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

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.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.033
• wR factor = 0.075
• Data-to-parameter ratio = 17.4

checkCIF/PLATON results

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Alert level G
PLAT004_ALERT_5_G Polymeric Structure Found with Dimension .......          2 Info
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          2 Report
PLAT899_ALERT_4_G SHELXL97   is Deprecated and Succeeded by SHELXL       2014 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600        456 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   0 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   5 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
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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).

S1. Experimental

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).

S2. Refinement

Hydrogen atoms bonded to C atoms of the 5-hydroxynicotinate anions were positioned geometrically and refined as riding atoms, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C). H atoms of the hydroxy functions were found from difference maps and were included in the refinement as riding atoms, with O—H = 0.82 Å and U_iso(H) = 1.5U_eq(O).

Computing details

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

	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]

Crystal data

[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) Å^3	0.41 × 0.37 × 0.17 mm

Data collection

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

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.075	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0271P)^2 + 0.5488P] where P = (Fo^2 + 2Fc^2)/3
3345 reflections	(Δ/σ)max = 0.001
192 parameters	Δρmax = 0.42 e Å^−3
0 restraints	Δρmin = −0.43 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
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

C1—O2	1.239 (3)	C8—C12	1.387 (3)
C1—O1	1.270 (3)	C8—C9	1.389 (3)
C1—C2^i	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—C1^ii	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—C8^iii	1.509 (3)	O6—H6A	0.8200
O2—C1—O1	125.5 (2)	C10—C9—H9	120.9
O2—C1—C2^i	120.3 (2)	O6—C10—C11	116.6 (2)
O1—C1—C2^i	114.1 (2)	O6—C10—C9	124.5 (2)
C3—C2—C6	119.3 (2)	C11—C10—C9	118.9 (2)
C3—C2—C1^ii	120.8 (2)	N2—C11—C10	122.8 (2)
C6—C2—C1^ii	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—C8^iii	119.4 (2)	C10—O6—H6A	109.5
O4—C7—C8^iii	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)

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.