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Acta Cryst. (2007). E63, m2229    [ doi:10.1107/S1600536807036173 ]

Chlorido(11-methyldipyrido[3,2-a:2',3'-c]phenazine-[kappa]2N4,N5)copper(I)

C.-B. Li, S. Zhou, G.-G. Gao and B. Liu

Abstract top

In the title compound, [CuCl(C19H11N4)], the CuI ion is coordinated by one Cl- ion and two N atoms from a chelating 11-methyldipyrido[3,2-a:2',3'-c]phenazine ligand. The CuI and Cl- ions are situated on a mirror plane and the terminal methyl group of the ligand is disordered equally over two positions. Aromatic [pi]-[pi] stacking interactions [centroid separations = 3.609 (3)-3.669 (3) Å] help to stabilize the crystal packing.

Comment top

Recently, the construction of supramolecular architectures has attracted much attention for their intriguing structural features (Lu, 2003; Cheng et al., 2004). The 1,10-phenanthroline ligand has been widely used for the synthesis of coordination complexes; these are sometimes assembled into supramolecular architectures through aromatic π-π interactions (Chen & Liu, 2002). Dipyrido[3,2 - a:2',3'-c]phenazine is a similarly useful ligand, and several complexes have been reported (Li, Fang, Gao et al., 2006). To extend our recent work, we obtained the title compound, (I), by using 11-methyldipyrido[3,2 - a:2',3'-c]phenazine (MDPPz), 1,3-benzene dicarboxylic acid (which was not incorporated into the product) and CuCl2 as starting materials. The starting CuII was reduced to CuI by an unknown process.

In complex (I), the CuI ion is coordinated by two N atoms belonging to the bidentate MDPPz ligand and one Cl- ion, resulting in a CuN2Cl triangular geometry (Table 1, Fig. 1). The CuI and Cl- ions are situated on a mirror plane which also perpendicularly passes through the MSPPz ligand, thus the methyl group belonging to the MSPPz ligand is disordered and its occupancy is assigned as 0.5. There are π-π stacking interactions between the neighboring parallel MSDPPz liands, which the nearer centroid-to-centroid distance of aromatic rings is in the range 3.609 (3)—3.669 (3)Å (Fig. 2). These weak interactions consolidate the packing of (I).

Related literature top

For related structures, see: Li, Fang, Dong et al. (2006); Li, Fang, Gao et al. (2006). For background, see: Lu (2003); Cheng et al. (2004); Chen & Liu (2002). For the ligand synthesis, see: Steck & Day (1943).

Experimental top

The MDPPz ligand was synthesized by the literature method of Steck & Day (1943). A mixture of CuCl2 (0.3 mmol), MDPPz (0.3 mmol) and 1,3-benzene dicarboxylic acid (0.6 mmol) in distilled water (30 ml) was stirred thoroughly for 1 h at ambient temperature. The pH was adjusted to about 5 with aqueous NaOH solution. The suspension was then sealed in a Teflon-lined stainless steel reaction vessel (40 ml) and heated at 443 K for 4 d. The vessel was then cooled slowly to room temperature at a rate of 5 K /h before opening, and reddish brown crystals of (I) were collected.

Refinement top

The positional parameters of the H atoms were calculated geometrically (C—H = 0.93–0.96 Å) and refined as riding with Uiso = 1.2Ueq(C) or 1.5Ueq(methyl C).

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at 30% probability level (H atoms are omitted for clarity) [Symmetry code: i) x, 1/2 - y, z.].
[Figure 2] Fig. 2. The packing diagram of (I) (H atoms were omitted for clarity; the centroid-to-centroid distances are shown as dashed line.).
Chlorido(11-methyldipyrido[3,2 - a:2',3'-c]phenazine-κ2N4,N5)copper(I) top
Crystal data top
[CuCl(C19H11N4)]Dx = 1.678 Mg m−3
Mr = 394.31Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PnmaCell parameters from 2310 reflections
a = 25.947 (4) Åθ = 2.1–25.3°
b = 12.1604 (17) ŵ = 1.58 mm−1
c = 4.9456 (7) ÅT = 293 K
V = 1560.5 (4) Å3Block, reddish brown
Z = 40.49 × 0.11 × 0.05 mm
F(000) = 796
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer		1615 independent reflections
Radiation source: fine-focus sealed tube822 reflections with I > 2σ(I)
graphiteRint = 0.066
ω scansθmax = 26.1°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Bruker, 2002)		h = −16→32
Tmin = 0.812, Tmax = 0.924k = −14→15
7882 measured reflectionsl = −5→6
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)] = 0.057Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.203H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.1074P)2]
where P = (Fo2 + 2Fc2)/3
1615 reflections(Δ/σ)max = 0.001
121 parametersΔρmax = 0.50 e Å−3
0 restraintsΔρmin = −0.45 e Å−3
Crystal data top
[CuCl(C19H11N4)]V = 1560.5 (4) Å3
Mr = 394.31Z = 4
Orthorhombic, PnmaMo Kα radiation
a = 25.947 (4) ŵ = 1.58 mm−1
b = 12.1604 (17) ÅT = 293 K
c = 4.9456 (7) Å0.49 × 0.11 × 0.05 mm
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer		1615 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2002)		822 reflections with I > 2σ(I)
Tmin = 0.812, Tmax = 0.924Rint = 0.066
7882 measured reflectionsθmax = 26.1°
Refinement top
R[F2 > 2σ(F2)] = 0.057H-atom parameters constrained
wR(F2) = 0.203Δρmax = 0.50 e Å−3
S = 1.02Δρmin = −0.45 e Å−3
1615 reflectionsAbsolute structure: ?
121 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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*/UeqOcc. (<1)
Cu10.98473 (4)0.25000.1790 (2)0.1045 (6)
Cl11.04420 (8)0.2500−0.1105 (4)0.0798 (7)
N20.81629 (16)0.1340 (4)1.1113 (8)0.0742 (13)
N10.94108 (15)0.1397 (4)0.3947 (8)0.0660 (12)
C50.84651 (18)0.1914 (4)0.9473 (9)0.0625 (13)
C80.7193 (2)0.1927 (7)1.6198 (11)0.124 (4)
C40.87997 (17)0.1316 (5)0.7633 (10)0.0606 (13)
C90.91021 (18)0.1903 (4)0.5804 (9)0.0596 (13)
C10.9417 (2)0.0309 (6)0.3921 (12)0.0786 (16)
H1A0.9617−0.00410.26210.094*
C20.9142 (2)−0.0339 (5)0.5726 (13)0.0851 (17)
H2A0.9168−0.11020.56770.102*
C30.8830 (2)0.0173 (5)0.7586 (13)0.0772 (16)
H3A0.8641−0.02420.88110.093*
C70.7512 (2)0.1350 (7)1.4547 (12)0.103 (2)
H7A0.75050.05851.45680.124*
C60.7858 (2)0.1912 (5)1.2780 (10)0.0812 (19)
C100.6809 (4)0.1629 (11)1.814 (2)0.089 (4)0.50
H10A0.66690.22821.89440.133*0.50
H10B0.69620.11791.95180.133*0.50
H10C0.65390.12261.72590.133*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0553 (7)0.1961 (15)0.0621 (8)0.0000.0113 (5)0.000
Cl10.0772 (14)0.0847 (14)0.0774 (12)0.0000.0374 (10)0.000
N20.046 (3)0.126 (4)0.051 (2)−0.010 (2)−0.002 (2)0.012 (2)
N10.050 (3)0.096 (4)0.052 (2)0.009 (2)−0.0027 (19)−0.009 (2)
C50.044 (3)0.100 (4)0.043 (2)−0.005 (2)−0.008 (2)0.004 (2)
C80.047 (3)0.274 (12)0.051 (3)−0.013 (4)−0.002 (3)0.019 (4)
C40.041 (3)0.087 (4)0.053 (3)−0.004 (3)−0.002 (2)0.002 (3)
C90.045 (3)0.086 (3)0.047 (3)0.001 (2)−0.008 (2)−0.002 (2)
C10.059 (4)0.101 (5)0.076 (4)0.015 (3)−0.005 (3)−0.020 (4)
C20.075 (4)0.096 (4)0.085 (4)0.004 (3)0.002 (3)−0.004 (4)
C30.070 (4)0.091 (4)0.070 (3)−0.003 (3)−0.001 (3)0.011 (3)
C70.054 (4)0.192 (7)0.063 (4)−0.016 (4)0.000 (3)0.025 (4)
C60.043 (3)0.157 (6)0.043 (3)−0.007 (3)0.000 (2)0.008 (3)
C100.061 (7)0.133 (10)0.072 (8)−0.022 (7)0.011 (6)0.008 (7)
Geometric parameters (Å, °) top
Cu1—N1i2.054 (5)C4—C91.394 (6)
Cu1—N12.054 (5)C9—C9i1.453 (10)
Cu1—Cl12.105 (2)C1—C21.389 (8)
N2—C51.326 (6)C1—H1A0.9300
N2—C61.337 (7)C2—C31.374 (8)
N1—C11.323 (7)C2—H2A0.9300
N1—C91.365 (6)C3—H3A0.9300
C5—C5i1.425 (10)C7—C61.428 (8)
C5—C41.453 (7)C7—H7A0.9300
C8—C71.358 (9)C6—C6i1.429 (12)
C8—C8i1.395 (17)C10—H10A0.9600
C8—C101.430 (11)C10—H10B0.9600
C4—C31.392 (7)C10—H10C0.9600
N1i—Cu1—N181.5 (3)N1—C1—H1A118.1
N1i—Cu1—Cl1139.24 (13)C2—C1—H1A118.1
N1—Cu1—Cl1139.24 (13)C3—C2—C1118.4 (6)
C5—N2—C6116.9 (5)C3—C2—H2A120.8
C1—N1—C9117.6 (5)C1—C2—H2A120.8
C1—N1—Cu1129.9 (4)C2—C3—C4119.8 (6)
C9—N1—Cu1112.3 (4)C2—C3—H3A120.1
N2—C5—C5i121.7 (3)C4—C3—H3A120.1
N2—C5—C4118.2 (5)C8—C7—C6120.3 (8)
C5i—C5—C4120.0 (3)C8—C7—H7A119.9
C7—C8—C8i121.1 (5)C6—C7—H7A119.9
C7—C8—C10134.3 (9)N2—C6—C7120.0 (6)
C8i—C8—C10104.6 (6)N2—C6—C6i121.3 (3)
C3—C4—C9117.9 (5)C7—C6—C6i118.6 (4)
C3—C4—C5123.0 (5)C8—C10—H10A109.5
C9—C4—C5119.1 (5)C8—C10—H10B109.5
N1—C9—C4122.4 (5)H10A—C10—H10B109.5
N1—C9—C9i116.8 (3)C8—C10—H10C109.5
C4—C9—C9i120.8 (3)H10A—C10—H10C109.5
N1—C1—C2123.7 (6)H10B—C10—H10C109.5
Symmetry codes: (i) x, −y+1/2, z.
Table 1
Selected geometric parameters (Å, °) top
Cu1—N12.054 (5)Cu1—Cl12.105 (2)
N1i—Cu1—N181.5 (3)N1—Cu1—Cl1139.24 (13)
Symmetry codes: (i) x, −y+1/2, z.
Acknowledgements top

This work was supported by the Natural Science Foundation of Jilin Province (grant No. 2005103).

references
References top

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