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Acta Cryst. (2011). E67, m1157    [ doi:10.1107/S160053681102856X ]

catena-Poly[[(1,10-phenanthroline)zinc]-[mu]-2,2'-oxydibenzoato]

X. Cai

Abstract top

In the title one-dimensional coordination polymer, [Zn(C14H8O5)(C12H8N2)]n, the ZnII ion is in a distorted octahedral coordination geometry with four O atoms from two carboxylate groups in bidentate chelating modes and two N atoms from a 1,10-phenanthroline ligand. The two terminal carboxylate groups bind the ZnII ions, leading to a chain along the c axis. Adjacent chains are further linked by intermolecular [pi]-[pi] interactions with a shortest centroid-centroid distance of 3.586 (3) Å, forming a two-dimensional supramolecular architecture with (6,3)-network topology.

Comment top

The design and synthesis of coordination polymers in supramolecular chemistry and crystal engineering, have been emerging as an ongoing field owing to their structural aesthetics and topologies as well as diverse functional properties (Evans et al., 1999; Yaghi et al., 1998) The semirigid V-shaped multicarboxylate ligands with two benzene rings bridged by an oxygen atom as central molecular framework are of increasing flexibility and therefore able to lead to metal complexes with diverse structures because of the free rotation of two benzene rings around the bridged atom (Wang et al., 2005).

The compound (I) crystallizes in the monoclinic system. As shown in Fig. 1, the Zn(II) ion is located in a distorted octahedral coordination geometry completed by four oxygen atoms from two carboxyl substituents of organic carboxylic acid in a bidentate chelating mode and two nitrogen atoms from the 1,10-phenanthroline ligand. The head and terminal carboxylate groups bind Zn(II) ions to lead to a one-dimensional chain. The neighboring chains are further linked by an intermolecular π–π interaction between the phenanthroline ring systems with a shortest centroid-centroid distance 3.586 (3) Å, forming a two-dimensional supramolecular architecture (Fig. 2) with 3-connect (6,3) network topology (Li et al., 2003)

Related literature top

For related structures and the properties of coordination polymers, see, for example: Evans et al. (1999); Yaghi et al. (1998); Wang et al. (2005); Li et al. (2003). For the synthesis of 3-(4-carboxyphenoxy)phthalic acid, see: Wang et al. (2009).

Experimental top

The mixture of Zn(OAc)2.2H2O (0.044 g, 0.2 mmol), 1,10-phenanthroline (0.0360 g, 0.2 mmol), 3-(4-carboxyphenoxy)phthalic acid (H3L, 0.0302 g, 0.1 mmol), KOH (0.0168 g, 0.3 mmol) and H2O (15 ml) was sealed in 25 ml Teflon-lined stainless steel reactor, which was heated to 160 °C. Colourless block-shaped crystals suitable for X-ray diffraction analysis were separated by filtration with the yield of 0.022 g.

Refinement top

All H atoms were refined using a riding model, with C—H = 0.93 Å, and with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at 30% probability level. All hydrogen atoms have been omitted. The suffix A corresponds to symmetry code (i) in Table 1.
[Figure 2] Fig. 2. A view of the two-dimensional supramolecular architecture of the title compound.
catena-Poly[[(1,10-phenanthroline)zinc]-µ-2,2'-oxydibenzoato] top
Crystal data top
[Zn(C14H8O5)(C12H8N2)]F(000) = 1024
Mr = 501.78Dx = 1.532 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1776 reflections
a = 7.7033 (18) Åθ = 2.3–21.9°
b = 17.403 (4) ŵ = 1.17 mm−1
c = 16.230 (4) ÅT = 293 K
β = 90.184 (4)°Block, colourless
V = 2175.8 (9) Å30.15 × 0.08 × 0.06 mm
Z = 4
Data collection top
Bruker APEXII CCD area-detector
diffractometer		3843 independent reflections
Radiation source: fine-focus sealed tube2320 reflections with I > 2σ(I)
graphiteRint = 0.056
Detector resolution: 0 pixels mm-1θmax = 25.0°, θmin = 1.7°
φ and ω scansh = −9→9
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		k = −20→16
Tmin = 0.901, Tmax = 0.913l = −18→19
10511 measured reflections
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)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.112H-atom parameters constrained
S = 0.94 w = 1/[σ2(Fo2) + (0.0558P)2]
where P = (Fo2 + 2Fc2)/3
3843 reflections(Δ/σ)max = 0.001
307 parametersΔρmax = 0.49 e Å−3
0 restraintsΔρmin = −0.41 e Å−3
Crystal data top
[Zn(C14H8O5)(C12H8N2)]V = 2175.8 (9) Å3
Mr = 501.78Z = 4
Monoclinic, P21/nMo Kα radiation
a = 7.7033 (18) ŵ = 1.17 mm−1
b = 17.403 (4) ÅT = 293 K
c = 16.230 (4) Å0.15 × 0.08 × 0.06 mm
β = 90.184 (4)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer		3843 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		2320 reflections with I > 2σ(I)
Tmin = 0.901, Tmax = 0.913Rint = 0.056
10511 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.112Δρmax = 0.49 e Å−3
S = 0.94Δρmin = −0.41 e Å−3
3843 reflectionsAbsolute structure: ?
307 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
Zn10.13817 (6)0.13631 (3)0.83696 (3)0.04575 (18)
O3−0.2343 (3)0.10169 (15)0.42299 (15)0.0501 (7)
O4−0.1006 (3)0.32154 (16)0.33955 (16)0.0508 (7)
N10.2187 (4)0.02020 (18)0.83600 (18)0.0427 (8)
O5−0.3157 (3)0.24285 (15)0.36218 (17)0.0576 (8)
O2−0.0997 (3)0.14036 (15)0.78576 (15)0.0505 (7)
C250.2064 (5)0.0400 (2)0.9814 (2)0.0449 (10)
O10.1008 (3)0.14258 (19)0.69057 (16)0.0687 (9)
N20.1358 (4)0.1102 (2)0.96511 (19)0.0488 (8)
C180.3184 (5)−0.0821 (3)0.9262 (3)0.0527 (11)
C260.2485 (4)−0.0083 (2)0.9126 (2)0.0431 (10)
C1−0.0532 (5)0.1416 (2)0.7110 (2)0.0446 (10)
C100.2189 (6)0.0738 (3)0.3682 (3)0.0603 (12)
H100.29960.03400.36750.072*
C13−0.0274 (4)0.1917 (2)0.3654 (2)0.0366 (9)
C110.2659 (5)0.1464 (3)0.3426 (2)0.0568 (12)
H110.37930.15610.32620.068*
C5−0.4461 (5)0.1157 (2)0.5263 (3)0.0558 (11)
H5−0.53050.10670.48640.067*
C210.2411 (5)0.0138 (3)1.0612 (3)0.0599 (13)
C120.1449 (4)0.2045 (2)0.3413 (2)0.0431 (9)
H120.17810.25330.32420.052*
C3−0.1465 (4)0.1308 (2)0.5634 (2)0.0379 (9)
H3−0.03040.13450.54830.046*
C14−0.1562 (5)0.2555 (2)0.3559 (2)0.0403 (9)
C2−0.1942 (4)0.1381 (2)0.6454 (2)0.0369 (8)
C4−0.2722 (5)0.1181 (2)0.5043 (2)0.0407 (9)
C150.2555 (5)−0.0236 (3)0.7719 (3)0.0528 (11)
H150.2365−0.00420.71930.063*
C90.0534 (6)0.0604 (2)0.3947 (2)0.0559 (11)
H90.02220.01160.41270.067*
C170.3525 (5)−0.1265 (3)0.8556 (3)0.0688 (13)
H170.3966−0.17600.86130.083*
C220.2001 (6)0.0634 (4)1.1255 (3)0.0769 (16)
H220.21930.04821.17970.092*
C8−0.0682 (5)0.1189 (2)0.3951 (2)0.0400 (9)
C160.3218 (5)−0.0979 (3)0.7799 (3)0.0649 (13)
H160.3446−0.12740.73340.078*
C200.3170 (6)−0.0615 (3)1.0716 (3)0.0721 (15)
H200.3415−0.07931.12440.086*
C240.0998 (6)0.1566 (3)1.0270 (3)0.0647 (13)
H240.05250.20481.01640.078*
C6−0.4932 (5)0.1267 (3)0.6066 (3)0.0585 (12)
H6−0.61000.12750.62080.070*
C230.1324 (7)0.1338 (4)1.1098 (3)0.0764 (15)
H230.10730.16711.15300.092*
C7−0.3675 (5)0.1366 (2)0.6669 (2)0.0484 (10)
H7−0.39980.14220.72180.058*
C190.3527 (6)−0.1059 (3)1.0072 (3)0.0713 (14)
H190.4017−0.15411.01610.086*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0362 (3)0.0535 (3)0.0475 (3)−0.0081 (2)−0.0086 (2)0.0039 (2)
O30.0465 (17)0.0655 (19)0.0382 (15)−0.0152 (14)−0.0071 (13)0.0035 (13)
O40.0418 (16)0.0465 (17)0.0641 (18)0.0019 (13)0.0034 (13)0.0047 (14)
N10.0335 (17)0.056 (2)0.0385 (19)−0.0111 (15)−0.0066 (14)0.0001 (17)
O50.0310 (16)0.0534 (18)0.088 (2)0.0039 (13)−0.0074 (14)−0.0064 (15)
O20.0432 (16)0.074 (2)0.0344 (15)−0.0024 (14)−0.0046 (12)−0.0032 (14)
C250.031 (2)0.060 (3)0.044 (2)−0.0180 (19)−0.0070 (18)0.005 (2)
O10.0240 (15)0.129 (3)0.0530 (17)−0.0026 (16)−0.0029 (13)−0.0030 (18)
N20.042 (2)0.060 (2)0.045 (2)−0.0138 (17)0.0019 (16)−0.0062 (18)
C180.033 (2)0.065 (3)0.060 (3)−0.008 (2)−0.009 (2)0.011 (2)
C260.027 (2)0.057 (3)0.046 (2)−0.0136 (18)−0.0087 (17)0.007 (2)
C10.038 (2)0.052 (3)0.044 (2)0.0057 (19)−0.0039 (19)−0.002 (2)
C100.055 (3)0.061 (3)0.065 (3)0.025 (2)−0.017 (2)−0.012 (3)
C130.033 (2)0.046 (2)0.030 (2)0.0025 (17)−0.0037 (16)−0.0015 (17)
C110.037 (2)0.084 (4)0.049 (3)0.013 (2)−0.0012 (19)−0.010 (2)
C50.035 (2)0.081 (3)0.051 (3)−0.003 (2)−0.015 (2)0.003 (2)
C210.037 (2)0.102 (4)0.040 (3)−0.025 (2)−0.006 (2)0.009 (3)
C120.032 (2)0.052 (2)0.045 (2)−0.002 (2)0.0015 (17)0.004 (2)
C30.0273 (19)0.047 (2)0.039 (2)0.0002 (17)−0.0036 (16)0.0049 (18)
C140.035 (2)0.049 (3)0.036 (2)0.0019 (19)−0.0065 (17)−0.0057 (18)
C20.0287 (19)0.042 (2)0.040 (2)0.0005 (17)−0.0034 (16)0.0002 (18)
C40.036 (2)0.047 (2)0.039 (2)−0.0042 (17)−0.0059 (17)0.0071 (18)
C150.040 (2)0.069 (3)0.049 (3)−0.006 (2)−0.0082 (19)−0.005 (2)
C90.064 (3)0.051 (3)0.053 (3)0.012 (2)−0.014 (2)0.001 (2)
C170.040 (3)0.059 (3)0.107 (4)0.004 (2)−0.008 (3)0.005 (3)
C220.058 (3)0.133 (5)0.040 (3)−0.032 (3)−0.002 (2)0.007 (3)
C80.039 (2)0.051 (3)0.030 (2)−0.0003 (19)−0.0073 (17)−0.0003 (18)
C160.040 (3)0.074 (3)0.081 (3)0.002 (2)−0.010 (2)−0.020 (3)
C200.043 (3)0.111 (5)0.062 (3)−0.016 (3)−0.014 (2)0.047 (3)
C240.053 (3)0.081 (4)0.060 (3)−0.017 (2)0.008 (2)−0.012 (3)
C60.025 (2)0.089 (3)0.062 (3)−0.001 (2)−0.004 (2)−0.002 (3)
C230.064 (3)0.120 (5)0.045 (3)−0.028 (3)0.007 (2)−0.024 (3)
C70.038 (2)0.063 (3)0.044 (2)0.005 (2)0.0032 (18)0.001 (2)
C190.043 (3)0.091 (4)0.080 (4)−0.005 (3)−0.009 (3)0.032 (3)
Geometric parameters (Å, °) top
Zn1—O22.011 (2)C11—H110.9300
Zn1—N12.114 (3)C5—C61.369 (6)
Zn1—N22.129 (3)C5—C41.387 (5)
Zn1—O4i2.143 (3)C5—H50.9300
Zn1—O5i2.172 (3)C21—C221.391 (7)
Zn1—O12.395 (3)C21—C201.446 (7)
O3—C41.383 (4)C12—H120.9300
O3—C81.392 (4)C3—C41.378 (5)
O4—C141.255 (4)C3—C21.389 (5)
N1—C151.321 (5)C3—H30.9300
N1—C261.358 (4)C2—C71.381 (5)
O5—C141.253 (4)C15—C161.396 (6)
O2—C11.266 (4)C15—H150.9300
C25—N21.362 (5)C9—C81.383 (5)
C25—C211.398 (5)C9—H90.9300
C25—C261.437 (5)C17—C161.345 (6)
O1—C11.233 (4)C17—H170.9300
N2—C241.319 (5)C22—C231.355 (7)
C18—C191.402 (6)C22—H220.9300
C18—C171.407 (6)C16—H160.9300
C18—C261.410 (6)C20—C191.329 (6)
C1—C21.520 (5)C20—H200.9300
C10—C91.367 (6)C24—C231.423 (6)
C10—C111.379 (6)C24—H240.9300
C10—H100.9300C6—C71.385 (5)
C13—C81.393 (5)C6—H60.9300
C13—C121.403 (5)C23—H230.9300
C13—C141.496 (5)C7—H70.9300
C11—C121.375 (5)C19—H190.9300
O2—Zn1—N1107.31 (11)C25—C21—C20118.6 (4)
O2—Zn1—N2113.60 (11)C11—C12—C13121.4 (4)
N1—Zn1—N278.85 (13)C11—C12—H12119.3
O2—Zn1—O4i148.31 (11)C13—C12—H12119.3
N1—Zn1—O4i92.97 (11)C4—C3—C2119.6 (3)
N2—Zn1—O4i93.73 (11)C4—C3—H3120.2
O2—Zn1—O5i101.10 (10)C2—C3—H3120.2
N1—Zn1—O5i151.55 (10)O5—C14—O4120.9 (3)
N2—Zn1—O5i91.41 (12)O5—C14—C13120.8 (4)
O4i—Zn1—O5i60.75 (10)O4—C14—C13118.3 (3)
O2—Zn1—O158.81 (10)O5—C14—Zn1ii61.1 (2)
N1—Zn1—O194.05 (11)O4—C14—Zn1ii59.79 (19)
N2—Zn1—O1167.82 (11)C13—C14—Zn1ii177.9 (3)
O4i—Zn1—O196.52 (10)C7—C2—C3119.9 (3)
O5i—Zn1—O199.32 (11)C7—C2—C1120.9 (3)
C4—O3—C8117.7 (3)C3—C2—C1119.0 (3)
C14—O4—Zn1ii89.8 (2)C3—C4—O3123.2 (3)
C15—N1—C26118.3 (4)C3—C4—C5120.2 (4)
C15—N1—Zn1128.4 (3)O3—C4—C5116.5 (3)
C26—N1—Zn1113.1 (3)N1—C15—C16122.7 (4)
C14—O5—Zn1ii88.5 (2)N1—C15—H15118.6
C1—O2—Zn197.8 (2)C16—C15—H15118.6
N2—C25—C21123.2 (4)C10—C9—C8120.6 (4)
N2—C25—C26117.7 (3)C10—C9—H9119.7
C21—C25—C26119.1 (4)C8—C9—H9119.7
C1—O1—Zn181.1 (2)C16—C17—C18120.5 (4)
C24—N2—C25119.0 (4)C16—C17—H17119.8
C24—N2—Zn1128.0 (3)C18—C17—H17119.8
C25—N2—Zn1112.1 (3)C23—C22—C21120.5 (5)
C19—C18—C17124.5 (5)C23—C22—H22119.7
C19—C18—C26119.1 (4)C21—C22—H22119.7
C17—C18—C26116.5 (4)C9—C8—O3117.8 (4)
N1—C26—C18122.7 (4)C9—C8—C13121.0 (4)
N1—C26—C25117.4 (4)O3—C8—C13121.1 (3)
C18—C26—C25120.0 (4)C17—C16—C15119.4 (5)
O1—C1—O2122.3 (3)C17—C16—H16120.3
O1—C1—C2119.9 (3)C15—C16—H16120.3
O2—C1—C2117.8 (3)C19—C20—C21121.4 (4)
O1—C1—Zn170.0 (2)C19—C20—H20119.3
O2—C1—Zn152.30 (17)C21—C20—H20119.3
C2—C1—Zn1169.3 (3)N2—C24—C23120.8 (5)
C9—C10—C11119.8 (4)N2—C24—H24119.6
C9—C10—H10120.1C23—C24—H24119.6
C11—C10—H10120.1C5—C6—C7120.3 (4)
C8—C13—C12117.1 (3)C5—C6—H6119.9
C8—C13—C14124.1 (3)C7—C6—H6119.9
C12—C13—C14118.8 (3)C22—C23—C24119.8 (5)
C12—C11—C10120.0 (4)C22—C23—H23120.1
C12—C11—H11120.0C24—C23—H23120.1
C10—C11—H11120.0C2—C7—C6119.9 (4)
C6—C5—C4120.0 (4)C2—C7—H7120.1
C6—C5—H5120.0C6—C7—H7120.1
C4—C5—H5120.0C20—C19—C18121.8 (5)
C22—C21—C25116.7 (5)C20—C19—H19119.1
C22—C21—C20124.7 (5)C18—C19—H19119.1
Symmetry codes: (i) x+1/2, −y+1/2, z+1/2; (ii) x−1/2, −y+1/2, z−1/2.
Table 1
Selected geometric parameters (Å) top
Zn1—O22.011 (2)Zn1—O4i2.143 (3)
Zn1—N12.114 (3)Zn1—O5i2.172 (3)
Zn1—N22.129 (3)Zn1—O12.395 (3)
Symmetry codes: (i) x+1/2, −y+1/2, z+1/2.
Acknowledgements top

The project was supported by the Excellent Young Scholars in Higher Universities of Heilongjiang Province, China (1155 G57), the Natural Science Foundation of Heilongjiang Province, China (B201016), the Doctoral Research Fund of Mudanjiang Teachers College, China (MSB: 200902) and the Research Fund of Mudanjiang Teachers College, China (KY: 200902).

references
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