Poly[(μ5-2,6-dimethyl­pyridine-3,5-dicarboxyl­ato)zinc]

Zhang, M.-X.; Chen, X.; Zhu, Y.

doi:10.1107/S1600536811024172

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page m977

doi:10.1107/S1600536811024172

Open

access

Poly[(μ₅-2,6-dimethylpyridine-3,5-dicarboxylato)zinc]

Ming-Xing Zhang,^a ^* Xin Chen ^a and Yi Zhu ^b

^aCollege of Chemistry, Chongqing Normal University, Chongqing 400047, People's Republic of China, and ^bCollege of Life Science, Chongqing Normal University, Chongqing 400047, People's Republic of China
^*Correspondence e-mail: zmx0102@hotmail.com

(Received 18 June 2011; accepted 20 June 2011; online 25 June 2011)

In the polymeric title complex, [Zn(C₉H₇NO₄)]_n, the Zn^II cation is located on a twofold rotation axis and is coordinated by five 2,6-dimethylpyridine-3,5-dicarboxylate (mpdc) anions in a distorted ZnNO₄ trigonal–bipyramidal geometry. The mpdc anion is also located on the twofold rotation axis and bridges five Zn^II cations, forming the three-dimensional polymeric complex. Weak C—H⋯π interactions are present in the crystal structure.

Related literature

For a related structure, see: Huang et al. (2007 ). For background to metal-organic frameworks (MOFs), see: Long & Yaghi (2009 ); Zhao et al. (2003 ).

Experimental

Crystal data

[Zn(C₉H₇NO₄)]
M_r = 258.53
Monoclinic, C 2/c
a = 8.578 (7) Å
b = 14.016 (11) Å
c = 7.382 (7) Å
β = 112.176 (17)°
V = 821.9 (12) Å³
Z = 4
Mo Kα radiation
μ = 2.98 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.16 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.469, T_max = 0.647
2615 measured reflections
732 independent reflections
709 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.067
S = 1.00
732 reflections
71 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Table 1
Selected bond lengths (Å)

Zn1—O1	2.207 (3)
Zn1—O2ⁱ	1.977 (2)
Zn1—N1ⁱⁱ	2.089 (3)
Symmetry codes: (i) $[x, -y, z-{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Table 2
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the pyridine ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5C⋯Cgⁱⁱ	0.96	2.67	3.573 (4)	158
Symmetry code: (ii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2008 ) and ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811024172/xu5247sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811024172/xu5247Isup2.hkl

checkCIF report

Comment top

Recently, research on metal-organic frameworks (MOFs) has become of increasing interest (Long & Yaghi, 2009). However, it is still a great challenge to assemble a predicted structure because there are numerous influences that can play decisive roles on the structure and crystal packing. Fortunately, these uncertainties can be reduced by the use of well selected spacers that have the ability to aggregate metal ions into different secondary building units (Zhao et al., 2003). Herein we reports an interesting five-connected zeolite-like coordination polymer based on highly-substituted pyridinedicarboxylates.

The title compound is a three-dimensional framework built from Zn cations that are linked by mpdc anions. From this arrangement cavities are formed. Zn1 is coordinated by four oxygen atoms from four different CO₂^- groups of mpdc ligands and one pyridyl nitrogen atom from another mpdc ligand. The mpdc ligand bridges five different Zn atoms and favors the construction of the structure with zeolite-like topology.The topology of the title compound is identical with the reported [Cd(mpdc)]_n (Huang et al., 2007), but the coordination sphere of cation, the binding mode of the carboxylate group and the synthesis condition are different.

The combination of the dramatic twists between two carboxylate groups in mpdc ligands results in the formation of the intersecting double-stranded helical chain comprised of [Zn(CO₂)₂]_n (Zn atoms as nodes).

Related literature top

For a related structure, see: Huang et al. (2007). For background to metal-organic frameworks (MOFs), see: Long & Yaghi (2009); Zhao et al. (2003).

Experimental top

All chemicals were of reagent grade and used as purchased without further purification. A mixture of Zn(NO₃)₂.6H₂O (450 mg, 1.5 mmol), H₂mpdc (97.5 mg, 0.5 mmol), (Et)₃N 0.07 mL and H₂O 10 mL was sealed in a 25 ml stainless steel reactor with Teflon liner and directly heated to 180 °C for 3 days, and then cooled to room temperature. The crystal samples were washed with methanol to give the title compound in about 35% yield (based on H₂mpdc ligand).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2008) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. The coordination environments of Zinc ions, showing 30% probability displacement ellipsoids and hydrogen atoms have been removed for clarity. Symmetry codes: (i) -x, -y, -z+1; (ii) -x + 1/2, -y + 1/2,-z + 1; (iii) -x, y, -z+1/2; (iv) x, -y, z - 1/2; (v) -x + 1, +y, -z + 3/2.
	Fig. 2. The presentation of the 3-D zeolite-like architecture. Methyl groups and hydrogen atoms have been removed for clarity. Polyhedra represent the ZnNO₄ groups.

Poly[(µ₅-2,6-dimethylpyridine-3,5-dicarboxylato)zinc] top

Crystal data top

[Zn(C₉H₇NO₄)]	F(000) = 520
M_r = 258.53	D_x = 2.089 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 535 reflections
a = 8.578 (7) Å	θ = 2.9–27.5°
b = 14.016 (11) Å	µ = 2.98 mm⁻¹
c = 7.382 (7) Å	T = 293 K
β = 112.176 (17)°	Prism, colorless
V = 821.9 (12) Å³	0.30 × 0.25 × 0.16 mm
Z = 4

Data collection top

Rigaku Mercury2 diffractometer	732 independent reflections
Radiation source: fine-focus sealed tube	709 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.9°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −10→10
T_min = 0.469, T_max = 0.647	k = −14→16
2615 measured reflections	l = −8→8

Refinement top

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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.067	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0519P)² + 0.6817P] where P = (F_o² + 2F_c²)/3
732 reflections	(Δ/σ)_max < 0.001
71 parameters	Δρ_max = 0.50 e Å⁻³
1 restraint	Δρ_min = −0.59 e Å⁻³

Crystal data top

[Zn(C₉H₇NO₄)]	V = 821.9 (12) Å³
M_r = 258.53	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 8.578 (7) Å	µ = 2.98 mm⁻¹
b = 14.016 (11) Å	T = 293 K
c = 7.382 (7) Å	0.30 × 0.25 × 0.16 mm
β = 112.176 (17)°

Data collection top

Rigaku Mercury2 diffractometer	732 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	709 reflections with I > 2σ(I)
T_min = 0.469, T_max = 0.647	R_int = 0.022
2615 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	1 restraint
wR(F²) = 0.067	H-atom parameters constrained
S = 1.00	Δρ_max = 0.50 e Å⁻³
732 reflections	Δρ_min = −0.59 e Å⁻³
71 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Zn1	0.0000	0.08158 (2)	0.2500	0.01616 (18)
N1	0.5000	0.26938 (18)	0.7500	0.0137 (5)
O1	0.0625 (2)	0.09690 (11)	0.5672 (2)	0.0189 (4)
O2	0.20746 (19)	−0.00679 (11)	0.7999 (2)	0.0192 (4)
C1	0.1949 (3)	0.06763 (15)	0.6979 (3)	0.0147 (5)
C2	0.3560 (3)	0.12188 (16)	0.7360 (3)	0.0147 (5)
C3	0.5000	0.0730 (2)	0.7500	0.0168 (7)
H3	0.5000	0.0066	0.7500	0.020*
C4	0.3618 (3)	0.22210 (15)	0.7464 (3)	0.0137 (5)
C5	0.2202 (3)	0.28064 (16)	0.7589 (4)	0.0195 (5)
H5A	0.2644	0.3278	0.8596	0.029*
H5B	0.1434	0.2399	0.7893	0.029*
H5C	0.1621	0.3117	0.6358	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0108 (2)	0.0106 (3)	0.0269 (3)	0.000	0.00690 (17)	0.000
N1	0.0128 (13)	0.0115 (13)	0.0166 (12)	0.000	0.0054 (10)	0.000
O1	0.0143 (8)	0.0178 (8)	0.0228 (7)	0.0007 (7)	0.0050 (7)	0.0013 (6)
O2	0.0146 (8)	0.0135 (8)	0.0277 (8)	−0.0012 (6)	0.0061 (6)	0.0048 (6)
C1	0.0143 (12)	0.0124 (11)	0.0202 (11)	−0.0012 (9)	0.0095 (9)	−0.0039 (8)
C2	0.0145 (11)	0.0121 (12)	0.0175 (10)	−0.0004 (9)	0.0058 (9)	0.0007 (8)
C3	0.0161 (17)	0.0107 (16)	0.0226 (17)	0.000	0.0064 (14)	0.000
C4	0.0111 (11)	0.0133 (11)	0.0165 (10)	−0.0011 (8)	0.0049 (8)	−0.0001 (8)
C5	0.0160 (11)	0.0150 (12)	0.0302 (12)	0.0005 (9)	0.0118 (10)	−0.0021 (9)

Geometric parameters (Å, º) top

Zn1—O1	2.207 (3)	O2—Zn1ⁱⁱⁱ	1.977 (2)
Zn1—O1ⁱ	2.207 (3)	C1—C2	1.507 (3)
Zn1—O2ⁱⁱ	1.977 (2)	C2—C3	1.382 (3)
Zn1—O2ⁱⁱⁱ	1.977 (2)	C2—C4	1.407 (3)
Zn1—N1^iv	2.089 (3)	C3—C2^v	1.382 (3)
N1—C4	1.349 (3)	C3—H3	0.9300
N1—C4^v	1.349 (3)	C4—C5	1.497 (3)
N1—Zn1^iv	2.089 (3)	C5—H5A	0.9600
O1—C1	1.250 (3)	C5—H5B	0.9600
O2—C1	1.267 (3)	C5—H5C	0.9600

O2ⁱⁱⁱ—Zn1—O2ⁱⁱ	115.94 (11)	O2—C1—C2	116.0 (2)
O2ⁱⁱⁱ—Zn1—N1^iv	122.03 (5)	C3—C2—C4	118.6 (2)
O2ⁱⁱ—Zn1—N1^iv	122.03 (5)	C3—C2—C1	119.6 (2)
O2ⁱⁱⁱ—Zn1—O1	95.17 (6)	C4—C2—C1	121.69 (19)
O2ⁱⁱ—Zn1—O1	90.75 (6)	C2^v—C3—C2	120.5 (3)
N1^iv—Zn1—O1	84.42 (4)	C2^v—C3—H3	119.7
O2ⁱⁱⁱ—Zn1—O1ⁱ	90.75 (6)	C2—C3—H3	119.7
O2ⁱⁱ—Zn1—O1ⁱ	95.17 (6)	N1—C4—C2	120.30 (19)
N1^iv—Zn1—O1ⁱ	84.42 (4)	N1—C4—C5	117.2 (2)
O1—Zn1—O1ⁱ	168.83 (9)	C2—C4—C5	122.51 (19)
C4—N1—C4^v	121.2 (3)	C4—C5—H5A	109.5
C4—N1—Zn1^iv	119.41 (13)	C4—C5—H5B	109.5
C4^v—N1—Zn1^iv	119.41 (13)	H5A—C5—H5B	109.5
C1—O1—Zn1	124.94 (16)	C4—C5—H5C	109.5
C1—O2—Zn1ⁱⁱⁱ	117.23 (15)	H5A—C5—H5C	109.5
O1—C1—O2	125.3 (2)	H5B—C5—H5C	109.5
O1—C1—C2	118.7 (2)

O2ⁱⁱⁱ—Zn1—O1—C1	120.17 (19)	O2—C1—C2—C4	−137.8 (2)
O2ⁱⁱ—Zn1—O1—C1	4.03 (18)	C4—C2—C3—C2^v	−3.21 (13)
N1^iv—Zn1—O1—C1	−118.08 (18)	C1—C2—C3—C2^v	173.1 (2)
O1ⁱ—Zn1—O1—C1	−118.08 (18)	C4^v—N1—C4—C2	−3.33 (14)
Zn1—O1—C1—O2	−103.1 (2)	Zn1^iv—N1—C4—C2	176.67 (14)
Zn1—O1—C1—C2	74.7 (2)	C4^v—N1—C4—C5	175.2 (2)
Zn1ⁱⁱⁱ—O2—C1—O1	−0.8 (3)	Zn1^iv—N1—C4—C5	−4.8 (2)
Zn1ⁱⁱⁱ—O2—C1—C2	−178.63 (14)	C3—C2—C4—N1	6.6 (3)
O1—C1—C2—C3	−131.9 (2)	C1—C2—C4—N1	−169.61 (17)
O2—C1—C2—C3	46.1 (3)	C3—C2—C4—C5	−171.85 (17)
O1—C1—C2—C4	44.2 (3)	C1—C2—C4—C5	11.9 (3)

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

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the pyridine ring.

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5C···Cg^iv	0.96	2.67	3.573 (4)	158

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

Experimental details

Crystal data
Chemical formula	[Zn(C₉H₇NO₄)]
M_r	258.53
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	8.578 (7), 14.016 (11), 7.382 (7)
β (°)	112.176 (17)
V (Å³)	821.9 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.98
Crystal size (mm)	0.30 × 0.25 × 0.16

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.469, 0.647
No. of measured, independent and observed [I > 2σ(I)] reflections	2615, 732, 709
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.067, 1.00
No. of reflections	732
No. of parameters	71
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.59

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2008) and ORTEP-3 (Farrugia, 1997), PLATON (Spek, 2009).

Selected bond lengths (Å) top

Zn1—O1	2.207 (3)	Zn1—N1ⁱⁱ	2.089 (3)
Zn1—O2ⁱ	1.977 (2)

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

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the pyridine ring.

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5C···Cgⁱⁱ	0.96	2.67	3.573 (4)	157.76

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

Acknowledgements

This work was supported by Science and Technology Projects of Chongqing Municipal Education Commission (KJ100602) and Chongqing Normal University Scientific Research Foundation Project (10XLZ005).

References

Brandenburg, K. (2008). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Huang, K.-L., He, Y.-T., Wang, D.-Q., Pan, W.-L. & Hu, C.-W. (2007). J. Mol. Struct. 832, 146–149. CrossRef CAS Google Scholar
Long, J. R. & Yaghi, O. M. (2009). Chem. Soc. Rev. 38, 1213–1214. Web of Science CrossRef PubMed CAS Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhao, B., Cheng, P., Dai, Y., Cheng, C., Liao, D.-Z., Yan, S.-P., Jiang, Z.-H. & Wang, G.-L. (2003). Angew. Chem. Int. Ed. 42, 934–936. Web of Science CSD CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page m977

doi:10.1107/S1600536811024172

Open

access