metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

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 ZnII 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.

1. Related literature

For transition metal complexes with 5-hy­droxy­nicotinate ligands, see: Jiang & Feng (2008[Jiang, M.-X. & Feng, Y.-L. (2008). Acta Cryst. E64, m1517.]); Zhang et al. (2011[Zhang, J., Chen, H.-J. & Huang, J. (2011). Chin. J. Struct. Chem. 30, 1069-1073.]); Yang et al. (2010[Yang, J., Chen, H. J. & Tsz, H. L. (2010). Inorg. Chem. Commun. 10, 1016-1019.]). For corresponding rare earth metal complexes, see: Zhang et al. (2012[Zhang, J., Huang, J., Yang, J. & Chen, H.-J. (2012). Inorg. Chem. Commun. 17, 163-168.]); Mi et al. (2012[Mi, J.-L., Huang, J. & Chen, H.-J. (2012). Acta Cryst. E68, m1146-m1147.]); Xu et al. (2013[Xu, S.-S., Mi, J.-L. & Chen, H.-J. (2013). Acta Cryst. E69, m294-m295.]).

[Scheme 1]

2. Experimental

2.1. Crystal data

  • [Zn(C6H4NO3)2]

  • Mr = 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[Bruker (2007). APEX2, SAINT and SADABS. Bruker AXS Inc. Madison, Wisconsin, USA.]) Tmin = 0.488, Tmax = 0.723

  • 7054 measured reflections

  • 2891 independent reflections

  • 2397 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.42 e Å−3

  • Δρmin = −0.43 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Bruker (2007). APEX2, SAINT and SADABS. Bruker AXS Inc. Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). APEX2, SAINT and SADABS. Bruker AXS Inc. Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2005[Brandenburg, K. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


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).

Refinement top

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 Uiso(H) = 1.2Ueq(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 Uiso(H) = 1.5Ueq(O).

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
[Figure 1] Fig. 1. The coordination environment of the ZnII ion in the title compound, showing displacement ellipsoids at the 50% probability level.
[Figure 2] 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
Mr = 341.57F(000) = 688
Monoclinic, P21/nDx = 1.858 Mg m3
Hall symbol: -P 2ynMo Kα radiation, λ = 0.71073 Å
a = 9.4299 (6) Åθ = 3.0–29.1°
b = 10.5453 (7) ŵ = 2.04 mm1
c = 12.6914 (8) ÅT = 150 K
β = 104.640 (7)°Block, yellow
V = 1221.07 (14) Å30.41 × 0.37 × 0.17 mm
Data collection top
Bruker APEXII CCD
diffractometer
2891 independent reflections
Radiation source: fine-focus sealed tube2397 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
ϕ and ω scansθmax = 29.3°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Bruker, 2007)
h = 1212
Tmin = 0.488, Tmax = 0.723k = 1412
7054 measured reflectionsl = 1717
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.075H-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 parametersΔρmax = 0.42 e Å3
0 restraintsΔρmin = 0.43 e Å3
Crystal data top
[Zn(C6H4NO3)2]V = 1221.07 (14) Å3
Mr = 341.57Z = 4
Monoclinic, P21/nMo Kα radiation
a = 9.4299 (6) ŵ = 2.04 mm1
b = 10.5453 (7) ÅT = 150 K
c = 12.6914 (8) Å0.41 × 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)
Tmin = 0.488, Tmax = 0.723Rint = 0.034
7054 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0330 restraints
wR(F2) = 0.075H-atom parameters constrained
S = 1.07Δρmax = 0.42 e Å3
3345 reflectionsΔρmin = 0.43 e Å3
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
xyzUiso*/Ueq
C10.8597 (2)0.3757 (2)0.30816 (18)0.0111 (5)
C20.4890 (2)0.1376 (2)0.09332 (18)0.0104 (5)
C30.6200 (2)0.0759 (2)0.08906 (19)0.0118 (5)
H30.63250.03050.14890.014*
C40.7328 (2)0.0828 (2)0.00604 (19)0.0114 (5)
C50.7092 (2)0.1514 (2)0.09361 (19)0.0114 (5)
H50.78280.15400.15810.014*
C60.4744 (2)0.2077 (2)0.00397 (19)0.0123 (5)
H60.38750.25120.00780.015*
C70.3884 (2)0.5320 (2)0.19736 (19)0.0135 (5)
C80.2504 (2)0.1059 (2)0.34892 (19)0.0121 (5)
C90.3220 (3)0.0977 (2)0.45873 (19)0.0122 (5)
H90.28240.05090.50650.015*
C100.4545 (3)0.1615 (2)0.49542 (19)0.0126 (5)
C110.5125 (3)0.2258 (2)0.42054 (19)0.0131 (5)
H110.60290.26560.44500.016*
C120.3118 (3)0.1758 (2)0.27914 (19)0.0117 (5)
H120.26100.18360.20640.014*
N10.5831 (2)0.21429 (19)0.08815 (15)0.0108 (4)
N20.4436 (2)0.2330 (2)0.31413 (15)0.0122 (4)
O10.74133 (17)0.32799 (17)0.32074 (13)0.0154 (4)
O20.87405 (18)0.43130 (18)0.22547 (13)0.0179 (4)
O30.85858 (17)0.02136 (18)0.00882 (14)0.0168 (4)
H3A0.91340.02640.07020.025*
O40.41994 (18)0.44819 (17)0.13440 (13)0.0178 (4)
O50.45953 (19)0.55268 (19)0.29152 (14)0.0238 (5)
O60.53504 (19)0.16272 (18)0.60036 (13)0.0188 (4)
H6A0.48850.12880.63910.028*
Zn10.55375 (3)0.32108 (3)0.21439 (2)0.01009 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0105 (10)0.0118 (12)0.0110 (11)0.0024 (10)0.0028 (9)0.0023 (9)
C20.0105 (10)0.0102 (12)0.0101 (11)0.0001 (10)0.0016 (9)0.0015 (9)
C30.0130 (11)0.0122 (13)0.0113 (11)0.0013 (10)0.0050 (9)0.0009 (10)
C40.0083 (10)0.0120 (13)0.0139 (12)0.0006 (10)0.0026 (9)0.0016 (10)
C50.0097 (10)0.0129 (13)0.0104 (11)0.0005 (10)0.0006 (9)0.0001 (9)
C60.0089 (11)0.0160 (13)0.0111 (12)0.0011 (10)0.0008 (9)0.0005 (9)
C70.0107 (11)0.0143 (13)0.0158 (13)0.0011 (10)0.0039 (10)0.0019 (10)
C80.0122 (11)0.0104 (12)0.0132 (12)0.0004 (10)0.0021 (9)0.0021 (9)
C90.0154 (11)0.0100 (12)0.0122 (11)0.0003 (10)0.0058 (9)0.0001 (9)
C100.0129 (11)0.0143 (13)0.0097 (11)0.0017 (10)0.0012 (9)0.0017 (9)
C110.0100 (11)0.0159 (13)0.0128 (12)0.0013 (10)0.0016 (10)0.0029 (10)
C120.0123 (11)0.0128 (13)0.0102 (11)0.0026 (10)0.0034 (9)0.0011 (9)
N10.0097 (9)0.0127 (11)0.0093 (9)0.0001 (8)0.0011 (8)0.0007 (8)
N20.0121 (9)0.0131 (11)0.0113 (10)0.0014 (9)0.0028 (8)0.0009 (8)
O10.0096 (8)0.0246 (10)0.0109 (8)0.0041 (7)0.0006 (7)0.0016 (7)
O20.0157 (8)0.0280 (11)0.0097 (8)0.0012 (8)0.0025 (7)0.0045 (7)
O30.0092 (8)0.0250 (10)0.0144 (9)0.0079 (8)0.0002 (7)0.0027 (8)
O40.0190 (9)0.0203 (10)0.0136 (9)0.0090 (8)0.0029 (7)0.0021 (7)
O50.0191 (9)0.0302 (12)0.0164 (10)0.0070 (8)0.0060 (8)0.0029 (8)
O60.0184 (9)0.0295 (12)0.0071 (8)0.0073 (8)0.0008 (7)0.0013 (7)
Zn10.00810 (14)0.01335 (17)0.00817 (15)0.00045 (11)0.00084 (10)0.00090 (11)
Geometric parameters (Å, º) top
C1—O21.239 (3)C8—C121.387 (3)
C1—O11.270 (3)C8—C91.389 (3)
C1—C2i1.516 (3)C8—C7iv1.509 (3)
C2—C31.385 (3)C9—C101.392 (3)
C2—C61.390 (3)C9—H90.9300
C2—C1ii1.516 (3)C10—O61.356 (3)
C3—C41.395 (3)C10—C111.387 (3)
C3—H30.9300C11—N21.345 (3)
C4—O31.344 (3)C11—H110.9300
C4—C51.390 (3)C12—N21.351 (3)
C5—N11.348 (3)C12—H120.9300
C5—H50.9300N1—Zn12.034 (2)
C6—N11.348 (3)N2—Zn12.052 (2)
C6—H60.9300O1—Zn11.9364 (15)
C7—O51.233 (3)O3—H3A0.8200
C7—O41.276 (3)O4—Zn11.9421 (17)
C7—C8iii1.509 (3)O6—H6A0.8200
O2—C1—O1125.5 (2)C10—C9—H9120.9
O2—C1—C2i120.3 (2)O6—C10—C11116.6 (2)
O1—C1—C2i114.1 (2)O6—C10—C9124.5 (2)
C3—C2—C6119.3 (2)C11—C10—C9118.9 (2)
C3—C2—C1ii120.8 (2)N2—C11—C10122.8 (2)
C6—C2—C1ii119.8 (2)N2—C11—H11118.6
C2—C3—C4119.1 (2)C10—C11—H11118.6
C2—C3—H3120.4N2—C12—C8121.7 (2)
C4—C3—H3120.4N2—C12—H12119.2
O3—C4—C5123.2 (2)C8—C12—H12119.2
O3—C4—C3118.2 (2)C5—N1—C6119.1 (2)
C5—C4—C3118.5 (2)C5—N1—Zn1121.74 (15)
N1—C5—C4122.2 (2)C6—N1—Zn1119.12 (16)
N1—C5—H5118.9C11—N2—C12118.4 (2)
C4—C5—H5118.9C11—N2—Zn1116.97 (15)
N1—C6—C2121.7 (2)C12—N2—Zn1124.49 (16)
N1—C6—H6119.2C1—O1—Zn1127.16 (15)
C2—C6—H6119.2C4—O3—H3A109.5
O5—C7—O4125.0 (2)C7—O4—Zn1111.97 (15)
O5—C7—C8iii119.4 (2)C10—O6—H6A109.5
O4—C7—C8iii115.5 (2)O1—Zn1—O4134.17 (8)
C12—C8—C9119.9 (2)O1—Zn1—N1106.71 (7)
C12—C8—C7iv119.2 (2)O4—Zn1—N199.80 (8)
C9—C8—C7iv120.8 (2)O1—Zn1—N295.90 (7)
C8—C9—C10118.2 (2)O4—Zn1—N2105.76 (8)
C8—C9—H9120.9N1—Zn1—N2115.24 (8)
Symmetry codes: (i) x+1/2, y+1/2, z+1/2; (ii) x1/2, y+1/2, z1/2; (iii) x+1/2, y+1/2, z+1/2; (iv) x+1/2, y1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3A···O5v0.821.882.697 (2)175
O6—H6A···O2vi0.821.832.651 (3)174
Symmetry codes: (v) x+3/2, y1/2, z+1/2; (vi) x1/2, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3A···O5i0.821.882.697 (2)175.2
O6—H6A···O2ii0.821.832.651 (3)174.0
Symmetry codes: (i) x+3/2, y1/2, z+1/2; (ii) x1/2, y+1/2, z+1/2.
 

References

First citationBrandenburg, K. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany.  Google Scholar
First citationBruker (2007). APEX2, SAINT and SADABS. Bruker AXS Inc. Madison, Wisconsin, USA.  Google Scholar
First citationJiang, M.-X. & Feng, Y.-L. (2008). Acta Cryst. E64, m1517.  Google Scholar
First citationMi, J.-L., Huang, J. & Chen, H.-J. (2012). Acta Cryst. E68, m1146–m1147.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationXu, S.-S., Mi, J.-L. & Chen, H.-J. (2013). Acta Cryst. E69, m294–m295.  Google Scholar
First citationYang, J., Chen, H. J. & Tsz, H. L. (2010). Inorg. Chem. Commun. 10, 1016–1019.  Google Scholar
First citationZhang, J., Chen, H.-J. & Huang, J. (2011). Chin. J. Struct. Chem. 30, 1069–1073.  Google Scholar
First citationZhang, 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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