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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): m90.
Published online 2007 December 6. doi:  10.1107/S1600536807063155
PMCID: PMC2914964

catena-Poly[[[bis­(methyl­amine)zinc(II)]-μ-4,4′-oxydibenzoato] N,N-dimethyl­acetamide solvate]

Abstract

In the title zinc(II) coordination polymer, {[Zn(C14H8O5)(CH5N)2]·C4H9NO}n, each Zn(II) cation is tetra­hedrally coordinated by two carboxyl­ato O atoms of two oba anions (H2oba is 4,4′-oxydibenzoic acid), and two N atoms from two methyl­amine mol­ecules. Each oba anion bridges two Zn(II) cations through the two carboxyl­ate groups in a monodentate fashion, forming one-dimensional polymeric chains. These chains are linked via N–H(...)O hydrogen bonds, forming a two-dimensional supra­molecular network.

Related literature

For related literature, see: Kondo et al. (2004 [triangle]); Luo et al. (2003 [triangle]); Sun et al. (2005 [triangle]); Yaghi et al. (1998 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-00m90-scheme1.jpg

Experimental

Crystal data

  • [Zn(C14H8O5)(CH5N)2]·C4H9NO
  • M r = 470.82
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-00m90-efi2.jpg
  • a = 27.617 (6) Å
  • b = 8.9276 (18) Å
  • c = 21.212 (4) Å
  • β = 122.46 (3)°
  • V = 4413 (2) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 1.15 mm−1
  • T = 293 (2) K
  • 0.35 × 0.34 × 0.15 mm

Data collection

  • Rigaku R-AXIS RAPID diffractometer
  • Absorption correction: multi-scan (Higashi, 1995 [triangle]) T min = 0.690, T max = 0.850
  • 20180 measured reflections
  • 4942 independent reflections
  • 2843 reflections with I > 2σ(I)
  • R int = 0.056

Refinement

  • R[F 2 > 2σ(F 2)] = 0.053
  • wR(F 2) = 0.149
  • S = 1.04
  • 4942 reflections
  • 276 parameters
  • H-atom parameters constrained
  • Δρmax = 0.43 e Å−3
  • Δρmin = −0.47 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 [triangle]); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: SHELXTL (Bruker, 2000 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807063155/fj2083sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807063155/fj2083Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was supported by the National Science Foundation of China (50678045), the Science Foundation of Heilongjiang Province (E200519), the China Postdoctoral Science Foundation and Heilongjiang Postdoctoral Financial Assistance.

supplementary crystallographic information

Comment

Recently, great interest has been focused on the design and synthesis of coordination polymers because of their intriguing network topologies and promising applications (Yaghi et al., 1998). It is well known that the selection of appropriate organic ligands is crucial to the design and synthesis of the supramolecular architectures. In preparing target metal complexes, carboxylate and organic amine ligands have been frequently employed (Luo et al., 2003). More and more interest has focused on long flexible ligands recently, and how to avoid, or make use of, their interpenetration to construct novel coordination polymers is an interesting challenge. 4,4'-oxybis(benzoic acid) (H2oba) ligand, in which two benzene moieties are linked together by a µ2-O bridge, is the typical example of flexible ligand and may offer more possibilities in geometry configuration and coordination modes towards the metal ions. As far as we know, several coordination polymers based on 4,4'-oxybis(benzoic acid) have been obtained (Kondo et al., 2004; Sun et al., 2005). We present here the solvothermal synthesis and crystal structure of title coordination polymer, [Zn(C14H8O5)(CNH5)2.(C4NOH9)]n, (I).

The asymmetric unit of (I) consists of one crystallogaphically independent Zn(II) cation, one oba ligand, two methylamine and one dimethylacetamide molecule. Fig.1 shows the molecular structure of (I) with the atom-labelling scheme. The Zn(II) cation has a slightly distorted tetrahedral coordination geometry and formed by two carboxy oxygen atoms (O1 and O5A) from two oba ligands and two nitrogen atoms (N1 and N2) from two methylamine molecule, with Zn—O distances of 1.949 (3)–1.952 (3) Å and Zn—N distances in the range of 1.996 (4)–2.047 (4) Å. These values are in good agreement with those found in other extended structures (Kondo et al., 2004). The O—Zn—O and N—Zn—N bond angles are 106.28 (11)° and 106.15 (19)°, respectively. The N—Zn—O angles are in the range from 98.65 (12) to 115.75 (14)°. In (I), two carboxylate groups of each oba exhibit bis-monodentate coordination modes, namely oba anion acts as µ2-bridging ligand to connect with two Zn(II) centers and each Zn(II) center connects with two oba anions to form the chain arrangement with Zn···Zn distance of 14.512 (4) Å (Fig. 2). It is found that there are hydrogen bonding interactions between adjacent chains. The N—H···O hydrogen bonds involve the uncoordinated carboxylic oxygen atoms of oba and N—H groups of methylamine molecules from adjacent chains (Table 2). In addition, dimethylacetamide molecules located in the crystal lattice with N—H···O hydrogen bonding interactions involving the oxygen atoms of dimethylacetamide molecules and N—H groups of methylamine molecules (Table 2). Finally, the chains are linked together by hydrogen bonds to form two-dimensional supramolecular network (Fig. 2).

Experimental

(I) was solvothermally prepared from a mixture of Zn(NO3)2.6H2O (0.044 g, 0.2 mmol), 4,4'-oxybis(benzoic acid) (0.051 g, 0.2 mmol), methylamine (0.05 ml) and dimethylacetamide (10 ml). The slurry was stirred for 30 min and heated at 120 °C for 72 h in a Teflon-lined stainless steel autoclave (25 ml) under autogenous pressure. After cooling to room temperature, the block-shaped crystals were washed with water and dried in air.

Refinement

The H atoms were placed in geometrical calculated positions, with C—H distances of 0.93–0.96 Å and N—H distances of 0.90 Å. A common displacement parameter was refined for all H atoms.

Figures

Fig. 1.
A perspective view of molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are represented as spheres of arbitrary radii. [symmetry code: (A) x + 1/2,y - 1/2,z.].
Fig. 2.
A packing diagram of (I). The dashed lines indicate the hydrogen bonds.

Crystal data

[Zn(C14H8O5)(CH5N)2]·C4H9NOF000 = 1968
Mr = 470.82Dx = 1.417 Mg m3
Monoclinic, C2/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 11100 reflections
a = 27.617 (6) Åθ = 3.0–27.5º
b = 8.9276 (18) ŵ = 1.15 mm1
c = 21.212 (4) ÅT = 293 (2) K
β = 122.46 (3)ºBlock, colorless
V = 4413 (2) Å30.35 × 0.34 × 0.15 mm
Z = 8

Data collection

Rigaku RAXIS-RAPID diffractometer4942 independent reflections
Radiation source: fine-focus sealed tube2843 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.056
Detector resolution: 10.0 pixels mm-1θmax = 27.5º
T = 293(2) Kθmin = 3.0º
ω scanh = −34→35
Absorption correction: multi-scan(Higashi, 1995)k = −11→11
Tmin = 0.690, Tmax = 0.850l = −27→27
20180 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.053H-atom parameters constrained
wR(F2) = 0.149  w = 1/[σ2(Fo2) + (0.065P)2 + 3.5742P] where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.016
4942 reflectionsΔρmax = 0.43 e Å3
276 parametersΔρmin = −0.47 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

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 (Å2)

xyzUiso*/Ueq
Zn11.006041 (17)0.74836 (5)0.42522 (2)0.05793 (17)
O10.92334 (11)0.7166 (3)0.37118 (16)0.0679 (7)
O20.92687 (11)0.9063 (3)0.44038 (16)0.0727 (8)
O30.66245 (11)0.7259 (3)0.26587 (18)0.0794 (9)
O40.53662 (14)0.9180 (4)0.43119 (19)0.0892 (10)
O50.53394 (11)1.1281 (3)0.37427 (16)0.0699 (7)
O60.6660 (2)0.4181 (4)0.4624 (3)0.1244 (15)
N11.04661 (18)0.7142 (7)0.5352 (2)0.1189 (18)
H1A1.04130.79670.55520.143*
H1B1.02840.63870.54220.143*
N21.03183 (15)0.9546 (4)0.4121 (2)0.0781 (11)
H2A1.03741.01440.44970.094*
H2B1.06570.94470.41590.094*
N30.7274 (2)0.3980 (5)0.4262 (3)0.1002 (14)
C10.90007 (16)0.8060 (4)0.3942 (2)0.0561 (9)
C20.83754 (14)0.7855 (4)0.3618 (2)0.0489 (8)
C30.80568 (15)0.6814 (4)0.3053 (2)0.0563 (9)
H30.82410.62280.28810.068*
C40.74798 (15)0.6634 (4)0.2745 (2)0.0588 (9)
H40.72750.59350.23670.071*
C50.72034 (15)0.7500 (4)0.3001 (2)0.0550 (9)
C60.75117 (15)0.8530 (4)0.3565 (2)0.0581 (9)
H60.73280.91030.37410.070*
C70.80910 (15)0.8709 (4)0.3866 (2)0.0538 (9)
H70.82940.94140.42410.065*
C80.63392 (16)0.7940 (5)0.2969 (2)0.0612 (10)
C90.63948 (19)0.7328 (4)0.3591 (3)0.0736 (12)
H90.66310.65010.38170.088*
C100.60983 (17)0.7938 (4)0.3885 (2)0.0660 (11)
H100.61260.75050.43020.079*
C110.57618 (14)0.9188 (4)0.3560 (2)0.0532 (9)
C120.57183 (15)0.9781 (4)0.2931 (2)0.0578 (9)
H120.54931.06270.27100.069*
C130.60007 (15)0.9151 (4)0.2624 (2)0.0615 (10)
H130.59610.95430.21920.074*
C140.54638 (16)0.9909 (5)0.3901 (2)0.0618 (10)
C151.1043 (2)0.6820 (8)0.5769 (3)0.1136 (18)
H15A1.10970.57590.57650.170*
H15B1.12030.71510.62740.170*
H15C1.12310.73250.55590.170*
C160.9915 (2)1.0269 (6)0.3416 (3)0.1081 (17)
H16A0.98650.96620.30120.162*
H16B1.00611.12340.33990.162*
H16C0.95531.03880.33720.162*
C170.7729 (4)0.4772 (9)0.4917 (4)0.176 (3)
H17A0.77560.57800.47810.264*
H17B0.80880.42680.51020.264*
H17C0.76420.47900.52980.264*
C180.7438 (3)0.3428 (8)0.3747 (4)0.135 (2)
H18A0.76270.24770.39200.202*
H18B0.76940.41320.37310.202*
H18C0.71010.33150.32560.202*
C190.6771 (3)0.3747 (5)0.4157 (4)0.0996 (17)
C200.6342 (3)0.3043 (9)0.3452 (5)0.155 (3)
H20A0.63800.19730.35020.233*
H20B0.63980.33630.30640.233*
H20C0.59650.33290.33260.233*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Zn10.0438 (3)0.0778 (3)0.0601 (3)0.00039 (19)0.0331 (2)−0.0105 (2)
O10.0482 (14)0.0878 (19)0.0793 (19)−0.0015 (12)0.0420 (14)−0.0218 (14)
O20.0553 (16)0.092 (2)0.077 (2)−0.0088 (14)0.0396 (15)−0.0233 (16)
O30.0444 (15)0.107 (2)0.092 (2)−0.0008 (13)0.0398 (15)−0.0396 (17)
O40.094 (2)0.116 (2)0.095 (2)−0.0078 (19)0.076 (2)−0.0023 (19)
O50.0635 (17)0.086 (2)0.078 (2)0.0096 (14)0.0498 (15)−0.0068 (15)
O60.172 (4)0.111 (3)0.147 (4)0.017 (3)0.123 (4)0.000 (3)
N10.062 (3)0.237 (6)0.069 (3)0.002 (3)0.043 (2)0.012 (3)
N20.069 (2)0.094 (3)0.084 (3)−0.0183 (19)0.049 (2)−0.030 (2)
N30.104 (4)0.096 (3)0.117 (4)0.025 (3)0.070 (3)0.018 (3)
C10.048 (2)0.069 (2)0.060 (2)0.0024 (18)0.0350 (19)−0.0031 (19)
C20.0444 (19)0.061 (2)0.049 (2)0.0049 (14)0.0307 (17)0.0014 (15)
C30.047 (2)0.069 (2)0.060 (2)0.0050 (17)0.0333 (19)−0.0123 (19)
C40.047 (2)0.076 (2)0.058 (2)0.0005 (17)0.0308 (18)−0.0182 (19)
C50.0406 (18)0.066 (2)0.064 (2)0.0024 (16)0.0320 (17)−0.0103 (19)
C60.052 (2)0.063 (2)0.074 (3)0.0047 (17)0.044 (2)−0.0121 (19)
C70.049 (2)0.060 (2)0.059 (2)0.0008 (15)0.0335 (18)−0.0095 (17)
C80.042 (2)0.078 (2)0.071 (3)−0.0061 (17)0.0349 (19)−0.020 (2)
C90.063 (3)0.064 (2)0.099 (4)0.0134 (19)0.046 (3)0.000 (2)
C100.060 (2)0.071 (2)0.076 (3)−0.0045 (19)0.042 (2)0.005 (2)
C110.0364 (18)0.067 (2)0.063 (2)−0.0029 (15)0.0306 (17)−0.0053 (18)
C120.0427 (19)0.070 (2)0.064 (2)0.0070 (16)0.0313 (18)0.0011 (19)
C130.045 (2)0.085 (3)0.064 (2)0.0033 (18)0.0356 (19)−0.005 (2)
C140.044 (2)0.088 (3)0.064 (3)−0.0047 (19)0.0354 (19)−0.009 (2)
C150.080 (4)0.155 (5)0.082 (4)0.006 (4)0.028 (3)0.022 (4)
C160.105 (4)0.109 (4)0.104 (4)−0.023 (3)0.052 (4)0.005 (3)
C170.157 (7)0.146 (6)0.115 (6)−0.024 (6)0.000 (5)−0.023 (5)
C180.159 (6)0.149 (6)0.153 (6)0.025 (5)0.121 (6)0.012 (5)
C190.126 (5)0.068 (3)0.117 (5)0.005 (3)0.073 (4)0.005 (3)
C200.125 (6)0.154 (6)0.180 (8)−0.054 (5)0.077 (6)−0.062 (6)

Geometric parameters (Å, °)

Zn1—O11.949 (3)C6—H60.9300
Zn1—O5i1.952 (3)C7—H70.9300
Zn1—N11.996 (4)C8—C91.358 (6)
Zn1—N22.047 (4)C8—C131.358 (5)
O1—C11.275 (4)C9—C101.380 (6)
O2—C11.238 (4)C9—H90.9300
O3—C51.372 (4)C10—C111.377 (5)
O3—C81.407 (4)C10—H100.9300
O4—C141.228 (5)C11—C121.379 (5)
O5—C141.267 (5)C11—C141.501 (5)
O5—Zn1ii1.952 (3)C12—C131.378 (5)
O6—C191.246 (6)C12—H120.9300
N1—C151.374 (7)C13—H130.9300
N1—H1A0.9000C15—H15A0.9600
N1—H1B0.9000C15—H15B0.9600
N2—C161.450 (6)C15—H15C0.9600
N2—H2A0.9000C16—H16A0.9600
N2—H2B0.9000C16—H16B0.9600
N3—C191.302 (7)C16—H16C0.9600
N3—C171.462 (8)C17—H17A0.9600
N3—C181.472 (7)C17—H17B0.9600
C1—C21.488 (5)C17—H17C0.9600
C2—C71.386 (4)C18—H18A0.9600
C2—C31.393 (5)C18—H18B0.9600
C3—C41.369 (5)C18—H18C0.9600
C3—H30.9300C19—C201.460 (9)
C4—C51.386 (5)C20—H20A0.9600
C4—H40.9300C20—H20B0.9600
C5—C61.380 (5)C20—H20C0.9600
C6—C71.377 (5)
O1—Zn1—O5i106.28 (11)C10—C9—H9120.2
O1—Zn1—N1114.24 (15)C11—C10—C9119.9 (4)
O5i—Zn1—N1114.99 (17)C11—C10—H10120.1
O1—Zn1—N2115.75 (14)C9—C10—H10120.1
O5i—Zn1—N298.65 (12)C10—C11—C12118.7 (3)
N1—Zn1—N2106.15 (19)C10—C11—C14120.2 (4)
C1—O1—Zn1110.9 (2)C12—C11—C14121.0 (3)
C5—O3—C8118.1 (3)C13—C12—C11121.6 (4)
C14—O5—Zn1ii121.1 (3)C13—C12—H12119.2
C15—N1—Zn1120.9 (3)C11—C12—H12119.2
C15—N1—H1A107.1C8—C13—C12118.0 (4)
Zn1—N1—H1A107.1C8—C13—H13121.0
C15—N1—H1B107.1C12—C13—H13121.0
Zn1—N1—H1B107.1O4—C14—O5124.7 (4)
H1A—N1—H1B106.8O4—C14—C11120.0 (4)
C16—N2—Zn1114.2 (3)O5—C14—C11115.3 (4)
C16—N2—H2A108.7N1—C15—H15A109.5
Zn1—N2—H2A108.7N1—C15—H15B109.5
C16—N2—H2B108.7H15A—C15—H15B109.5
Zn1—N2—H2B108.7N1—C15—H15C109.5
H2A—N2—H2B107.6H15A—C15—H15C109.5
C19—N3—C17122.3 (6)H15B—C15—H15C109.5
C19—N3—C18123.1 (6)N2—C16—H16A109.5
C17—N3—C18114.7 (6)N2—C16—H16B109.5
O2—C1—O1123.1 (3)H16A—C16—H16B109.5
O2—C1—C2120.5 (3)N2—C16—H16C109.5
O1—C1—C2116.4 (3)H16A—C16—H16C109.5
C7—C2—C3117.9 (3)H16B—C16—H16C109.5
C7—C2—C1120.7 (3)N3—C17—H17A109.5
C3—C2—C1121.3 (3)N3—C17—H17B109.5
C4—C3—C2121.7 (3)H17A—C17—H17B109.5
C4—C3—H3119.2N3—C17—H17C109.5
C2—C3—H3119.2H17A—C17—H17C109.5
C3—C4—C5119.5 (3)H17B—C17—H17C109.5
C3—C4—H4120.3N3—C18—H18A109.5
C5—C4—H4120.3N3—C18—H18B109.5
O3—C5—C6124.4 (3)H18A—C18—H18B109.5
O3—C5—C4115.8 (3)N3—C18—H18C109.5
C6—C5—C4119.8 (3)H18A—C18—H18C109.5
C7—C6—C5120.2 (3)H18B—C18—H18C109.5
C7—C6—H6119.9O6—C19—N3120.7 (6)
C5—C6—H6119.9O6—C19—C20122.5 (7)
C6—C7—C2120.9 (3)N3—C19—C20116.7 (6)
C6—C7—H7119.5C19—C20—H20A109.5
C2—C7—H7119.5C19—C20—H20B109.5
C9—C8—C13122.1 (4)H20A—C20—H20B109.5
C9—C8—O3118.7 (4)C19—C20—H20C109.5
C13—C8—O3119.2 (4)H20A—C20—H20C109.5
C8—C9—C10119.7 (4)H20B—C20—H20C109.5
C8—C9—H9120.2

Symmetry codes: (i) x+1/2, y−1/2, z; (ii) x−1/2, y+1/2, z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1B···O4iii0.902.212.991 (5)145
N2—H2A···O2iv0.902.112.966 (4)159
N2—H2B···O6v0.902.403.276 (6)164

Symmetry codes: (iii) −x+3/2, −y+3/2, −z+1; (iv) −x+2, −y+2, −z+1; (v) x+1/2, y+1/2, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FJ2083).

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