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Acta Crystallogr Sect E Struct Rep Online. 2010 October 1; 66(Pt 10): m1236.
Published online 2010 September 11. doi:  10.1107/S1600536810035531
PMCID: PMC2983147

Dichlorido(2,9-dimethyl-1,10-phenanthroline-κ2 N,N′)cobalt(II)

Abstract

In the title compound, [CoCl2(C14H12N2)], the CoII atom is four-coordinated in a distorted tetra­hedral geometry by two N atoms from a 2,9-dimethyl-1,10-phenanthroline ligand and two Cl atoms. The Co atom and the phenanthroline unit are located on a mirror plane. The methyl H atoms are disordered about the mirror plane and areeach half-occupied. In the crystal structure, π–π inter­actions between the pyridine and benzene rings and between the pyridine rings [centroid–centroid distances = 3.8821 (9) and 3.9502 (10) Å, respectively] stabilize the structure.

Related literature

For related structures, see: Alizadeh et al. (2009 [triangle]); Buttery et al. (2006 [triangle]); Ding et al. (2006 [triangle]); Fanizzi et al. (1991 [triangle]); Lemoine et al. (2003 [triangle]); Preston & Kennard (1969 [triangle]); Robinson & Sinn (1975 [triangle]).

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Object name is e-66-m1236-scheme1.jpg

Experimental

Crystal data

  • [CoCl2(C14H12N2)]
  • M r = 338.09
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-m1236-efi1.jpg
  • a = 11.2434 (12) Å
  • b = 7.441 (1) Å
  • c = 17.690 (3) Å
  • V = 1480.0 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 1.51 mm−1
  • T = 298 K
  • 0.50 × 0.22 × 0.20 mm

Data collection

  • Stoe IPDS-2 diffractometer
  • Absorption correction: numerical (X-SHAPE and X-RED; Stoe & Cie, 2002 [triangle]) T min = 0.681, T max = 0.749
  • 9742 measured reflections
  • 2124 independent reflections
  • 1871 reflections with I > 2σ(I)
  • R int = 0.067

Refinement

  • R[F 2 > 2σ(F 2)] = 0.044
  • wR(F 2) = 0.139
  • S = 1.20
  • 2124 reflections
  • 114 parameters
  • H-atom parameters constrained
  • Δρmax = 0.51 e Å−3
  • Δρmin = −0.55 e Å−3

Data collection: X-AREA (Stoe & Cie, 2002 [triangle]); cell refinement: X-AREA; data reduction: X-RED (Stoe & Cie, 2002 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Table 1
Selected bond lengths (Å)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810035531/hy2350sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810035531/hy2350Isup2.hkl

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

Acknowledgments

We are grateful to the University of Sistan and Baluchestan, and Shahid Beheshti University for financial support.

supplementary crystallographic information

Comment

2,9-Dimethyl-1,10-phenanthroline (dmphen) is a good bidentate ligand, and numerous complexes with dmphen have been prepared, such as those of mercury (Alizadeh et al., 2009), zinc (Preston & Kennard, 1969), copper (Lemoine et al., 2003), nickel (Ding et al., 2006), gold (Robinson & Sinn, 1975), platinum (Fanizzi et al., 1991) and lithium (Buttery et al., 2006). Here, we report the synthesis and structure of the title compound.

In the title compound (Fig. 1), the CoII atom is four-coordinated in a distorted tetrahedral configuration by two N atoms from one dmphen ligand and two Cl atoms (Table 1). In the crystal structure, π–π interactions (Fig. 2) between the pyridyl and benzene rings, Cg3···Cg4i and Cg3···Cg3ii [symmetry codes: (i) -x, 1-y, 2-z; (ii) -x, -1/2+y, 2-z; where Cg3 and Cg4 are the centroids of the N2, C8–C11, C13 ring and C5–C8, C13–C14 ring], with centroid–centroid distances of 3.8821 (9) and 3.9502 (10) Å, stabilize the structure.

Experimental

For the preparation of the title compound, a solution of dmphen (0.42 g, 2.00 mmol) in methanol (20 ml) was added to a solution of CoCl2.6H2O (0.48 g, 2.00 mmol) in methanol (20 ml) at room temperature. Crystals suitable for X-ray diffraction analysis were obtained by methanol diffusion into a blue solution of the title compound in DMSO after one week (yield: 0.50 g, 73.9%; m.p. > 573 K).

Refinement

H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 (aromatic) and 0.96 (methyl) Å and with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (i) x, 3/2-y, z.]
Fig. 2.
Crystal packing diagram for the title compound.

Crystal data

[CoCl2(C14H12N2)]F(000) = 684
Mr = 338.09Dx = 1.517 Mg m3
Orthorhombic, PnmaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2nCell parameters from 1670 reflections
a = 11.2434 (12) Åθ = 2.2–29.3°
b = 7.441 (1) ŵ = 1.51 mm1
c = 17.690 (3) ÅT = 298 K
V = 1480.0 (4) Å3Block, blue
Z = 40.50 × 0.22 × 0.20 mm

Data collection

Stoe IPDS-2 diffractometer2124 independent reflections
Radiation source: fine-focus sealed tube1871 reflections with I > 2σ(I)
graphiteRint = 0.067
rotation method scansθmax = 29.3°, θmin = 2.2°
Absorption correction: numerical (X-SHAPE and X-RED; Stoe & Cie, 2002)h = −14→15
Tmin = 0.681, Tmax = 0.749k = −10→10
9742 measured reflectionsl = −15→24

Refinement

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) = 0.139H-atom parameters constrained
S = 1.20w = 1/[σ2(Fo2) + (0.0692P)2 + 0.4334P] where P = (Fo2 + 2Fc2)/3
2124 reflections(Δ/σ)max = 0.001
114 parametersΔρmax = 0.51 e Å3
0 restraintsΔρmin = −0.55 e Å3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/UeqOcc. (<1)
C10.5096 (3)0.75000.9952 (3)0.0677 (12)
H1A0.49530.68800.94840.102*0.50
H1B0.57190.69041.02240.102*0.50
H1C0.53290.87160.98490.102*0.50
C20.3980 (3)0.75001.0417 (2)0.0502 (8)
C30.4022 (4)0.75001.1208 (3)0.0670 (12)
H30.47540.75001.14540.080*
C40.3002 (4)0.75001.1619 (2)0.0661 (11)
H40.30380.75001.21450.079*
C50.1893 (3)0.75001.1254 (2)0.0470 (7)
C60.0776 (4)0.75001.1635 (2)0.0599 (10)
H60.07630.75001.21610.072*
C7−0.0259 (4)0.75001.1254 (3)0.0602 (10)
H7−0.09740.75001.15180.072*
C8−0.0270 (3)0.75001.0444 (2)0.0486 (8)
C9−0.1318 (3)0.75001.0008 (3)0.0648 (11)
H9−0.20570.75001.02440.078*
C10−0.1246 (4)0.75000.9245 (3)0.0687 (12)
H10−0.19390.75000.89590.082*
C11−0.0128 (4)0.75000.8877 (2)0.0556 (9)
C12−0.0018 (5)0.75000.8039 (3)0.0775 (14)
H12A−0.07180.80260.78210.116*0.50
H12B0.00670.62870.78610.116*0.50
H12C0.06680.81870.78940.116*0.50
C130.0806 (3)0.75001.00504 (19)0.0393 (6)
C140.1911 (3)0.75001.04563 (19)0.0387 (6)
N10.2938 (2)0.75001.00521 (16)0.0392 (5)
N20.0873 (2)0.75000.92773 (17)0.0423 (6)
Cl10.31373 (7)0.49607 (9)0.83732 (5)0.0645 (2)
Co10.26015 (4)0.75000.89154 (3)0.04234 (18)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0351 (16)0.082 (3)0.086 (3)0.0000.0071 (19)0.000
C20.0353 (14)0.058 (2)0.058 (2)0.000−0.0052 (14)0.000
C30.050 (2)0.093 (3)0.058 (2)0.000−0.0196 (18)0.000
C40.062 (2)0.093 (3)0.043 (2)0.000−0.0126 (18)0.000
C50.0494 (18)0.0531 (18)0.0387 (16)0.0000.0011 (13)0.000
C60.064 (2)0.073 (2)0.0425 (19)0.0000.0116 (17)0.000
C70.0507 (19)0.070 (2)0.060 (2)0.0000.0188 (17)0.000
C80.0363 (15)0.0488 (17)0.061 (2)0.0000.0026 (14)0.000
C90.0357 (16)0.070 (3)0.088 (3)0.000−0.0046 (18)0.000
C100.0415 (18)0.075 (3)0.089 (3)0.000−0.024 (2)0.000
C110.056 (2)0.0505 (19)0.061 (2)0.000−0.0229 (17)0.000
C120.096 (4)0.087 (3)0.049 (2)0.000−0.033 (2)0.000
C130.0353 (13)0.0386 (13)0.0441 (16)0.000−0.0016 (12)0.000
C140.0353 (13)0.0421 (14)0.0388 (14)0.000−0.0013 (11)0.000
N10.0331 (11)0.0438 (13)0.0409 (14)0.000−0.0001 (10)0.000
N20.0413 (13)0.0436 (13)0.0420 (14)0.000−0.0063 (11)0.000
Cl10.0738 (5)0.0488 (4)0.0707 (5)0.0020 (3)0.0176 (4)−0.0121 (3)
Co10.0470 (3)0.0423 (3)0.0378 (3)0.0000.00572 (17)0.000

Geometric parameters (Å, °)

C1—C21.500 (5)C8—C91.408 (5)
C1—H1A0.9600C9—C101.352 (8)
C1—H1B0.9600C9—H90.9300
C1—H1C0.9600C10—C111.416 (7)
C2—N11.337 (4)C10—H100.9300
C2—C31.401 (6)C11—N21.330 (4)
C3—C41.358 (7)C11—C121.487 (6)
C3—H30.9300C12—H12A0.9600
C4—C51.405 (6)C12—H12B0.9600
C4—H40.9300C12—H12C0.9600
C5—C141.411 (5)C13—N21.370 (4)
C5—C61.426 (5)C13—C141.434 (4)
C6—C71.345 (6)C14—N11.359 (4)
C6—H60.9300N1—Co12.046 (3)
C7—C81.433 (6)N2—Co12.046 (3)
C7—H70.9300Cl1—Co12.2030 (9)
C8—C131.396 (5)Co1—Cl1i2.2030 (9)
C2—C1—H1A109.5C9—C10—C11120.9 (4)
C2—C1—H1B109.5C9—C10—H10119.6
H1A—C1—H1B109.5C11—C10—H10119.6
C2—C1—H1C109.5N2—C11—C10120.4 (4)
H1A—C1—H1C109.5N2—C11—C12117.4 (4)
H1B—C1—H1C109.5C10—C11—C12122.2 (4)
N1—C2—C3120.8 (4)C11—C12—H12A109.5
N1—C2—C1117.9 (4)C11—C12—H12B109.5
C3—C2—C1121.4 (4)H12A—C12—H12B109.5
C4—C3—C2120.4 (4)C11—C12—H12C109.5
C4—C3—H3119.8H12A—C12—H12C109.5
C2—C3—H3119.8H12B—C12—H12C109.5
C3—C4—C5120.2 (4)N2—C13—C8123.0 (3)
C3—C4—H4119.9N2—C13—C14116.9 (3)
C5—C4—H4119.9C8—C13—C14120.1 (3)
C4—C5—C14116.6 (3)N1—C14—C5122.6 (3)
C4—C5—C6124.3 (4)N1—C14—C13118.2 (3)
C14—C5—C6119.1 (3)C5—C14—C13119.2 (3)
C7—C6—C5121.6 (4)C2—N1—C14119.4 (3)
C7—C6—H6119.2C2—N1—Co1129.5 (2)
C5—C6—H6119.2C14—N1—Co1111.1 (2)
C6—C7—C8120.6 (3)C11—N2—C13119.1 (3)
C6—C7—H7119.7C11—N2—Co1129.6 (3)
C8—C7—H7119.7C13—N2—Co1111.3 (2)
C13—C8—C9116.9 (4)N1—Co1—N282.44 (11)
C13—C8—C7119.4 (3)N1—Co1—Cl1112.17 (4)
C9—C8—C7123.7 (4)N2—Co1—Cl1113.31 (4)
C10—C9—C8119.7 (4)N1—Co1—Cl1i112.17 (4)
C10—C9—H9120.1N2—Co1—Cl1i113.34 (4)
C8—C9—H9120.1Cl1—Co1—Cl1i118.12 (5)
N1—C2—C3—C40.000 (3)C1—C2—N1—C14180.000 (1)
C1—C2—C3—C4180.000 (2)C3—C2—N1—Co1180.000 (1)
C2—C3—C4—C50.000 (3)C1—C2—N1—Co10.000 (2)
C3—C4—C5—C140.000 (2)C5—C14—N1—C20.000 (2)
C3—C4—C5—C6180.000 (2)C13—C14—N1—C2180.000 (1)
C4—C5—C6—C7180.000 (2)C5—C14—N1—Co1180.000 (1)
C14—C5—C6—C70.000 (3)C13—C14—N1—Co10.000 (1)
C5—C6—C7—C80.000 (3)C10—C11—N2—C130.000 (2)
C6—C7—C8—C130.000 (2)C12—C11—N2—C13180.000 (2)
C6—C7—C8—C9180.000 (2)C10—C11—N2—Co1180.000 (1)
C13—C8—C9—C100.000 (2)C12—C11—N2—Co10.000 (1)
C7—C8—C9—C10180.000 (2)C8—C13—N2—C110.000 (2)
C8—C9—C10—C110.000 (2)C14—C13—N2—C11180.000 (1)
C9—C10—C11—N20.000 (2)C8—C13—N2—Co1180.000 (1)
C9—C10—C11—C12180.000 (2)C14—C13—N2—Co10.000 (1)
C9—C8—C13—N20.000 (2)C2—N1—Co1—N2180.000 (1)
C7—C8—C13—N2180.000 (2)C14—N1—Co1—N20.000 (1)
C9—C8—C13—C14180.000 (1)C2—N1—Co1—Cl167.86 (4)
C7—C8—C13—C140.000 (2)C14—N1—Co1—Cl1−112.14 (4)
C4—C5—C14—N10.000 (2)C2—N1—Co1—Cl1i−67.82 (4)
C6—C5—C14—N1180.000 (2)C14—N1—Co1—Cl1i112.18 (4)
C4—C5—C14—C13180.000 (2)C11—N2—Co1—N1180.000 (1)
C6—C5—C14—C130.000 (2)C13—N2—Co1—N10.000 (1)
N2—C13—C14—N10.000 (2)C11—N2—Co1—Cl1−69.07 (5)
C8—C13—C14—N1180.000 (1)C13—N2—Co1—Cl1110.93 (5)
N2—C13—C14—C5180.000 (2)C11—N2—Co1—Cl1i69.07 (5)
C8—C13—C14—C50.000 (2)C13—N2—Co1—Cl1i−110.93 (5)
C3—C2—N1—C140.000 (2)

Symmetry codes: (i) x, −y+3/2, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HY2350).

References

  • Alizadeh, R., Heidari, A., Ahmadi, R. & Amani, V. (2009). Acta Cryst. E65, m483–m484. [PMC free article] [PubMed]
  • Buttery, J. H. N., Effendy, Mutrofin, S., Plackett, N. C., Skelton, B. W., Whitaker, C. R. & White, A. H. (2006). Z. Anorg. Allg. Chem.632, 1809–1828.
  • Ding, C.-F., Miao, Y.-F., Tian, B.-Q., Li, X.-M. & Zhang, S.-S. (2006). Acta Cryst. E62, m1062–m1063.
  • Fanizzi, F. P., Intini, F. P., Maresca, L., Natile, G., Lanfranchi, M. & Tiripicchio, A. (1991). J. Chem. Soc. Dalton Trans. pp. 1007–1015.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Lemoine, P., Viossat, B. & Daran, J.-C. (2003). Acta Cryst. E59, m17–m19.
  • Preston, H. S. & Kennard, C. H. L. (1969). J. Chem. Soc. A, pp. 1956–1961.
  • Robinson, W. T. & Sinn, E. (1975). J. Chem. Soc. Dalton Trans. pp. 726–731.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Stoe & Cie (2002). X-AREA, X-RED and X-SHAPE Stoe & Cie, Darmstadt, Germany.

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