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

Melardi, M.R.; Aghamohamadi, M.; Attar Gharamaleki, J.; Rofouei, M.K.; Notash, B.

doi:10.1107/S1600536812005132

organic compounds

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Volume 68| Part 3| March 2012| Page o724

doi:10.1107/S1600536812005132

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

Mohammad Reza Melardi,^a Maryam Aghamohamadi,^a Jafar Attar Gharamaleki,^b ^* Mohammad Kazem Rofouei ^b and Behrouz Notash ^c

^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 π–π stacking interactions are also observed.

Related literature

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

Crystal data

C₁₃H₁₁Cl₂N₃O
M_r = 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)
R_int = 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
Δρ_max = 0.24 e Å⁻³
Δρ_min = −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	D⋯A	D—H⋯A
N1—H1⋯Cl1ⁱ	0.85 (2)	2.69 (2)	3.529 (2)	170 (3)
C1—H1C⋯Cg1ⁱⁱ	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 ); cell refinement: X-AREA; 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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812005132/pv2511sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812005132/pv2511Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812005132/pv2511Isup3.cml

checkCIF report

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 (–N2═N3–) 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 π–π [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.

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

	Fig. 1. Molecular structure of the title compound with ellipsoids drawn at 50% probability level.
	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

C₁₃H₁₁Cl₂N₃O	F(000) = 1216
M_r = 296.15	D_x = 1.454 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3659 reflections
a = 15.422 (3) Å	θ = 1.6–29.4°
b = 23.068 (5) Å	µ = 0.47 mm⁻¹
c = 7.6141 (15) Å	T = 298 K
β = 92.60 (3)°	Needle, orange
V = 2706.0 (9) Å³	0.5 × 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 tube	R_int = 0.162
Graphite monochromator	θ_max = 29.4°, θ_min = 1.6°
Detector resolution: 0.15 pixels mm^-1	h = −21→20
rotation method scans	k = −31→31
15133 measured reflections	l = −10→10
3659 independent 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)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.137	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0234P)² + 2.1152P] where P = (F_o² + 2F_c²)/3
3659 reflections	(Δ/σ)_max < 0.001
177 parameters	Δρ_max = 0.24 e Å⁻³
1 restraint	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₁₃H₁₁Cl₂N₃O	V = 2706.0 (9) Å³
M_r = 296.15	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 15.422 (3) Å	µ = 0.47 mm⁻¹
b = 23.068 (5) Å	T = 298 K
c = 7.6141 (15) Å	0.5 × 0.3 × 0.15 mm
β = 92.60 (3)°

Data collection top

Stoe IPDS 2T diffractometer	2178 reflections with I > 2σ(I)
15133 measured reflections	R_int = 0.162
3659 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.066	1 restraint
wR(F²) = 0.137	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.24 e Å⁻³
3659 reflections	Δρ_min = −0.28 e Å⁻³
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

	x	y	z	U_iso*/U_eq
Cl1	0.15277 (6)	0.62694 (3)	0.38482 (14)	0.0726 (3)
Cl2	0.38395 (5)	0.46656 (4)	0.20924 (14)	0.0697 (3)
O1	−0.07732 (12)	0.25239 (8)	0.5479 (3)	0.0541 (5)
N1	0.04554 (15)	0.32351 (9)	0.4565 (4)	0.0510 (6)
N2	0.10429 (14)	0.36171 (9)	0.4104 (3)	0.0461 (6)
N3	0.07934 (15)	0.41328 (9)	0.4243 (3)	0.0515 (6)
C1	−0.14585 (18)	0.21619 (13)	0.6009 (5)	0.0577 (8)
H1A	−0.1640	0.1912	0.5054	0.087*
H1B	−0.1939	0.2397	0.6335	0.087*
H1C	−0.1260	0.1932	0.6998	0.087*
C2	−0.00257 (17)	0.22621 (11)	0.5001 (4)	0.0438 (6)
C3	0.01140 (19)	0.16686 (11)	0.4955 (4)	0.0494 (7)
H3	−0.0323	0.1414	0.5256	0.059*
C4	0.0906 (2)	0.14548 (12)	0.4459 (4)	0.0552 (7)
H4	0.1001	0.1057	0.4434	0.066*
C5	0.15531 (19)	0.18293 (13)	0.4004 (4)	0.0544 (7)
H5	0.2086	0.1684	0.3685	0.065*
C6	0.14148 (18)	0.24231 (12)	0.4020 (4)	0.0488 (7)
H6	0.1852	0.2674	0.3703	0.059*
C7	0.06270 (17)	0.26414 (10)	0.4508 (4)	0.0416 (6)
C8	0.14307 (17)	0.45444 (11)	0.3765 (4)	0.0435 (6)
C9	0.12052 (17)	0.51217 (11)	0.3953 (4)	0.0484 (7)
H9	0.0659	0.5222	0.4327	0.058*
C10	0.17985 (18)	0.55468 (11)	0.3581 (4)	0.0495 (7)
C11	0.26112 (18)	0.54131 (12)	0.3013 (4)	0.0520 (7)
H11	0.3009	0.5703	0.2776	0.062*
C12	0.28154 (17)	0.48354 (12)	0.2808 (4)	0.0491 (7)
C13	0.22487 (17)	0.43961 (11)	0.3177 (4)	0.0482 (7)
H13	0.2405	0.4010	0.3041	0.058*
H1	−0.0038 (13)	0.3373 (12)	0.481 (4)	0.059 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0684 (5)	0.0384 (3)	0.1140 (8)	0.0020 (3)	0.0377 (5)	0.0057 (4)
Cl2	0.0474 (4)	0.0709 (5)	0.0930 (7)	0.0123 (4)	0.0281 (4)	0.0165 (4)
O1	0.0418 (10)	0.0424 (9)	0.0791 (15)	−0.0020 (8)	0.0160 (10)	0.0022 (9)
N1	0.0397 (12)	0.0396 (11)	0.0748 (18)	−0.0021 (10)	0.0150 (12)	0.0018 (11)
N2	0.0435 (12)	0.0408 (11)	0.0546 (15)	−0.0040 (9)	0.0080 (11)	0.0038 (10)
N3	0.0459 (12)	0.0395 (11)	0.0699 (17)	−0.0025 (10)	0.0140 (11)	0.0055 (11)
C1	0.0398 (14)	0.0620 (17)	0.072 (2)	−0.0061 (13)	0.0109 (15)	0.0102 (16)
C2	0.0407 (13)	0.0432 (12)	0.0476 (16)	−0.0006 (11)	0.0034 (12)	−0.0013 (12)
C3	0.0539 (16)	0.0411 (13)	0.0535 (18)	−0.0062 (12)	0.0065 (14)	0.0026 (12)
C4	0.0650 (18)	0.0421 (13)	0.059 (2)	0.0071 (13)	0.0111 (16)	−0.0018 (13)
C5	0.0501 (15)	0.0554 (15)	0.0585 (19)	0.0131 (14)	0.0107 (14)	−0.0068 (14)
C6	0.0419 (14)	0.0493 (14)	0.0559 (19)	−0.0012 (12)	0.0089 (13)	−0.0008 (13)
C7	0.0430 (14)	0.0371 (12)	0.0446 (16)	−0.0022 (11)	0.0028 (12)	−0.0007 (11)
C8	0.0427 (13)	0.0417 (12)	0.0465 (16)	−0.0021 (11)	0.0087 (12)	0.0062 (11)
C9	0.0438 (14)	0.0438 (13)	0.0589 (19)	0.0034 (11)	0.0155 (13)	0.0044 (13)
C10	0.0498 (15)	0.0369 (12)	0.063 (2)	0.0025 (11)	0.0147 (14)	0.0079 (12)
C11	0.0457 (15)	0.0467 (14)	0.065 (2)	−0.0014 (12)	0.0157 (14)	0.0126 (13)
C12	0.0399 (13)	0.0515 (14)	0.0570 (19)	0.0058 (12)	0.0151 (13)	0.0093 (13)
C13	0.0500 (16)	0.0418 (13)	0.0538 (19)	0.0057 (12)	0.0118 (14)	0.0057 (12)

Geometric parameters (Å, º) top

Cl1—C10	1.733 (3)	C4—C5	1.376 (4)
Cl2—C12	1.739 (3)	C4—H4	0.9300
O1—C2	1.365 (3)	C5—C6	1.386 (4)
O1—C1	1.420 (3)	C5—H5	0.9300
N1—N2	1.323 (3)	C6—C7	1.381 (4)
N1—C7	1.396 (3)	C6—H6	0.9300
N1—H1	0.854 (17)	C8—C9	1.386 (4)
N2—N3	1.256 (3)	C8—C13	1.400 (4)
N3—C8	1.426 (3)	C9—C10	1.379 (4)
C1—H1A	0.9600	C9—H9	0.9300
C1—H1B	0.9600	C10—C11	1.379 (4)
C1—H1C	0.9600	C11—C12	1.380 (4)
C2—C3	1.387 (4)	C11—H11	0.9300
C2—C7	1.398 (4)	C12—C13	1.375 (4)
C3—C4	1.386 (4)	C13—H13	0.9300
C3—H3	0.9300

C2—O1—C1	117.7 (2)	C7—C6—C5	120.0 (3)
N2—N1—C7	120.8 (2)	C7—C6—H6	120.0
N2—N1—H1	116 (2)	C5—C6—H6	120.0
C7—N1—H1	123 (2)	C6—C7—N1	122.4 (2)
N3—N2—N1	113.1 (2)	C6—C7—C2	119.8 (2)
N2—N3—C8	113.0 (2)	N1—C7—C2	117.8 (2)
O1—C1—H1A	109.5	C9—C8—C13	120.1 (2)
O1—C1—H1B	109.5	C9—C8—N3	115.7 (2)
H1A—C1—H1B	109.5	C13—C8—N3	124.1 (2)
O1—C1—H1C	109.5	C10—C9—C8	119.4 (2)
H1A—C1—H1C	109.5	C10—C9—H9	120.3
H1B—C1—H1C	109.5	C8—C9—H9	120.3
O1—C2—C3	125.3 (2)	C11—C10—C9	121.7 (2)
O1—C2—C7	115.0 (2)	C11—C10—Cl1	118.6 (2)
C3—C2—C7	119.8 (3)	C9—C10—Cl1	119.6 (2)
C4—C3—C2	119.9 (3)	C10—C11—C12	117.8 (2)
C4—C3—H3	120.1	C10—C11—H11	121.1
C2—C3—H3	120.1	C12—C11—H11	121.1
C5—C4—C3	120.2 (3)	C13—C12—C11	122.5 (2)
C5—C4—H4	119.9	C13—C12—Cl2	119.5 (2)
C3—C4—H4	119.9	C11—C12—Cl2	117.9 (2)
C4—C5—C6	120.3 (3)	C12—C13—C8	118.4 (2)
C4—C5—H5	119.8	C12—C13—H13	120.8
C6—C5—H5	119.8	C8—C13—H13	120.8

C7—N1—N2—N3	−179.4 (3)	C3—C2—C7—N1	179.6 (3)
N1—N2—N3—C8	179.4 (3)	N2—N3—C8—C9	−177.7 (3)
C1—O1—C2—C3	1.4 (4)	N2—N3—C8—C13	0.7 (4)
C1—O1—C2—C7	−179.4 (3)	C13—C8—C9—C10	−0.9 (5)
O1—C2—C3—C4	−179.4 (3)	N3—C8—C9—C10	177.6 (3)
C7—C2—C3—C4	1.5 (5)	C8—C9—C10—C11	0.5 (5)
C2—C3—C4—C5	−0.3 (5)	C8—C9—C10—Cl1	−178.9 (2)
C3—C4—C5—C6	−0.7 (5)	C9—C10—C11—C12	0.6 (5)
C4—C5—C6—C7	0.5 (5)	Cl1—C10—C11—C12	180.0 (3)
C5—C6—C7—N1	179.3 (3)	C10—C11—C12—C13	−1.2 (5)
C5—C6—C7—C2	0.6 (5)	C10—C11—C12—Cl2	−180.0 (2)
N2—N1—C7—C6	1.8 (4)	C11—C12—C13—C8	0.8 (5)
N2—N1—C7—C2	−179.5 (3)	Cl2—C12—C13—C8	179.5 (2)
O1—C2—C7—C6	179.2 (3)	C9—C8—C13—C12	0.3 (4)
C3—C2—C7—C6	−1.6 (5)	N3—C8—C13—C12	−178.0 (3)
O1—C2—C7—N1	0.4 (4)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C2–C7 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl1ⁱ	0.85 (2)	2.69 (2)	3.529 (2)	170 (3)
N1—H1···O1	0.85 (2)	2.33 (3)	2.624 (3)	100 (2)
C1—H1C···Cg1ⁱⁱ	0.96	2.76	3.553 (4)	140

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, y, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₁Cl₂N₃O
M_r	296.15
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	15.422 (3), 23.068 (5), 7.6141 (15)
β (°)	92.60 (3)
V (Å³)	2706.0 (9)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.47
Crystal size (mm)	0.5 × 0.3 × 0.15

Data collection
Diffractometer	Stoe IPDS 2T diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	15133, 3659, 2178
R_int	0.162
(sin θ/λ)_max (Å⁻¹)	0.691

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.066, 0.137, 1.07
No. of reflections	3659
No. of parameters	177
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl1ⁱ	0.85 (2)	2.686 (18)	3.529 (2)	170 (3)
C1—H1C···Cg1ⁱⁱ	0.96	2.76	3.553 (4)	140

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, y, −z+3/2.

References

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

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o724

doi:10.1107/S1600536812005132

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