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ISSN: 2056-9890

1-(3,5-Di­chloro­phen­yl)-3-(2-meth­­oxy­phen­yl)triaz-1-ene

aDepartment of Chemistry, Islamic Azad University, Karaj Branch, Karaj, Iran, bFaculty of Chemistry, Tarbiat Moallem University, Tehran, Iran, and cDepartment of Chemistry, Shahid Beheshti University, G.C., Evin, Tehran 1983963113, Iran
*Correspondence e-mail: attar_jafar@yahoo.com

(Received 2 February 2012; accepted 6 February 2012; online 17 February 2012)

The title mol­ecule, C13H11Cl2N3O, is almost planar and adopts a trans conformation with respect to the –N=N– bond; the dihedral angle between the rings is 3.47 (2)°. The N—N bond lengths indicate the presence of single- and double-bond characters and hence the –N=N—NH– moiety. In the crystal, inversion dimers linked by pairs of N—H⋯Cl hydrogen bonds occur, and C—H⋯π and ππ stacking interactions are also observed.

Related literature

For background literature and the synthesis of related compounds, see: Rofouei et al. (2009[Rofouei, M. K., Hematyar, M., Ghoulipour, V. & Attar Gharamaleki, J. (2009). Inorg. Chim. Acta, 362, 3777-3784.]). For the synthesis and mol­ecular structure of a similar monochloro-substituted triazene, see: Rofouei et al. (2012[Rofouei, M. K., Attar Gharamaleki, J., Ghalami, Z., Bruno, G. & Amiri Rudbari, H. (2012). Z. Anorg. Allg. Chem. Accepted.]).

[Scheme 1]

Experimental

Crystal data
  • C13H11Cl2N3O

  • Mr = 296.15

  • Monoclinic, C 2/c

  • a = 15.422 (3) Å

  • b = 23.068 (5) Å

  • c = 7.6141 (15) Å

  • β = 92.60 (3)°

  • V = 2706.0 (9) Å3

  • Z = 8

  • Mo Kα radiation

  • μ = 0.47 mm−1

  • T = 298 K

  • 0.5 × 0.3 × 0.15 mm

Data collection
  • Stoe IPDS 2T diffractometer

  • 15133 measured reflections

  • 3659 independent reflections

  • 2178 reflections with I > 2σ(I)

  • Rint = 0.162

Refinement
  • R[F2 > 2σ(F2)] = 0.066

  • wR(F2) = 0.137

  • S = 1.07

  • 3659 reflections

  • 177 parameters

  • 1 restraint

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.24 e Å−3

  • Δρmin = −0.28 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C2–C7 ring.

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1⋯Cl1i 0.85 (2) 2.69 (2) 3.529 (2) 170 (3)
C1—H1CCg1ii 0.96 2.76 3.553 (4) 140
Symmetry codes: (i) -x, -y+1, -z+1; (ii) [-x, y, -z+{\script{3\over 2}}].

Data collection: X-AREA (Stoe & Cie, 2005[Stoe & Cie (2005). X-AREA and X-RED32. Stoe & Cie, Darmstadt, Germany.]); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2005[Stoe & Cie (2005). X-AREA and X-RED32. Stoe & Cie, Darmstadt, Germany.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: WinGX (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]).

Supporting information


Comment top

In continuation of our studies on the synthesis and characterization of trizene compounds as ligands in our laboratory (Rofouei et al., 2012; Rofouei et al., 2009), we now report the crystal structure of the title compound.

The title molecule (Fig. 1) adopts trans configuration about the (–N2N3–) bond and is almost planar with the dihedral angel between two aromatic rings 3.47 (2) °. Non-Classic N—H···Cl hydrogen bond with D···A distance of 3.529 (2) Å connect the individual molecules into dimers. The N1—N2 and N2—N3 bond distances are 1.323 (3) and 1.256 (3) Å, which indicate the presence of a single and a double bond characters, respectively. Another interesting feature of the title compound is the presence of ππ [Cg1···Cg1 distance of 3.757 (2) Å] and edge-to-face C1—H1C···Cg1 stacking interactions between the methoxy hydrogen and the phenyl ring with H···π distance of 2.76 Å, in which Cg1 is the center of (C2—C7) ring. Unit cell packing diagram of the title compound is presented in Fig. 2, showing N—H···Cl hydrogen bonds.

The bond distances and bond angles in the title compoiund are in agreement with the corresponding bond distances and bond angles reported for a closely related structure, [1-(2-methoxyphenyl)-3-(4-chlorophenyl)]triazene (Rofouei et al., 2012).

Related literature top

For background literature and the synthesis of related compounds, see: Rofouei et al. (2009). For the synthesis and molecular structure of a similar monochloro-substituted triazene, see: Rofouei et al. (2012).

Experimental top

To a 1 L flask in an ice bath, was added dichloroaniline (6.36 g, 0.05 mol) and HCl (4.68 g, 0.13 mol; d = 1.18 g.ml-1). To the obtained solution was added dropwise a solution of sodium nitrite (4.14 g in 25 ml H2O). Then, a diluted solution of o-anisidine (6.15 g, 0.05 mol) in methanol (10 ml) was added to the solution. The pH of the solution was adjusted at about 7–8 by adding a solution of sodium acetate ( 14.76 g, 0.18 mol) in 45 ml H2O as solvent. The solution was stirred for about 45 minutes, giving an orange precipitate. It was then filtered off and dried under vacuum. After dissolving in dichloromethane and recrystallization, orange crystals of the title compound were obtained.

Refinement top

N—H hydrogen atom were found in a difference Fourier map and refined isotropically with distance restraint of 0.85 (2) Å. All C—H hydrogen atoms were positioned geometrically and refined as riding atoms with C—H = 0.93 and 0.96 Å, Uiso(H) = 1.2Ueq(C) and 1.5Ueq(C) for aryl and methyl H atoms, respectively.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA (Stoe & Cie, 2005); data reduction: X-RED32 (Stoe & Cie, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound with ellipsoids drawn at 50% probability level.
[Figure 2] Fig. 2. Part of the unit-cell packing of the title compound showing C—H···π interactions between a methoxy H atom and the phenyl ring with a H···π distance of 2.76 Å.
1-(3,5-Dichlorophenyl)-3-(2-methoxyphenyl)triaz-1-ene top
Crystal data top
C13H11Cl2N3OF(000) = 1216
Mr = 296.15Dx = 1.454 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 3659 reflections
a = 15.422 (3) Åθ = 1.6–29.4°
b = 23.068 (5) ŵ = 0.47 mm1
c = 7.6141 (15) ÅT = 298 K
β = 92.60 (3)°Needle, orange
V = 2706.0 (9) Å30.5 × 0.3 × 0.15 mm
Z = 8
Data collection top
Stoe IPDS 2T
diffractometer
2178 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.162
Graphite monochromatorθmax = 29.4°, θmin = 1.6°
Detector resolution: 0.15 pixels mm-1h = 2120
rotation method scansk = 3131
15133 measured reflectionsl = 1010
3659 independent reflections
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)] = 0.066Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.137H atoms treated by a mixture of independent and constrained refinement
S = 1.07 w = 1/[σ2(Fo2) + (0.0234P)2 + 2.1152P]
where P = (Fo2 + 2Fc2)/3
3659 reflections(Δ/σ)max < 0.001
177 parametersΔρmax = 0.24 e Å3
1 restraintΔρmin = 0.28 e Å3
Crystal data top
C13H11Cl2N3OV = 2706.0 (9) Å3
Mr = 296.15Z = 8
Monoclinic, C2/cMo Kα radiation
a = 15.422 (3) ŵ = 0.47 mm1
b = 23.068 (5) ÅT = 298 K
c = 7.6141 (15) Å0.5 × 0.3 × 0.15 mm
β = 92.60 (3)°
Data collection top
Stoe IPDS 2T
diffractometer
2178 reflections with I > 2σ(I)
15133 measured reflectionsRint = 0.162
3659 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0661 restraint
wR(F2) = 0.137H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 0.24 e Å3
3659 reflectionsΔρmin = 0.28 e Å3
177 parameters
Special details top

Experimental. 1H-NMR (300 MHz, d6-DMSO) δ, p.p.m.: 3.83 (3H, CH3), 6.73–7.69 (7H, aromatic groups) and 12.93(1H, NH group). 13C-NMR (100 MHz, DMSO) δ, p.p.m.: 55.8 (O—CH3), 111.9–153.8 (C atoms of aromatic rings). IR (KBr): 3314, 1601, 1566, 1473, 1255, 754 cm-1.

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*/Ueq
Cl10.15277 (6)0.62694 (3)0.38482 (14)0.0726 (3)
Cl20.38395 (5)0.46656 (4)0.20924 (14)0.0697 (3)
O10.07732 (12)0.25239 (8)0.5479 (3)0.0541 (5)
N10.04554 (15)0.32351 (9)0.4565 (4)0.0510 (6)
N20.10429 (14)0.36171 (9)0.4104 (3)0.0461 (6)
N30.07934 (15)0.41328 (9)0.4243 (3)0.0515 (6)
C10.14585 (18)0.21619 (13)0.6009 (5)0.0577 (8)
H1A0.16400.19120.50540.087*
H1B0.19390.23970.63350.087*
H1C0.12600.19320.69980.087*
C20.00257 (17)0.22621 (11)0.5001 (4)0.0438 (6)
C30.01140 (19)0.16686 (11)0.4955 (4)0.0494 (7)
H30.03230.14140.52560.059*
C40.0906 (2)0.14548 (12)0.4459 (4)0.0552 (7)
H40.10010.10570.44340.066*
C50.15531 (19)0.18293 (13)0.4004 (4)0.0544 (7)
H50.20860.16840.36850.065*
C60.14148 (18)0.24231 (12)0.4020 (4)0.0488 (7)
H60.18520.26740.37030.059*
C70.06270 (17)0.26414 (10)0.4508 (4)0.0416 (6)
C80.14307 (17)0.45444 (11)0.3765 (4)0.0435 (6)
C90.12052 (17)0.51217 (11)0.3953 (4)0.0484 (7)
H90.06590.52220.43270.058*
C100.17985 (18)0.55468 (11)0.3581 (4)0.0495 (7)
C110.26112 (18)0.54131 (12)0.3013 (4)0.0520 (7)
H110.30090.57030.27760.062*
C120.28154 (17)0.48354 (12)0.2808 (4)0.0491 (7)
C130.22487 (17)0.43961 (11)0.3177 (4)0.0482 (7)
H130.24050.40100.30410.058*
H10.0038 (13)0.3373 (12)0.481 (4)0.059 (9)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0684 (5)0.0384 (3)0.1140 (8)0.0020 (3)0.0377 (5)0.0057 (4)
Cl20.0474 (4)0.0709 (5)0.0930 (7)0.0123 (4)0.0281 (4)0.0165 (4)
O10.0418 (10)0.0424 (9)0.0791 (15)0.0020 (8)0.0160 (10)0.0022 (9)
N10.0397 (12)0.0396 (11)0.0748 (18)0.0021 (10)0.0150 (12)0.0018 (11)
N20.0435 (12)0.0408 (11)0.0546 (15)0.0040 (9)0.0080 (11)0.0038 (10)
N30.0459 (12)0.0395 (11)0.0699 (17)0.0025 (10)0.0140 (11)0.0055 (11)
C10.0398 (14)0.0620 (17)0.072 (2)0.0061 (13)0.0109 (15)0.0102 (16)
C20.0407 (13)0.0432 (12)0.0476 (16)0.0006 (11)0.0034 (12)0.0013 (12)
C30.0539 (16)0.0411 (13)0.0535 (18)0.0062 (12)0.0065 (14)0.0026 (12)
C40.0650 (18)0.0421 (13)0.059 (2)0.0071 (13)0.0111 (16)0.0018 (13)
C50.0501 (15)0.0554 (15)0.0585 (19)0.0131 (14)0.0107 (14)0.0068 (14)
C60.0419 (14)0.0493 (14)0.0559 (19)0.0012 (12)0.0089 (13)0.0008 (13)
C70.0430 (14)0.0371 (12)0.0446 (16)0.0022 (11)0.0028 (12)0.0007 (11)
C80.0427 (13)0.0417 (12)0.0465 (16)0.0021 (11)0.0087 (12)0.0062 (11)
C90.0438 (14)0.0438 (13)0.0589 (19)0.0034 (11)0.0155 (13)0.0044 (13)
C100.0498 (15)0.0369 (12)0.063 (2)0.0025 (11)0.0147 (14)0.0079 (12)
C110.0457 (15)0.0467 (14)0.065 (2)0.0014 (12)0.0157 (14)0.0126 (13)
C120.0399 (13)0.0515 (14)0.0570 (19)0.0058 (12)0.0151 (13)0.0093 (13)
C130.0500 (16)0.0418 (13)0.0538 (19)0.0057 (12)0.0118 (14)0.0057 (12)
Geometric parameters (Å, º) top
Cl1—C101.733 (3)C4—C51.376 (4)
Cl2—C121.739 (3)C4—H40.9300
O1—C21.365 (3)C5—C61.386 (4)
O1—C11.420 (3)C5—H50.9300
N1—N21.323 (3)C6—C71.381 (4)
N1—C71.396 (3)C6—H60.9300
N1—H10.854 (17)C8—C91.386 (4)
N2—N31.256 (3)C8—C131.400 (4)
N3—C81.426 (3)C9—C101.379 (4)
C1—H1A0.9600C9—H90.9300
C1—H1B0.9600C10—C111.379 (4)
C1—H1C0.9600C11—C121.380 (4)
C2—C31.387 (4)C11—H110.9300
C2—C71.398 (4)C12—C131.375 (4)
C3—C41.386 (4)C13—H130.9300
C3—H30.9300
C2—O1—C1117.7 (2)C7—C6—C5120.0 (3)
N2—N1—C7120.8 (2)C7—C6—H6120.0
N2—N1—H1116 (2)C5—C6—H6120.0
C7—N1—H1123 (2)C6—C7—N1122.4 (2)
N3—N2—N1113.1 (2)C6—C7—C2119.8 (2)
N2—N3—C8113.0 (2)N1—C7—C2117.8 (2)
O1—C1—H1A109.5C9—C8—C13120.1 (2)
O1—C1—H1B109.5C9—C8—N3115.7 (2)
H1A—C1—H1B109.5C13—C8—N3124.1 (2)
O1—C1—H1C109.5C10—C9—C8119.4 (2)
H1A—C1—H1C109.5C10—C9—H9120.3
H1B—C1—H1C109.5C8—C9—H9120.3
O1—C2—C3125.3 (2)C11—C10—C9121.7 (2)
O1—C2—C7115.0 (2)C11—C10—Cl1118.6 (2)
C3—C2—C7119.8 (3)C9—C10—Cl1119.6 (2)
C4—C3—C2119.9 (3)C10—C11—C12117.8 (2)
C4—C3—H3120.1C10—C11—H11121.1
C2—C3—H3120.1C12—C11—H11121.1
C5—C4—C3120.2 (3)C13—C12—C11122.5 (2)
C5—C4—H4119.9C13—C12—Cl2119.5 (2)
C3—C4—H4119.9C11—C12—Cl2117.9 (2)
C4—C5—C6120.3 (3)C12—C13—C8118.4 (2)
C4—C5—H5119.8C12—C13—H13120.8
C6—C5—H5119.8C8—C13—H13120.8
C7—N1—N2—N3179.4 (3)C3—C2—C7—N1179.6 (3)
N1—N2—N3—C8179.4 (3)N2—N3—C8—C9177.7 (3)
C1—O1—C2—C31.4 (4)N2—N3—C8—C130.7 (4)
C1—O1—C2—C7179.4 (3)C13—C8—C9—C100.9 (5)
O1—C2—C3—C4179.4 (3)N3—C8—C9—C10177.6 (3)
C7—C2—C3—C41.5 (5)C8—C9—C10—C110.5 (5)
C2—C3—C4—C50.3 (5)C8—C9—C10—Cl1178.9 (2)
C3—C4—C5—C60.7 (5)C9—C10—C11—C120.6 (5)
C4—C5—C6—C70.5 (5)Cl1—C10—C11—C12180.0 (3)
C5—C6—C7—N1179.3 (3)C10—C11—C12—C131.2 (5)
C5—C6—C7—C20.6 (5)C10—C11—C12—Cl2180.0 (2)
N2—N1—C7—C61.8 (4)C11—C12—C13—C80.8 (5)
N2—N1—C7—C2179.5 (3)Cl2—C12—C13—C8179.5 (2)
O1—C2—C7—C6179.2 (3)C9—C8—C13—C120.3 (4)
C3—C2—C7—C61.6 (5)N3—C8—C13—C12178.0 (3)
O1—C2—C7—N10.4 (4)
Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the C2–C7 ring.
D—H···AD—HH···AD···AD—H···A
N1—H1···Cl1i0.85 (2)2.69 (2)3.529 (2)170 (3)
N1—H1···O10.85 (2)2.33 (3)2.624 (3)100 (2)
C1—H1C···Cg1ii0.962.763.553 (4)140
Symmetry codes: (i) x, y+1, z+1; (ii) x, y, z+3/2.

Experimental details

Crystal data
Chemical formulaC13H11Cl2N3O
Mr296.15
Crystal system, space groupMonoclinic, C2/c
Temperature (K)298
a, b, c (Å)15.422 (3), 23.068 (5), 7.6141 (15)
β (°) 92.60 (3)
V3)2706.0 (9)
Z8
Radiation typeMo Kα
µ (mm1)0.47
Crystal size (mm)0.5 × 0.3 × 0.15
Data collection
DiffractometerStoe IPDS 2T
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
15133, 3659, 2178
Rint0.162
(sin θ/λ)max1)0.691
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.066, 0.137, 1.07
No. of reflections3659
No. of parameters177
No. of restraints1
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.24, 0.28

Computer programs: X-AREA (Stoe & Cie, 2005), X-RED32 (Stoe & Cie, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the C2–C7 ring.
D—H···AD—HH···AD···AD—H···A
N1—H1···Cl1i0.85 (2)2.686 (18)3.529 (2)170 (3)
C1—H1C···Cg1ii0.962.763.553 (4)140
Symmetry codes: (i) x, y+1, z+1; (ii) x, y, z+3/2.
 

References

First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
First citationFarrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.  CrossRef CAS IUCr Journals Google Scholar
First citationRofouei, M. K., Attar Gharamaleki, J., Ghalami, Z., Bruno, G. & Amiri Rudbari, H. (2012). Z. Anorg. Allg. Chem. Accepted.  Google Scholar
First citationRofouei, M. K., Hematyar, M., Ghoulipour, V. & Attar Gharamaleki, J. (2009). Inorg. Chim. Acta, 362, 3777–3784.  Web of Science CSD CrossRef CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationStoe & Cie (2005). X-AREA and X-RED32. Stoe & Cie, Darmstadt, Germany.  Google Scholar

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