Chlorido(11-methyl­dipyrido[3,2-a:2′,3′-c]phenazine-κ²N⁴,N⁵)copper(I)

In the title compound, [CuCl(C₁₉H₁₁N₄)], the Cu^I 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 Cu^I and Cl⁻ ions are situated on a mirror plane and the terminal methyl group of the ligand is disordered equally over two positions. Aromatic π–π stacking inter­actions [centroid separations = 3.609 (3)–3.669 (3) Å] help to stabilize the crystal packing.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.008 Å
• Disorder in main residue
• R factor = 0.057
• wR factor = 0.203
• Data-to-parameter ratio = 13.3

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT241_ALERT_2_B Check High      Ueq as Compared to Neighbors for        Cu1

Alert level C
CRYSC01_ALERT_1_C The word below has not been recognised as a standard
            identifier.
            reddish
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         C8
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.43
PLAT301_ALERT_3_C Main Residue  Disorder .........................       4.00 Perc.
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          8
PLAT413_ALERT_2_C Short Inter XH3 .. XHn     H3A    ..  H10C    ..       2.13 Ang.
PLAT432_ALERT_2_C Short Inter X...Y Contact  C2     ..  C10     ..       3.19 Ang.

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   9 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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 Cu^II was reduced to Cu^I by an unknown process.

In complex (I), the Cu^I 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 Cu^I 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

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).

S2. Experimental

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.

S3. Refinement

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

Computing details

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

	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.].
	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)

Crystal data

[CuCl(C19H11N4)]	Dx = 1.678 Mg m^−3
Mr = 394.31	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 2310 reflections
a = 25.947 (4) Å	θ = 2.1–25.3°
b = 12.1604 (17) Å	µ = 1.58 mm^−1
c = 4.9456 (7) Å	T = 293 K
V = 1560.5 (4) Å^3	Block, reddish brown
Z = 4	0.49 × 0.11 × 0.05 mm
F(000) = 796

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	1615 independent reflections
Radiation source: fine-focus sealed tube	822 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.066
ω scans	θmax = 26.1°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −16→32
Tmin = 0.812, Tmax = 0.924	k = −14→15
7882 measured reflections	l = −5→6

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.203	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.1074P)^2] where P = (Fo^2 + 2Fc^2)/3
1615 reflections	(Δ/σ)max = 0.001
121 parameters	Δρmax = 0.50 e Å^−3
0 restraints	Δρmin = −0.45 e Å^−3

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.98473 (4)	0.2500	0.1790 (2)	0.1045 (6)
Cl1	1.04420 (8)	0.2500	−0.1105 (4)	0.0798 (7)
N2	0.81629 (16)	0.1340 (4)	1.1113 (8)	0.0742 (13)
N1	0.94108 (15)	0.1397 (4)	0.3947 (8)	0.0660 (12)
C5	0.84651 (18)	0.1914 (4)	0.9473 (9)	0.0625 (13)
C8	0.7193 (2)	0.1927 (7)	1.6198 (11)	0.124 (4)
C4	0.87997 (17)	0.1316 (5)	0.7633 (10)	0.0606 (13)
C9	0.91021 (18)	0.1903 (4)	0.5804 (9)	0.0596 (13)
C1	0.9417 (2)	0.0309 (6)	0.3921 (12)	0.0786 (16)
H1A	0.9617	−0.0041	0.2621	0.094*
C2	0.9142 (2)	−0.0339 (5)	0.5726 (13)	0.0851 (17)
H2A	0.9168	−0.1102	0.5677	0.102*
C3	0.8830 (2)	0.0173 (5)	0.7586 (13)	0.0772 (16)
H3A	0.8641	−0.0242	0.8811	0.093*
C7	0.7512 (2)	0.1350 (7)	1.4547 (12)	0.103 (2)
H7A	0.7505	0.0585	1.4568	0.124*
C6	0.7858 (2)	0.1912 (5)	1.2780 (10)	0.0812 (19)
C10	0.6809 (4)	0.1629 (11)	1.814 (2)	0.089 (4)	0.50
H10A	0.6669	0.2282	1.8944	0.133*	0.50
H10B	0.6962	0.1179	1.9518	0.133*	0.50
H10C	0.6539	0.1226	1.7259	0.133*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0553 (7)	0.1961 (15)	0.0621 (8)	0.000	0.0113 (5)	0.000
Cl1	0.0772 (14)	0.0847 (14)	0.0774 (12)	0.000	0.0374 (10)	0.000
N2	0.046 (3)	0.126 (4)	0.051 (2)	−0.010 (2)	−0.002 (2)	0.012 (2)
N1	0.050 (3)	0.096 (4)	0.052 (2)	0.009 (2)	−0.0027 (19)	−0.009 (2)
C5	0.044 (3)	0.100 (4)	0.043 (2)	−0.005 (2)	−0.008 (2)	0.004 (2)
C8	0.047 (3)	0.274 (12)	0.051 (3)	−0.013 (4)	−0.002 (3)	0.019 (4)
C4	0.041 (3)	0.087 (4)	0.053 (3)	−0.004 (3)	−0.002 (2)	0.002 (3)
C9	0.045 (3)	0.086 (3)	0.047 (3)	0.001 (2)	−0.008 (2)	−0.002 (2)
C1	0.059 (4)	0.101 (5)	0.076 (4)	0.015 (3)	−0.005 (3)	−0.020 (4)
C2	0.075 (4)	0.096 (4)	0.085 (4)	0.004 (3)	0.002 (3)	−0.004 (4)
C3	0.070 (4)	0.091 (4)	0.070 (3)	−0.003 (3)	−0.001 (3)	0.011 (3)
C7	0.054 (4)	0.192 (7)	0.063 (4)	−0.016 (4)	0.000 (3)	0.025 (4)
C6	0.043 (3)	0.157 (6)	0.043 (3)	−0.007 (3)	0.000 (2)	0.008 (3)
C10	0.061 (7)	0.133 (10)	0.072 (8)	−0.022 (7)	0.011 (6)	0.008 (7)

Geometric parameters (Å, º)

Cu1—N1^i	2.054 (5)	C4—C9	1.394 (6)
Cu1—N1	2.054 (5)	C9—C9^i	1.453 (10)
Cu1—Cl1	2.105 (2)	C1—C2	1.389 (8)
N2—C5	1.326 (6)	C1—H1A	0.9300
N2—C6	1.337 (7)	C2—C3	1.374 (8)
N1—C1	1.323 (7)	C2—H2A	0.9300
N1—C9	1.365 (6)	C3—H3A	0.9300
C5—C5^i	1.425 (10)	C7—C6	1.428 (8)
C5—C4	1.453 (7)	C7—H7A	0.9300
C8—C7	1.358 (9)	C6—C6^i	1.429 (12)
C8—C8^i	1.395 (17)	C10—H10A	0.9600
C8—C10	1.430 (11)	C10—H10B	0.9600
C4—C3	1.392 (7)	C10—H10C	0.9600
N1^i—Cu1—N1	81.5 (3)	N1—C1—H1A	118.1
N1^i—Cu1—Cl1	139.24 (13)	C2—C1—H1A	118.1
N1—Cu1—Cl1	139.24 (13)	C3—C2—C1	118.4 (6)
C5—N2—C6	116.9 (5)	C3—C2—H2A	120.8
C1—N1—C9	117.6 (5)	C1—C2—H2A	120.8
C1—N1—Cu1	129.9 (4)	C2—C3—C4	119.8 (6)
C9—N1—Cu1	112.3 (4)	C2—C3—H3A	120.1
N2—C5—C5^i	121.7 (3)	C4—C3—H3A	120.1
N2—C5—C4	118.2 (5)	C8—C7—C6	120.3 (8)
C5^i—C5—C4	120.0 (3)	C8—C7—H7A	119.9
C7—C8—C8^i	121.1 (5)	C6—C7—H7A	119.9
C7—C8—C10	134.3 (9)	N2—C6—C7	120.0 (6)
C8^i—C8—C10	104.6 (6)	N2—C6—C6^i	121.3 (3)
C3—C4—C9	117.9 (5)	C7—C6—C6^i	118.6 (4)
C3—C4—C5	123.0 (5)	C8—C10—H10A	109.5
C9—C4—C5	119.1 (5)	C8—C10—H10B	109.5
N1—C9—C4	122.4 (5)	H10A—C10—H10B	109.5
N1—C9—C9^i	116.8 (3)	C8—C10—H10C	109.5
C4—C9—C9^i	120.8 (3)	H10A—C10—H10C	109.5
N1—C1—C2	123.7 (6)	H10B—C10—H10C	109.5

Symmetry code: (i) x, −y+1/2, z.