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Acta Cryst. (2007). E63, m1520    [ doi:10.1107/S1600536807019836 ]

Bis(2-chlorobenzoato-[kappa]2O,O')bis[methyl N-(3-pyridyl)carbamato-[kappa]N]zinc(II)

J. Maroszová, L. Findoráková, K. Györyvá, J. Moncol and M. Melník

Abstract top

In the title compound, [Zn(C7H4ClO2)2(C7H8N2O2)2], the ZnII ion is coordinated by two N atoms from two methyl N-(3-pyridyl)carbamate ligands and four O atoms from two bidentate 2-chlorobenzoate anions in a pseudo-octahedral geometry. The Zn-O distances are in the range 2.0484 (16)-2.380 (2) Å, and the Zn-N distance is 2.1012 (18) Å. The molecules are linked into a chain along the c axis by N-H...O and C-H...Cl hydrogen bonds.

Comment top

Compound (I) is a mononuclear zinc(II) compound (Fig. 1). The ZnII atom exists in a pseudo-octahedral coordination environment, created by two pyridine N atoms from two methyl-3-pyridylcarbamate (mpc) ligands and four O atoms from two bidentate 2-chlorobenzoate anions. But a tetrahedral arrangement is found for the ZnII atoms in related structures, viz. [Zn(benzoato)2(mpc)2] (Zeleňák et al., 2004) and [Zn(cinnamato)2(mpc)] (Zeleňák et al., 2007). The mean Zn–N distances of 2.032 Å (in the former) and 2.021 Å (in the latter) are shorter than that in compound (I) (2.181 Å), as expected for a tetrahedral arrangement. The Zn—O distances are in the range 2.0484 (16)–2.380 (2) Å, and the Zn—N and Zn—Cl distances are 2.1012 (18) and 2.546 (2) Å, respectively.

In the crystal structure of (I), the molecules are linked by N2–H2···O2ii and C8–H8···Clii [symmetry code: (ii) x, 1/2 - y, 1/2 + z] hydrogen bonds (Table 1), forming a chain along the c axis (Fig. 2).

Related literature top

The ZnII atom adopts a tetrahedral geometry in related complexes with methyl N-(3-pyridyl)carbamate ligands (Zeleňák et al., 2004, 2007).

Experimental top

A mixture of ZnCO3 (0.4180 g, 3.33 mmol) and 2-chlorobenzoic acid (1.0438 g, 3.33 mmol) in ethanol (50 ml) was stirred at room temperature for 1 h and then filtered. An ethanol solution (50 ml) of methyl-3-pyridylcarbamate (1.0143 g, 3.33 mmol) was added to the filtrate and the mixture was stirred for 3 h. The resulting clear solution was allowed to stand in air at room temperature for two weeks, yielding colourless crystals of (I). The crystals were separated and dried at ambient temperature.

Refinement top

H atoms were placed in calculated positions [N–H = 0.86 Å and C–H = 0.93 (aromatic) or 0.96 Å (methyl)] and refined using a riding model, with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).

Computing details top

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: enCIFer (Allen et al., 2004).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Unlabelled atoms are related to labelled atoms by (-x + 1/2, -y + 1/2, z).
[Figure 2] Fig. 2. The crystal packing of (I), viewed along the a axis. [symmetry code: (ii) x, 1/2 - y, 1/2 + z.]
Bis(2-chlorobenzoato-κ2O,O')bis[methyl N-(3-pyridyl)carbamato-κN]zinc(II) top
Crystal data top
[Zn(C7H4ClO2)2(C7H8N2O2)2]F(000) = 1392
Mr = 680.78Dx = 1.574 Mg m−3
Orthorhombic, PccnMo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ab 2acCell parameters from 25 reflections
a = 15.444 (3) Åθ = 4.5–8.6°
b = 13.650 (3) ŵ = 1.10 mm−1
c = 13.627 (3) ÅT = 293 K
V = 2872.7 (10) Å3Prism, colourless
Z = 40.70 × 0.50 × 0.40 mm
Data collection top
Siemens P4
diffractometer		2566 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.021
graphiteθmax = 28.0°, θmin = 2.5°
2θ/ω scansh = −1→20
Absorption correction: ψ scan
(XEMP; Siemens, 1994)		k = −1→18
Tmin = 0.304, Tmax = 0.339l = −1→18
4275 measured reflections3 standard reflections every 97 reflections
3429 independent reflections intensity decay: 4.3%
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)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.096H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0406P)2 + 0.9964P]
where P = (Fo2 + 2Fc2)/3
3429 reflections(Δ/σ)max = 0.001
196 parametersΔρmax = 0.27 e Å−3
0 restraintsΔρmin = −0.36 e Å−3
Crystal data top
[Zn(C7H4ClO2)2(C7H8N2O2)2]V = 2872.7 (10) Å3
Mr = 680.78Z = 4
Orthorhombic, PccnMo Kα radiation
a = 15.444 (3) ŵ = 1.10 mm−1
b = 13.650 (3) ÅT = 293 K
c = 13.627 (3) Å0.70 × 0.50 × 0.40 mm
Data collection top
Siemens P4
diffractometer		2566 reflections with I > 2σ(I)
Absorption correction: ψ scan
(XEMP; Siemens, 1994)		Rint = 0.021
Tmin = 0.304, Tmax = 0.339θmax = 28.0°
4275 measured reflections3 standard reflections every 97 reflections
3429 independent reflections intensity decay: 4.3%
Refinement top
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.096Δρmax = 0.27 e Å−3
S = 1.02Δρmin = −0.36 e Å−3
3429 reflectionsAbsolute structure: ?
196 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
Zn0.25000.25000.00830 (3)0.04173 (11)
Cl0.02319 (4)0.17755 (6)−0.27367 (6)0.0697 (2)
N10.30551 (11)0.34776 (13)0.10944 (13)0.0420 (4)
N20.22484 (13)0.47062 (13)0.32673 (15)0.0503 (5)
H20.18610.42810.34230.060*
O10.14614 (11)0.33727 (13)−0.02481 (14)0.0577 (4)
O20.14705 (12)0.20595 (14)−0.11392 (15)0.0677 (5)
O30.27541 (12)0.62242 (13)0.36654 (14)0.0632 (5)
O40.15579 (14)0.55887 (13)0.43625 (14)0.0683 (5)
C10.11059 (14)0.28121 (17)−0.08633 (17)0.0458 (5)
C20.02036 (13)0.30729 (14)−0.11921 (16)0.0402 (4)
C3−0.02401 (14)0.26336 (16)−0.19616 (17)0.0450 (5)
C4−0.10918 (16)0.2880 (2)−0.21635 (19)0.0567 (6)
H4−0.13820.2570−0.26750.068*
C5−0.15084 (17)0.3575 (2)−0.1616 (2)0.0647 (7)
H5−0.20820.3732−0.17520.078*
C6−0.10790 (17)0.4042 (2)−0.0863 (2)0.0643 (7)
H6−0.13560.4525−0.04990.077*
C7−0.02320 (15)0.37853 (18)−0.06538 (18)0.0519 (5)
H70.00530.4097−0.01400.062*
C80.25616 (14)0.37803 (15)0.18363 (16)0.0423 (4)
H80.20050.35250.18910.051*
C90.28322 (14)0.44532 (15)0.25299 (15)0.0411 (4)
C100.36653 (15)0.48203 (17)0.24529 (17)0.0494 (5)
H100.38770.52660.29100.059*
C110.41724 (15)0.45099 (18)0.16834 (19)0.0539 (6)
H110.47320.47510.16120.065*
C120.38551 (14)0.38477 (18)0.10245 (17)0.0502 (5)
H120.42070.36470.05090.060*
C130.22424 (16)0.55699 (17)0.37586 (17)0.0492 (5)
C140.1445 (2)0.6486 (2)0.4903 (2)0.0798 (9)
H14A0.12800.70000.44610.120*
H14B0.19790.66560.52200.120*
H14C0.10010.63980.53880.120*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn0.04048 (17)0.04280 (18)0.0419 (2)0.00580 (14)0.0000.000
Cl0.0637 (4)0.0734 (4)0.0720 (4)−0.0131 (3)0.0083 (3)−0.0261 (4)
N10.0427 (8)0.0407 (9)0.0427 (10)0.0003 (7)−0.0003 (8)−0.0004 (7)
N20.0636 (11)0.0395 (9)0.0477 (11)−0.0067 (8)0.0129 (9)−0.0020 (8)
O10.0516 (9)0.0575 (10)0.0642 (11)0.0012 (8)−0.0142 (8)0.0015 (8)
O20.0678 (11)0.0697 (12)0.0656 (12)0.0302 (10)−0.0050 (9)−0.0042 (10)
O30.0788 (12)0.0477 (9)0.0632 (11)−0.0113 (9)0.0033 (9)−0.0093 (8)
O40.0933 (13)0.0544 (10)0.0572 (11)−0.0041 (10)0.0267 (10)−0.0112 (9)
C10.0470 (11)0.0482 (11)0.0422 (12)0.0033 (10)0.0020 (9)0.0115 (9)
C20.0443 (10)0.0386 (10)0.0378 (11)0.0021 (8)0.0008 (8)0.0102 (8)
C30.0458 (11)0.0465 (12)0.0428 (11)−0.0061 (9)0.0028 (9)0.0082 (9)
C40.0503 (12)0.0734 (16)0.0463 (13)−0.0089 (12)−0.0075 (11)0.0143 (12)
C50.0470 (12)0.0817 (19)0.0653 (17)0.0114 (13)−0.0039 (12)0.0221 (15)
C60.0609 (15)0.0689 (16)0.0633 (16)0.0260 (13)0.0045 (13)0.0061 (13)
C70.0551 (13)0.0530 (13)0.0477 (13)0.0085 (11)−0.0024 (10)0.0003 (10)
C80.0417 (10)0.0370 (9)0.0481 (11)−0.0023 (8)0.0017 (10)0.0004 (9)
C90.0497 (10)0.0329 (9)0.0406 (11)0.0005 (8)0.0009 (9)0.0072 (9)
C100.0540 (12)0.0459 (12)0.0484 (13)−0.0060 (10)−0.0070 (10)−0.0027 (10)
C110.0428 (11)0.0586 (14)0.0601 (15)−0.0090 (10)−0.0009 (10)−0.0018 (12)
C120.0437 (11)0.0585 (13)0.0484 (13)−0.0012 (10)0.0032 (10)0.0003 (11)
C130.0665 (13)0.0432 (11)0.0379 (11)0.0005 (10)0.0013 (10)0.0025 (9)
C140.104 (2)0.0697 (18)0.0658 (19)0.0088 (17)0.0153 (17)−0.0246 (15)
Geometric parameters (Å, °) top
Zn—O12.0484 (16)C2—C71.391 (3)
Zn—O1i2.0484 (16)C3—C41.385 (3)
Zn—N12.1012 (18)C4—C51.368 (4)
Zn—N1i2.1012 (18)C4—H40.93
Zn—O22.380 (2)C5—C61.378 (4)
Zn—O2i2.380 (2)C5—H50.93
Zn—C1i2.546 (2)C6—C71.384 (3)
Cl—C31.737 (2)C6—H60.93
N1—C81.332 (3)C7—H70.93
N1—C121.338 (3)C8—C91.383 (3)
N2—C131.356 (3)C8—H80.93
N2—C91.394 (3)C9—C101.385 (3)
N2—H20.86C10—C111.376 (3)
O1—C11.261 (3)C10—H100.93
O2—C11.230 (3)C11—C121.365 (3)
O3—C131.199 (3)C11—H110.93
O4—C131.340 (3)C12—H120.93
O4—C141.439 (3)C14—H14A0.96
C1—C21.506 (3)C14—H14B0.96
C2—C31.389 (3)C14—H14C0.96
O1—Zn—O1i154.55 (11)C2—C3—Cl122.89 (17)
O1—Zn—N195.43 (7)C5—C4—C3120.4 (2)
O1i—Zn—N1101.20 (7)C5—C4—H4119.8
O1—Zn—N1i101.20 (7)C3—C4—H4119.8
O1i—Zn—N1i95.43 (7)C4—C5—C6120.0 (2)
N1—Zn—N1i98.02 (10)C4—C5—H5120.0
O1—Zn—O257.97 (6)C6—C5—H5120.0
O1i—Zn—O2102.83 (7)C5—C6—C7119.4 (3)
N1—Zn—O2153.14 (6)C5—C6—H6120.3
N1i—Zn—O291.49 (7)C7—C6—H6120.3
O1—Zn—O2i102.83 (7)C6—C7—C2121.7 (2)
O1i—Zn—O2i57.97 (6)C6—C7—H7119.2
N1—Zn—O2i91.49 (7)C2—C7—H7119.2
N1i—Zn—O2i153.14 (6)N1—C8—C9123.51 (19)
O2—Zn—O2i91.17 (10)N1—C8—H8118.2
O1—Zn—C1i130.40 (8)C9—C8—H8118.2
O1i—Zn—C1i29.39 (7)C8—C9—C10118.0 (2)
N1—Zn—C1i95.36 (7)C8—C9—N2117.5 (2)
N1i—Zn—C1i124.83 (7)C10—C9—N2124.5 (2)
O2—Zn—C1i99.69 (7)C11—C10—C9118.4 (2)
O2i—Zn—C1i28.68 (7)C11—C10—H10120.8
C8—N1—C12117.73 (19)C9—C10—H10120.8
C8—N1—Zn117.48 (14)C12—C11—C10120.1 (2)
C12—N1—Zn124.73 (15)C12—C11—H11120.0
C13—N2—C9125.2 (2)C10—C11—H11120.0
C13—N2—H2117.4N1—C12—C11122.3 (2)
C9—N2—H2117.4N1—C12—H12118.8
C1—O1—Zn97.73 (14)C11—C12—H12118.8
C1—O2—Zn83.16 (15)O3—C13—O4124.8 (2)
C13—O4—C14115.2 (2)O3—C13—N2126.2 (2)
O2—C1—O1120.7 (2)O4—C13—N2109.0 (2)
O2—C1—C2122.0 (2)O4—C14—H14A109.5
O1—C1—C2117.2 (2)O4—C14—H14B109.5
C3—C2—C7117.46 (19)H14A—C14—H14B109.5
C3—C2—C1125.4 (2)O4—C14—H14C109.5
C7—C2—C1117.1 (2)H14A—C14—H14C109.5
C4—C3—C2120.9 (2)H14B—C14—H14C109.5
C4—C3—Cl116.18 (19)
O1—Zn—N1—C855.12 (16)O2—C1—C2—C7163.7 (2)
O1i—Zn—N1—C8−144.24 (15)O1—C1—C2—C7−12.7 (3)
N1i—Zn—N1—C8−47.03 (13)C7—C2—C3—C4−1.8 (3)
O2—Zn—N1—C862.6 (2)C1—C2—C3—C4175.5 (2)
O2i—Zn—N1—C8158.16 (15)C7—C2—C3—Cl176.85 (17)
C1i—Zn—N1—C8−173.37 (15)C1—C2—C3—Cl−5.9 (3)
O1—Zn—N1—C12−122.03 (18)C2—C3—C4—C51.1 (3)
O1i—Zn—N1—C1238.62 (19)Cl—C3—C4—C5−177.63 (19)
N1i—Zn—N1—C12135.8 (2)C3—C4—C5—C60.6 (4)
O2—Zn—N1—C12−114.5 (2)C4—C5—C6—C7−1.5 (4)
O2i—Zn—N1—C12−18.99 (18)C5—C6—C7—C20.7 (4)
C1i—Zn—N1—C129.49 (19)C3—C2—C7—C60.9 (3)
O1i—Zn—O1—C148.91 (13)C1—C2—C7—C6−176.6 (2)
N1—Zn—O1—C1179.75 (14)C12—N1—C8—C90.1 (3)
N1i—Zn—O1—C1−80.94 (15)Zn—N1—C8—C9−177.22 (16)
O2—Zn—O1—C13.74 (13)N1—C8—C9—C10−0.9 (3)
O2i—Zn—O1—C186.97 (15)N1—C8—C9—N2179.92 (19)
C1i—Zn—O1—C177.97 (19)C13—N2—C9—C8−153.2 (2)
O1—Zn—O2—C1−3.83 (13)C13—N2—C9—C1027.6 (4)
O1i—Zn—O2—C1−165.62 (14)C8—C9—C10—C111.1 (3)
N1—Zn—O2—C1−12.6 (2)N2—C9—C10—C11−179.7 (2)
N1i—Zn—O2—C198.47 (15)C9—C10—C11—C12−0.7 (4)
O2i—Zn—O2—C1−108.26 (15)C8—N1—C12—C110.3 (3)
C1i—Zn—O2—C1−135.80 (13)Zn—N1—C12—C11177.46 (18)
Zn—O2—C1—O16.1 (2)C10—C11—C12—N10.0 (4)
Zn—O2—C1—C2−170.09 (19)C14—O4—C13—O31.7 (4)
Zn—O1—C1—O2−7.2 (2)C14—O4—C13—N2−177.3 (2)
Zn—O1—C1—C2169.25 (16)C9—N2—C13—O3−3.4 (4)
O2—C1—C2—C3−13.6 (3)C9—N2—C13—O4175.6 (2)
O1—C1—C2—C3170.0 (2)
Symmetry codes: (i) −x+1/2, −y+1/2, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O2ii0.862.022.812 (3)153
C8—H8···Clii0.932.823.723 (2)165
Symmetry codes: (ii) x, −y+1/2, z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O2i0.862.022.812 (3)153
C8—H8···Cli0.932.823.723 (2)165
Symmetry codes: (i) x, −y+1/2, z+1/2.
Acknowledgements top

The authors thank the Slovak Ministry of Education (VEGA Project Nos. 1/2474/05 and 1/2452/05) and the Research and Development Support Agency (APVT-20–005504) for financial support.

references
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