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Acta Crystallogr Sect E Struct Rep Online. 2008 August 1; 64(Pt 8): m993.
Published online 2008 July 5. doi:  10.1107/S1600536808019880
PMCID: PMC2961919

catena-Poly[[bis­(3-benzoyl­pyridine-κN)zinc(II)]-di-μ-dicyanamido-κ4 N 1:N 5]

Abstract

The title compound, [Zn(C2N3)2(C12H9NO)2]n, is a polymeric zinc(II) complex with the metal ion located on an inversion centre. The ZnII ion is six-coordinated by two N atoms of two 3-benzoyl­pyridine ligands and four N atoms from four dicyanamide ligands, forming a slightly distorted octa­hedral configuration. In the crystal structure, neighboring Zn atoms are linked together by double dicyanamide bridges to form a polymeric zinc(II) complex.

Related literature

For related literature, see: Armentano et al. (2006 [triangle]); Claramunt et al. (2000 [triangle]); Manson et al. (1998 [triangle]); Miller (2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0m993-scheme1.jpg

Experimental

Crystal data

  • [Zn(C2N3)2(C12H9NO)2]
  • M r = 563.89
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0m993-efi1.jpg
  • a = 6.463 (4) Å
  • b = 7.490 (4) Å
  • c = 26.300 (15) Å
  • β = 98.399 (16)°
  • V = 1259.5 (13) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 1.02 mm−1
  • T = 293 (2) K
  • 0.07 × 0.04 × 0.03 mm

Data collection

  • Rigaku Scxmini 1K CCD area-detector diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.867, T max = 1.000 (expected range = 0.841–0.970)
  • 12079 measured reflections
  • 2880 independent reflections
  • 2342 reflections with I > 2σ(I)
  • R int = 0.045

Refinement

  • R[F 2 > 2σ(F 2)] = 0.050
  • wR(F 2) = 0.129
  • S = 1.09
  • 2880 reflections
  • 178 parameters
  • H-atom parameters constrained
  • Δρmax = 0.60 e Å−3
  • Δρmin = −0.56 e Å−3

Data collection: CrystalClear (Rigaku, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear ; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Selected geometric parameters (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808019880/bq2086sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808019880/bq2086Isup2.hkl

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

supplementary crystallographic information

Comment

The dicyanamide ligand has frequently been used to bridge polynuclear transition metal complexes in the study of multidimensional molecule-based magnetic materials and other areas. Many such compounds have been reported (Manson et al., 1998; Claramunt et al., 2000; Armentano et al., 2006; Miller, 2006;). Here, we report the structure of the title ZnII compound, (I). The structure of (I) is illustrated in Fig. 1, and bond distances and angles are given in Table 1. The ZnII ion, which lies on the inversion centre, is in an octahedral geometry and is six-coordinated by six N atoms, from four dicyanamide ligands and two 3-benzoylpyridine ligands in a trans arrangement. The resulting coordination geometry is very close to that expected for an ideal octahedral complex. In the crystal structure, the ZnII ions are bridged to form a one-dimensional chain by dicyanamide ligands, through single end-to-end coordination, the dicyanamide ligand acts as a bidentate bridging ligand by coordinating to adjacent ZnII centres through its two terminal nitrile N atoms. No significant contacts are observed between adjacent chains in the crystal structure.

Experimental

All chemicals used (reagent grade) were commercially available. 3-benzoylpyridine (18.3 mg, 0.1 mmol) was added slowly with stirring in aqueous solution (5 ml) of Zn(CH3COO)2.2H2O (21.9 mg, 0.1 mmol) and then sodium dicyanamide (17.8 mg, 0.2 mmol) in aqueous solution (5 ml) was added slowly. The resulting colorless solution was continuously stirred for about 30 min at room temperature and then filtered. The filtrate was slowly evaporated at room temperature over several days, and colorless needles crystals suitable for X-ray analysis were obtained.

Refinement

Positional parameters of all H atoms were calculated geometrically.

Figures

Fig. 1.
The molecular structure of the title compound with the atom-numbering scheme and all dydrogen atoms. Displacement ellipsoids are drawn at the 30% probability level.
Fig. 2.
One-dimensional structure in the title compound. Displacement ellipsoids are drawn at the 30% probability level and all dydrogen atoms.

Crystal data

[Zn(C2N3)2(C12H9NO)2]F000 = 576
Mr = 563.89Dx = 1.487 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2637 reflections
a = 6.463 (4) Åθ = 3.1–27.5º
b = 7.490 (4) ŵ = 1.02 mm1
c = 26.300 (15) ÅT = 293 (2) K
β = 98.399 (16)ºBlock, colorless
V = 1259.5 (13) Å30.07 × 0.04 × 0.03 mm
Z = 2

Data collection

Rigaku Scxmini 1K CCD area-detector diffractometer2880 independent reflections
Radiation source: fine-focus sealed tube2342 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.045
Detector resolution: 8.192 pixels mm-1θmax = 27.5º
T = 293(2) Kθmin = 3.1º
thin–slice ω scansh = −8→8
Absorption correction: Multi-scan(CrystalClear; Rigaku, 2005)k = −9→9
Tmin = 0.867, Tmax = 1.000l = −34→33
12079 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)] = 0.050H-atom parameters constrained
wR(F2) = 0.129  w = 1/[σ2(Fo2) + (0.0563P)2 + 0.6329P] where P = (Fo2 + 2Fc2)/3
S = 1.09(Δ/σ)max < 0.001
2880 reflectionsΔρmax = 0.60 e Å3
178 parametersΔρmin = −0.56 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
Zn10.5000−0.50000.00000.03523 (16)
O10.1648 (4)−0.5269 (5)−0.20379 (11)0.1080 (15)
N20.7192 (4)−0.2827 (3)0.01736 (10)0.0467 (6)
N30.7294 (4)−0.6966 (3)0.03187 (9)0.0441 (6)
N40.5973 (4)−0.5346 (3)−0.07500 (9)0.0374 (5)
N50.8571 (7)−0.9980 (3)0.05024 (17)0.0911 (15)
C10.7821 (4)−0.8411 (4)0.03808 (11)0.0405 (6)
C20.7750 (4)−0.1441 (4)0.03062 (11)0.0411 (6)
C40.7925 (4)−0.5898 (4)−0.07850 (11)0.0442 (7)
H4A0.8899−0.5924−0.04870.053*
C50.8557 (5)−0.6427 (4)−0.12406 (11)0.0488 (7)
H5C0.9914−0.6831−0.12470.059*
C60.7130 (5)−0.6347 (4)−0.16892 (11)0.0465 (7)
H6A0.7504−0.6728−0.20000.056*
C70.5141 (5)−0.5690 (4)−0.16669 (11)0.0435 (6)
C80.4633 (4)−0.5223 (3)−0.11864 (11)0.0395 (6)
H8A0.3290−0.4805−0.11690.047*
C90.3436 (5)−0.5503 (5)−0.21175 (12)0.0568 (8)
C100.3845 (5)−0.5665 (4)−0.26610 (11)0.0491 (7)
C110.5699 (6)−0.5147 (4)−0.28267 (13)0.0553 (8)
H11A0.6808−0.4735−0.25910.066*
C120.2197 (6)−0.6285 (5)−0.30199 (13)0.0635 (9)
H12A0.0948−0.6634−0.29130.076*
C130.2419 (8)−0.6382 (5)−0.35361 (14)0.0783 (13)
H13A0.1321−0.6804−0.37740.094*
C140.4252 (8)−0.5857 (6)−0.36965 (15)0.0811 (14)
H14A0.4386−0.5915−0.40430.097*
C150.5896 (8)−0.5245 (5)−0.33469 (14)0.0707 (12)
H15A0.7137−0.4898−0.34580.085*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Zn10.0407 (3)0.0283 (2)0.0361 (3)0.00125 (17)0.00358 (18)−0.00050 (17)
O10.0444 (14)0.232 (5)0.0468 (15)0.0126 (19)0.0035 (12)−0.0020 (19)
N20.0456 (13)0.0353 (13)0.0569 (15)−0.0031 (10)0.0002 (11)−0.0015 (11)
N30.0486 (14)0.0348 (13)0.0479 (14)0.0061 (10)0.0033 (11)0.0023 (10)
N40.0400 (12)0.0358 (12)0.0364 (11)0.0012 (9)0.0055 (9)0.0000 (9)
N50.097 (3)0.0326 (15)0.121 (3)0.0078 (15)−0.060 (2)−0.0090 (15)
C10.0391 (14)0.0354 (15)0.0438 (15)0.0003 (11)−0.0044 (12)−0.0041 (11)
C20.0414 (15)0.0348 (15)0.0444 (15)0.0057 (12)−0.0024 (12)0.0006 (12)
C40.0394 (14)0.0520 (18)0.0407 (15)0.0017 (13)0.0047 (12)0.0034 (13)
C50.0421 (15)0.0588 (19)0.0459 (16)0.0102 (14)0.0078 (13)0.0037 (14)
C60.0481 (16)0.0505 (17)0.0432 (15)0.0007 (13)0.0142 (13)−0.0029 (13)
C70.0442 (15)0.0478 (16)0.0387 (15)−0.0025 (13)0.0065 (12)−0.0015 (12)
C80.0390 (14)0.0392 (15)0.0402 (14)0.0013 (11)0.0052 (11)0.0001 (11)
C90.0495 (18)0.079 (2)0.0413 (17)0.0025 (17)0.0050 (14)0.0018 (16)
C100.0579 (19)0.0500 (17)0.0378 (15)0.0099 (15)0.0017 (13)−0.0014 (13)
C110.071 (2)0.0519 (19)0.0445 (17)0.0105 (16)0.0125 (16)0.0005 (14)
C120.068 (2)0.066 (2)0.0512 (19)0.0146 (18)−0.0106 (16)−0.0011 (16)
C130.105 (3)0.072 (3)0.048 (2)0.034 (2)−0.021 (2)−0.0112 (18)
C140.119 (4)0.081 (3)0.043 (2)0.044 (3)0.011 (2)0.0005 (19)
C150.097 (3)0.070 (3)0.049 (2)0.028 (2)0.025 (2)0.0075 (17)

Geometric parameters (Å, °)

Zn1—N22.162 (3)C6—C71.385 (4)
Zn1—N2i2.162 (3)C6—H6A0.9300
Zn1—N3i2.169 (2)C7—C81.396 (4)
Zn1—N32.169 (2)C7—C91.502 (4)
Zn1—N42.172 (3)C8—H8A0.9300
Zn1—N4i2.172 (3)C9—C101.496 (4)
O1—C91.217 (4)C10—C111.389 (5)
N2—C21.137 (4)C10—C121.395 (5)
N3—C11.139 (4)C11—C151.395 (5)
N4—C81.337 (4)C11—H11A0.9300
N4—C41.343 (4)C12—C131.388 (5)
N5—C2ii1.290 (4)C12—H12A0.9300
N5—C11.293 (4)C13—C141.372 (6)
C2—N5iii1.290 (4)C13—H13A0.9300
C4—C51.379 (4)C14—C151.378 (6)
C4—H4A0.9300C14—H14A0.9300
C5—C61.389 (4)C15—H15A0.9300
C5—H5C0.9300
N2—Zn1—N2i180.00 (9)C7—C6—H6A120.5
N2—Zn1—N3i87.73 (11)C5—C6—H6A120.5
N2i—Zn1—N3i92.27 (11)C6—C7—C8118.0 (3)
N2—Zn1—N392.27 (11)C6—C7—C9125.3 (3)
N2i—Zn1—N387.73 (11)C8—C7—C9116.6 (3)
N3i—Zn1—N3180.0N4—C8—C7123.5 (3)
N2—Zn1—N490.79 (9)N4—C8—H8A118.3
N2i—Zn1—N489.21 (9)C7—C8—H8A118.3
N3i—Zn1—N490.13 (9)O1—C9—C10118.7 (3)
N3—Zn1—N489.87 (9)O1—C9—C7118.9 (3)
N2—Zn1—N4i89.21 (9)C10—C9—C7122.3 (3)
N2i—Zn1—N4i90.79 (9)C11—C10—C12119.3 (3)
N3i—Zn1—N4i89.87 (9)C11—C10—C9123.9 (3)
N3—Zn1—N4i90.13 (9)C12—C10—C9116.7 (3)
N4—Zn1—N4i180.00 (4)C10—C11—C15120.0 (4)
C2—N2—Zn1157.0 (2)C10—C11—H11A120.0
C1—N3—Zn1150.9 (2)C15—C11—H11A120.0
C8—N4—C4117.4 (2)C13—C12—C10120.1 (4)
C8—N4—Zn1122.30 (19)C13—C12—H12A120.0
C4—N4—Zn1119.90 (18)C10—C12—H12A120.0
C2ii—N5—C1123.7 (3)C14—C13—C12120.2 (4)
N3—C1—N5172.8 (3)C14—C13—H13A119.9
N2—C2—N5iii172.0 (3)C12—C13—H13A119.9
N4—C4—C5123.2 (3)C13—C14—C15120.4 (4)
N4—C4—H4A118.4C13—C14—H14A119.8
C5—C4—H4A118.4C15—C14—H14A119.8
C4—C5—C6118.8 (3)C14—C15—C11120.0 (4)
C4—C5—H5C120.6C14—C15—H15A120.0
C6—C5—H5C120.6C11—C15—H15A120.0
C7—C6—C5119.0 (3)
N3i—Zn1—N2—C240.5 (6)C4—N4—C8—C72.1 (4)
N3—Zn1—N2—C2−139.5 (6)Zn1—N4—C8—C7−170.4 (2)
N4—Zn1—N2—C2130.6 (6)C6—C7—C8—N41.3 (4)
N4i—Zn1—N2—C2−49.4 (6)C9—C7—C8—N4178.9 (3)
N2—Zn1—N3—C1−168.8 (5)C6—C7—C9—O1164.8 (4)
N2i—Zn1—N3—C111.2 (5)C8—C7—C9—O1−12.6 (5)
N4—Zn1—N3—C1−78.0 (5)C6—C7—C9—C10−12.8 (5)
N4i—Zn1—N3—C1102.0 (5)C8—C7—C9—C10169.8 (3)
N2i—Zn1—N4—C858.2 (2)O1—C9—C10—C11150.0 (4)
N3i—Zn1—N4—C8−34.0 (2)C7—C9—C10—C11−32.4 (5)
N3—Zn1—N4—C8146.0 (2)O1—C9—C10—C12−26.4 (5)
N2—Zn1—N4—C465.9 (2)C7—C9—C10—C12151.2 (3)
N2i—Zn1—N4—C4−114.1 (2)C12—C10—C11—C150.2 (5)
N3i—Zn1—N4—C4153.6 (2)C9—C10—C11—C15−176.1 (3)
N3—Zn1—N4—C4−26.4 (2)C11—C10—C12—C130.1 (5)
C8—N4—C4—C5−3.7 (4)C9—C10—C12—C13176.6 (3)
Zn1—N4—C4—C5169.0 (2)C10—C12—C13—C14−0.5 (6)
N4—C4—C5—C61.7 (5)C12—C13—C14—C150.6 (6)
C4—C5—C6—C71.8 (5)C13—C14—C15—C11−0.4 (6)
C5—C6—C7—C8−3.2 (5)C10—C11—C15—C140.0 (5)
C5—C6—C7—C9179.4 (3)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BQ2086).

References

  • Armentano, D., De Munno, G., Guerra, F., Julve, M. & Lloret, F. (2006). Inorg. Chem.45, 4626–4636. [PubMed]
  • Claramunt, A., Escuer, A., Mautner, F. A., Sanz, N. & Vicente, R. (2000). J. Chem. Soc. Dalton Trans. pp. 2627–2630.
  • Manson, J. L., Lee, D. W., Rheingold, A. L. & Miller, J. S. (1998). Inorg. Chem.37, 5966–5967. [PubMed]
  • Miller, J. S. (2006). Pramana, 67, 1–16.
  • Rigaku (2005). CrystalClear Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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