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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807019836/ci2367sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807019836/ci2367Isup2.hkl
Contains datablock I

CCDC reference: 646660

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.037
  • wR factor = 0.096
  • Data-to-parameter ratio = 17.5

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X) Zn - O1 .. 11.78 su PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X) Zn - O2 .. 23.00 su
Alert level C PLAT060_ALERT_3_C Ratio Tmax/Tmin (Exp-to-Rep) (too) Large ....... 1.11 PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 1.90 PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size ....... 0.70 mm PLAT153_ALERT_1_C The su's on the Cell Axes are Equal (x 100000) . 300 Ang. PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O2
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 1.901 Tmax scaled 0.644 Tmin scaled 0.578 PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
0 ALERT level A = In general: serious problem 2 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

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).

Structure description 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).

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

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 m3
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 mm1
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
Graphite monochromatorθmax = 28.0°, θmin = 2.5°
2θ/ω scansh = 120
Absorption correction: ψ scan
(XEMP; Siemens, 1994)
k = 118
Tmin = 0.304, Tmax = 0.339l = 118
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 Å3
0 restraintsΔρmin = 0.36 e Å3
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 mm1
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 = 0.3393 standard reflections every 97 reflections
4275 measured reflections intensity decay: 4.3%
3429 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.096H-atom parameters constrained
S = 1.02Δρmax = 0.27 e Å3
3429 reflectionsΔρmin = 0.36 e Å3
196 parameters
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)
C30.02401 (14)0.26336 (16)0.19616 (17)0.0450 (5)
C40.10918 (16)0.2880 (2)0.21635 (19)0.0567 (6)
H40.13820.25700.26750.068*
C50.15084 (17)0.3575 (2)0.1616 (2)0.0647 (7)
H50.20820.37320.17520.078*
C60.10790 (17)0.4042 (2)0.0863 (2)0.0643 (7)
H60.13560.45250.04990.077*
C70.02320 (15)0.37853 (18)0.06538 (18)0.0519 (5)
H70.00530.40970.01400.062*
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, º) 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—C8144.24 (15)O1—C1—C2—C712.7 (3)
N1i—Zn—N1—C847.03 (13)C7—C2—C3—C41.8 (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—C8173.37 (15)C1—C2—C3—Cl5.9 (3)
O1—Zn—N1—C12122.03 (18)C2—C3—C4—C51.1 (3)
O1i—Zn—N1—C1238.62 (19)Cl—C3—C4—C5177.63 (19)
N1i—Zn—N1—C12135.8 (2)C3—C4—C5—C60.6 (4)
O2—Zn—N1—C12114.5 (2)C4—C5—C6—C71.5 (4)
O2i—Zn—N1—C1218.99 (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—C6176.6 (2)
N1—Zn—O1—C1179.75 (14)C12—N1—C8—C90.1 (3)
N1i—Zn—O1—C180.94 (15)Zn—N1—C8—C9177.22 (16)
O2—Zn—O1—C13.74 (13)N1—C8—C9—C100.9 (3)
O2i—Zn—O1—C186.97 (15)N1—C8—C9—N2179.92 (19)
C1i—Zn—O1—C177.97 (19)C13—N2—C9—C8153.2 (2)
O1—Zn—O2—C13.83 (13)C13—N2—C9—C1027.6 (4)
O1i—Zn—O2—C1165.62 (14)C8—C9—C10—C111.1 (3)
N1—Zn—O2—C112.6 (2)N2—C9—C10—C11179.7 (2)
N1i—Zn—O2—C198.47 (15)C9—C10—C11—C120.7 (4)
O2i—Zn—O2—C1108.26 (15)C8—N1—C12—C110.3 (3)
C1i—Zn—O2—C1135.80 (13)Zn—N1—C12—C11177.46 (18)
Zn—O2—C1—O16.1 (2)C10—C11—C12—N10.0 (4)
Zn—O2—C1—C2170.09 (19)C14—O4—C13—O31.7 (4)
Zn—O1—C1—O27.2 (2)C14—O4—C13—N2177.3 (2)
Zn—O1—C1—C2169.25 (16)C9—N2—C13—O33.4 (4)
O2—C1—C2—C313.6 (3)C9—N2—C13—O4175.6 (2)
O1—C1—C2—C3170.0 (2)
Symmetry code: (i) x+1/2, y+1/2, z.
Hydrogen-bond geometry (Å, º) 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 code: (ii) x, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula[Zn(C7H4ClO2)2(C7H8N2O2)2]
Mr680.78
Crystal system, space groupOrthorhombic, Pccn
Temperature (K)293
a, b, c (Å)15.444 (3), 13.650 (3), 13.627 (3)
V3)2872.7 (10)
Z4
Radiation typeMo Kα
µ (mm1)1.10
Crystal size (mm)0.70 × 0.50 × 0.40
Data collection
DiffractometerSiemens P4
Absorption correctionψ scan
(XEMP; Siemens, 1994)
Tmin, Tmax0.304, 0.339
No. of measured, independent and
observed [I > 2σ(I)] reflections
4275, 3429, 2566
Rint0.021
(sin θ/λ)max1)0.661
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.096, 1.02
No. of reflections3429
No. of parameters196
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.27, 0.36

Computer programs: XSCANS (Siemens, 1994), XSCANS, SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), enCIFer (Allen et al., 2004).

Hydrogen-bond geometry (Å, º) 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 code: (i) x, y+1/2, z+1/2.
 

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