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 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
|
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) . | |
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
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.
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.
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).
1-(3,5-Dichlorophenyl)-3-(2-methoxyphenyl)triaz-1-ene
top Crystal data top C13H11Cl2N3O | F(000) = 1216 |
Mr = 296.15 | Dx = 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 | Rint = 0.162 |
Graphite monochromator | θmax = 29.4°, θmin = 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(Fo2) + (0.0234P)2 + 2.1152P] where P = (Fo2 + 2Fc2)/3 |
3659 reflections | (Δ/σ)max < 0.001 |
177 parameters | Δρmax = 0.24 e Å−3 |
1 restraint | Δρmin = −0.28 e Å−3 |
Crystal data top C13H11Cl2N3O | V = 2706.0 (9) Å3 |
Mr = 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 | Rint = 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 | Δρmax = 0.24 e Å−3 |
3659 reflections | Δρmin = −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 | Uiso*/Ueq | |
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) topCg1 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 |
Mr | 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 |
Rint | 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 |
Δρmax, Δρmin (e Å−3) | 0.24, −0.28 |
Hydrogen-bond geometry (Å, º) topCg1 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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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).