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Acta Cryst. (2007). E63, m2565    [ doi:10.1107/S1600536807044868 ]

Poly[bis([mu]2-quinoline-3-carboxylato-[kappa]2N:O)zinc(II)]

S. Hu, S.-H. Zhang and M.-H. Zeng

Abstract top

In the title compound, [Zn(L)2]n (HL is quinoline-3-carboxylic acid, C10H7NO2), the ZnII atom is coordinated by two N atoms from two bis-monodentate L- ligands and two O atoms from two bis-monodentate L- ligands, forming a slightly distorted tetrahedral geometry. Each bis-monodentate ligand links two Zn atoms, constructing a two-dimensional layer parallel to the (100) plane. The layers pack together into an abab pattern. These layers are linked by [pi]-[pi] interactions [face-to-face separation 3.59 (1) Å] into a supramolecular structure.

Comment top

Organic nitriles ligands and their hydroxlyate derivatives (carboxylates) have been widely used for hydrothermal synthesis of coordination polymers (Lin, et al., 1998; Tong, et al., 2003). Notably, these kinds of ligand reactions, relatively straight forward in the context of reaction chemistry, have become an important approach in the crystal engineering of metal-organic frameworks exhibiting novel physical properties. In the title compound, (I), the quin-3 − c group evidently results from the hydrolysis of quinoline-3-carbonitrile. The quin-3 − c ligands used in this work exhibit bridging mode different from other quinoline derivatives (Odoko, et al., 2001; Okabe & Muranishi, 2003). To the best of our knowledge, this is the first isolated quin-3 − c coordination polymer.

There are one ZnII atom and two quin-3 − c ligands in the asymmetric unit. The ZnII atom has a tetrahedral environment formed by two N atoms [Co – N 2.097 (2) − 2.102 (2) Å] and two O atoms [Co – O 1.927 (2) − 1.963 (2) Å] belonging to for different quin-3 − c ligands. The quin-3 − c ion binds to zinc in a bridge mode, through the carboxylate O atom and the quinoline N atom. The carboxylato group is monodentate. Each ZnII atom is connected by four ditopic quin-3 − c ligands, which construct a two-dimensional layer parallel to the (100) plane (Fig. 2) and generate two-dimensional square grids based on the (4, 4) topology. The quinoline rings of quin-3 − c penetrating into the adjacent layers are parallel to each other, and face-to-face separations are about 3.59 (1) Å (the second quinoline rings symmetry code: x, y, 1 − z) indicating π···π interaction.

Related literature top

For related literature, see: Odoko et al. (2001); Okabe & Muranishi (2003); Lin et al. (1998); Tong et al. (2003).

Experimental top

Quinoline-3-carbonitrile (1 mmol, 0.154 g), Zn(NO3)2·6H2O (0.5 mmol, 0.10 g) in water (10 ml). The mixture solution was stirred for 30 min at room temperature. The mixed solution were added to 15 ml sealed teflon-lined stainless steel vessels and the teflon-lined stainless steel vessels was left at 433 K vacuum case for 3 d under autogenous pressure. After cooled to room temperature, colourless crystals were obtained (yield: 80%, based on Zn).

Refinement top

All other H atoms were positioned geometrically and refined as riding, with C–H distances of 0.93 Å and Uiso(H) = 1.2 Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).

Figures top
[Figure 1] Fig. 1. The molecular stucture of (I) showing the coordination geometry around zinc with the 50% probability ellipsoids for non-H atoms. Hydrogen atoms have been omitted. [Symmetry codes: (i) x, 2 − y, z − 1/2; (ii) x, y + 1, z.]
[Figure 2] Fig. 2. Packing diagram of (I); hydrogen atoms have been omited.
Poly[bis(µ2-quinoline-3-carboxylato-κ2N:O)zinc(II)] top
Crystal data top
[Zn(C10H6NO2)2]F000 = 1664
Mr = 409.69Dx = 1.685 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
a = 28.7995 (17) ÅCell parameters from 3505 reflections
b = 8.0475 (5) Åθ = 1.6–27.0º
c = 15.2845 (9) ŵ = 1.55 mm−1
β = 114.2620 (10)ºT = 293 (2) K
V = 3229.5 (3) Å3Block, yellow
Z = 80.15 × 0.10 × 0.04 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		3505 independent reflections
Radiation source: fine-focus sealed tube3139 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.030
T = 293(2) Kθmax = 27.0º
phi and ω scansθmin = 1.6º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −35→36
Tmin = 0.801, Tmax = 0.941k = −10→10
12965 measured reflectionsl = −19→19
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)] = 0.036H-atom parameters constrained
wR(F2) = 0.097  w = 1/[σ2(Fo2) + (0.0609P)2 + 2.5142P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.001
3505 reflectionsΔρmax = 1.47 e Å−3
244 parametersΔρmin = −0.30 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Zn(C10H6NO2)2]V = 3229.5 (3) Å3
Mr = 409.69Z = 8
Monoclinic, C2/cMo Kα
a = 28.7995 (17) ŵ = 1.55 mm−1
b = 8.0475 (5) ÅT = 293 (2) K
c = 15.2845 (9) Å0.15 × 0.10 × 0.04 mm
β = 114.2620 (10)º
Data collection top
Bruker SMART CCD area-detector
diffractometer		3505 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		3139 reflections with I > 2σ(I)
Tmin = 0.801, Tmax = 0.941Rint = 0.030
12965 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.036244 parameters
wR(F2) = 0.097H-atom parameters constrained
S = 1.07Δρmax = 1.47 e Å−3
3505 reflectionsΔρmin = −0.30 e Å−3
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
Zn10.126630 (9)0.87864 (3)0.431899 (16)0.02379 (11)
N20.08079 (7)0.8761 (2)0.50917 (13)0.0245 (4)
O40.07901 (6)1.0274 (2)0.80930 (11)0.0339 (4)
O30.14500 (7)1.0907 (2)0.77747 (13)0.0414 (4)
C190.10001 (8)0.9447 (3)0.59501 (15)0.0271 (4)
H19A0.13120.99880.61410.033*
C170.03160 (9)0.8594 (3)0.63348 (16)0.0297 (5)
H17A0.01550.85440.67520.036*
C160.00951 (8)0.7822 (3)0.54283 (15)0.0276 (4)
C180.07678 (8)0.9417 (3)0.65969 (15)0.0265 (4)
C200.10280 (9)1.0280 (3)0.75489 (15)0.0300 (5)
C120.01183 (9)0.7247 (3)0.38800 (15)0.0305 (5)
H12A0.02780.73400.34620.037*
C14−0.05816 (10)0.6271 (3)0.4220 (2)0.0411 (6)
H14A−0.08890.57030.40190.049*
C110.03451 (8)0.7944 (2)0.48051 (14)0.0242 (4)
C13−0.03377 (10)0.6432 (3)0.35961 (18)0.0374 (5)
H13A−0.04880.59790.29830.045*
C15−0.03718 (9)0.6940 (3)0.51180 (18)0.0362 (5)
H15A−0.05350.68190.55280.043*
N10.17247 (7)0.0863 (2)0.49329 (13)0.0232 (3)
O10.16472 (6)0.67676 (19)0.47914 (12)0.0349 (4)
O20.10349 (7)0.5261 (2)0.36969 (13)0.0435 (4)
C80.17215 (8)0.3862 (2)0.49059 (16)0.0242 (4)
C90.15142 (8)0.2295 (2)0.45446 (15)0.0244 (4)
H9A0.12100.22630.39980.029*
C100.14361 (9)0.5398 (3)0.44045 (16)0.0274 (4)
C60.24106 (8)0.2430 (3)0.61467 (15)0.0256 (4)
C70.21666 (8)0.3917 (2)0.57096 (16)0.0270 (5)
H7A0.23090.49370.59690.032*
C20.24291 (9)−0.0598 (3)0.61506 (17)0.0326 (5)
H2A0.2283−0.16110.58860.039*
C10.21828 (8)0.0899 (2)0.57371 (15)0.0233 (4)
C30.28822 (9)−0.0562 (3)0.69407 (18)0.0394 (6)
H3A0.3045−0.15540.72040.047*
C40.31046 (10)0.0950 (3)0.7359 (2)0.0415 (6)
H4A0.34100.09510.79030.050*
C50.28758 (8)0.2421 (3)0.69749 (17)0.0345 (5)
H5A0.30260.34200.72570.041*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.02945 (17)0.01509 (15)0.02426 (16)0.00046 (8)0.00844 (11)0.00107 (8)
N20.0269 (9)0.0225 (9)0.0220 (9)−0.0012 (6)0.0080 (7)0.0001 (6)
O40.0402 (9)0.0345 (9)0.0235 (7)0.0045 (7)0.0095 (7)−0.0047 (6)
O30.0431 (10)0.0376 (9)0.0365 (9)−0.0101 (8)0.0094 (8)−0.0105 (7)
C190.0285 (11)0.0237 (11)0.0262 (10)−0.0040 (8)0.0084 (9)−0.0016 (8)
C170.0337 (12)0.0296 (11)0.0277 (11)0.0002 (9)0.0147 (9)−0.0003 (8)
C160.0282 (11)0.0231 (10)0.0285 (10)−0.0003 (8)0.0087 (9)−0.0007 (8)
C180.0318 (11)0.0222 (10)0.0223 (10)0.0010 (8)0.0079 (8)−0.0006 (8)
C200.0392 (12)0.0195 (10)0.0237 (10)0.0059 (9)0.0052 (9)−0.0010 (8)
C120.0350 (12)0.0253 (11)0.0264 (11)0.0001 (9)0.0078 (9)−0.0014 (8)
C140.0285 (12)0.0366 (14)0.0487 (15)−0.0099 (10)0.0061 (11)−0.0057 (10)
C110.0268 (10)0.0165 (9)0.0252 (10)0.0012 (7)0.0066 (8)0.0004 (7)
C130.0383 (13)0.0297 (12)0.0308 (12)−0.0034 (10)0.0008 (10)−0.0054 (9)
C150.0296 (12)0.0355 (13)0.0436 (13)−0.0054 (9)0.0150 (10)−0.0026 (10)
N10.0254 (9)0.0157 (8)0.0264 (9)−0.0003 (6)0.0085 (7)0.0011 (6)
O10.0412 (9)0.0132 (7)0.0431 (9)0.0018 (6)0.0102 (8)0.0008 (6)
O20.0402 (10)0.0279 (9)0.0456 (10)0.0076 (7)0.0006 (8)0.0077 (7)
C80.0283 (11)0.0140 (9)0.0306 (11)0.0028 (7)0.0124 (9)0.0025 (7)
C90.0242 (10)0.0187 (10)0.0273 (10)−0.0007 (8)0.0074 (8)0.0003 (8)
C100.0321 (11)0.0174 (10)0.0327 (11)0.0050 (8)0.0134 (9)0.0039 (8)
C60.0255 (10)0.0204 (10)0.0291 (11)−0.0001 (8)0.0094 (9)0.0004 (8)
C70.0304 (11)0.0170 (10)0.0313 (11)−0.0025 (8)0.0102 (9)−0.0021 (7)
C20.0342 (12)0.0216 (11)0.0381 (12)0.0029 (9)0.0109 (10)0.0038 (9)
C10.0234 (10)0.0201 (9)0.0256 (10)0.0020 (7)0.0093 (8)0.0027 (7)
C30.0368 (13)0.0324 (13)0.0423 (13)0.0124 (10)0.0093 (11)0.0135 (10)
C40.0288 (12)0.0443 (14)0.0386 (14)0.0045 (10)0.0010 (11)0.0052 (11)
C50.0299 (11)0.0299 (12)0.0355 (12)−0.0029 (9)0.0052 (10)−0.0024 (9)
Geometric parameters (Å, °) top
Zn1—O11.927 (2)C13—H13A0.9300
Zn1—O4i1.963 (2)C15—H15A0.9300
Zn1—N1ii2.097 (2)N1—C91.323 (3)
Zn1—N22.102 (2)N1—C11.385 (3)
N2—C191.317 (3)N1—Zn1iv2.0974 (17)
N2—C111.386 (3)O1—C101.280 (3)
O4—C201.277 (3)O2—C101.221 (3)
O4—Zn1iii1.9626 (15)C8—C71.364 (3)
O3—C201.227 (3)C8—C91.407 (3)
C19—C181.403 (3)C8—C101.508 (3)
C19—H19A0.9300C9—H9A0.9300
C17—C181.365 (3)C6—C71.410 (3)
C17—C161.410 (3)C6—C11.415 (3)
C17—H17A0.9300C6—C51.415 (3)
C16—C111.414 (3)C7—H7A0.9300
C16—C151.419 (3)C2—C31.366 (3)
C18—C201.505 (3)C2—C11.409 (3)
C12—C131.370 (3)C2—H2A0.9300
C12—C111.408 (3)C3—C41.401 (4)
C12—H12A0.9300C3—H3A0.9300
C14—C151.362 (4)C4—C51.365 (3)
C14—C131.404 (4)C4—H4A0.9300
C14—H14A0.9300C5—H5A0.9300
O1—Zn1—O4i138.54 (7)C14—C15—C16120.1 (2)
O1—Zn1—N1ii110.34 (7)C14—C15—H15A119.9
O4i—Zn1—N1ii100.64 (7)C16—C15—H15A119.9
O1—Zn1—N2100.00 (7)C9—N1—C1118.26 (18)
O4i—Zn1—N2100.73 (7)C9—N1—Zn1iv113.89 (14)
N1ii—Zn1—N2100.45 (7)C1—N1—Zn1iv127.47 (14)
C19—N2—C11118.00 (18)C10—O1—Zn1117.62 (14)
C19—N2—Zn1116.85 (14)C7—C8—C9118.22 (18)
C11—N2—Zn1124.84 (14)C7—C8—C10123.04 (18)
C20—O4—Zn1iii105.61 (14)C9—C8—C10118.7 (2)
N2—C19—C18124.6 (2)N1—C9—C8124.18 (19)
N2—C19—H19A117.7N1—C9—H9A117.9
C18—C19—H19A117.7C8—C9—H9A117.9
C18—C17—C16119.6 (2)O2—C10—O1125.8 (2)
C18—C17—H17A120.2O2—C10—C8119.73 (19)
C16—C17—H17A120.2O1—C10—C8114.51 (19)
C17—C16—C11118.84 (19)C7—C6—C1118.64 (18)
C17—C16—C15122.2 (2)C7—C6—C5122.1 (2)
C11—C16—C15119.0 (2)C1—C6—C5119.22 (19)
C17—C18—C19118.3 (2)C8—C7—C6120.00 (18)
C17—C18—C20122.9 (2)C8—C7—H7A120.0
C19—C18—C20118.8 (2)C6—C7—H7A120.0
O3—C20—O4123.6 (2)C3—C2—C1120.0 (2)
O3—C20—C18120.3 (2)C3—C2—H2A120.0
O4—C20—C18116.2 (2)C1—C2—H2A120.0
C13—C12—C11119.9 (2)N1—C1—C2120.02 (19)
C13—C12—H12A120.1N1—C1—C6120.68 (18)
C11—C12—H12A120.1C2—C1—C6119.30 (19)
C15—C14—C13120.6 (2)C2—C3—C4120.9 (2)
C15—C14—H14A119.7C2—C3—H3A119.5
C13—C14—H14A119.7C4—C3—H3A119.5
N2—C11—C12119.71 (19)C5—C4—C3120.5 (2)
N2—C11—C16120.66 (18)C5—C4—H4A119.8
C12—C11—C16119.63 (19)C3—C4—H4A119.8
C12—C13—C14120.7 (2)C4—C5—C6120.1 (2)
C12—C13—H13A119.6C4—C5—H5A120.0
C14—C13—H13A119.6C6—C5—H5A120.0
Symmetry codes: (i) x, −y+2, z−1/2; (ii) x, y+1, z; (iii) x, −y+2, z+1/2; (iv) x, y−1, z.
Table 1
Selected geometric parameters (Å, °) top
Zn1—O11.927 (2)Zn1—N1ii2.097 (2)
Zn1—O4i1.963 (2)Zn1—N22.102 (2)
O1—Zn1—O4i138.54 (7)O1—Zn1—N2100.00 (7)
O1—Zn1—N1ii110.34 (7)O4i—Zn1—N2100.73 (7)
O4i—Zn1—N1ii100.64 (7)N1ii—Zn1—N2100.45 (7)
Symmetry codes: (i) x, −y+2, z−1/2; (ii) x, y+1, z.
Acknowledgements top

We acknowledge financial support by the NSFC (No. 20561001) and the Patent Special Foundation of the Ministry of Education of Guangxi Province (No. 2006–26).

references
References top

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