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

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296

A chiral inter­digitated supra­molecular network assembled from single-stranded helical tubes

aFaculty of Materials Science and Chemical Engineering, Ningbo University, Ningbo, Zhejiang 315211, People's Republic of China, bState Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, People's Republic of China, and cKey Laboratory for Molecular Design and Nutrition Engineering of Ningbo, Ningbo Institute of Technology, Zhejiang University, Ningbo, Zhejiang 315100, People's Republic of China
*Correspondence e-mail: hanlei@nbu.edu.cn

(Received 21 March 2011; accepted 10 June 2011; online 17 June 2011)

The amino-functionalized helical chiral one-dimensional coordination polymer catena-poly[[bis­(pyridine-κN)zinc(II)]-μ-2-amino­benzene-1,4-dicarboxyl­ato-κ4O1,O1′:O4,O4′], [Zn(C8H5NO4)(C5H5N)2]n, has an extended structure that is assembled from 2-amino­benzene-1,4-dicarboxyl­ate anions and Zn2+ cations and which presents a left-handed 43 helix with a pitch of 25.6975 (9) Å. All the pyridine rings and all the amino groups point away from the helix to generate a hollow tube with a cross-section of approximately 8 × 8 Å running parallel to the crystallographic c direction. Each single-stranded helix is inter­digitated with four neighbouring helices via N—H⋯O hydrogen bonds, which gives rise to a dense homochiral three-dimensional supra­molecular network.

Comment

Considerable effort has been devoted to the synthesis and characterization of metal–organic coordination polymers because of their fascinating topologies and potential applications. One-dimensional coordination polymers, being the simplest topological type of coordination network, are commonly encountered in a number of forms, such as helices, ladders, ribbons and zigzag chains (Leong & Vittal, 2011[Leong, W. L. & Vittal, J. J. (2011). Chem. Rev. 111, 688-764.]). Extended helical coordination polymers have attracted growing inter­est because of their similarities to biological systems and because of their potential utility in enanti­oselective catalysis (Han & Hong, 2005[Han, L. & Hong, M. C. (2005). Inorg. Chem. Commun. 8, 406-419.]; Zheng & Lu, 2010[Zheng, X.-D. & Lu, T.-B. (2010). CrystEngComm, 12, 324-336.]). Arguably the most important feature of a helix is its chirality, and to investigate this a number of helical chiral coordination polymers have been assembled using flexible chiral or achiral organic linkers (Anokhina & Jacobson, 2004[Anokhina, E. V. & Jacobson, A. J. (2004). J. Am. Chem. Soc. 126, 3044-3045.]; Cui et al., 2003[Cui, Y., Lee, S. J. & Lin, W. B. (2003). J. Am. Chem. Soc. 125, 6014-6015.]; Reger et al., 2011[Reger, D. L., Horger, J. J., Smith, M. D., Long, G. J. & Grandjean, F. (2011). Inorg. Chem. 50, 686-704.]; Yuan et al., 2009[Yuan, G. Z., Zhu, C. F., Liu, Y., Xuan, W. M. & Cui, Y. (2009). J. Am. Chem. Soc. 131, 10452-10460.]). When achiral organic ligands are used, many successful examples of spontaneous chiral induction have been reported in the literature (Balamurugan & Mukherjee, 2005[Balamurugan, V. & Mukherjee, R. (2005). CrystEngComm, 7, 337-341.]; Ezuhara et al., 1999[Ezuhara, T., Endo, K. & Aoyama, Y. (1999). J. Am. Chem. Soc. 121, 3279-3283.]; Han et al., 2007[Han, L., Valle, H. & Bu, X. H. (2007). Inorg. Chem. 46, 1511-1513.]; He et al., 2007[He, C., Zhao, Y. G., Guo, D., Lin, Z. H. & Duan, C. Y. (2007). Eur. J. Inorg. Chem. pp. 3451-3463.]; Wang et al., 2005[Wang, Y.-T., Tong, M.-L., Fan, H.-H., Wang, H.-Z. & Chen, X.-M. (2005). Dalton Trans. pp. 424-426.]).

[Scheme 1]

For the lower-dimensional helical chiral coordination polymers, it is easy and desirable to incorporate functional properties at the metal centres or in the backbone of the organic linkers. Furthermore, it is possible to develop strategies for engineering higher-dimensional materials through supra­molecular entanglement (Cui et al., 2003[Cui, Y., Lee, S. J. & Lin, W. B. (2003). J. Am. Chem. Soc. 125, 6014-6015.]; Han & Zhou, 2008[Han, L. & Zhou, Y. (2008). Inorg. Chem. Commun. 11, 385-387.]; Leong & Vittal, 2011[Leong, W. L. & Vittal, J. J. (2011). Chem. Rev. 111, 688-764.]; Wang et al., 2004[Wang, X.-L., Qin, C., Wang, E.-B., Xu, L., Su, Z.-M. & Hu, C.-W. (2004). Angew. Chem. Int. Ed. 43, 5036-5039.]). These entangled porous frameworks usually display tuneable flexibility, which is useful for various applications and is often associated with weak inter­actions, including hydrogen bonds, ππ stacking and van der Waals inter­actions. In this study, we have synthesized a one-dimensional amino-functionalized helical chiral coordination polymer from achiral ligands; [Zn(NH2-BDC)(py)2]n (NH2-BDC is 2-amino­benzene-1,4-dicarboxyl­ate and py is pyridine), (I)[link], forms a three-dimensional inter­digitated supra­molecular network via N—H⋯O hydrogen bonds.

Colourless crystals of (I)[link] were obtained following a hydrothermal synthesis using Zn(NO3)2·6H2O, 2-amino­benzene-1,4-dicarb­oxy­lic acid and pyridine at 423 K for 3 d. Compound (I)[link] crystallizes in the chiral space group P43 with one Zn2+ cation, one NH2-BDC anion and two pyridine ligands per asymmetric unit, as shown in Fig. 1[link]. The Zn2+ centre is coordinated by four O atoms from the carboxyl­ate groups of two different NH2-BDC ligands and two mutually cis N atoms from the pyridine groups, giving a distorted octa­hedral geometry. The bond angles around the Zn2+ centre are given in Table 1[link]. The Zn—O bond lengths range from 2.011 (3) to 2.480 (3) Å, a large spread, which is due to the highly asymmetric coordination mode adopted by the carboxyl­ate groups. The amino group in the ligand backbone forms an N3—H3B⋯O3 intramolecular hydrogen bond (see Table 2). Amino-functionalized porous coordination frameworks have recently attracted much attention because of an enhanced capacity for CO2 adsorption (Couck et al., 2009[Couck, S., Denayer, J. F. M., Baron, G. V., Rémy, T., Gascon, J. & Kapteijn, F. (2009). J. Am. Chem. Soc. 131, 6326-6327.]; Vaidhyanathan et al., 2009[Vaidhyanathan, R., Iremonger, S. S., Dawson, K. W. & Shimizu, G. K. H. (2009). Chem. Commun. pp. 5230-5232.]).

The coordination behaviour of the bridging NH2-BDC ligand of (I)[link] results in an extended helical architecture running along the crystallographic c axis (Fig.2). The left-handed helix is generated around the crystallographic 43 axis with a pitch of 25.6975 (9) Å. Each `turn' of the helix consists of four Zn/NH2-BDC units. All the pyridine rings and all the amino groups point away from the helical axis to generate a hollow tube with an opening of approximately 8 × 8 Å. Each left-handed helix inter­weaves with four similar helices and is linked to them via strong inter­molecular N—H⋯O hydrogen bonds (see Table 2[link]). These combine to give a dense three-dimensional inter­digitated supra­molecular network (Fig. 3[link]). All helices have, of crystallographic necessity, the same left-handed chirality and run along the c direction. This leads to an enanti­opure network, despite being formed solely from achiral mol­ecular units. As no other crystals from the sample were analysed, it is not possible to determine whether the bulk sample is enantiomerically pure or a conglomerate containing both possible hands.

In conclusion, (I)[link] is an inter­esting example of an amino-functionalized one-dimensional helical coordination polymer assembled from achiral ligands.

[Figure 1]
Figure 1
The asymmetric unit of (I)[link], showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 20% probability level. [Symmetry codes: (i) −y + 1, x + 1, z − [{1\over 4}]; (ii) y − 1, −x + 1, z + [{1\over 4}].]
[Figure 2]
Figure 2
Views of (a) the one-dimensional helical tube and (b) and left-handed helix of (I)[link]. All H atoms have been omitted for clarity.
[Figure 3]
Figure 3
(a) A view of the three-dimensional supra­molecular network assembled from helices by N—H⋯O hydrogen bonds. All pyridine mol­ecules and some of the H atoms have been omitted for clarity. (b) Schematic representation of the chiral inter­digitated network of (I)[link].

Experimental

A mixture of Zn(NO3)2·6H2O (92.6 mg, 0.5 mmol), 2-amino­benzene-1,4-dicarb­oxy­lic acid (149.6 mg, 0.5 mmol) and pyridine (1.0 g) in H2O (5 ml) was sealed in a 25 ml Teflon-lined stainless steel reactor and heated at 423 K for 3 d. A crop of colourless single crystals of the title compound was obtained after cooling the solution to room temperature. Block-shaped crystals of (I)[link] were collected and washed with distilled water. The yield was approximately 40% based on Zn2+.

Crystal data
  • [Zn(C8H5NO4)(C5H5N)2]

  • Mr = 402.70

  • Tetragonal, P 43

  • a = 8.4243 (1) Å

  • c = 25.6975 (9) Å

  • V = 1823.72 (7) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 1.37 mm−1

  • T = 298 K

  • 0.26 × 0.24 × 0.20 mm

Data collection
  • Rigaku R-AXIS RAPID diffractometer

  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995[Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.716, Tmax = 0.771

  • 11175 measured reflections

  • 3172 independent reflections

  • 2082 reflections with I > 2σ(I)

  • Rint = 0.057

Refinement
  • R[F2 > 2σ(F2)] = 0.043

  • wR(F2) = 0.071

  • S = 1.01

  • 3172 reflections

  • 235 parameters

  • 1 restraint

  • H-atom parameters constrained

  • Δρmax = 0.47 e Å−3

  • Δρmin = −0.29 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), with 1546 Friedel pairs

  • Flack parameter: 0.030 (17)

Table 1
Selected geometric parameters (Å, °)

Zn1—O1 2.011 (3)
Zn1—N1 2.066 (4)
Zn1—N2 2.069 (5)
Zn1—O4i 2.072 (5)
Zn1—O3i 2.296 (5)
Zn1—O2 2.480 (3)
O1—Zn1—N1 103.86 (15)
O1—Zn1—N2 98.92 (17)
N1—Zn1—N2 96.93 (19)
O1—Zn1—O4i 101.20 (18)
N1—Zn1—O4i 148.31 (19)
N2—Zn1—O4i 98.03 (19)
O1—Zn1—O3i 154.57 (18)
N1—Zn1—O3i 90.48 (18)
N2—Zn1—O3i 100.06 (17)
O4i—Zn1—O3i 59.46 (17)
O1—Zn1—O2 56.93 (14)
N1—Zn1—O2 86.47 (15)
N2—Zn1—O2 155.54 (15)
O4i—Zn1—O2 91.23 (15)
O3i—Zn1—O2 104.13 (16)
Symmetry code: (i) [-y+1, x+1, z-{\script{1\over 4}}].

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N3—H3B⋯O3 0.86 2.10 2.715 (8) 128
N3—H3C⋯O4ii 0.86 2.14 2.966 (9) 162
Symmetry code: (ii) [-y, x+1, z-{\script{1\over 4}}].

All H atoms were positioned geometrically and allowed to ride on their respective parent atoms at distances of C—H = 0.93 Å and N—H = 0.86 Å, and with Uiso(H) = 1.2Ueq(C,N). Displacement ellipsoids indicate some considerable vibrational movement or disorder in the NH2-BDC ligands, but we were unable to develop an alternative disorder model.

Data collection: RAPID-AUTO (Rigaku, 1998[Rigaku (1998). RAPID-AUTO. Version 1.06. Rigaku Corporation, Tokyo, Japan.]); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004[Rigaku/MSC (2004). CrystalStructure. Version 3.6.0. Rigaku/MSC, The Woodlands, Texas, USA.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

Considerable effort has been devoted to the synthesis and characterization of metal–organic coordination polymers because of their fascinating topologies and potential applications. One-dimensional coordination polymers, being the simplest topological type of coordination network, are commonly encountered in a number of forms such as helices, ladders, ribbons and zigzag chains (Leong & Vittal, 2011). Infinite helical coordination polymers have attracted growing interest because of their similarities to biological systems and because of their potential utility in enantioselective catalysis (Han & Hong, 2005; Zheng & Lu, 2010). Argueably the most important feature of a helix is its chirality, and to investigate this a number of helical chiral coordination polymers have been assembled using flexible chiral or achiral organic linkers (Anokhina & Jacobson, 2004; Cui et al., 2003; Reger et al., 2011; Yuan et al., 2009). When achiral organic ligands are used, many successful examples of spontaneous chiral induction have also been reported in the literature (Balamurugan & Mukherjee, 2005; Ezuhara et al., 1999; Han et al., 2007; He et al., 2007; Wang et al., 2005).

For the lower-dimensional helical chiral coordination polymers, it is easy and desirable to incorporate functional properties at the metal centres or in the backbone of the organic linkers. Furthermore, it is possible to develop strategies for engineering higher-dimensional materials through supramolecular entanglement (Cui et al., 2003; Han & Zhou, 2008; Leong & Vittal, 2011; Wang et al., 2004). These entangled porous frameworks usually display tuneable flexibility, which is useful for various applications and often associated with weak interactions, including hydrogen bonds, π-electron stacking and van der Waals interactions. In this study, we have synthesized a one-dimensional amino-functionalized helical chiral coordination polymer from achiral ligands, [Zn(NH2-BDC)(py)2]n (NH2-BDC is 2-aminobenzene-1,4-dicarboxylate and py is pyridine), (I), which forms a three-dimensional interdigitated supramolecular network via N—H···O hydrogen bonds.

The colourless crystals of (I) were synthesized hydrothermally by reacting Zn(NO3)2.6H2O, 2-aminobenzene-1,4-dicarboxylic acid and pyridine at 423 K for 3 d. Compound (I) crystallizes in the chiral space group P43 with one Zn2+ cation, one NH2-BDC anion and two pyridine molecules per asymmetric unit, as shown in Fig. 1. The Zn2+ centre is coordinated by four O atoms from the carboxylate groups of two different NH2-BDC ligands and two mutually cis N atoms from the pyridine groups, giving a distorted octahedral geometry. The bond angles around the Zn2+ centre are given in Table 1. The Zn—O bond lengths range from 2.011 (3) to 2.480 (3) Å, a large spread, which is due to the highly asymmetric coordination mode adopted by the carboxylate groups. Introducing the amino group into the backbone of the ligand results in an intramolecular hydrogen bond, N3—H3B···O3, with a donor-to-acceptor distance of 2.715 (8) Å. It should be pointed out that amino-functionalized porous coordination frameworks have recently gained much attention because of an enhanced capacity for CO2 adsorption (Couck et al., 2009; Vaidhyanathan et al., 2009).

The coordination behaviour of the bridging NH2-BDC ligand of (I) results in an infinite helical architecture running along the crystallographic c axis (Fig.2). The left-handed helix is generated around the crystallographic 43 axis with a pitch of 25.6975 (9) Å. Each `turn' of the helix consists of four Zn/NH2-BDC units. All the pyridine rings and the amino groups point away from the helical axis to generate a hollow tube with an opening of approximately 8 × 8 Å. Each left-handed helix further interweaves with four similar helices and links to them via strong intermolecular N—H···O hydrogen bonds (see Table 2). This combines to give a dense three-dimensional interdigitated supramolecular network (Fig. 3). All helices have, of crystallographic necessity, the same left-handed chirality and run along the c direction. This leads to an enantiopure network, despite being formed solely from achiral molecular units. As other crystals from the sample were not analysed, we must assume that the bulk sample is a conglomerate containing both possible handed forms.

In conclusion, (I) is an interesting example of an amino-functionalized helical one-dimensional coordination polymer assembled from achiral ligands.

Related literature top

For related literature, see: Anokhina & Jacobson (2004); Balamurugan & Mukherjee (2005); Couck et al. (2009); Cui et al. (2003); Ezuhara et al. (1999); Han & Hong (2005); Han & Zhou (2008); Han et al. (2007); He et al. (2007); Leong & Vittal (2011); Reger et al. (2011); Vaidhyanathan et al. (2009); Wang et al. (2004, 2005); Yuan et al. (2009); Zheng & Lu (2010).

Experimental top

A mixture of Zn(NO3)2.6H2O (92.6 mg, 0.5 mmol), 2-aminobenzene-1,4-dicarboxylic acid (149.6 mg, 0.5 mmol) and pyridine (1.0 g) in H2O (5 ml) was sealed in a 25 ml Teflon-lined stainless steel reactor and heated at 423 K for 3 d. A crop of colourless single crystals of the title compound was obtained after cooling the solution to room temperature. Block-shaped crystals of (I) were collected and washed with distilled water. The yield was approximately 40% based on Zn2+.

Refinement top

All H atoms were positioned geometrically and allowed to ride on their respective parent atoms at distances of C—H = 0.93 Å and N—H = 0.86 Å, and with Uiso(H) = 1.2 Ueq(C,N). Displacement ellipsoids indicate some considerable vibrational movement or disorder in the NH2-BDC ligands, but we were unable to model this.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) 1 + x, 1 - y, z - 1/4; (ii) 1 - x, y - 1, z + 1/4.]
[Figure 2] Fig. 2. Views of (a) the one-dimensional helical tube and (b) and left-handed helix of (I). All H atoms have been omitted for clarity.
[Figure 3] Fig. 3. (a) A view of the three-dimensional supramolecular network assembled from helices by N—H···O hydrogen bonds. All pyridine molecules and some of the H atoms have been omitted for clarity. (b) Schematic representation of the chiral interdigitated network of (I).
catena-poly[[bis(pyridine-κN)zinc(II)]-µ-2-aminobenzene-1,4- dicarboxylato-κ4O1,O1':O4,O4'] top
Crystal data top
[Zn(C8H5NO4)(C5H5N)2]Dx = 1.467 Mg m3
Mr = 402.70Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P43Cell parameters from 3397 reflections
Hall symbol: P 4cwθ = 3.8–25.5°
a = 8.4243 (1) ŵ = 1.37 mm1
c = 25.6975 (9) ÅT = 298 K
V = 1823.72 (7) Å3Block, colourless
Z = 40.26 × 0.24 × 0.20 mm
F(000) = 824
Data collection top
Rigaku R-AXIS RAPID
diffractometer
3172 independent reflections
Radiation source: fine-focus sealed tube2082 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.057
Detector resolution: 0 pixels mm-1θmax = 25.0°, θmin = 3.8°
ω scansh = 810
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
k = 910
Tmin = 0.716, Tmax = 0.771l = 3030
11175 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.043H-atom parameters constrained
wR(F2) = 0.071 w = 1/[σ2(Fo2) + (0.0204P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max = 0.005
3172 reflectionsΔρmax = 0.47 e Å3
235 parametersΔρmin = 0.29 e Å3
1 restraintAbsolute structure: Flack (1983), 1546 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.030 (17)
Crystal data top
[Zn(C8H5NO4)(C5H5N)2]Z = 4
Mr = 402.70Mo Kα radiation
Tetragonal, P43µ = 1.37 mm1
a = 8.4243 (1) ÅT = 298 K
c = 25.6975 (9) Å0.26 × 0.24 × 0.20 mm
V = 1823.72 (7) Å3
Data collection top
Rigaku R-AXIS RAPID
diffractometer
3172 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
2082 reflections with I > 2σ(I)
Tmin = 0.716, Tmax = 0.771Rint = 0.057
11175 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.043H-atom parameters constrained
wR(F2) = 0.071Δρmax = 0.47 e Å3
S = 1.01Δρmin = 0.29 e Å3
3172 reflectionsAbsolute structure: Flack (1983), 1546 Friedel pairs
235 parametersAbsolute structure parameter: 0.030 (17)
1 restraint
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Zn10.13367 (7)0.28865 (6)0.22997 (3)0.05215 (18)
O10.0108 (5)0.3604 (4)0.29281 (14)0.0684 (10)
O20.1383 (4)0.4001 (4)0.22471 (16)0.0665 (10)
O30.6869 (7)0.7693 (6)0.39686 (18)0.1087 (16)
O40.4988 (6)0.7690 (5)0.45486 (19)0.0921 (16)
N10.0322 (5)0.0729 (5)0.21115 (18)0.0555 (13)
N20.3322 (5)0.1989 (6)0.26715 (17)0.0597 (12)
N30.6359 (8)0.6390 (7)0.3017 (3)0.139 (2)
H3B0.70690.68580.32020.166*
H3C0.65740.61060.27030.166*
C10.1159 (7)0.4141 (6)0.2713 (2)0.0518 (14)
C20.2307 (7)0.4956 (6)0.3073 (2)0.0497 (15)
C30.1873 (7)0.5372 (6)0.3570 (2)0.0640 (16)
H3A0.08630.51330.36930.077*
C40.2944 (9)0.6144 (7)0.3883 (2)0.0756 (19)
H4A0.26360.64250.42180.091*
C50.4462 (8)0.6519 (7)0.3720 (3)0.0607 (16)
C60.4836 (6)0.6087 (6)0.3228 (3)0.0583 (15)
C70.3820 (6)0.5343 (5)0.2872 (3)0.0622 (16)
H7A0.41180.51220.25310.075*
C80.5454 (10)0.7367 (8)0.4115 (3)0.078 (2)
C90.4413 (8)0.1131 (8)0.2414 (3)0.092 (2)
H9A0.43240.10580.20540.111*
C100.5621 (9)0.0377 (9)0.2644 (4)0.113 (3)
H10A0.63410.02110.24490.136*
C110.5773 (9)0.0489 (9)0.3167 (4)0.100 (2)
H11A0.65960.00330.33370.121*
C120.4739 (9)0.1348 (9)0.3435 (3)0.087 (2)
H12A0.48380.14410.37940.104*
C130.3527 (7)0.2094 (8)0.3182 (2)0.0699 (15)
H13A0.28170.27010.33740.084*
C140.0490 (7)0.0512 (8)0.1669 (3)0.0773 (18)
H14A0.04890.13240.14240.093*
C150.1310 (8)0.0826 (10)0.1560 (3)0.096 (2)
H15A0.18810.09250.12520.115*
C160.1274 (10)0.2025 (9)0.1915 (4)0.101 (3)
H16A0.18510.29500.18570.121*
C170.0399 (8)0.1867 (7)0.2351 (4)0.101 (2)
H17A0.03230.27090.25830.122*
C180.0372 (7)0.0488 (8)0.2452 (3)0.082 (2)
H18A0.09410.03800.27600.098*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0575 (4)0.0499 (4)0.0491 (3)0.0020 (4)0.0135 (4)0.0004 (4)
O10.067 (3)0.076 (3)0.062 (3)0.011 (2)0.017 (2)0.002 (2)
O20.081 (3)0.070 (2)0.049 (2)0.0060 (19)0.018 (2)0.002 (2)
O30.119 (4)0.115 (4)0.092 (4)0.042 (3)0.037 (3)0.007 (3)
O40.111 (4)0.084 (4)0.082 (4)0.010 (3)0.028 (3)0.027 (3)
N10.061 (3)0.049 (3)0.056 (4)0.002 (2)0.015 (2)0.004 (3)
N20.053 (3)0.073 (3)0.052 (3)0.008 (3)0.012 (2)0.008 (3)
N30.139 (6)0.137 (6)0.139 (6)0.010 (5)0.026 (5)0.031 (5)
C10.044 (4)0.049 (3)0.062 (4)0.008 (3)0.017 (3)0.006 (3)
C20.058 (4)0.035 (3)0.056 (4)0.000 (3)0.018 (3)0.005 (3)
C30.058 (4)0.076 (4)0.058 (4)0.015 (3)0.006 (3)0.017 (3)
C40.101 (6)0.057 (4)0.070 (4)0.005 (4)0.026 (5)0.006 (3)
C50.065 (4)0.054 (4)0.063 (4)0.009 (3)0.019 (4)0.001 (3)
C60.035 (3)0.053 (4)0.087 (5)0.003 (3)0.002 (3)0.007 (3)
C70.044 (4)0.038 (3)0.105 (5)0.006 (3)0.037 (3)0.004 (3)
C80.080 (6)0.055 (4)0.099 (6)0.018 (4)0.040 (5)0.023 (5)
C90.081 (5)0.118 (6)0.077 (6)0.036 (4)0.010 (4)0.027 (4)
C100.084 (6)0.138 (7)0.117 (8)0.056 (5)0.007 (5)0.004 (6)
C110.071 (6)0.101 (6)0.129 (8)0.001 (5)0.022 (6)0.026 (6)
C120.071 (5)0.127 (6)0.062 (5)0.008 (5)0.013 (4)0.013 (4)
C130.061 (4)0.087 (5)0.062 (4)0.004 (4)0.003 (4)0.008 (4)
C140.094 (5)0.073 (5)0.065 (4)0.008 (4)0.011 (4)0.009 (4)
C150.112 (6)0.096 (6)0.078 (5)0.045 (5)0.005 (4)0.042 (5)
C160.130 (8)0.054 (5)0.118 (8)0.031 (5)0.038 (6)0.027 (5)
C170.118 (6)0.060 (5)0.126 (8)0.019 (4)0.021 (6)0.031 (5)
C180.087 (5)0.064 (4)0.094 (6)0.017 (4)0.002 (4)0.032 (4)
Geometric parameters (Å, º) top
Zn1—O12.011 (3)C4—C51.382 (8)
Zn1—N12.066 (4)C4—H4A0.9300
Zn1—N22.069 (5)C5—C61.353 (7)
Zn1—O4i2.072 (5)C5—C81.496 (9)
Zn1—O3i2.296 (5)C6—C71.401 (7)
Zn1—O22.480 (3)C7—H7A0.9300
Zn1—C8i2.498 (7)C8—Zn1ii2.498 (7)
Zn1—C12.582 (5)C9—C101.337 (8)
O1—C11.284 (6)C9—H9A0.9300
O2—C11.219 (6)C10—C111.352 (8)
O3—C81.279 (8)C10—H10A0.9300
O3—Zn1ii2.296 (5)C11—C121.326 (10)
O4—C81.212 (8)C11—H11A0.9300
O4—Zn1ii2.072 (4)C12—C131.364 (8)
N1—C141.340 (7)C12—H12A0.9300
N1—C181.348 (6)C13—H13A0.9300
N2—C131.325 (6)C14—C151.351 (8)
N2—C91.343 (6)C14—H14A0.9300
N3—C61.416 (8)C15—C161.362 (9)
N3—H3B0.8600C15—H15A0.9300
N3—H3C0.8600C16—C171.347 (10)
C1—C21.503 (7)C16—H16A0.9300
C2—C31.374 (7)C17—C181.356 (8)
C2—C71.413 (7)C17—H17A0.9300
C3—C41.373 (7)C18—H18A0.9300
C3—H3A0.9300
O1—Zn1—N1103.86 (15)C2—C3—H3A120.3
O1—Zn1—N298.92 (17)C4—C3—H3A120.3
N1—Zn1—N296.93 (19)C3—C4—C5122.6 (6)
O1—Zn1—O4i101.20 (18)C3—C4—H4A118.7
N1—Zn1—O4i148.31 (19)C5—C4—H4A118.7
N2—Zn1—O4i98.03 (19)C6—C5—C4115.9 (6)
O1—Zn1—O3i154.57 (18)C6—C5—C8129.2 (7)
N1—Zn1—O3i90.48 (18)C4—C5—C8114.9 (7)
N2—Zn1—O3i100.06 (17)C5—C6—C7126.0 (5)
O4i—Zn1—O3i59.46 (17)C5—C6—N3121.4 (6)
O1—Zn1—O256.93 (14)C7—C6—N3112.5 (6)
N1—Zn1—O286.47 (15)C6—C7—C2114.6 (6)
N2—Zn1—O2155.54 (15)C6—C7—H7A122.7
O4i—Zn1—O291.23 (15)C2—C7—H7A122.7
O3i—Zn1—O2104.13 (16)O4—C8—O3121.6 (7)
O1—Zn1—C8i128.5 (3)O4—C8—C5123.3 (8)
N1—Zn1—C8i120.5 (3)O3—C8—C5115.1 (8)
N2—Zn1—C8i100.16 (18)O4—C8—Zn1ii55.7 (4)
O4i—Zn1—C8i28.9 (2)O3—C8—Zn1ii65.9 (4)
O3i—Zn1—C8i30.6 (2)C5—C8—Zn1ii177.2 (5)
O2—Zn1—C8i98.84 (18)C10—C9—N2123.9 (7)
O1—Zn1—C129.22 (15)C10—C9—H9A118.0
N1—Zn1—C196.88 (17)N2—C9—H9A118.0
N2—Zn1—C1128.13 (19)C9—C10—C11118.6 (8)
O4i—Zn1—C195.56 (18)C9—C10—H10A120.7
O3i—Zn1—C1129.50 (19)C11—C10—H10A120.7
O2—Zn1—C127.77 (14)C12—C11—C10119.5 (8)
C8i—Zn1—C1114.6 (2)C12—C11—H11A120.3
C1—O1—Zn1100.9 (3)C10—C11—H11A120.3
C1—O2—Zn180.8 (3)C11—C12—C13119.7 (7)
C8—O3—Zn1ii83.5 (4)C11—C12—H12A120.2
C8—O4—Zn1ii95.5 (5)C13—C12—H12A120.2
C14—N1—C18117.6 (5)N2—C13—C12122.6 (6)
C14—N1—Zn1122.0 (4)N2—C13—H13A118.7
C18—N1—Zn1120.3 (4)C12—C13—H13A118.7
C13—N2—C9115.7 (5)N1—C14—C15123.4 (6)
C13—N2—Zn1122.5 (4)N1—C14—H14A118.3
C9—N2—Zn1121.5 (4)C15—C14—H14A118.3
C6—N3—H3B120.0C14—C15—C16117.9 (7)
C6—N3—H3C120.0C14—C15—H15A121.0
H3B—N3—H3C120.0C16—C15—H15A121.0
O2—C1—O1121.1 (5)C17—C16—C15119.7 (7)
O2—C1—C2123.2 (5)C17—C16—H16A120.1
O1—C1—C2115.6 (6)C15—C16—H16A120.1
O2—C1—Zn171.4 (3)C16—C17—C18120.4 (7)
O1—C1—Zn149.9 (2)C16—C17—H17A119.8
C2—C1—Zn1164.6 (5)C18—C17—H17A119.8
C3—C2—C7121.4 (5)N1—C18—C17120.8 (6)
C3—C2—C1121.1 (5)N1—C18—H18A119.6
C7—C2—C1117.5 (5)C17—C18—H18A119.6
C2—C3—C4119.4 (6)
Symmetry codes: (i) y+1, x+1, z1/4; (ii) y1, x+1, z+1/4.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3B···O30.862.102.715 (8)128
N3—H3C···O4iii0.862.142.966 (9)162
Symmetry code: (iii) y, x+1, z1/4.

Experimental details

Crystal data
Chemical formula[Zn(C8H5NO4)(C5H5N)2]
Mr402.70
Crystal system, space groupTetragonal, P43
Temperature (K)298
a, c (Å)8.4243 (1), 25.6975 (9)
V3)1823.72 (7)
Z4
Radiation typeMo Kα
µ (mm1)1.37
Crystal size (mm)0.26 × 0.24 × 0.20
Data collection
DiffractometerRigaku R-AXIS RAPID
diffractometer
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.716, 0.771
No. of measured, independent and
observed [I > 2σ(I)] reflections
11175, 3172, 2082
Rint0.057
(sin θ/λ)max1)0.594
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.071, 1.01
No. of reflections3172
No. of parameters235
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.47, 0.29
Absolute structureFlack (1983), 1546 Friedel pairs
Absolute structure parameter0.030 (17)

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top
Zn1—O12.011 (3)Zn1—O4i2.072 (5)
Zn1—N12.066 (4)Zn1—O3i2.296 (5)
Zn1—N22.069 (5)Zn1—O22.480 (3)
O1—Zn1—N1103.86 (15)N2—Zn1—O3i100.06 (17)
O1—Zn1—N298.92 (17)O4i—Zn1—O3i59.46 (17)
N1—Zn1—N296.93 (19)O1—Zn1—O256.93 (14)
O1—Zn1—O4i101.20 (18)N1—Zn1—O286.47 (15)
N1—Zn1—O4i148.31 (19)N2—Zn1—O2155.54 (15)
N2—Zn1—O4i98.03 (19)O4i—Zn1—O291.23 (15)
O1—Zn1—O3i154.57 (18)O3i—Zn1—O2104.13 (16)
N1—Zn1—O3i90.48 (18)
Symmetry code: (i) y+1, x+1, z1/4.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3B···O30.862.102.715 (8)128.1
N3—H3C···O4ii0.862.142.966 (9)161.9
Symmetry code: (ii) y, x+1, z1/4.
 

Acknowledgements

This work was supported by the National Natural Science Foundation of China (grant No. 21071087), the Natural Science Foundation of Zhejiang Province (grant No. Y4090578), the Natural Science Foundation of Ningbo Municipality (grant No. 2009A610129) and the K. C. Wong Magna Fund of Ningbo University.

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