Crystal structure of poly[bis­(μ2-5-hydroxy­nicotinato-κ2N:O3)zinc]

Wang, W.-B.; Xu, S.-S.; Chen, H.-J.

doi:10.1107/S2056989015000249

metal-organic compounds

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Volume 71| Part 2| February 2015| Page m23

doi:10.1107/S2056989015000249

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Crystal structure of poly[bis(μ₂-5-hydroxynicotinato-κ²N:O³)zinc]

Wen-Bing Wang,^a Shan-Shan Xu ^a and Hong-Ji Chen ^a ^*

^aDepartment of Material Science and Engineering, Jinan University, Guangzhou 510632, People's Republic of China
^*Correspondence e-mail: thjchen@jnu.edu.cn

Edited by M. Weil, Vienna University of Technology, Austria (Received 16 December 2014; accepted 7 January 2015; online 14 January 2015)

The title coordination polymer, [Zn(C₆H₄NO₃)₂]_n, was prepared under hydrothermal conditions by the reaction of zinc nitrate with 5-hydroxynicotinic acid in the presence of malonic acid. In the structure, the Zn^II ion is coordinated by two carboxylate O atoms and two pyridine N atoms of four 5-hydroxynicotinate ligands in a distorted tetrahedral coordination environment. The μ₂-bridging mode of each anion leads to the formation of a three-dimensional framework structure. Intermolecular hydrogen bonds between the hydroxy groups of one anion and the non-coordinating carboxylate O atoms of neighbouring anions consolidate the crystal packing.

Keywords: crystal structure; zinc coordination polymer; 5-hydroxynicotinate ligand; hydrogen bonding.

CCDC reference: 1042412

1. Related literature

For transition metal complexes with 5-hydroxynicotinate ligands, see: Jiang & Feng (2008 ); Zhang et al. (2011 ); Yang et al. (2010 ). For corresponding rare earth metal complexes, see: Zhang et al. (2012 ); Mi et al. (2012 ); Xu et al. (2013 ).

2. Experimental

2.1. Crystal data

[Zn(C₆H₄NO₃)₂]
M_r = 341.57
Monoclinic, P 2₁ /n
a = 9.4299 (6) Å
b = 10.5453 (7) Å
c = 12.6914 (8) Å
β = 104.640 (7)°
V = 1221.07 (14) Å³
Z = 4
Mo Kα radiation
μ = 2.04 mm⁻¹
T = 150 K
0.41 × 0.37 × 0.17 mm

2.2. Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.488, T_max = 0.723
7054 measured reflections
2891 independent reflections
2397 reflections with I > 2σ(I)
R_int = 0.034

2.3. Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.075
S = 1.07
3345 reflections
192 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯O5ⁱ	0.82	1.88	2.697 (2)	175
O6—H6A⋯O2ⁱⁱ	0.82	1.83	2.651 (3)	174
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2005 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1042412

Crystal structure: contains datablocks I, global. DOI: 10.1107/S2056989015000249/wm5106sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015000249/wm5106Isup2.hkl

checkCIF report

Related literature top

For transition metal complexes with 5-hydroxynicotinate ligands, see: Jiang & Feng (2008); Zhang et al. (2011); Yang et al. (2010). For corresponding rare earth metal complexes, see: Zhang et al. (2012); Mi et al. (2012); Xu et al. (2013).

Experimental top

A mixture of zinc nitrate, 5-hydroxynicotinic acid, malonic acid and water in a mole ratio of ca 1:2:1:550 was added to a 25 ml Teflon-lined cup, and the pH value of the mixture was adjusted to 6.5 by 5%_wt ammonia/water at room temperature. The Teflon-lined cup was sealed in a stainless steel vessel and heated to 443 K, kept at that temperature for 3 days, and then slowly cooled to room temperature at a rate of 5 K per hour. Yellow block-like crystals of the title compound were obtained. The yield was about 55%. Elemental anal. calc. for C₁₂H₈N₂O₆Zn (341.57): C 28.60, H 2.79, N, 3.28. Found: C 28.65, H 2.81, N, 3.13. IR (cm^-1, KBr): 3454(s), 3104(m), 1856(w), 1632(s), 1586(s), 1487(m), 1432(m), 1400(s), 1302(w), 1279(s), 1239(m), 1158(w), 1119(w), 1026(s), 968(w), 936(s), 898(s), 822(s), 787(s), 732(m), 710(m), 687(s), 594(m), 539(m), 485(m), 453(w).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2005); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The coordination environment of the Zn^II ion in the title compound, showing displacement ellipsoids at the 50% probability level.
	Fig. 2. The packing in the structure of [Zn(C₆H₄O₃N)₂]_n, showing the polymeric character of the title compound.

Poly[bis(µ₂-5-hydroxynicotinato-κ²N:O³)zinc] top

Crystal data top

[Zn(C₆H₄NO₃)₂]	Z = 4
M_r = 341.57	F(000) = 688
Monoclinic, P2₁/n	D_x = 1.858 Mg m⁻³
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 9.4299 (6) Å	θ = 3.0–29.1°
b = 10.5453 (7) Å	µ = 2.04 mm⁻¹
c = 12.6914 (8) Å	T = 150 K
β = 104.640 (7)°	Block, yellow
V = 1221.07 (14) Å³	0.41 × 0.37 × 0.17 mm

Data collection top

Bruker APEXII CCD diffractometer	2891 independent reflections
Radiation source: fine-focus sealed tube	2397 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ϕ and ω scans	θ_max = 29.3°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −12→12
T_min = 0.488, T_max = 0.723	k = −14→12
7054 measured reflections	l = −17→17

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.075	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0271P)² + 0.5488P] where P = (F_o² + 2F_c²)/3
3345 reflections	(Δ/σ)_max = 0.001
192 parameters	Δρ_max = 0.42 e Å⁻³
0 restraints	Δρ_min = −0.43 e Å⁻³

Crystal data top

[Zn(C₆H₄NO₃)₂]	V = 1221.07 (14) Å³
M_r = 341.57	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.4299 (6) Å	µ = 2.04 mm⁻¹
b = 10.5453 (7) Å	T = 150 K
c = 12.6914 (8) Å	0.41 × 0.37 × 0.17 mm
β = 104.640 (7)°

Data collection top

Bruker APEXII CCD diffractometer	2891 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	2397 reflections with I > 2σ(I)
T_min = 0.488, T_max = 0.723	R_int = 0.034
7054 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.075	H-atom parameters constrained
S = 1.07	Δρ_max = 0.42 e Å⁻³
3345 reflections	Δρ_min = −0.43 e Å⁻³
192 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
C1	0.8597 (2)	0.3757 (2)	0.30816 (18)	0.0111 (5)
C2	0.4890 (2)	0.1376 (2)	−0.09332 (18)	0.0104 (5)
C3	0.6200 (2)	0.0759 (2)	−0.08906 (19)	0.0118 (5)
H3	0.6325	0.0305	−0.1489	0.014*
C4	0.7328 (2)	0.0828 (2)	0.00604 (19)	0.0114 (5)
C5	0.7092 (2)	0.1514 (2)	0.09361 (19)	0.0114 (5)
H5	0.7828	0.1540	0.1581	0.014*
C6	0.4744 (2)	0.2077 (2)	−0.00397 (19)	0.0123 (5)
H6	0.3875	0.2512	−0.0078	0.015*
C7	0.3884 (2)	0.5320 (2)	0.19736 (19)	0.0135 (5)
C8	0.2504 (2)	0.1059 (2)	0.34892 (19)	0.0121 (5)
C9	0.3220 (3)	0.0977 (2)	0.45873 (19)	0.0122 (5)
H9	0.2824	0.0509	0.5065	0.015*
C10	0.4545 (3)	0.1615 (2)	0.49542 (19)	0.0126 (5)
C11	0.5125 (3)	0.2258 (2)	0.42054 (19)	0.0131 (5)
H11	0.6029	0.2656	0.4450	0.016*
C12	0.3118 (3)	0.1758 (2)	0.27914 (19)	0.0117 (5)
H12	0.2610	0.1836	0.2064	0.014*
N1	0.5831 (2)	0.21429 (19)	0.08815 (15)	0.0108 (4)
N2	0.4436 (2)	0.2330 (2)	0.31413 (15)	0.0122 (4)
O1	0.74133 (17)	0.32799 (17)	0.32074 (13)	0.0154 (4)
O2	0.87405 (18)	0.43130 (18)	0.22547 (13)	0.0179 (4)
O3	0.85858 (17)	0.02136 (18)	0.00882 (14)	0.0168 (4)
H3A	0.9134	0.0264	0.0702	0.025*
O4	0.41994 (18)	0.44819 (17)	0.13440 (13)	0.0178 (4)
O5	0.45953 (19)	0.55268 (19)	0.29152 (14)	0.0238 (5)
O6	0.53504 (19)	0.16272 (18)	0.60036 (13)	0.0188 (4)
H6A	0.4885	0.1288	0.6391	0.028*
Zn1	0.55375 (3)	0.32108 (3)	0.21439 (2)	0.01009 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0105 (10)	0.0118 (12)	0.0110 (11)	0.0024 (10)	0.0028 (9)	−0.0023 (9)
C2	0.0105 (10)	0.0102 (12)	0.0101 (11)	0.0001 (10)	0.0016 (9)	0.0015 (9)
C3	0.0130 (11)	0.0122 (13)	0.0113 (11)	−0.0013 (10)	0.0050 (9)	−0.0009 (10)
C4	0.0083 (10)	0.0120 (13)	0.0139 (12)	0.0006 (10)	0.0026 (9)	0.0016 (10)
C5	0.0097 (10)	0.0129 (13)	0.0104 (11)	0.0005 (10)	0.0006 (9)	0.0001 (9)
C6	0.0089 (11)	0.0160 (13)	0.0111 (12)	0.0011 (10)	0.0008 (9)	0.0005 (9)
C7	0.0107 (11)	0.0143 (13)	0.0158 (13)	−0.0011 (10)	0.0039 (10)	0.0019 (10)
C8	0.0122 (11)	0.0104 (12)	0.0132 (12)	0.0004 (10)	0.0021 (9)	−0.0021 (9)
C9	0.0154 (11)	0.0100 (12)	0.0122 (11)	−0.0003 (10)	0.0058 (9)	0.0001 (9)
C10	0.0129 (11)	0.0143 (13)	0.0097 (11)	0.0017 (10)	0.0012 (9)	−0.0017 (9)
C11	0.0100 (11)	0.0159 (13)	0.0128 (12)	−0.0013 (10)	0.0016 (10)	−0.0029 (10)
C12	0.0123 (11)	0.0128 (13)	0.0102 (11)	0.0026 (10)	0.0034 (9)	−0.0011 (9)
N1	0.0097 (9)	0.0127 (11)	0.0093 (9)	0.0001 (8)	0.0011 (8)	−0.0007 (8)
N2	0.0121 (9)	0.0131 (11)	0.0113 (10)	−0.0014 (9)	0.0028 (8)	−0.0009 (8)
O1	0.0096 (8)	0.0246 (10)	0.0109 (8)	−0.0041 (7)	0.0006 (7)	0.0016 (7)
O2	0.0157 (8)	0.0280 (11)	0.0097 (8)	0.0012 (8)	0.0025 (7)	0.0045 (7)
O3	0.0092 (8)	0.0250 (10)	0.0144 (9)	0.0079 (8)	−0.0002 (7)	−0.0027 (8)
O4	0.0190 (9)	0.0203 (10)	0.0136 (9)	0.0090 (8)	0.0029 (7)	0.0021 (7)
O5	0.0191 (9)	0.0302 (12)	0.0164 (10)	0.0070 (8)	−0.0060 (8)	−0.0029 (8)
O6	0.0184 (9)	0.0295 (12)	0.0071 (8)	−0.0073 (8)	0.0008 (7)	−0.0013 (7)
Zn1	0.00810 (14)	0.01335 (17)	0.00817 (15)	0.00045 (11)	0.00084 (10)	−0.00090 (11)

Geometric parameters (Å, º) top

C1—O2	1.239 (3)	C8—C12	1.387 (3)
C1—O1	1.270 (3)	C8—C9	1.389 (3)
C1—C2ⁱ	1.516 (3)	C8—C7^iv	1.509 (3)
C2—C3	1.385 (3)	C9—C10	1.392 (3)
C2—C6	1.390 (3)	C9—H9	0.9300
C2—C1ⁱⁱ	1.516 (3)	C10—O6	1.356 (3)
C3—C4	1.395 (3)	C10—C11	1.387 (3)
C3—H3	0.9300	C11—N2	1.345 (3)
C4—O3	1.344 (3)	C11—H11	0.9300
C4—C5	1.390 (3)	C12—N2	1.351 (3)
C5—N1	1.348 (3)	C12—H12	0.9300
C5—H5	0.9300	N1—Zn1	2.034 (2)
C6—N1	1.348 (3)	N2—Zn1	2.052 (2)
C6—H6	0.9300	O1—Zn1	1.9364 (15)
C7—O5	1.233 (3)	O3—H3A	0.8200
C7—O4	1.276 (3)	O4—Zn1	1.9421 (17)
C7—C8ⁱⁱⁱ	1.509 (3)	O6—H6A	0.8200

O2—C1—O1	125.5 (2)	C10—C9—H9	120.9
O2—C1—C2ⁱ	120.3 (2)	O6—C10—C11	116.6 (2)
O1—C1—C2ⁱ	114.1 (2)	O6—C10—C9	124.5 (2)
C3—C2—C6	119.3 (2)	C11—C10—C9	118.9 (2)
C3—C2—C1ⁱⁱ	120.8 (2)	N2—C11—C10	122.8 (2)
C6—C2—C1ⁱⁱ	119.8 (2)	N2—C11—H11	118.6
C2—C3—C4	119.1 (2)	C10—C11—H11	118.6
C2—C3—H3	120.4	N2—C12—C8	121.7 (2)
C4—C3—H3	120.4	N2—C12—H12	119.2
O3—C4—C5	123.2 (2)	C8—C12—H12	119.2
O3—C4—C3	118.2 (2)	C5—N1—C6	119.1 (2)
C5—C4—C3	118.5 (2)	C5—N1—Zn1	121.74 (15)
N1—C5—C4	122.2 (2)	C6—N1—Zn1	119.12 (16)
N1—C5—H5	118.9	C11—N2—C12	118.4 (2)
C4—C5—H5	118.9	C11—N2—Zn1	116.97 (15)
N1—C6—C2	121.7 (2)	C12—N2—Zn1	124.49 (16)
N1—C6—H6	119.2	C1—O1—Zn1	127.16 (15)
C2—C6—H6	119.2	C4—O3—H3A	109.5
O5—C7—O4	125.0 (2)	C7—O4—Zn1	111.97 (15)
O5—C7—C8ⁱⁱⁱ	119.4 (2)	C10—O6—H6A	109.5
O4—C7—C8ⁱⁱⁱ	115.5 (2)	O1—Zn1—O4	134.17 (8)
C12—C8—C9	119.9 (2)	O1—Zn1—N1	106.71 (7)
C12—C8—C7^iv	119.2 (2)	O4—Zn1—N1	99.80 (8)
C9—C8—C7^iv	120.8 (2)	O1—Zn1—N2	95.90 (7)
C8—C9—C10	118.2 (2)	O4—Zn1—N2	105.76 (8)
C8—C9—H9	120.9	N1—Zn1—N2	115.24 (8)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O5^v	0.82	1.88	2.697 (2)	175
O6—H6A···O2^vi	0.82	1.83	2.651 (3)	174

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O5ⁱ	0.82	1.88	2.697 (2)	175.2
O6—H6A···O2ⁱⁱ	0.82	1.83	2.651 (3)	174.0

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

References

Brandenburg, K. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2007). APEX2, SAINT and SADABS. Bruker AXS Inc. Madison, Wisconsin, USA. Google Scholar
Jiang, M.-X. & Feng, Y.-L. (2008). Acta Cryst. E64, m1517. Google Scholar
Mi, J.-L., Huang, J. & Chen, H.-J. (2012). Acta Cryst. E68, m1146–m1147. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xu, S.-S., Mi, J.-L. & Chen, H.-J. (2013). Acta Cryst. E69, m294–m295. Google Scholar
Yang, J., Chen, H. J. & Tsz, H. L. (2010). Inorg. Chem. Commun. 10, 1016–1019. Google Scholar
Zhang, J., Chen, H.-J. & Huang, J. (2011). Chin. J. Struct. Chem. 30, 1069–1073. Google Scholar
Zhang, J., Huang, J., Yang, J. & Chen, H.-J. (2012). Inorg. Chem. Commun. 17, 163–168. Web of Science CSD CrossRef CAS Google Scholar

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 71| Part 2| February 2015| Page m23

doi:10.1107/S2056989015000249

Open

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