	3.636 (14)	142

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