4-(Phenyl­hydrazonometh­yl)benzonitrile

The title compound, C₁₄H₁₁N₃, was synthesized by the reaction of phenyl­hydrazine and 4-formyl­benzonitrile. The mol­ecule adopts an E configuration with respect to the N=N bond. The dihedral angle between the two benzene rings is 13.56 (15)°. In the crystal structure, inter­molecular N—H...N hydrogen bonds form one-dimensional chains along the b axis.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.058
• wR factor = 0.170
• Data-to-parameter ratio = 10.2

checkCIF/PLATON results

No syntax errors found



Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.812     1.000
            Tmin(prime) and Tmax expected:      0.985     0.994
            RR(prime) =      0.820
            Please check that your absorption correction is appropriate.
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.82
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          5
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C5     -   C8     ...       1.43 Ang.

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.994
            Tmax scaled      0.994 Tmin scaled      0.807
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.48
           From the CIF: _reflns_number_total               1565
           Count of symmetry unique reflns         1568
           Completeness (_total/calc)             99.81%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

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

   2 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
   4 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

Nitrile compounds are the precursor of tetrazole derivatives (Dunica, et al., 1991; Wittenberger, et al., 1993), which we have focused on for the design of noncentrosymmetric bulk materials (Xiong, et al.(2002)). We report here the crystal structure of the title compound, 4-(phenyl-hydrazonomethyl)benzonitrile, (I), Fig. 1.

In I, the C=N double bond (1.359 (4) Å) is in the range 1.34–1.38 Å found in other similar hydrazone complexes with a trans configuration (Szczesna & Urbanczyk-Lipkowska (2002); Drew, et al.(1984). The torsion angles of C9 - N2 - N1 - C1 is -178.7 (3)°. Dihedral angle between the two benzene rings is 13.56 (0.15) °. In the crystal structure molecules related by translation along b axis are connected by N2—H2B···N3 hydrogen bonds resulting in the formation of one dimensional chains along the b axis.

Related literature

For the preparation of tetrazole derivatives from nitrile compounds, see: Drew et al. (1984); Dunica et al. (1991); Szczesna & Urbanczyk-Lipkowska (2002); Wittenberger & Donner (1993). For the general chemistry of tetrazole compounds, see: Xiong et al. (2002).

S2. Experimental

To a solution of 4-formylbenzonitrile (6.55 g, 0.05 mol) in methanol (40 ml) was added phenylhydrazine (5.40 g, 0.05 mol) with stirring at room temperature. After 20 minutes, a mass of yellow precipitate appeared and was filtered. The crude product was recrystallized by slowly evaporating an ethanol solution to yield pale yellow block-like crystals, suitable for X-ray analysis.

S3. Refinement

Positional parameters of all the H atoms were calculated geometrically and were allowed to ride on the C atoms to which they are bonded, with d(C—H) = 0.93 and d(N—H) = 0.90 Å and U_iso(H) = 1.2Ueq(C or N). In the absence of significant anomalous scattering effects, Friedel pairs were merged.

Computing details

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 1999).

Figures

	Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A view of the chain structure of the molecules related by translation along b axis and all hydrogen atoms not involved in hydrogen bonding (dashed lines) were omitted for clarity.
	Fig. 3. The crystal packing of the title compound viewed along the a axis. all hydrogen atoms not involved in hydrogen bonding (dashed lines) were omitted for clarity.

4-(Phenylhydrazonomethyl)benzonitrile

Crystal data

C14H11N3	F(000) = 464
Mr = 221.26	Dx = 1.253 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 9243 reflections
a = 7.1442 (14) Å	θ = 3.2–27.5°
b = 11.147 (2) Å	µ = 0.08 mm^−1
c = 14.726 (3) Å	T = 293 K
V = 1172.7 (4) Å^3	Block, yellow
Z = 4	0.2 × 0.08 × 0.08 mm

Data collection

Mercury2 diffractometer	1565 independent reflections
Radiation source: fine-focus sealed tube	984 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.074
Detector resolution: 13.6612 pixels mm^-1	θmax = 27.5°, θmin = 3.2°
ω scans	h = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −14→14
Tmin = 0.812, Tmax = 1.0	l = −19→19
11983 measured reflections

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.170	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0863P)^2] where P = (Fo^2 + 2Fc^2)/3
1565 reflections	(Δ/σ)max < 0.001
154 parameters	Δρmax = 0.14 e Å^−3
0 restraints	Δρmin = −0.14 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
N1	0.4559 (4)	0.4066 (3)	0.51082 (19)	0.0665 (8)
N2	0.4212 (5)	0.2870 (3)	0.5177 (2)	0.0756 (9)
H2B	0.4864	0.2514	0.4729	0.091*
N3	0.4871 (6)	1.0614 (3)	0.3748 (2)	0.1010 (13)
C1	0.4160 (5)	0.4567 (3)	0.4354 (2)	0.0671 (9)
H1	0.3704	0.4100	0.3880	0.081*
C2	0.4400 (4)	0.5844 (3)	0.4218 (2)	0.0606 (9)
C3	0.5107 (5)	0.6589 (3)	0.4901 (2)	0.0639 (9)
H3	0.5493	0.6256	0.5449	0.077*
C4	0.5241 (5)	0.7814 (3)	0.4772 (2)	0.0674 (10)
H4	0.5704	0.8301	0.5233	0.081*
C5	0.4680 (5)	0.8315 (3)	0.3950 (2)	0.0642 (9)
C6	0.4008 (5)	0.7585 (3)	0.3266 (2)	0.0704 (10)
H6	0.3649	0.7915	0.2713	0.084*
C7	0.3871 (5)	0.6374 (4)	0.3406 (2)	0.0675 (10)
H7	0.3410	0.5892	0.2941	0.081*
C8	0.4797 (6)	0.9587 (4)	0.3826 (2)	0.0759 (11)
C9	0.4638 (5)	0.2253 (3)	0.5963 (2)	0.0606 (8)
C10	0.5663 (5)	0.2755 (3)	0.6664 (2)	0.0657 (9)
H10	0.6101	0.3538	0.6618	0.079*
C11	0.6031 (5)	0.2089 (3)	0.7430 (2)	0.0732 (10)
H11	0.6708	0.2436	0.7902	0.088*
C12	0.5428 (6)	0.0933 (3)	0.7515 (3)	0.0745 (11)
H12	0.5711	0.0490	0.8032	0.089*
C13	0.4383 (6)	0.0427 (3)	0.6814 (3)	0.0752 (11)
H13	0.3935	−0.0353	0.6866	0.090*
C14	0.4019 (5)	0.1080 (3)	0.6053 (2)	0.0703 (10)
H14	0.3340	0.0732	0.5583	0.084*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0649 (17)	0.0672 (19)	0.0674 (19)	0.0050 (15)	−0.0015 (15)	0.0044 (14)
N2	0.090 (2)	0.069 (2)	0.0686 (19)	0.0038 (19)	−0.0102 (17)	−0.0012 (15)
N3	0.131 (3)	0.089 (2)	0.083 (2)	0.003 (3)	0.007 (2)	0.0146 (19)
C1	0.067 (2)	0.075 (2)	0.060 (2)	−0.0034 (19)	−0.0108 (18)	−0.0002 (18)
C2	0.0475 (17)	0.084 (2)	0.0508 (19)	0.0019 (18)	−0.0020 (15)	0.0015 (16)
C3	0.0601 (19)	0.077 (3)	0.054 (2)	−0.0017 (18)	−0.0092 (17)	0.0133 (17)
C4	0.061 (2)	0.082 (3)	0.059 (2)	−0.007 (2)	−0.0104 (17)	0.0004 (17)
C5	0.057 (2)	0.077 (2)	0.058 (2)	0.0018 (19)	0.0046 (17)	0.0081 (17)
C6	0.068 (2)	0.096 (3)	0.0477 (19)	0.007 (2)	−0.0026 (18)	0.0090 (19)
C7	0.068 (2)	0.088 (3)	0.0472 (18)	−0.003 (2)	−0.0016 (18)	0.0006 (17)
C8	0.078 (3)	0.079 (3)	0.070 (2)	0.005 (2)	0.009 (2)	0.013 (2)
C9	0.0610 (18)	0.059 (2)	0.062 (2)	0.0036 (17)	−0.0030 (16)	−0.0030 (15)
C10	0.073 (2)	0.0580 (19)	0.066 (2)	0.0036 (19)	−0.005 (2)	−0.0059 (17)
C11	0.088 (3)	0.072 (2)	0.060 (2)	0.019 (2)	−0.0115 (19)	−0.0099 (18)
C12	0.090 (3)	0.065 (2)	0.068 (2)	0.017 (2)	0.007 (2)	0.0052 (17)
C13	0.090 (3)	0.061 (2)	0.075 (2)	−0.004 (2)	0.009 (2)	0.0017 (18)
C14	0.072 (2)	0.069 (2)	0.070 (2)	−0.002 (2)	0.0021 (19)	−0.0084 (18)

Geometric parameters (Å, º)

N1—C1	1.275 (4)	C6—C7	1.370 (4)
N1—N2	1.359 (4)	C6—H6	0.9300
N2—C9	1.381 (4)	C7—H7	0.9300
N2—H2B	0.9000	C9—C10	1.384 (4)
N3—C8	1.151 (4)	C9—C14	1.387 (4)
C1—C2	1.448 (4)	C10—C11	1.375 (4)
C1—H1	0.9300	C10—H10	0.9300
C2—C7	1.387 (4)	C11—C12	1.365 (5)
C2—C3	1.399 (4)	C11—H11	0.9300
C3—C4	1.382 (4)	C12—C13	1.393 (5)
C3—H3	0.9300	C12—H12	0.9300
C4—C5	1.393 (5)	C13—C14	1.361 (5)
C4—H4	0.9300	C13—H13	0.9300
C5—C6	1.381 (4)	C14—H14	0.9300
C5—C8	1.433 (5)
C1—N1—N2	117.0 (3)	C6—C7—C2	122.0 (3)
N1—N2—C9	120.7 (3)	C6—C7—H7	119.0
N1—N2—H2B	106.5	C2—C7—H7	119.0
C9—N2—H2B	106.3	N3—C8—C5	178.3 (4)
N1—C1—C2	121.7 (3)	N2—C9—C10	122.8 (3)
N1—C1—H1	119.2	N2—C9—C14	118.6 (3)
C2—C1—H1	119.2	C10—C9—C14	118.6 (3)
C7—C2—C3	117.8 (3)	C11—C10—C9	119.7 (3)
C7—C2—C1	120.4 (3)	C11—C10—H10	120.2
C3—C2—C1	121.8 (3)	C9—C10—H10	120.2
C4—C3—C2	120.8 (3)	C12—C11—C10	121.6 (3)
C4—C3—H3	119.6	C12—C11—H11	119.2
C2—C3—H3	119.6	C10—C11—H11	119.2
C3—C4—C5	119.7 (3)	C11—C12—C13	118.9 (3)
C3—C4—H4	120.1	C11—C12—H12	120.5
C5—C4—H4	120.1	C13—C12—H12	120.5
C6—C5—C4	119.9 (3)	C14—C13—C12	119.8 (4)
C6—C5—C8	120.7 (3)	C14—C13—H13	120.1
C4—C5—C8	119.4 (3)	C12—C13—H13	120.1
C7—C6—C5	119.7 (3)	C13—C14—C9	121.4 (4)
C7—C6—H6	120.1	C13—C14—H14	119.3
C5—C6—H6	120.1	C9—C14—H14	119.3
C9—N2—N1—C1	178.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···N3^i	0.90	2.56	3.313 (5)	141

Symmetry code: (i) x, y−1, z.