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Acta Crystallogr Sect E Struct Rep Online. 2009 October 1; 65(Pt 10): m1156.
Published online 2009 September 5. doi:  10.1107/S1600536809034187
PMCID: PMC2970365

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

Abstract

In the title compound, [CuCl2(C14H12N2)], the complex molecule has m symmetry, with the mirror plane oriented parallel to the planar molecule and the ligated CuII atom. The metal centre has a distorted tetra­hedral coordination formed by two N atoms from one 2,9-dimethyl-1,10-phenanthroline ligand and two Cl atoms. There is inter­molecular π–π stacking between adjacent 2,9-dimethyl-1,10-phenanthroline ligands, with a centroid–centroid distance of 3.733 (2)Å.

Related literature

For backgroud to π-π stacking in metal complexes of phenanthroline and its derivatives, benzimidazole and quinoline, see: Wall et al. (1999 [triangle]); Wu et al. (2003 [triangle]); Pan & Xu (2004 [triangle]); Li et al. (2005 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-m1156-scheme1.jpg

Experimental

Crystal data

  • [CuCl2(C14H12N2)]
  • M r = 342.70
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-m1156-efi1.jpg
  • a = 11.239 (2) Å
  • b = 7.4651 (18) Å
  • c = 17.663 (5) Å
  • V = 1481.9 (6) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 1.82 mm−1
  • T = 273 K
  • 0.30 × 0.28 × 0.21 mm

Data collection

  • Bruker APEXII area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2000 [triangle]) T min = 0.611, T max = 0.701
  • 10738 measured reflections
  • 1951 independent reflections
  • 1601 reflections with I > 2σ(I)
  • R int = 0.023

Refinement

  • R[F 2 > 2σ(F 2)] = 0.026
  • wR(F 2) = 0.083
  • S = 1.00
  • 1951 reflections
  • 114 parameters
  • H-atom parameters constrained
  • Δρmax = 0.41 e Å−3
  • Δρmin = −0.29 e Å−3

Data collection: APEX2 (Bruker, 2000 [triangle]); cell refinement: SAINT (Bruker, 2000 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global. DOI: 10.1107/S1600536809034187/at2860sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809034187/at2860Isup2.hkl

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

Acknowledgments

We thank the Youth Program of Jingdezhen Comprehesive College for financial support of this work.

supplementary crystallographic information

Comment

In recent years, simple metal complexes of phenanthroline and its derivatives with π-π stacking have attracted great interest because they can be used to study the hydrolysis of biologically important phosphate diesters with poor leaving groups (Wall et al., 1999). A series of metal complexes incorporating different aromatic ligands such as phenanthroline(phen), benzimidazole and quinoline have been prepared and their crystal structures provide useful information about π-π stacking (Wu et al., 2003; Pan & Xu, 2004; Li et al., 2005). We report herein the crystal structure of the title compound, (I).

In the molecule of the title compound, (I), (Fig. 1), the bond lengths and angles (Table 1) are within normal ranges (Allen et al., 1987). The two N atoms of one phen ligand and two Cl atoms are coordinated to CuII atom, in a distorted tetrahedron arrangement. The Cu—N bonds [average 2.0665 Å] are somewhat shorter than the Cu—Cl distances [average 2.1958 Å].

In the crystal structure, there is intermolecular π-π stacking between adjacent phen, with a centroid-centroid distance of 3.733 Å (symmetry code: –x, y+1/2, -z). These π-π stacking interactions lead to a supramolecular network structure (Fig. 2).

Experimental

Crystals of the title compound were synthesized using hydrothermal method in a 23 ml Teflon-lined Parr bomb, which was then sealed. Copper chloride dihydrate (170.5 mg, 1 mmol), 2,9-Dimethyl-1,10-phenanthroline (416.5 mg, 2 mmol) and distilled water (10 g) were placed into the bomb and sealed. The bomb was then heated under autogenous pressure up to 433 K over the course of 7 d and allowed to cool at room temperature for 24 h. Upon opening the bomb, a clear colorless solution was decanted from small blue crystals. These crystals were washed with distilled water followed by ethanol, and allowed to air-dry at room temperature.

Refinement

H atoms were positioned geometrically, with C—H = 0.93 - 0.96 Å, and constrained to ride on their parent atoms, with Uiso(H) = 1.2 or 1.5Ueq(C).

Figures

Fig. 1.
View of the molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
Fig. 2.
A packing diagram of (I).

Crystal data

[CuCl2(C14H12N2)]F(000) = 692
Mr = 342.70Dx = 1.536 Mg m3
Orthorhombic, PnmaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2nCell parameters from 5426 reflections
a = 11.239 (2) Åθ = 2.3–28.0°
b = 7.4651 (18) ŵ = 1.82 mm1
c = 17.663 (5) ÅT = 273 K
V = 1481.9 (6) Å3Plane, blue
Z = 40.30 × 0.28 × 0.21 mm

Data collection

Bruker APEXII area-detector diffractometer1951 independent reflections
Radiation source: fine-focus sealed tube1601 reflections with I > 2σ(I)
graphiteRint = 0.023
[var phi] and ω scansθmax = 28.3°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2000)h = −14→14
Tmin = 0.611, Tmax = 0.701k = −9→9
10738 measured reflectionsl = −23→23

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)] = 0.026Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.083H-atom parameters constrained
S = 1.00w = 1/[σ2(Fo2) + (0.0553P)2 + 0.1694P] where P = (Fo2 + 2Fc2)/3
1951 reflections(Δ/σ)max = 0.001
114 parametersΔρmax = 0.41 e Å3
0 restraintsΔρmin = −0.29 e Å3

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*/UeqOcc. (<1)
Cu10.76127 (2)0.75000.610028 (14)0.04178 (12)
N10.79467 (16)0.75000.49476 (10)0.0418 (4)
N20.58758 (17)0.75000.57229 (11)0.0445 (4)
C11.0098 (2)0.75000.50503 (18)0.0684 (8)
H1A1.03160.87110.51700.103*0.50
H1B1.07280.69460.47670.103*0.50
H1C0.99670.68430.55100.103*0.50
C130.6920 (2)0.75000.45450 (12)0.0406 (5)
C110.4872 (3)0.75000.61234 (14)0.0558 (6)
C20.8982 (2)0.75000.45874 (15)0.0517 (6)
C120.58155 (19)0.75000.49535 (12)0.0403 (5)
C140.4987 (3)0.75000.69623 (17)0.0803 (10)
H14A0.56970.81300.71050.120*0.50
H14B0.50300.62880.71420.120*0.50
H14C0.43070.80820.71820.120*0.50
C100.3763 (2)0.75000.5751 (2)0.0711 (8)
H100.30670.75000.60350.085*
C80.4741 (2)0.75000.45551 (15)0.0500 (6)
C70.4757 (3)0.75000.37518 (16)0.0624 (7)
H70.40410.75000.34870.075*
C50.6901 (2)0.75000.37527 (13)0.0502 (6)
C60.5787 (3)0.75000.33689 (15)0.0610 (7)
H60.57740.75000.28420.073*
C90.3695 (2)0.75000.49900 (19)0.0664 (8)
H90.29570.75000.47530.080*
C30.9025 (3)0.75000.37937 (16)0.0676 (8)
H30.97560.75000.35470.081*
C40.8005 (3)0.75000.33845 (16)0.0687 (8)
H40.80380.75000.28580.082*
Cl10.81305 (5)1.00503 (6)0.66249 (3)0.06566 (17)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cu10.04754 (18)0.0423 (2)0.03548 (17)0.000−0.00528 (11)0.000
N10.0374 (9)0.0471 (11)0.0408 (10)0.0000.0006 (8)0.000
N20.0450 (10)0.0441 (11)0.0446 (10)0.0000.0081 (8)0.000
C10.0403 (13)0.082 (2)0.083 (2)0.000−0.0043 (13)0.000
C130.0403 (11)0.0429 (13)0.0387 (10)0.0000.0002 (9)0.000
C110.0560 (14)0.0532 (16)0.0581 (15)0.0000.0192 (12)0.000
C20.0404 (11)0.0570 (16)0.0576 (14)0.0000.0053 (10)0.000
C120.0393 (11)0.0395 (12)0.0421 (11)0.0000.0014 (9)0.000
C140.094 (2)0.090 (2)0.0565 (16)0.0000.0325 (17)0.000
C100.0436 (14)0.078 (2)0.092 (2)0.0000.0226 (15)0.000
C80.0412 (12)0.0492 (14)0.0596 (14)0.000−0.0044 (10)0.000
C70.0556 (15)0.0730 (19)0.0586 (15)0.000−0.0195 (12)0.000
C50.0559 (14)0.0558 (16)0.0388 (11)0.0000.0009 (10)0.000
C60.0660 (17)0.0736 (19)0.0434 (13)0.000−0.0118 (12)0.000
C90.0372 (12)0.078 (2)0.084 (2)0.0000.0030 (12)0.000
C30.0508 (15)0.096 (2)0.0560 (16)0.0000.0176 (12)0.000
C40.0656 (17)0.095 (3)0.0449 (14)0.0000.0135 (13)0.000
Cl10.0766 (3)0.0502 (3)0.0702 (3)−0.0019 (2)−0.0167 (3)−0.0113 (2)

Geometric parameters (Å, °)

Cu1—Cl12.1958 (6)C12—C81.398 (3)
Cu1—Cl1i2.1958 (6)C14—H14A0.9600
Cu1—N12.070 (2)C14—H14B0.9600
Cu1—N22.063 (2)C14—H14C0.9600
N1—C21.326 (3)C10—C91.346 (5)
N1—C131.355 (3)C10—H100.9300
N2—C111.331 (3)C8—C91.404 (4)
N2—C121.361 (3)C8—C71.419 (4)
C1—C21.498 (4)C7—C61.341 (4)
C1—H1A0.9600C7—H70.9300
C1—H1B0.9600C5—C41.401 (4)
C1—H1C0.9600C5—C61.423 (4)
C13—C51.400 (3)C6—H60.9300
C13—C121.436 (3)C9—H90.9300
C11—C101.409 (4)C3—C41.355 (4)
C11—C141.487 (4)C3—H30.9300
C2—C31.403 (3)C4—H40.9300
Cl1—Cu1—Cl1i120.23 (3)C11—C14—H14A109.5
N1—Cu1—Cl1111.53 (3)C11—C14—H14B109.5
N1—Cu1—Cl1i111.53 (3)H14A—C14—H14B109.5
N2—Cu1—N181.60 (7)C11—C14—H14C109.5
N2—Cu1—Cl1112.78 (2)H14A—C14—H14C109.5
N2—Cu1—Cl1i112.78 (2)H14B—C14—H14C109.5
C2—N1—C13119.7 (2)C9—C10—C11121.1 (3)
C2—N1—Cu1129.12 (17)C9—C10—H10119.4
C13—N1—Cu1111.21 (15)C11—C10—H10119.4
C11—N2—C12119.2 (2)C12—C8—C9116.6 (2)
C11—N2—Cu1129.05 (18)C12—C8—C7119.5 (2)
C12—N2—Cu1111.71 (14)C9—C8—C7123.9 (2)
C2—C1—H1A109.5C6—C7—C8121.0 (2)
C2—C1—H1B109.5C6—C7—H7119.5
H1A—C1—H1B109.5C8—C7—H7119.5
C2—C1—H1C109.5C13—C5—C4116.7 (2)
H1A—C1—H1C109.5C13—C5—C6119.4 (2)
H1B—C1—H1C109.5C4—C5—C6123.9 (2)
N1—C13—C5122.6 (2)C7—C6—C5121.3 (2)
N1—C13—C12118.2 (2)C7—C6—H6119.4
C5—C13—C12119.2 (2)C5—C6—H6119.4
N2—C11—C10120.1 (2)C10—C9—C8119.9 (3)
N2—C11—C14117.1 (3)C10—C9—H9120.0
C10—C11—C14122.8 (3)C8—C9—H9120.0
N1—C2—C3120.6 (2)C4—C3—C2120.3 (2)
N1—C2—C1118.2 (2)C4—C3—H3119.9
C3—C2—C1121.1 (2)C2—C3—H3119.9
N2—C12—C8123.1 (2)C3—C4—C5120.1 (3)
N2—C12—C13117.30 (19)C3—C4—H4119.9
C8—C12—C13119.6 (2)C5—C4—H4119.9

Symmetry codes: (i) x, −y+3/2, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: AT2860).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Bruker (2000). APEX2, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Li, H., Yin, K.-L. & Xu, D.-J. (2005). Acta Cryst. C61, m19–m21. [PubMed]
  • Pan, T.-T. & Xu, D.-J. (2004). Acta Cryst. E60, m56–m58.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Wall, M., Linkletter, B., Williams, D., Lebuis, A.-M., Hynes, R. C. & Chin, J. (1999). J. Am. Chem. Soc.121, 4710–4711.
  • Wu, Z.-Y., Xue, Y.-H. & Xu, D.-J. (2003). Acta Cryst. E59, m809–m811.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography