Poly[tris-(2,5-dimethyl-benzene-1,4--dicarboxyl-ato)bis-(pyridine)trizinc(II)].

The asymmetric unit of the title polymeric compound, [Zn(3)(C(10)H(8)O(4))(3)(C(5)H(5)N)(2)](n) or [Zn(3)(dmbdc)(3)(py)(2)](n) (dmbdc = 2,5-dimethyl-benzene-dicarboxyl-ate; py = pyridine) contains two Zn(II) ions, one of which is located on an inversion centre, one and a half 2,5-dimethyl-benzene-dicarboxyl-ate ligands and one pyridine ligand. Each ZnO(6) octa-hedron is sandwiched between two ZnO(4)N square-pyramids, forming a trinuclear zinc secondary building unit (SBU); each SBU is further linked by six 2,5-dimethyl-benzene-dicarboxyl-ate ligands with six adjacent trinuclear zinc SBU's, forming a two-dimensional layer structure with a (3,6) net. One of the three zinc ions is octa-hedrally coordinated and the other two are square-pyramidally coordinated. The coordination modes for 2,5-dimethyl-benzene-dicarboxyl-ates are bis-(bidentate) or bidentate-tridentate.

Related literature

For the potential applications of metal-organic frameworks formed from terephthalic acid and its derivatives, see Wang et al. (2007 ▶); Grzesiak et al. (2006 ▶); Rosi et al. (2005 ▶); Burrows et al. (2005 ▶); Liao et al. (2006 ▶); Yang et al. (2002 ▶); Eddaoudi et al. (2002 ▶). For related structures, see: Wang et al. (2008 ▶); Zhou et al. (2009 ▶).

Experimental

Crystal data

[Zn3(C10H8O4)3(C5H5N)2]

M = 930.80

Monoclinic,

a = 22.3372 (15) Å

b = 10.2643 (7) Å

c = 16.9261 (11) Å

β = 105.140 (1)°

V = 3746.0 (4) Å3

Z = 4

Mo Kα radiation

μ = 1.97 mm−1

T = 299 K

0.12 × 0.08 × 0.07 mm

Data collection

Bruker SMART APEX area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2002 ▶) T min = 0.798, T max = 0.874

16107 measured reflections

4487 independent reflections

3559 reflections with I > 2σ(I)

R int = 0.059

Refinement

R[F 2 > 2σ(F 2)] = 0.066

wR(F 2) = 0.156

S = 1.08

4487 reflections

262 parameters

H-atom parameters constrained

Δρmax = 0.74 e Å−3

Δρmin = −0.63 e Å−3

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I. DOI: 10.1107/S1600536810004848/bv2132sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810004848/bv2132Isup2.hkl

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

[Zn3(C10H8O4)3(C5H5N)2]	F(000) = 1896
Mr = 930.80	Dx = 1.650 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2781 reflections
a = 22.3372 (15) Å	θ = 2.2–25.0°
b = 10.2643 (7) Å	µ = 1.97 mm−1
c = 16.9261 (11) Å	T = 299 K
β = 105.140 (1)°	Block, colorless
V = 3746.0 (4) Å3	0.12 × 0.08 × 0.07 mm
Z = 4

Bruker SMART APEX area-detector diffractometer	4487 independent reflections
Radiation source: fine-focus sealed tube	3559 reflections with I > 2σ(I)
graphite	Rint = 0.059
φ and ω scan	θmax = 28.7°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −28→30
Tmin = 0.798, Tmax = 0.874	k = −13→13
16107 measured reflections	l = −21→22

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)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.156	H-atom parameters constrained
S = 1.08	w = 1/[σ2(Fo2) + (0.0282P)2 + 12.5564P] where P = (Fo2 + 2Fc2)/3
4487 reflections	(Δ/σ)max < 0.001
262 parameters	Δρmax = 0.74 e Å−3
0 restraints	Δρmin = −0.62 e Å−3

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.

	x	y	z	Uiso*/Ueq
Zn1	0.40381 (2)	0.67147 (5)	0.55736 (3)	0.02859 (17)
Zn2	0.2500	0.7500	0.5000	0.02465 (19)
O1	0.40247 (16)	0.7797 (3)	0.4622 (2)	0.0379 (8)
O2	0.31369 (15)	0.8673 (3)	0.4686 (2)	0.0347 (7)
O3	0.29594 (17)	1.2435 (4)	0.12228 (19)	0.0425 (9)
O4	0.39737 (16)	1.2197 (4)	0.1478 (2)	0.0426 (9)
O5	0.37531 (18)	0.4905 (4)	0.5713 (3)	0.0557 (11)
O6	0.30025 (18)	0.5819 (3)	0.4821 (2)	0.0444 (9)
N1	0.49686 (18)	0.6283 (4)	0.5907 (3)	0.0397 (10)
C1	0.3588 (2)	0.9476 (5)	0.3687 (3)	0.0309 (10)
C2	0.4095 (2)	0.9664 (5)	0.3361 (3)	0.0368 (11)
C3	0.4018 (2)	1.0506 (5)	0.2701 (3)	0.0362 (11)
H3A	0.4354	1.0645	0.2483	0.043*
C4	0.3476 (2)	1.1143 (4)	0.2354 (3)	0.0297 (9)
C5	0.2970 (2)	1.0983 (5)	0.2683 (3)	0.0310 (9)
C6	0.3049 (2)	1.0147 (5)	0.3343 (3)	0.0325 (10)
H6A	0.2716	1.0031	0.3570	0.039*
C7	0.3581 (2)	0.8590 (4)	0.4383 (3)	0.0297 (9)
C8	0.4722 (3)	0.9037 (8)	0.3691 (5)	0.074 (2)
H8A	0.5009	0.9382	0.3409	0.111*
H8B	0.4686	0.8112	0.3608	0.111*
H8C	0.4871	0.9218	0.4265	0.111*
C9	0.3457 (2)	1.1994 (4)	0.1631 (3)	0.0308 (10)
C10	0.2367 (3)	1.1692 (6)	0.2392 (4)	0.0521 (15)
H10A	0.2090	1.1424	0.2709	0.078*
H10B	0.2187	1.1493	0.1825	0.078*
H10C	0.2439	1.2613	0.2454	0.078*
C11	0.3226 (2)	0.4861 (5)	0.5232 (3)	0.0400 (12)
C12	0.2872 (2)	0.3605 (4)	0.5142 (3)	0.0322 (10)
C13	0.2293 (2)	0.3618 (4)	0.4598 (3)	0.0363 (11)
H13A	0.2154	0.4392	0.4327	0.044*
C14	0.3094 (2)	0.2458 (5)	0.5566 (3)	0.0381 (11)
C15	0.3713 (3)	0.2313 (6)	0.6163 (4)	0.0630 (18)
H15A	0.3768	0.1427	0.6351	0.095*
H15B	0.3738	0.2881	0.6621	0.095*
H15C	0.4033	0.2537	0.5903	0.095*
C16	0.5188 (3)	0.5242 (8)	0.6329 (6)	0.103 (4)
H16A	0.4911	0.4643	0.6447	0.124*
C17	0.5805 (4)	0.5003 (10)	0.6601 (8)	0.134 (5)
H17A	0.5944	0.4256	0.6906	0.161*
C18	0.6214 (3)	0.5840 (8)	0.6433 (6)	0.081 (2)
H18A	0.6638	0.5700	0.6634	0.098*
C19	0.6002 (3)	0.6877 (7)	0.5972 (4)	0.0612 (17)
H19A	0.6274	0.7453	0.5821	0.073*
C20	0.5379 (3)	0.7074 (6)	0.5725 (4)	0.0536 (15)
H20A	0.5234	0.7808	0.5411	0.064*

	U11	U22	U33	U12	U13	U23
Zn1	0.0302 (3)	0.0257 (3)	0.0305 (3)	−0.0001 (2)	0.0090 (2)	0.0002 (2)
Zn2	0.0236 (4)	0.0256 (4)	0.0249 (3)	−0.0023 (3)	0.0067 (3)	−0.0003 (3)
O1	0.0374 (18)	0.0410 (19)	0.0380 (18)	0.0055 (15)	0.0149 (15)	0.0153 (15)
O2	0.0362 (18)	0.0304 (17)	0.0437 (19)	−0.0038 (14)	0.0213 (15)	0.0055 (14)
O3	0.042 (2)	0.060 (2)	0.0234 (15)	0.0153 (17)	0.0050 (15)	0.0087 (16)
O4	0.0374 (19)	0.053 (2)	0.0365 (18)	−0.0024 (16)	0.0089 (15)	0.0189 (16)
O5	0.042 (2)	0.035 (2)	0.087 (3)	−0.0140 (17)	0.011 (2)	−0.007 (2)
O6	0.065 (2)	0.0217 (16)	0.058 (2)	−0.0018 (16)	0.038 (2)	−0.0008 (16)
N1	0.028 (2)	0.037 (2)	0.052 (3)	0.0043 (17)	0.0073 (18)	0.002 (2)
C1	0.029 (2)	0.036 (2)	0.030 (2)	−0.0017 (18)	0.0097 (18)	0.0038 (19)
C2	0.031 (2)	0.040 (3)	0.044 (3)	0.004 (2)	0.018 (2)	0.009 (2)
C3	0.032 (2)	0.045 (3)	0.036 (2)	0.002 (2)	0.016 (2)	0.009 (2)
C4	0.030 (2)	0.031 (2)	0.026 (2)	−0.0008 (18)	0.0042 (18)	0.0016 (18)
C5	0.027 (2)	0.033 (2)	0.031 (2)	−0.0005 (18)	0.0057 (18)	0.0025 (19)
C6	0.029 (2)	0.035 (2)	0.037 (2)	0.0010 (19)	0.0134 (19)	0.004 (2)
C7	0.031 (2)	0.026 (2)	0.033 (2)	−0.0048 (18)	0.0113 (19)	0.0013 (18)
C8	0.041 (3)	0.100 (5)	0.092 (5)	0.031 (4)	0.037 (3)	0.060 (5)
C9	0.036 (3)	0.028 (2)	0.027 (2)	−0.0017 (19)	0.0062 (19)	−0.0019 (18)
C10	0.036 (3)	0.070 (4)	0.051 (3)	0.013 (3)	0.014 (2)	0.020 (3)
C11	0.045 (3)	0.027 (2)	0.055 (3)	−0.005 (2)	0.027 (3)	−0.011 (2)
C12	0.032 (2)	0.021 (2)	0.049 (3)	−0.0012 (17)	0.019 (2)	−0.0027 (19)
C13	0.034 (2)	0.023 (2)	0.053 (3)	0.0055 (18)	0.012 (2)	0.007 (2)
C14	0.033 (2)	0.031 (2)	0.050 (3)	0.0039 (19)	0.009 (2)	0.002 (2)
C15	0.042 (3)	0.049 (4)	0.084 (5)	0.002 (3)	−0.008 (3)	0.014 (3)
C16	0.047 (4)	0.083 (6)	0.166 (9)	0.003 (4)	0.006 (5)	0.071 (6)
C17	0.045 (4)	0.109 (7)	0.231 (13)	0.015 (5)	0.006 (6)	0.098 (9)
C18	0.037 (3)	0.081 (5)	0.121 (7)	0.012 (4)	0.010 (4)	−0.002 (5)
C19	0.038 (3)	0.078 (5)	0.069 (4)	−0.011 (3)	0.015 (3)	−0.014 (4)
C20	0.043 (3)	0.059 (4)	0.059 (4)	−0.006 (3)	0.014 (3)	0.007 (3)

Zn1—O4i	1.931 (3)	C4—C9	1.496 (6)
Zn1—O1	1.950 (3)	C5—C6	1.384 (6)
Zn1—O5	1.998 (4)	C5—C10	1.495 (7)
Zn1—N1	2.055 (4)	C6—H6A	0.9300
Zn1—C11	2.588 (5)	C8—H8A	0.9600
Zn2—O2	2.037 (3)	C8—H8B	0.9600
Zn2—O2ii	2.037 (3)	C8—H8C	0.9600
Zn2—O3iii	2.057 (3)	C10—H10A	0.9600
Zn2—O3i	2.057 (3)	C10—H10B	0.9600
Zn2—O6	2.123 (3)	C10—H10C	0.9600
Zn2—O6ii	2.123 (3)	C11—C12	1.500 (6)
O1—C7	1.265 (6)	C12—C13	1.378 (7)
O2—C7	1.233 (5)	C12—C14	1.401 (7)
O3—C9	1.231 (6)	C13—C14vi	1.385 (7)
O3—Zn2iv	2.057 (3)	C13—H13A	0.9300
O4—C9	1.264 (6)	C14—C13vi	1.385 (7)
O4—Zn1v	1.931 (3)	C14—C15	1.492 (7)
O5—C11	1.245 (6)	C15—H15A	0.9600
O6—C11	1.233 (6)	C15—H15B	0.9600
N1—C16	1.308 (8)	C15—H15C	0.9600
N1—C20	1.320 (7)	C16—C17	1.356 (10)
C1—C6	1.378 (6)	C16—H16A	0.9300
C1—C2	1.395 (6)	C17—C18	1.337 (11)
C1—C7	1.492 (6)	C17—H17A	0.9300
C2—C3	1.387 (7)	C18—C19	1.332 (10)
C2—C8	1.511 (7)	C18—H18A	0.9300
C3—C4	1.367 (6)	C19—C20	1.359 (8)
C3—H3A	0.9300	C19—H19A	0.9300
C4—C5	1.393 (6)	C20—H20A	0.9300
O4i—Zn1—O1	109.70 (17)	O2—C7—C1	117.6 (4)
O4i—Zn1—O5	110.64 (18)	O1—C7—C1	118.4 (4)
O1—Zn1—O5	133.67 (17)	C2—C8—H8A	109.5
O4i—Zn1—N1	100.73 (17)	C2—C8—H8B	109.5
O1—Zn1—N1	98.40 (16)	H8A—C8—H8B	109.5
O5—Zn1—N1	95.60 (17)	C2—C8—H8C	109.5
O4i—Zn1—C11	114.20 (16)	H8A—C8—H8C	109.5
O1—Zn1—C11	112.05 (17)	H8B—C8—H8C	109.5
O5—Zn1—C11	27.91 (16)	O3—C9—O4	124.3 (4)
N1—Zn1—C11	120.16 (17)	O3—C9—C4	120.2 (4)
O2—Zn2—O2ii	180.00 (18)	O4—C9—C4	115.5 (4)
O2—Zn2—O3iii	87.46 (14)	C5—C10—H10A	109.5
O2ii—Zn2—O3iii	92.54 (14)	C5—C10—H10B	109.5
O2—Zn2—O3i	92.54 (14)	H10A—C10—H10B	109.5
O2ii—Zn2—O3i	87.46 (14)	C5—C10—H10C	109.5
O3iii—Zn2—O3i	180.000 (1)	H10A—C10—H10C	109.5
O2—Zn2—O6	90.67 (13)	H10B—C10—H10C	109.5
O2ii—Zn2—O6	89.33 (13)	O6—C11—O5	121.0 (5)
O3iii—Zn2—O6	88.47 (15)	O6—C11—C12	120.2 (5)
O3i—Zn2—O6	91.53 (15)	O5—C11—C12	118.8 (5)
O2—Zn2—O6ii	89.33 (13)	O6—C11—Zn1	72.3 (3)
O2ii—Zn2—O6ii	90.67 (13)	O5—C11—Zn1	48.7 (2)
O3iii—Zn2—O6ii	91.53 (15)	C12—C11—Zn1	167.2 (4)
O3i—Zn2—O6ii	88.47 (15)	C13—C12—C14	119.8 (4)
O6—Zn2—O6ii	180.0 (2)	C13—C12—C11	116.0 (4)
C7—O1—Zn1	118.2 (3)	C14—C12—C11	124.3 (5)
C7—O2—Zn2	139.4 (3)	C12—C13—C14vi	123.7 (4)
C9—O3—Zn2iv	135.7 (3)	C12—C13—H13A	118.2
C9—O4—Zn1v	121.2 (3)	C14vi—C13—H13A	118.2
C11—O5—Zn1	103.4 (3)	C13vi—C14—C12	116.6 (5)
C11—O6—Zn2	136.0 (3)	C13vi—C14—C15	118.4 (5)
C16—N1—C20	116.5 (5)	C12—C14—C15	125.0 (5)
C16—N1—Zn1	122.3 (4)	C14—C15—H15A	109.5
C20—N1—Zn1	121.2 (4)	C14—C15—H15B	109.5
C6—C1—C2	118.3 (4)	H15A—C15—H15B	109.5
C6—C1—C7	116.7 (4)	C14—C15—H15C	109.5
C2—C1—C7	125.1 (4)	H15A—C15—H15C	109.5
C3—C2—C1	117.6 (4)	H15B—C15—H15C	109.5
C3—C2—C8	118.1 (4)	N1—C16—C17	122.5 (7)
C1—C2—C8	124.4 (4)	N1—C16—H16A	118.8
C4—C3—C2	123.6 (4)	C17—C16—H16A	118.8
C4—C3—H3A	118.2	C18—C17—C16	120.0 (8)
C2—C3—H3A	118.2	C18—C17—H17A	120.0
C3—C4—C5	119.5 (4)	C16—C17—H17A	120.0
C3—C4—C9	117.6 (4)	C19—C18—C17	118.8 (7)
C5—C4—C9	122.9 (4)	C19—C18—H18A	120.6
C6—C5—C4	116.7 (4)	C17—C18—H18A	120.6
C6—C5—C10	118.8 (4)	C18—C19—C20	118.5 (7)
C4—C5—C10	124.5 (4)	C18—C19—H19A	120.7
C1—C6—C5	124.3 (4)	C20—C19—H19A	120.7
C1—C6—H6A	117.8	N1—C20—C19	123.7 (6)
C5—C6—H6A	117.8	N1—C20—H20A	118.2
O2—C7—O1	124.0 (4)	C19—C20—H20A	118.2