N-(2,4-Dichloro­benzyl­idene)-N′-phenyl­hydrazine

The mol­ecule of the title compound, C₁₃H₁₀Cl₂N₂, is nearly planar and adopts an E conformation about the carbon–nitro­gen double bond. The dihedral angle between the two benzene rings is 6.70 (13)°. Mol­ecules are inter­connected through weak N—H...π inter­ations.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.060
• wR factor = 0.132
• Data-to-parameter ratio = 16.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       1.02
PLAT074_ALERT_1_C Occupancy Parameter = 0.0 for ..................        CG1
PLAT420_ALERT_2_C D-H Without Acceptor       N2     -   H2     ...          ?
PLAT481_ALERT_4_C Long D...A H-Bond Reported N2     ..  CG1     ..       3.94 Ang.

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 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
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

The chemistry of hydrazones has been widely investigated in recent years, owning to their coordinating capability, pharmacological activity, antibacterial properties and their use in analytical chemistry as highly selective extractants (Domino et al., 1984; Li et al., 1998).

The title molecule crystallizes in the E conformation, with an N2—N1—C7—C1 torsion angle of 179.6 (2)°. The N1—N2 and N1=C7 bond distances are comparable to those in the related hydrazones derivates (Özçelik et al. 2004). There is more pronounced asymmetry in the exocyclic angles at C1 and C8. The dihedral angles between the two benzene ring is 6.70 (13)°, the dichlorophenyl ring make dihedral angle with the central hydrazone bridge (N2/N1/C7) of 6.49 (11)°, while the central hydrazone bridge is co-planar. with the phenyl ring

The molecules are linked by N—H···π interaction (Table 1).

Related literature

For related literature, see: Domino et al. (1984); Li et al. (1998); Özçelik et al. (2004).

S2. Experimental

Phenylhydrazine (1 mmol, 0.108 g) was dissolved in anhydrous methanol, H₂SO₄ (98% 0.5 ml) was added to this, the mixture was stirred for several minitutes at 351 K, 2,4-dichlorobenzyaldehyde (1 mmol 0.175 g) in methanol (8 ml) was added dropwise and the mixture was stirred at refluxing temperature for 2 h. The product was isolated and recrystallized in dichloromethane, brown single crystals of (I) was obtained after 5 d.

S3. Refinement

All H atoms were placed in calculated positions and treated as riding on their parent atoms, with C—H=0.93 Å and N—H= 0.86 Å with U_iso(H)=1.2U_eq(C,N).

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL/PC (Sheldrick, 1995); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

Fig. 1. Molecular view of the title compound. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small spheres of arbitrary radii.

N-(2,4-Dichlorobenzylidene)-N'-phenylhydrazine

Crystal data

C13H10Cl2N2	F(000) = 1088
Mr = 265.13	Dx = 1.401 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 1225 reflections
a = 16.074 (3) Å	θ = 2.5–24.1°
b = 8.0870 (16) Å	µ = 0.49 mm^−1
c = 19.333 (4) Å	T = 298 K
V = 2513.1 (9) Å^3	Block, brown
Z = 8	0.30 × 0.25 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer	2599 independent reflections
Radiation source: fine-focus sealed tube	2395 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
ω scans	θmax = 26.5°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −20→20
Tmin = 0.908, Tmax = 0.908	k = −10→8
15692 measured reflections	l = −22→24

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.132	H-atom parameters constrained
S = 1.22	w = 1/[σ^2(Fo^2) + (0.0417P)^2 + 1.2232P] where P = (Fo^2 + 2Fc^2)/3
2599 reflections	(Δ/σ)max < 0.001
154 parameters	Δρmax = 0.28 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

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	Occ. (<1)
Cl1	0.30414 (6)	0.64104 (12)	0.50050 (4)	0.0915 (3)
Cl2	0.36390 (6)	0.12890 (10)	0.33193 (4)	0.0806 (3)
N1	0.49038 (12)	0.4273 (2)	0.63809 (10)	0.0488 (5)
N2	0.50608 (13)	0.5073 (3)	0.69797 (10)	0.0549 (5)
H2	0.4763	0.5911	0.7096	0.066*
C1	0.41639 (14)	0.4009 (3)	0.53262 (12)	0.0466 (5)
C2	0.35838 (14)	0.4587 (3)	0.48464 (12)	0.0503 (6)
C3	0.34205 (15)	0.3774 (3)	0.42305 (13)	0.0546 (6)
H3	0.3028	0.4188	0.3922	0.066*
C4	0.38476 (16)	0.2352 (3)	0.40837 (13)	0.0539 (6)
C5	0.44459 (19)	0.1751 (3)	0.45313 (14)	0.0632 (7)
H5	0.4746	0.0804	0.4421	0.076*
C6	0.45912 (17)	0.2577 (3)	0.51431 (13)	0.0580 (6)
H6	0.4990	0.2162	0.5445	0.070*
C7	0.43389 (15)	0.4853 (3)	0.59798 (12)	0.0501 (6)
H7	0.4044	0.5798	0.6103	0.060*
C8	0.57047 (15)	0.4544 (3)	0.74095 (11)	0.0479 (5)
C9	0.58364 (17)	0.5361 (3)	0.80344 (13)	0.0602 (7)
H9	0.5495	0.6240	0.8160	0.072*
C10	0.64752 (19)	0.4865 (4)	0.84683 (14)	0.0686 (8)
H10	0.6561	0.5421	0.8883	0.082*
C11	0.69857 (17)	0.3561 (4)	0.82948 (15)	0.0663 (8)
H11	0.7414	0.3236	0.8588	0.080*
C12	0.68496 (16)	0.2745 (4)	0.76772 (14)	0.0640 (7)
H12	0.7189	0.1859	0.7557	0.077*
C13	0.62166 (16)	0.3221 (3)	0.72330 (13)	0.0546 (6)
H13	0.6134	0.2659	0.6819	0.066*
CG1	0.6345	0.4049	0.7853	0.010*	0.00

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0915 (6)	0.1023 (7)	0.0807 (5)	0.0577 (5)	−0.0167 (4)	−0.0143 (4)
Cl2	0.0948 (6)	0.0796 (5)	0.0673 (5)	−0.0035 (4)	−0.0170 (4)	−0.0152 (4)
N1	0.0540 (11)	0.0473 (10)	0.0452 (11)	0.0003 (9)	0.0038 (9)	0.0036 (9)
N2	0.0637 (12)	0.0536 (11)	0.0473 (11)	0.0126 (10)	−0.0010 (9)	−0.0038 (9)
C1	0.0452 (12)	0.0473 (12)	0.0473 (13)	−0.0006 (10)	0.0037 (10)	0.0079 (10)
C2	0.0419 (12)	0.0555 (14)	0.0535 (14)	0.0061 (10)	0.0045 (10)	0.0046 (11)
C3	0.0421 (12)	0.0691 (16)	0.0528 (14)	0.0010 (12)	−0.0036 (11)	0.0080 (12)
C4	0.0589 (14)	0.0528 (14)	0.0500 (13)	−0.0094 (12)	−0.0002 (11)	0.0019 (11)
C5	0.0787 (18)	0.0467 (13)	0.0642 (16)	0.0103 (13)	−0.0102 (14)	−0.0012 (12)
C6	0.0686 (16)	0.0482 (13)	0.0573 (15)	0.0107 (12)	−0.0099 (12)	0.0056 (11)
C7	0.0514 (13)	0.0491 (13)	0.0497 (13)	0.0071 (11)	0.0061 (11)	0.0047 (10)
C8	0.0506 (13)	0.0491 (12)	0.0439 (12)	−0.0032 (11)	0.0055 (10)	0.0059 (10)
C9	0.0683 (16)	0.0602 (15)	0.0521 (14)	0.0004 (13)	0.0036 (12)	−0.0047 (12)
C10	0.0743 (18)	0.0794 (19)	0.0521 (15)	−0.0137 (16)	−0.0063 (14)	−0.0038 (14)
C11	0.0558 (15)	0.0811 (19)	0.0619 (17)	−0.0080 (14)	−0.0077 (13)	0.0158 (15)
C12	0.0591 (15)	0.0633 (16)	0.0697 (17)	0.0047 (13)	0.0031 (13)	0.0108 (14)
C13	0.0588 (15)	0.0555 (14)	0.0495 (13)	0.0025 (12)	0.0040 (11)	0.0000 (11)

Geometric parameters (Å, º)

Cl1—C2	1.741 (2)	C6—H6	0.9300
Cl2—C4	1.742 (3)	C7—H7	0.9300
N1—C7	1.283 (3)	C8—C13	1.392 (3)
N1—N2	1.350 (3)	C8—C9	1.393 (3)
N2—C8	1.395 (3)	C8—CG1	1.397 (2)
N2—H2	0.8600	C9—C10	1.385 (4)
C1—C6	1.392 (3)	C9—H9	0.9300
C1—C2	1.396 (3)	C10—C11	1.377 (4)
C1—C7	1.463 (3)	C10—H10	0.9300
C2—C3	1.385 (3)	C11—C12	1.382 (4)
C3—C4	1.369 (4)	C11—H11	0.9300
C3—H3	0.9300	C12—C13	1.386 (4)
C4—C5	1.382 (4)	C12—H12	0.9300
C5—C6	1.378 (4)	C13—H13	0.9300
C5—H5	0.9300
C7—N1—N2	118.4 (2)	N1—C7—H7	120.4
N1—N2—C8	120.2 (2)	C1—C7—H7	120.4
N1—N2—H2	119.9	C13—C8—C9	119.2 (2)
C8—N2—H2	119.9	C13—C8—N2	121.9 (2)
C6—C1—C2	116.0 (2)	C9—C8—N2	118.9 (2)
C6—C1—C7	120.9 (2)	C13—C8—CG1	59.69 (14)
C2—C1—C7	123.1 (2)	C9—C8—CG1	59.47 (15)
C3—C2—C1	122.6 (2)	N2—C8—CG1	178.4 (2)
C3—C2—Cl1	117.29 (18)	C10—C9—C8	120.0 (3)
C1—C2—Cl1	120.08 (19)	C10—C9—H9	120.0
C4—C3—C2	118.8 (2)	C8—C9—H9	120.0
C4—C3—H3	120.6	C11—C10—C9	121.1 (3)
C2—C3—H3	120.6	C11—C10—H10	119.5
C3—C4—C5	121.0 (2)	C9—C10—H10	119.5
C3—C4—Cl2	119.6 (2)	C10—C11—C12	118.8 (3)
C5—C4—Cl2	119.4 (2)	C10—C11—H11	120.6
C6—C5—C4	119.0 (2)	C12—C11—H11	120.6
C6—C5—H5	120.5	C11—C12—C13	121.3 (3)
C4—C5—H5	120.5	C11—C12—H12	119.4
C5—C6—C1	122.5 (2)	C13—C12—H12	119.4
C5—C6—H6	118.7	C12—C13—C8	119.7 (2)
C1—C6—H6	118.7	C12—C13—H13	120.1
N1—C7—C1	119.2 (2)	C8—C13—H13	120.1

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Cg1^i	0.86	3.10	3.943 (2)	167

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