Crystal structure of poly[bis-(μ2-5-hydroxy-nicotinato-κ(2) N:O (3))zinc].

The title coordination polymer, [Zn(C6H4NO3)2] n , was prepared under hydro-thermal conditions by the reaction of zinc nitrate with 5-hy-droxy-nicotinic acid in the presence of malonic acid. In the structure, the Zn(II) ion is coordinated by two carboxyl-ate O atoms and two pyridine N atoms of four 5-hy-droxy-nicotinate ligands in a distorted tetra-hedral coordin-ation environment. The μ2-bridging mode of each anion leads to the formation of a three-dimensional framework structure. Inter-molecular hydrogen bonds between the hy-droxy groups of one anion and the non-coordinating carboxyl-ate O atoms of neighbouring anions consolidate the crystal packing.

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 n class="Chemical">metal complexes, see: Zhang et al. (2012 ▸); Mi et al. (2012 ▸); Xu et al. (2013 ▸).

Experimental

Crystal data

[Zn(C6H4NO3)2]

M = 341.57

Monoclinic,

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

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

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.075

S = 1.07

3345 reflections

192 parameters

H-atom parameters constrained

Δρmax = 0.42 e Å−3

Δρmin = −0.43 e Å−3

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 ▸).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015000249/wm5106sup1.cif

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

Click here for additional data file.

II . DOI: 10.1107/S2056989015000249/wm5106fig1.tif

The coordination environment of the ZnII ion in the title compound, showing displacement ellipsoids at the 50% probability level.

Click here for additional data file.

6 4 3 2 n . DOI: 10.1107/S2056989015000249/wm5106fig2.tif

The packing in the structure of [Zn(C6H4O3N)2]n, showing the n class="Chemical">polymeric character of the title compound.

CCDC reference: 1042412

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Zn(C6H4NO3)2]	Z = 4
Mr = 341.57	F(000) = 688
Monoclinic, P21/n	Dx = 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

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

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(Fo2) + (0.0271P)2 + 0.5488P] where P = (Fo2 + 2Fc2)/3
3345 reflections	(Δ/σ)max = 0.001
192 parameters	Δρmax = 0.42 e Å−3
0 restraints	Δρmin = −0.43 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
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)

	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)

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—C7iv	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—C7iv	119.2 (2)	O4—Zn1—N1	99.80 (8)
C9—C8—C7iv	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)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O5v	0.82	1.88	2.697 (2)	175
O6—H6A···O2vi	0.82	1.83	2.651 (3)	174

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
O3H3AO5i	0.82	1.88	2.697(2)	175
O6H6AO2ii	0.82	1.83	2.651(3)	174

Symmetry codes: (i) ; (ii) .