Acta Cryst. (2007). E63, o3841 [ doi:10.1107/S1600536807032874 ]
In the structure of the title compound, C12H10Cl2N2, the cyclohexene ring adopts a half-chair conformation.
A 20 ml test tube was charged with 4,5-Dichloro-o-phenylenediamine (177 mg, 1 mmol) and 1,2-Cyclohexanedione (112 mg, 1 mmol). This was heated in a boiling water bath for 1 h, until the reaction mixture was homogeneous. The residue was then dissolved in boiling ethanol (100% EtOH, 15 ml). Upon cooling to 0° C, light yellow crystals of (1) were obtained (215 mg, 85% yield) mp 215–216° C.
H atoms were treated as riding, with C—H = 1.00 with Uiso(H) = 1.2 Ueq(C) for all H atoms.
Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: XSHELL (Bruker, 2004); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
![[Figure 1]](./rt2001fig1thm.gif)
| Fig. 1. ORTEP drawing of (I) (Farrugia, 1997). Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as spheres. |
| C12H10Cl2N2 | Z = 2 |
| Mr = 253.12 | F000 = 260 |
| Triclinic, P1 | Dx = 1.549 Mg m−3 |
| Hall symbol: -P 1 | Cu Kα radiation λ = 1.54178 Å |
| a = 6.3442 (3) Å | Cell parameters from 71 reflections |
| b = 7.3885 (3) Å | θ = 9.5–41.0º |
| c = 11.7831 (5) Å | µ = 5.13 mm−1 |
| α = 85.720 (2)º | T = 200 (2) K |
| β = 82.122 (2)º | Block, yellow |
| γ = 83.572 (2)º | 0.35 × 0.21 × 0.08 mm |
| V = 542.68 (4) Å3 |
| Bruker SMART APEX II CCD diffractometer | 1868 independent reflections |
| Radiation source: fine-focus sealed tube | 1810 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.034 |
| T = 200(2) K | θmax = 67.0º |
| ω and ψ scans | θmin = 3.8º |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −7→7 |
| Tmin = 0.267, Tmax = 0.685 | k = −8→8 |
| 9473 measured reflections | l = −14→14 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.032 | All H-atom parameters refined |
| wR(F2) = 0.089 | w = 1/[σ2(Fo2) + (0.067P)2 + 0.0594P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.05 | (Δ/σ)max = 0.001 |
| 1868 reflections | Δρmax = 0.23 e Å−3 |
| 185 parameters | Δρmin = −0.29 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| C12H10Cl2N2 | γ = 83.572 (2)º |
| Mr = 253.12 | V = 542.68 (4) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 6.3442 (3) Å | Cu Kα |
| b = 7.3885 (3) Å | µ = 5.13 mm−1 |
| c = 11.7831 (5) Å | T = 200 (2) K |
| α = 85.720 (2)º | 0.35 × 0.21 × 0.08 mm |
| β = 82.122 (2)º |
| Bruker SMART APEX II CCD diffractometer | 1868 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 1810 reflections with I > 2σ(I) |
| Tmin = 0.267, Tmax = 0.685 | Rint = 0.034 |
| 9473 measured reflections |
| R[F2 > 2σ(F2)] = 0.032 | 185 parameters |
| wR(F2) = 0.089 | All H-atom parameters refined |
| S = 1.05 | Δρmax = 0.23 e Å−3 |
| 1868 reflections | Δρmin = −0.29 e Å−3 |
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 > 2sigma(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. |
| x | y | z | Uiso*/Ueq | ||
| Cl1 | 0.93385 (5) | 0.65523 (4) | 0.28885 (3) | 0.04023 (16) | |
| Cl2 | 0.50704 (6) | 0.83977 (5) | 0.20124 (3) | 0.04102 (16) | |
| N1 | 0.54783 (19) | 0.67203 (16) | 0.69452 (11) | 0.0335 (3) | |
| N2 | 0.16607 (18) | 0.84040 (15) | 0.61792 (10) | 0.0314 (3) | |
| C1 | 0.3736 (2) | 0.71175 (17) | 0.76619 (11) | 0.0313 (3) | |
| C2 | 0.3837 (3) | 0.6595 (2) | 0.89145 (13) | 0.0402 (3) | |
| C3 | 0.2006 (2) | 0.7516 (2) | 0.97160 (12) | 0.0395 (3) | |
| C4 | −0.0116 (2) | 0.7388 (2) | 0.92727 (12) | 0.0390 (3) | |
| C5 | −0.0180 (2) | 0.8423 (2) | 0.81112 (13) | 0.0382 (3) | |
| C6 | 0.1794 (2) | 0.79711 (17) | 0.72703 (11) | 0.0307 (3) | |
| C7 | 0.3461 (2) | 0.79900 (16) | 0.54201 (11) | 0.0294 (3) | |
| C8 | 0.3393 (2) | 0.83969 (17) | 0.42346 (12) | 0.0322 (3) | |
| C9 | 0.5173 (2) | 0.79438 (17) | 0.34757 (11) | 0.0322 (3) | |
| C10 | 0.7083 (2) | 0.71125 (16) | 0.38628 (11) | 0.0316 (3) | |
| C11 | 0.7188 (2) | 0.67350 (18) | 0.50048 (12) | 0.0340 (3) | |
| C12 | 0.5361 (2) | 0.71473 (17) | 0.58085 (11) | 0.0298 (3) | |
| H8 | 0.202 (3) | 0.896 (2) | 0.3985 (14) | 0.039 (4)* | |
| H11 | 0.855 (3) | 0.616 (2) | 0.5315 (13) | 0.037 (4)* | |
| H2A | 0.376 (3) | 0.524 (3) | 0.9028 (15) | 0.047 (4)* | |
| H3A | 0.205 (3) | 0.698 (2) | 1.0494 (15) | 0.037 (4)* | |
| H4A | −0.025 (3) | 0.613 (2) | 0.9204 (13) | 0.036 (4)* | |
| H5A | −0.142 (3) | 0.818 (3) | 0.7777 (16) | 0.050 (5)* | |
| H2B | 0.523 (3) | 0.682 (3) | 0.9123 (17) | 0.057 (5)* | |
| H3B | 0.218 (3) | 0.880 (2) | 0.9745 (14) | 0.043 (4)* | |
| H4B | −0.127 (3) | 0.781 (2) | 0.9851 (15) | 0.043 (4)* | |
| H5B | −0.032 (3) | 0.976 (2) | 0.8240 (15) | 0.046 (4)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cl1 | 0.0375 (2) | 0.0407 (2) | 0.0404 (2) | −0.00292 (16) | 0.00363 (15) | −0.00642 (15) |
| Cl2 | 0.0478 (2) | 0.0431 (2) | 0.0313 (2) | −0.00231 (17) | −0.00522 (15) | 0.00027 (15) |
| N1 | 0.0326 (6) | 0.0321 (6) | 0.0357 (6) | −0.0007 (5) | −0.0071 (5) | −0.0007 (5) |
| N2 | 0.0302 (6) | 0.0283 (6) | 0.0354 (6) | −0.0037 (5) | −0.0041 (5) | 0.0023 (4) |
| C1 | 0.0332 (7) | 0.0272 (6) | 0.0337 (7) | −0.0040 (5) | −0.0056 (5) | 0.0001 (5) |
| C2 | 0.0387 (8) | 0.0460 (8) | 0.0348 (7) | −0.0002 (7) | −0.0069 (6) | 0.0016 (6) |
| C3 | 0.0451 (8) | 0.0406 (8) | 0.0329 (7) | −0.0077 (6) | −0.0032 (6) | −0.0014 (6) |
| C4 | 0.0387 (7) | 0.0392 (8) | 0.0373 (7) | −0.0057 (6) | 0.0011 (6) | 0.0008 (6) |
| C5 | 0.0336 (7) | 0.0381 (8) | 0.0402 (8) | −0.0006 (6) | −0.0004 (6) | 0.0025 (6) |
| C6 | 0.0325 (6) | 0.0242 (6) | 0.0354 (7) | −0.0051 (5) | −0.0048 (5) | 0.0013 (5) |
| C7 | 0.0297 (6) | 0.0231 (6) | 0.0358 (7) | −0.0046 (5) | −0.0051 (5) | 0.0001 (5) |
| C8 | 0.0337 (7) | 0.0274 (6) | 0.0363 (7) | −0.0043 (6) | −0.0077 (5) | 0.0009 (5) |
| C9 | 0.0398 (7) | 0.0261 (6) | 0.0318 (6) | −0.0078 (5) | −0.0059 (5) | 0.0003 (5) |
| C10 | 0.0328 (6) | 0.0246 (6) | 0.0372 (7) | −0.0044 (5) | −0.0013 (5) | −0.0041 (5) |
| C11 | 0.0318 (7) | 0.0301 (6) | 0.0399 (7) | −0.0012 (6) | −0.0059 (6) | −0.0024 (5) |
| C12 | 0.0320 (6) | 0.0249 (6) | 0.0331 (6) | −0.0039 (5) | −0.0066 (5) | −0.0002 (5) |
| Cl1—C10 | 1.7394 (13) | C4—C5 | 1.520 (2) |
| Cl2—C9 | 1.7405 (13) | C4—H4A | 0.955 (17) |
| N1—C1 | 1.3151 (19) | C4—H4B | 0.970 (18) |
| N1—C12 | 1.3632 (19) | C5—C6 | 1.5090 (19) |
| N2—C6 | 1.3132 (18) | C5—H5A | 0.97 (2) |
| N2—C7 | 1.3716 (18) | C5—H5B | 1.001 (18) |
| C1—C6 | 1.4378 (19) | C7—C12 | 1.4104 (19) |
| C1—C2 | 1.506 (2) | C7—C8 | 1.412 (2) |
| C2—C3 | 1.524 (2) | C8—C9 | 1.368 (2) |
| C2—H2A | 1.006 (19) | C8—H8 | 0.995 (18) |
| C2—H2B | 0.99 (2) | C9—C10 | 1.413 (2) |
| C3—C4 | 1.524 (2) | C10—C11 | 1.363 (2) |
| C3—H3A | 0.974 (18) | C11—C12 | 1.4133 (19) |
| C3—H3B | 0.969 (18) | C11—H11 | 1.019 (17) |
| C1—N1—C12 | 116.95 (11) | C4—C5—H5A | 110.3 (11) |
| C6—N2—C7 | 116.96 (12) | C6—C5—H5B | 108.7 (10) |
| N1—C1—C6 | 121.78 (13) | C4—C5—H5B | 107.7 (10) |
| N1—C1—C2 | 117.16 (12) | H5A—C5—H5B | 108.0 (16) |
| C6—C1—C2 | 121.04 (13) | N2—C6—C1 | 121.97 (13) |
| C1—C2—C3 | 113.99 (13) | N2—C6—C5 | 117.29 (12) |
| C1—C2—H2A | 107.4 (10) | C1—C6—C5 | 120.73 (13) |
| C3—C2—H2A | 107.6 (10) | N2—C7—C12 | 120.84 (12) |
| C1—C2—H2B | 110.1 (12) | N2—C7—C8 | 119.23 (12) |
| C3—C2—H2B | 111.0 (12) | C12—C7—C8 | 119.92 (12) |
| H2A—C2—H2B | 106.4 (16) | C9—C8—C7 | 119.21 (12) |
| C4—C3—C2 | 109.92 (12) | C9—C8—H8 | 122.7 (9) |
| C4—C3—H3A | 112.9 (10) | C7—C8—H8 | 118.0 (9) |
| C2—C3—H3A | 109.4 (10) | C8—C9—C10 | 120.99 (12) |
| C4—C3—H3B | 107.7 (10) | C8—C9—Cl2 | 119.22 (10) |
| C2—C3—H3B | 110.3 (10) | C10—C9—Cl2 | 119.79 (10) |
| H3A—C3—H3B | 106.5 (14) | C11—C10—C9 | 120.61 (12) |
| C5—C4—C3 | 110.68 (12) | C11—C10—Cl1 | 118.89 (11) |
| C5—C4—H4A | 109.9 (9) | C9—C10—Cl1 | 120.50 (10) |
| C3—C4—H4A | 107.9 (10) | C10—C11—C12 | 119.75 (13) |
| C5—C4—H4B | 113.5 (11) | C10—C11—H11 | 122.7 (9) |
| C3—C4—H4B | 108.5 (10) | C12—C11—H11 | 117.6 (9) |
| H4A—C4—H4B | 106.2 (14) | N1—C12—C7 | 121.50 (12) |
| C6—C5—C4 | 113.28 (12) | N1—C12—C11 | 119.01 (12) |
| C6—C5—H5A | 108.7 (11) | C7—C12—C11 | 119.49 (12) |
| C12—N1—C1—C6 | −0.29 (19) | C12—C7—C8—C9 | 0.80 (19) |
| C12—N1—C1—C2 | 178.13 (12) | C7—C8—C9—C10 | −1.3 (2) |
| N1—C1—C2—C3 | 164.89 (13) | C7—C8—C9—Cl2 | 178.55 (9) |
| C6—C1—C2—C3 | −16.7 (2) | C8—C9—C10—C11 | 0.3 (2) |
| C1—C2—C3—C4 | 46.64 (17) | Cl2—C9—C10—C11 | −179.53 (10) |
| C2—C3—C4—C5 | −63.51 (17) | C8—C9—C10—Cl1 | −179.73 (9) |
| C3—C4—C5—C6 | 48.59 (17) | Cl2—C9—C10—Cl1 | 0.43 (15) |
| C7—N2—C6—C1 | 0.57 (19) | C9—C10—C11—C12 | 1.2 (2) |
| C7—N2—C6—C5 | 179.97 (11) | Cl1—C10—C11—C12 | −178.78 (9) |
| N1—C1—C6—N2 | −0.3 (2) | C1—N1—C12—C7 | 0.49 (19) |
| C2—C1—C6—N2 | −178.61 (11) | C1—N1—C12—C11 | −179.57 (12) |
| N1—C1—C6—C5 | −179.63 (11) | N2—C7—C12—N1 | −0.18 (19) |
| C2—C1—C6—C5 | 2.0 (2) | C8—C7—C12—N1 | −179.40 (11) |
| C4—C5—C6—N2 | 162.46 (13) | N2—C7—C12—C11 | 179.88 (11) |
| C4—C5—C6—C1 | −18.14 (19) | C8—C7—C12—C11 | 0.66 (19) |
| C6—N2—C7—C12 | −0.36 (18) | C10—C11—C12—N1 | 178.41 (12) |
| C6—N2—C7—C8 | 178.87 (11) | C10—C11—C12—C7 | −1.6 (2) |
| N2—C7—C8—C9 | −178.43 (11) |
EED acknowledges the National Science Foundation for primary support of this research (EPSCOR grant No. 450901). RDP is indebted to the NSF (CHE-0443345) and the College of William and Mary for the purchase of the X-ray equipment.
Brown, D. J., Taylor, E. C. & Wipf, P. (2004). The Chemistry of Heterocyclic Compounds, Vol. 61, Quinoxalines: Supplement II, pp. 100–105. New York: Wiley.
Bruker (2004). APEX2 (Version 2.0), SAINT-Plus (Version 7.12A) and XSHELL (Version 6.3.1). Bruker AXS Inc., Madison Wisconsin, USA.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565–?.
Gibson, R. J. P., Kass, J. P., Zambrano, C. H., Fronczek, F. R. & Dueno, E. E. (2006). Acta Cryst. E62, o2947–o2948.
Page, S. E., Gordon, K. C. & Burrell, A. K. (1998). Inorg. Chem. 37, 4452–4459.
Pascal, R. A. Jr & Ho, D. M. (1993). J. Am. Chem. Soc. 115, 8507–8508.
Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.
Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany.
Simpson, T. J. & Gordon, K. C. (1995). Inorg. Chem. 34, 6323–6329.
Willett, R. D., Jeitler, R. J. & Twamley, B. (2001). Inorg. Chem. 40, 6502–6505.
Wozniak, K., Krygowski, T. M., Grech, E., Kolodziejski, W. & Klinowski, J. (1993). J. Phys. Chem. 97, 1862–1867.
Wu, C. D., Lu, C.-Z., Zhuang, H.-H. & Huang, J.-S. (2002). Inorg. Chem. 41, 5636–5637.
One of the primary interests of our lab is the synthesis and characterization of novel substituted quinoxalines and the closely related phenazines. Quinoxalines and their derivatives have received considerable attention in the past several years due to their electronic properties (Page et al., 1998; Simpson & Gordon, 1995), H-bonding ability (Pascal & Ho, 1993; Wozniak et al., 1993), and their capacity to coordinate to metals (Wu et al., 2002; Willett et al., 2001). During our investigations, we have prepared a number of substituted quinoxalines and phenazines, which readily coordinate to copper iodide forming novel structures. Our current work involves the synthesis of new nitrogen heterocycles (Gibson, et al., 2006) which may lead to novel three-dimensional structures upon coordination to cuprous salts. Here, we report the crystal structure of 7,8-dichloro-1,2,3,4-tetrahydrophenazine (I), (Figure 1).
The structure of (I) exhibits bond distances and angles that are normal, for all fall within ranges established in the literature for similar nitrogen heterocycles (Brown et al., 2004). There are two molecules per unit cell, related to each other by an inversion center. The chloride substituents are almost eclipsed with respect to each other, with a torsion angle Cl1—C10—C9—Cl2 of 0.36 (16)°. Both aromatic rings are essentially planar and almost co-planar with a dihedral angle of 1.20 (18)°, based on least-squares plane calculations on C12—C11—C10—C9—C8—C7 and C7—C12—N1—C1—C6—N2. The H-saturated fragment of the ring system adopts a twisted, cyclohexyl-like conformation as evidenced by the angles depicted by atoms C5 C4 C3 110.68 (12)°, C2 C3 C4 109.92 (12)°, and the C2—C3—C4—C5 torsion angle of 63.62 (17)°, which suggest the presence of some angle and torsional strain.