N,N′-Bis[(2-phenyl-2H-1,2,3-triazol-4-yl)­methyl­idene]benzene-1,4-diamine

The centrosymmetric title compound, C₂₄H₁₈N₈, was prepared by reaction of 2-phenyl-1,2,3-triazole-4-carbaldehyde with 1,4-phenyl­ene­di­amine. The dihedral angle between the outer phenyl ring and the triazole ring is 6.9 (3)°. The crystal structure is stabilized by inter­molecular aromatic π–π inter­actions between the parallel triazole and benzene rings [the centroid–centroid separation is 3.485 (2) Å].

Key indicators

• Single-crystal X-ray study
• T = 153 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.041
• wR factor = 0.120
• Data-to-parameter ratio = 15.6

checkCIF/PLATON results

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Alert level C
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1
              C24 H18 N8

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Aromatic nitrogen heterocycles are arguably the most facile and ligands used widely in coordination chemistry. Ligands based on heterocycles containing more than one nitrogen atom within the aromatic ring are capable of forming oligo- and polynuclear coordination compounds by bridging metal centres (Klingele et al., 2004). Schiff bases are condensation products of arylamines and carbonyl compounds. Unlike the aliphatic imines, these compounds are quite stable and represent versatile intermediates for preparation of a number of industrial and biological compounds, for example, arendiazonium nitrates, N-arylarencarboxamides, corresponding amines and cyanoamines, beta-lactams (Yan et al.,2005). 1,2,3-triazole and its derivatives are important in the synthesis of heteroarmatic compounds.

We report here the crystal structure of (I) (Fig. 1), synthesized by the reaction of 1,4-phenylene diamine with 2-phenyl-1,2,3-triazol-4-carbaldehyde. The bond lengths and angles in the (I), show normal values. In the crystal structure, π—π stacking interactions are observed between adjacent molecules, which is parallel (Fig. 2). The Cg1···Cg2^iv distance is 3.485 (2) Å (Cg1 and Cg2 are the centroids of the N1,N2/C7,C8/N3 and C1-C6 rings; symmetry code as in Fig. 2).

Related literature

For related literature, see: Li et al. (2006); Yan et al. (2005); Klingele & Brooker (2004).

S2. Experimental

Two drops of glacial acetic acid were added to a solution of 2-phenyl-1,2,3-triazole-4-carbaldehyde (0.346 g, 2 mmol) (Li et al., 2006) in absolute ethanol (20 ml), then dropwised 1,4-phenylene diamine (0.108 g, 1 mmol) in absolute ethanol (10 ml). The reaction mixture was refluxed for 0.5 hr., after cooling to room temperature,the precipitates were filtered and recrystallized: yield 91%, m.p. 475 K. Single-crystals were grown from a mixture solution of ethyl acetate and petroleum ether by slow evaporation.

S3. Refinement

All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: RAPID-AUTO (Rigaku, 2004); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: WinGX (Farrugia, 1998).

Figures

	Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 30% probabilty level for non H atoms. [Symmetry code: (i) -x, -y-1, 1-z.]
	Fig. 2. π–π stacking interations (dotted lines) in (I). Cg denotes the ring centroid. [Symmetry codes: (i) -x, -y-1, 1-z; (ii) x, 1+y, z; (iii) -x, -y, 1-z; (iv) x, y-1, z; (v)-x, -y-2, 1-z.]

N,N'-Bis[(2-phenyl-2H-1,2,3-triazol-4-yl)methylidene]benzene-1,4-diamine

Crystal data

C24H18N8	F(000) = 436
Mr = 418.46	Dx = 1.399 Mg m^−3
Monoclinic, P21/c	Melting point: 475 K
Hall symbol: -p 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 17.670 (4) Å	Cell parameters from 6687 reflections
b = 4.800 (1) Å	θ = 3.5–27.5°
c = 11.751 (2) Å	µ = 0.09 mm^−1
β = 94.42 (3)°	T = 153 K
V = 993.7 (4) Å^3	Sheet, light yellow
Z = 2	0.45 × 0.40 × 0.35 mm

Data collection

Rigaku R-AXIS SPIDER diffractometer	1743 reflections with I > 2σ(I)
Radiation source: Rotating Anode	Rint = 0.032
Graphite monochromator	θmax = 27.5°, θmin = 3.5°
ω scans	h = −22→22
8889 measured reflections	k = −6→6
2273 independent reflections	l = −12→15

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.041	H-atom parameters constrained
wR(F^2) = 0.120	w = 1/[σ^2(Fo^2) + (0.0729P)^2 + 0.1883P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
2273 reflections	Δρmax = 0.23 e Å^−3
146 parameters	Δρmin = −0.24 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.026 (5)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
N1	0.26955 (6)	0.5600 (2)	0.66669 (10)	0.0280 (3)
N2	0.22887 (6)	0.4250 (3)	0.58394 (10)	0.0306 (3)
N3	0.25656 (7)	0.4830 (3)	0.77298 (10)	0.0370 (3)
N4	0.09621 (6)	−0.1206 (3)	0.62525 (10)	0.0310 (3)
C1	0.37153 (7)	0.8752 (3)	0.73231 (13)	0.0347 (3)
H1A	0.3673	0.8152	0.8086	0.042*
C2	0.42482 (7)	1.0749 (3)	0.70784 (14)	0.0370 (4)
H2B	0.4571	1.1525	0.7680	0.044*
C3	0.43132 (8)	1.1617 (3)	0.59726 (14)	0.0381 (4)
H3B	0.4684	1.2965	0.5811	0.046*
C4	0.38356 (8)	1.0513 (4)	0.51003 (14)	0.0405 (4)
H4B	0.3874	1.1135	0.4339	0.049*
C5	0.33006 (7)	0.8506 (3)	0.53232 (13)	0.0357 (4)
H5A	0.2977	0.7737	0.4720	0.043*
C6	0.32462 (6)	0.7647 (3)	0.64333 (12)	0.0280 (3)
C7	0.18671 (7)	0.2479 (3)	0.63998 (11)	0.0288 (3)
C8	0.20430 (7)	0.2846 (3)	0.75709 (12)	0.0357 (3)
H8A	0.1824	0.1840	0.8159	0.043*
C9	0.13538 (7)	0.0576 (3)	0.57624 (12)	0.0313 (3)
H9A	0.1311	0.0673	0.4952	0.038*
C10	0.04894 (7)	−0.3064 (3)	0.55821 (12)	0.0277 (3)
C11	0.05561 (7)	−0.3664 (3)	0.44302 (12)	0.0309 (3)
H11A	0.0938	−0.2770	0.4036	0.037*
C12	−0.00713 (7)	−0.4452 (3)	0.61426 (12)	0.0291 (3)
H12A	−0.0120	−0.4095	0.6929	0.035*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0292 (5)	0.0276 (7)	0.0271 (6)	0.0006 (4)	0.0011 (4)	−0.0024 (5)
N2	0.0324 (5)	0.0279 (7)	0.0312 (7)	−0.0011 (4)	0.0000 (4)	−0.0033 (5)
N3	0.0419 (6)	0.0401 (8)	0.0293 (7)	−0.0083 (5)	0.0041 (5)	−0.0032 (5)
N4	0.0298 (5)	0.0277 (7)	0.0358 (7)	−0.0014 (4)	0.0038 (4)	−0.0062 (5)
C1	0.0352 (7)	0.0353 (8)	0.0334 (8)	−0.0030 (6)	0.0005 (5)	−0.0005 (6)
C2	0.0334 (7)	0.0337 (9)	0.0433 (9)	−0.0031 (5)	−0.0010 (5)	−0.0044 (6)
C3	0.0348 (7)	0.0319 (8)	0.0482 (9)	−0.0032 (6)	0.0078 (6)	−0.0022 (7)
C4	0.0453 (8)	0.0402 (10)	0.0369 (8)	−0.0043 (6)	0.0084 (6)	0.0037 (7)
C5	0.0367 (7)	0.0369 (9)	0.0333 (8)	−0.0024 (6)	0.0019 (5)	−0.0023 (6)
C6	0.0258 (6)	0.0231 (7)	0.0353 (8)	0.0028 (5)	0.0032 (5)	−0.0020 (5)
C7	0.0271 (6)	0.0249 (7)	0.0345 (8)	0.0017 (5)	0.0032 (5)	−0.0013 (5)
C8	0.0378 (7)	0.0368 (9)	0.0331 (8)	−0.0063 (6)	0.0069 (5)	−0.0026 (6)
C9	0.0341 (7)	0.0269 (8)	0.0325 (8)	−0.0005 (5)	0.0004 (5)	−0.0027 (6)
C10	0.0279 (6)	0.0229 (7)	0.0324 (7)	0.0020 (5)	0.0022 (5)	−0.0017 (5)
C11	0.0313 (6)	0.0281 (8)	0.0339 (8)	−0.0017 (5)	0.0076 (5)	−0.0013 (6)
C12	0.0341 (6)	0.0259 (7)	0.0278 (7)	0.0016 (5)	0.0055 (5)	−0.0022 (5)

Geometric parameters (Å, º)

N1—N2	1.332 (2)	C4—C5	1.389 (2)
N1—N3	1.339 (2)	C4—H4B	0.9500
N1—C6	1.424 (2)	C5—C6	1.379 (2)
N2—C7	1.337 (2)	C5—H5A	0.9500
N3—C8	1.329 (2)	C7—C8	1.398 (2)
N4—C9	1.267 (2)	C7—C9	1.4534 (19)
N4—C10	1.419 (2)	C8—H8A	0.9500
C1—C6	1.389 (2)	C9—H9A	0.9500
C1—C2	1.389 (2)	C10—C11	1.398 (2)
C1—H1A	0.9500	C10—C12	1.400 (2)
C2—C3	1.378 (2)	C11—C12^i	1.384 (2)
C2—H2B	0.9500	C11—H11A	0.9500
C3—C4	1.382 (2)	C12—C11^i	1.384 (2)
C3—H3B	0.9500	C12—H12A	0.9500
N2—N1—N3	115.1 (1)	C5—C6—C1	121.1 (1)
N2—N1—C6	122.2 (1)	C5—C6—N1	119.2 (1)
N3—N1—C6	122.6 (1)	C1—C6—N1	119.7 (1)
N1—N2—C7	103.9 (1)	N2—C7—C8	108.3 (1)
C8—N3—N1	103.5 (1)	N2—C7—C9	119.7 (1)
C9—N4—C10	119.4 (1)	C8—C7—C9	132.0 (1)
C6—C1—C2	118.9 (1)	N3—C8—C7	109.1 (1)
C6—C1—H1A	120.6	N3—C8—H8A	125.4
C2—C1—H1A	120.6	C7—C8—H8A	125.4
C3—C2—C1	120.7 (1)	N4—C9—C7	122.1 (1)
C3—C2—H2B	119.6	N4—C9—H9A	119.0
C1—C2—H2B	119.6	C7—C9—H9A	119.0
C2—C3—C4	119.5 (1)	C11—C10—C12	118.3 (1)
C2—C3—H3B	120.2	C11—C10—N4	125.3 (1)
C4—C3—H3B	120.2	C12—C10—N4	116.5 (1)
C3—C4—C5	120.8 (2)	C12^i—C11—C10	120.7 (1)
C3—C4—H4B	119.6	C12^i—C11—H11A	119.7
C5—C4—H4B	119.6	C10—C11—H11A	119.7
C6—C5—C4	119.0 (1)	C11^i—C12—C10	121.1 (1)
C6—C5—H5A	120.5	C11^i—C12—H12A	119.5
C4—C5—H5A	120.5	C10—C12—H12A	119.5
N3—N1—N2—C7	−0.15 (14)	N3—N1—C6—C1	5.34 (19)
C6—N1—N2—C7	177.84 (11)	N1—N2—C7—C8	−0.03 (14)
N2—N1—N3—C8	0.26 (16)	N1—N2—C7—C9	−178.61 (11)
C6—N1—N3—C8	−177.72 (12)	N1—N3—C8—C7	−0.26 (16)
C6—C1—C2—C3	−0.2 (2)	N2—C7—C8—N3	0.19 (16)
C1—C2—C3—C4	0.9 (2)	C9—C7—C8—N3	178.54 (14)
C2—C3—C4—C5	−1.1 (2)	C10—N4—C9—C7	−178.01 (12)
C3—C4—C5—C6	0.7 (2)	N2—C7—C9—N4	177.51 (12)
C4—C5—C6—C1	0.0 (2)	C8—C7—C9—N4	−0.7 (2)
C4—C5—C6—N1	179.65 (12)	C9—N4—C10—C11	18.5 (2)
C2—C1—C6—C5	−0.2 (2)	C9—N4—C10—C12	−163.55 (12)
C2—C1—C6—N1	−179.90 (12)	C12—C10—C11—C12^i	1.0 (2)
N2—N1—C6—C5	7.83 (18)	N4—C10—C11—C12^i	179.00 (12)
N3—N1—C6—C5	−174.33 (12)	C11—C10—C12—C11^i	−1.0 (2)
N2—N1—C6—C1	−172.50 (12)	N4—C10—C12—C11^i	−179.18 (12)

Symmetry code: (i) −x, −y−1, −z+1.