Dichlorido(2,9-dimethyl-1,10-phenanthroline-κ2N,N′)copper(II)

Wang, B.S.; Zhong, H.

doi:10.1107/S1600536809034187

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page m1156

doi:10.1107/S1600536809034187

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Dichlorido(2,9-dimethyl-1,10-phenanthroline-κ²N,N′)copper(II)

B. S. Wang ^a ^* and H. Zhong ^b

^aDepartment of Biochemistry, Jingdezhen Comprehesive College, Jingdezhen, Jiangxi 333000, People's Republic of China, and ^bThe Key Laboratory of Coordination Chemistry of Jiangxi Province, Jian 343009, People's Republic of China
^*Correspondence e-mail: bingshanwang09@126.com

(Received 13 August 2009; accepted 26 August 2009; online 5 September 2009)

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 Cu^II 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 ); Wu et al. (2003 ); Pan & Xu (2004 ); Li et al. (2005 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

[CuCl₂(C₁₄H₁₂N₂)]
M_r = 342.70
Orthorhombic, P n m a
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 ) 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[F² > 2σ(F²)] = 0.026
wR(F²) = 0.083
S = 1.00
1951 reflections
114 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.29 e Å⁻³

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

Supporting information

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

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

checkCIF report

Comment top

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 Cu^II 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).

Related literature top

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

Experimental top

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.

Computing details top

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

Figures top

	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).

Dichlorido(2,9-dimethyl-1,10-phenanthroline-κ²N,N')copper(II) top

Crystal data top

[CuCl₂(C₁₄H₁₂N₂)]	F(000) = 692
M_r = 342.70	D_x = 1.536 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 5426 reflections
a = 11.239 (2) Å	θ = 2.3–28.0°
b = 7.4651 (18) Å	µ = 1.82 mm⁻¹
c = 17.663 (5) Å	T = 273 K
V = 1481.9 (6) Å³	Plane, blue
Z = 4	0.30 × 0.28 × 0.21 mm

Data collection top

Bruker APEXII area-detector diffractometer	1951 independent reflections
Radiation source: fine-focus sealed tube	1601 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ϕ and ω scans	θ_max = 28.3°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −14→14
T_min = 0.611, T_max = 0.701	k = −9→9
10738 measured reflections	l = −23→23

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.083	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0553P)² + 0.1694P] where P = (F_o² + 2F_c²)/3
1951 reflections	(Δ/σ)_max = 0.001
114 parameters	Δρ_max = 0.41 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

[CuCl₂(C₁₄H₁₂N₂)]	V = 1481.9 (6) Å³
M_r = 342.70	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 11.239 (2) Å	µ = 1.82 mm⁻¹
b = 7.4651 (18) Å	T = 273 K
c = 17.663 (5) Å	0.30 × 0.28 × 0.21 mm

Data collection top

Bruker APEXII area-detector diffractometer	1951 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1601 reflections with I > 2σ(I)
T_min = 0.611, T_max = 0.701	R_int = 0.023
10738 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	0 restraints
wR(F²) = 0.083	H-atom parameters constrained
S = 1.00	Δρ_max = 0.41 e Å⁻³
1951 reflections	Δρ_min = −0.29 e Å⁻³
114 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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cu1	0.76127 (2)	0.7500	0.610028 (14)	0.04178 (12)
N1	0.79467 (16)	0.7500	0.49476 (10)	0.0418 (4)
N2	0.58758 (17)	0.7500	0.57229 (11)	0.0445 (4)
C1	1.0098 (2)	0.7500	0.50503 (18)	0.0684 (8)
H1A	1.0316	0.8711	0.5170	0.103*	0.50
H1B	1.0728	0.6946	0.4767	0.103*	0.50
H1C	0.9967	0.6843	0.5510	0.103*	0.50
C13	0.6920 (2)	0.7500	0.45450 (12)	0.0406 (5)
C11	0.4872 (3)	0.7500	0.61234 (14)	0.0558 (6)
C2	0.8982 (2)	0.7500	0.45874 (15)	0.0517 (6)
C12	0.58155 (19)	0.7500	0.49535 (12)	0.0403 (5)
C14	0.4987 (3)	0.7500	0.69623 (17)	0.0803 (10)
H14A	0.5697	0.8130	0.7105	0.120*	0.50
H14B	0.5030	0.6288	0.7142	0.120*	0.50
H14C	0.4307	0.8082	0.7182	0.120*	0.50
C10	0.3763 (2)	0.7500	0.5751 (2)	0.0711 (8)
H10	0.3067	0.7500	0.6035	0.085*
C8	0.4741 (2)	0.7500	0.45551 (15)	0.0500 (6)
C7	0.4757 (3)	0.7500	0.37518 (16)	0.0624 (7)
H7	0.4041	0.7500	0.3487	0.075*
C5	0.6901 (2)	0.7500	0.37527 (13)	0.0502 (6)
C6	0.5787 (3)	0.7500	0.33689 (15)	0.0610 (7)
H6	0.5774	0.7500	0.2842	0.073*
C9	0.3695 (2)	0.7500	0.49900 (19)	0.0664 (8)
H9	0.2957	0.7500	0.4753	0.080*
C3	0.9025 (3)	0.7500	0.37937 (16)	0.0676 (8)
H3	0.9756	0.7500	0.3547	0.081*
C4	0.8005 (3)	0.7500	0.33845 (16)	0.0687 (8)
H4	0.8038	0.7500	0.2858	0.082*
Cl1	0.81305 (5)	1.00503 (6)	0.66249 (3)	0.06566 (17)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.04754 (18)	0.0423 (2)	0.03548 (17)	0.000	−0.00528 (11)	0.000
N1	0.0374 (9)	0.0471 (11)	0.0408 (10)	0.000	0.0006 (8)	0.000
N2	0.0450 (10)	0.0441 (11)	0.0446 (10)	0.000	0.0081 (8)	0.000
C1	0.0403 (13)	0.082 (2)	0.083 (2)	0.000	−0.0043 (13)	0.000
C13	0.0403 (11)	0.0429 (13)	0.0387 (10)	0.000	0.0002 (9)	0.000
C11	0.0560 (14)	0.0532 (16)	0.0581 (15)	0.000	0.0192 (12)	0.000
C2	0.0404 (11)	0.0570 (16)	0.0576 (14)	0.000	0.0053 (10)	0.000
C12	0.0393 (11)	0.0395 (12)	0.0421 (11)	0.000	0.0014 (9)	0.000
C14	0.094 (2)	0.090 (2)	0.0565 (16)	0.000	0.0325 (17)	0.000
C10	0.0436 (14)	0.078 (2)	0.092 (2)	0.000	0.0226 (15)	0.000
C8	0.0412 (12)	0.0492 (14)	0.0596 (14)	0.000	−0.0044 (10)	0.000
C7	0.0556 (15)	0.0730 (19)	0.0586 (15)	0.000	−0.0195 (12)	0.000
C5	0.0559 (14)	0.0558 (16)	0.0388 (11)	0.000	0.0009 (10)	0.000
C6	0.0660 (17)	0.0736 (19)	0.0434 (13)	0.000	−0.0118 (12)	0.000
C9	0.0372 (12)	0.078 (2)	0.084 (2)	0.000	0.0030 (12)	0.000
C3	0.0508 (15)	0.096 (2)	0.0560 (16)	0.000	0.0176 (12)	0.000
C4	0.0656 (17)	0.095 (3)	0.0449 (14)	0.000	0.0135 (13)	0.000
Cl1	0.0766 (3)	0.0502 (3)	0.0702 (3)	−0.0019 (2)	−0.0167 (3)	−0.0113 (2)

Geometric parameters (Å, º) top

Cu1—Cl1	2.1958 (6)	C12—C8	1.398 (3)
Cu1—Cl1ⁱ	2.1958 (6)	C14—H14A	0.9600
Cu1—N1	2.070 (2)	C14—H14B	0.9600
Cu1—N2	2.063 (2)	C14—H14C	0.9600
N1—C2	1.326 (3)	C10—C9	1.346 (5)
N1—C13	1.355 (3)	C10—H10	0.9300
N2—C11	1.331 (3)	C8—C9	1.404 (4)
N2—C12	1.361 (3)	C8—C7	1.419 (4)
C1—C2	1.498 (4)	C7—C6	1.341 (4)
C1—H1A	0.9600	C7—H7	0.9300
C1—H1B	0.9600	C5—C4	1.401 (4)
C1—H1C	0.9600	C5—C6	1.423 (4)
C13—C5	1.400 (3)	C6—H6	0.9300
C13—C12	1.436 (3)	C9—H9	0.9300
C11—C10	1.409 (4)	C3—C4	1.355 (4)
C11—C14	1.487 (4)	C3—H3	0.9300
C2—C3	1.403 (3)	C4—H4	0.9300

Cl1—Cu1—Cl1ⁱ	120.23 (3)	C11—C14—H14A	109.5
N1—Cu1—Cl1	111.53 (3)	C11—C14—H14B	109.5
N1—Cu1—Cl1ⁱ	111.53 (3)	H14A—C14—H14B	109.5
N2—Cu1—N1	81.60 (7)	C11—C14—H14C	109.5
N2—Cu1—Cl1	112.78 (2)	H14A—C14—H14C	109.5
N2—Cu1—Cl1ⁱ	112.78 (2)	H14B—C14—H14C	109.5
C2—N1—C13	119.7 (2)	C9—C10—C11	121.1 (3)
C2—N1—Cu1	129.12 (17)	C9—C10—H10	119.4
C13—N1—Cu1	111.21 (15)	C11—C10—H10	119.4
C11—N2—C12	119.2 (2)	C12—C8—C9	116.6 (2)
C11—N2—Cu1	129.05 (18)	C12—C8—C7	119.5 (2)
C12—N2—Cu1	111.71 (14)	C9—C8—C7	123.9 (2)
C2—C1—H1A	109.5	C6—C7—C8	121.0 (2)
C2—C1—H1B	109.5	C6—C7—H7	119.5
H1A—C1—H1B	109.5	C8—C7—H7	119.5
C2—C1—H1C	109.5	C13—C5—C4	116.7 (2)
H1A—C1—H1C	109.5	C13—C5—C6	119.4 (2)
H1B—C1—H1C	109.5	C4—C5—C6	123.9 (2)
N1—C13—C5	122.6 (2)	C7—C6—C5	121.3 (2)
N1—C13—C12	118.2 (2)	C7—C6—H6	119.4
C5—C13—C12	119.2 (2)	C5—C6—H6	119.4
N2—C11—C10	120.1 (2)	C10—C9—C8	119.9 (3)
N2—C11—C14	117.1 (3)	C10—C9—H9	120.0
C10—C11—C14	122.8 (3)	C8—C9—H9	120.0
N1—C2—C3	120.6 (2)	C4—C3—C2	120.3 (2)
N1—C2—C1	118.2 (2)	C4—C3—H3	119.9
C3—C2—C1	121.1 (2)	C2—C3—H3	119.9
N2—C12—C8	123.1 (2)	C3—C4—C5	120.1 (3)
N2—C12—C13	117.30 (19)	C3—C4—H4	119.9
C8—C12—C13	119.6 (2)	C5—C4—H4	119.9

Symmetry code: (i) x, −y+3/2, z.

Experimental details

Crystal data
Chemical formula	[CuCl₂(C₁₄H₁₂N₂)]
M_r	342.70
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	273
a, b, c (Å)	11.239 (2), 7.4651 (18), 17.663 (5)
V (Å³)	1481.9 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.82
Crystal size (mm)	0.30 × 0.28 × 0.21

Data collection
Diffractometer	Bruker APEXII area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.611, 0.701
No. of measured, independent and observed [I > 2σ(I)] reflections	10738, 1951, 1601
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.083, 1.00
No. of reflections	1951
No. of parameters	114
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.29

Computer programs: APEX2 (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).

Acknowledgements

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

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. CrossRef Web of Science Google Scholar
Bruker (2000). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Li, H., Yin, K.-L. & Xu, D.-J. (2005). Acta Cryst. C61, m19–m21. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Pan, T.-T. & Xu, D.-J. (2004). Acta Cryst. E60, m56–m58. CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wall, M., Linkletter, B., Williams, D., Lebuis, A.-M., Hynes, R. C. & Chin, J. (1999). J. Am. Chem. Soc. 121, 4710–4711. Web of Science CSD CrossRef CAS Google Scholar
Wu, Z.-Y., Xue, Y.-H. & Xu, D.-J. (2003). Acta Cryst. E59, m809–m811. Web of Science CSD CrossRef IUCr Journals Google Scholar