11,12-Dichloro­dibenzo[a,c]phenazine

Imeri, A.; Glagovich, N.M.; Crundwell, G.

doi:10.1107/S1600536812049690

organic compounds

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Volume 69| Part 1| January 2013| Page o48

https://doi.org/10.1107/S1600536812049690

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11,12-Dichlorodibenzo[a,c]phenazine

Arta Imeri,^a Neil M. Glagovich ^a and Guy Crundwell ^a ^*

^aDepartment of Chemistry, Central Connecticut State University, New Britain, CT 06053, USA
^*Correspondence e-mail: crundwellg@mail.ccsu.edu

(Received 1 November 2012; accepted 4 December 2012; online 8 December 2012)

The title compound, C₂₀H₁₀Cl₂N₂, has crystallographic twofold rotational symmetry [maximum deviation from the least-squares plane = 0.038 (1) Å]. In the crystal, weak π–π ring stacking interactions occur down the a-axis direction [minimum centroid–centroid separation = 3.7163 (8) Å].

Related literature

For the synthesis of the title compound, see: Bellizzi et al. (2006 ). For the structures of similar compounds, see: Bellizzi et al. (2006); Day et al. (2002 ); Richards et al. (2009 ).

Experimental

Crystal data

C₂₀H₁₀Cl₂N₂
M_r = 349.20
Monoclinic, C 2/c
a = 3.8583 (3) Å
b = 26.2739 (13) Å
c = 15.1147 (10) Å
β = 94.877 (6)°
V = 1526.67 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.43 mm⁻¹
T = 293 K
0.32 × 0.14 × 0.09 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 CCD diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD, CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.915, T_max = 1.000
5082 measured reflections
2520 independent reflections
1372 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.104
S = 0.83
2520 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD, CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD, CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812049690/zs2242sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812049690/zs2242Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812049690/zs2242Isup3.cml

checkCIF report

Comment top

The title compound C₂₀H₁₀Cl₂N₂ is planar [maximum deviation from the l.s. plane over the 24 atoms = 0.038 (1) Å] and lies on a crystallographic twofold axis (Fig. 1). All bond lengths and angles fall within typical ranges found in other dibenzo[a,c]phenazines (Day et al., 2002; Richards et al., 2009). In the crystal, the molecules are involved in weak π–π-stacking interactions [minimum ring centroid separation = 3.7163 (8) Å], giving stacks down the a axial direction of the unit cell.

Related literature top

For the synthesis of the title compound, see: Bellizzi et al. (2006). For the structures of similar compounds, see: Bellizzi et al. (2006); Day et al. (2002); Richards et al. (2009).

Experimental top

To a 25 ml round bottom flask equipped with a reflux condenser was added 0.27 g (1.5 mmol) of 4,5-dichloro-1,2-phenylenediamine, 0.27 g (1.3 mmol) of phenanthraquinone, and 10 ml of glacial acetic acid (Bellizzi et al., 2006) and the mixture was heated with refluxing for 6 h. After this time, the resulting yellow solution was concentrated under reduced pressure, and the product obtained was purified by recrystallization from methanol, producing 0.48 g of the title compound as a yellow solid (m.p. 273 °C; yield: 92%). Rf 0.31 (SiO₂, 80% hexanes-ethyl acetate); ¹H NMR (300 MHz, CDCl₃) d 9.35 (dd, 2H, J = 8.0 Hz, J = 1.5 Hz), 8.58 (d, 2H, J = 8.0 Hz, J = 1.2 Hz), 8.47 (s, 2H), 7.86 (dt, 2H, J = 7.2 Hz, J = 1.5 Hz), 7.774 (dt, 2H, J =7.2 Hz, J = 1.2 Hz); ¹³C NMR (300 MHz, CDCl₃) d 143.30, 140.76, 134.30, 132.32, 130.92, 129.85, 129.79, 128.16, 126.45, 123.03; UV/Vis (CH₂Cl₂; λ_max) 260 nm.

Structure description top

For the synthesis of the title compound, see: Bellizzi et al. (2006). For the structures of similar compounds, see: Bellizzi et al. (2006); Day et al. (2002); Richards et al. (2009).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. A view of the title compound showing atom numbering, with displacement ellipsoids drawn at the 50% probability level. Symmetry code (i) (-x, y, -z + 1/2), indicates atoms related by twofold rotational symmetry.

11,12-Dichlorodibenzo[a,c]phenazine top

Crystal data top

C₂₀H₁₀Cl₂N₂	F(000) = 712
M_r = 349.20	D_x = 1.519 Mg m⁻³
Monoclinic, C2/c	Melting point: 546 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 3.8583 (3) Å	Cell parameters from 1714 reflections
b = 26.2739 (13) Å	θ = 4.1–32.5°
c = 15.1147 (10) Å	µ = 0.43 mm⁻¹
β = 94.877 (6)°	T = 293 K
V = 1526.67 (17) Å³	Needle, yellow
Z = 4	0.32 × 0.14 × 0.09 mm

Data collection top

Oxford Diffraction Xcalibur Sapphire3 CCD diffractometer	2520 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1372 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
Detector resolution: 16.1790 pixels mm^-1	θ_max = 32.6°, θ_min = 4.1°
ω scans	h = −5→5
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −27→38
T_min = 0.915, T_max = 1.000	l = −21→10
5082 measured reflections

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.104	H-atom parameters constrained
S = 0.83	w = 1/[σ²(F_o²) + (0.0575P)²] where P = (F_o² + 2F_c²)/3
2520 reflections	(Δ/σ)_max = 0.001
109 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₂₀H₁₀Cl₂N₂	V = 1526.67 (17) Å³
M_r = 349.20	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 3.8583 (3) Å	µ = 0.43 mm⁻¹
b = 26.2739 (13) Å	T = 293 K
c = 15.1147 (10) Å	0.32 × 0.14 × 0.09 mm
β = 94.877 (6)°

Data collection top

Oxford Diffraction Xcalibur Sapphire3 CCD diffractometer	2520 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	1372 reflections with I > 2σ(I)
T_min = 0.915, T_max = 1.000	R_int = 0.020
5082 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.104	H-atom parameters constrained
S = 0.83	Δρ_max = 0.26 e Å⁻³
2520 reflections	Δρ_min = −0.25 e Å⁻³
109 parameters

Special details top

Experimental. Hydrogen atoms were included in calculated positions with a C—H distance of 0.93 Å and were included in the refinement in riding motion approximation with U_iso = 1.2U_eq of the carrier atom.

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
Cl1	0.13563 (12)	1.243825 (14)	0.15408 (3)	0.07256 (18)
C1	0.0618 (3)	1.18700 (5)	0.20681 (10)	0.0463 (3)
C2	0.1244 (3)	1.14234 (5)	0.16590 (9)	0.0430 (3)
H2	0.2072	1.1427	0.1099	0.052*
C3	0.0651 (3)	1.09527 (4)	0.20751 (8)	0.0355 (3)
N1	0.1324 (3)	1.05122 (4)	0.16541 (7)	0.0356 (2)
C4	0.0669 (3)	1.00812 (4)	0.20704 (8)	0.0308 (3)
C5	0.1338 (3)	0.95984 (4)	0.16356 (8)	0.0306 (3)
C6	0.2605 (3)	0.95979 (5)	0.07952 (8)	0.0390 (3)
H6	0.3017	0.9906	0.0519	0.047*
C7	0.3246 (4)	0.91492 (5)	0.03731 (9)	0.0447 (3)
H7	0.4078	0.9152	−0.0187	0.054*
C8	0.2642 (4)	0.86907 (5)	0.07896 (9)	0.0472 (4)
H8	0.3089	0.8386	0.0508	0.057*
C9	0.1394 (3)	0.86825 (5)	0.16127 (9)	0.0421 (3)
H9	0.1010	0.8371	0.1880	0.051*
C10	0.0685 (3)	0.91342 (4)	0.20592 (8)	0.0321 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0829 (3)	0.0336 (2)	0.1023 (4)	−0.00414 (17)	0.0140 (3)	0.0163 (2)
C1	0.0413 (8)	0.0305 (6)	0.0665 (9)	−0.0025 (5)	0.0004 (7)	0.0067 (6)
C2	0.0440 (8)	0.0364 (7)	0.0490 (8)	−0.0003 (6)	0.0053 (6)	0.0062 (6)
C3	0.0333 (7)	0.0311 (6)	0.0417 (6)	−0.0006 (5)	0.0010 (5)	0.0014 (5)
N1	0.0380 (6)	0.0323 (5)	0.0366 (5)	0.0000 (4)	0.0047 (5)	0.0029 (4)
C4	0.0281 (7)	0.0325 (6)	0.0315 (6)	0.0005 (4)	0.0014 (5)	0.0018 (5)
C5	0.0272 (6)	0.0327 (6)	0.0315 (6)	0.0025 (5)	0.0006 (5)	−0.0012 (5)
C6	0.0393 (7)	0.0410 (7)	0.0375 (7)	0.0028 (5)	0.0074 (6)	0.0012 (5)
C7	0.0450 (8)	0.0526 (8)	0.0373 (7)	0.0081 (6)	0.0072 (6)	−0.0067 (6)
C8	0.0549 (9)	0.0403 (7)	0.0464 (8)	0.0090 (6)	0.0041 (6)	−0.0115 (6)
C9	0.0476 (8)	0.0317 (6)	0.0467 (8)	0.0028 (5)	0.0018 (6)	−0.0027 (5)
C10	0.0290 (6)	0.0316 (6)	0.0351 (6)	0.0014 (4)	−0.0012 (5)	−0.0011 (5)

Geometric parameters (Å, º) top

Cl1—C1	1.7274 (13)	C5—C10	1.4101 (15)
C1—C2	1.3576 (17)	C6—C7	1.3731 (17)
C1—C1ⁱ	1.428 (3)	C6—H6	0.9300
C2—C3	1.4147 (16)	C7—C8	1.3879 (18)
C2—H2	0.9300	C7—H7	0.9300
C3—N1	1.3564 (14)	C8—C9	1.3719 (18)
C3—C3ⁱ	1.418 (2)	C8—H8	0.9300
N1—C4	1.3301 (14)	C9—C10	1.4037 (15)
C4—C4ⁱ	1.438 (2)	C9—H9	0.9300
C4—C5	1.4616 (15)	C10—C10ⁱ	1.475 (2)
C5—C6	1.3991 (16)

C2—C1—C1ⁱ	120.17 (8)	C7—C6—C5	120.89 (12)
C2—C1—Cl1	119.62 (11)	C7—C6—H6	119.6
C1ⁱ—C1—Cl1	120.20 (5)	C5—C6—H6	119.6
C1—C2—C3	120.76 (12)	C6—C7—C8	119.38 (12)
C1—C2—H2	119.6	C6—C7—H7	120.3
C3—C2—H2	119.6	C8—C7—H7	120.3
N1—C3—C2	119.52 (11)	C9—C8—C7	120.69 (12)
N1—C3—C3ⁱ	121.43 (6)	C9—C8—H8	119.7
C2—C3—C3ⁱ	119.05 (7)	C7—C8—H8	119.7
C4—N1—C3	116.93 (10)	C8—C9—C10	121.36 (12)
N1—C4—C4ⁱ	121.64 (6)	C8—C9—H9	119.3
N1—C4—C5	118.57 (10)	C10—C9—H9	119.3
C4ⁱ—C4—C5	119.79 (6)	C9—C10—C5	117.61 (11)
C6—C5—C10	120.06 (11)	C9—C10—C10ⁱ	122.27 (7)
C6—C5—C4	119.85 (10)	C5—C10—C10ⁱ	120.12 (6)
C10—C5—C4	120.08 (10)

C3—N1—C4—C4ⁱ	−0.40 (17)	N1—C4—C4ⁱ—N1ⁱ	0.24 (19)
C4—N1—C3—C2	−179.01 (11)	N1—C4—C4ⁱ—C5ⁱ	−179.76 (11)
C4—N1—C3—C3ⁱ	0.75 (17)	C5—C4—C4ⁱ—N1ⁱ	−179.76 (11)
C3—N1—C4—C5	179.59 (11)	C5—C4—C4ⁱ—C5ⁱ	0.25 (17)
Cl1—C1—C1ⁱ—C2ⁱ	179.08 (10)	C4—C5—C6—C7	−179.86 (12)
C2—C1—C1ⁱ—C2ⁱ	−1.40 (19)	C10—C5—C6—C7	−0.32 (18)
Cl1—C1—C1ⁱ—Cl1ⁱ	−0.44 (15)	C4—C5—C10—C9	−179.65 (11)
C2—C1—C1ⁱ—Cl1ⁱ	179.08 (10)	C4—C5—C10—C10ⁱ	0.19 (17)
C1ⁱ—C1—C2—C3	0.67 (18)	C6—C5—C10—C9	0.80 (17)
Cl1—C1—C2—C3	−179.81 (10)	C6—C5—C10—C10ⁱ	−179.36 (11)
C1—C2—C3—C3ⁱ	0.74 (18)	C5—C6—C7—C8	−0.3 (2)
C1—C2—C3—N1	−179.50 (12)	C6—C7—C8—C9	0.4 (2)
N1—C3—C3ⁱ—N1ⁱ	−0.96 (18)	C7—C8—C9—C10	0.1 (2)
C2—C3—C3ⁱ—C2ⁱ	−1.44 (17)	C8—C9—C10—C5	−0.69 (18)
N1—C3—C3ⁱ—C2ⁱ	178.80 (11)	C8—C9—C10—C10ⁱ	179.48 (12)
C2—C3—C3ⁱ—N1ⁱ	178.80 (11)	C5—C10—C10ⁱ—C5ⁱ	−0.17 (17)
N1—C4—C5—C6	−0.68 (17)	C5—C10—C10ⁱ—C9ⁱ	179.66 (11)
N1—C4—C5—C10	179.77 (11)	C9—C10—C10ⁱ—C5ⁱ	179.66 (11)
C4ⁱ—C4—C5—C6	179.32 (11)	C9—C10—C10ⁱ—C9ⁱ	−0.51 (18)
C4ⁱ—C4—C5—C10	−0.24 (17)

Symmetry code: (i) −x, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₂₀H₁₀Cl₂N₂
M_r	349.20
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	3.8583 (3), 26.2739 (13), 15.1147 (10)
β (°)	94.877 (6)
V (Å³)	1526.67 (17)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.43
Crystal size (mm)	0.32 × 0.14 × 0.09

Data collection
Diffractometer	Oxford Diffraction Xcalibur Sapphire3 CCD
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)
T_min, T_max	0.915, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5082, 2520, 1372
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.757

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.104, 0.83
No. of reflections	2520
No. of parameters	109
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.25

Computer programs: CrysAlis CCD (Oxford Diffraction, 2009), CrysAlis RED (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).

Acknowledgements

This research was funded by a CCSU–AAUP research grant.

References

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