(Z)-N-(2-Iodo­phen­yl)-4-nitro­benzimidoyl cyanide

Moreno-Fuquen, R.; Garcia, A.C.; Abonia, R.; Jaramillo-Gómez, L.M.; Kennedy, A.R.

doi:10.1107/S2414314616003151

organic compounds

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ISSN: 2414-3146

Volume 1| Part 2| February 2016| x160315

https://doi.org/10.1107/S2414314616003151

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(Z)-N-(2-Iodophenyl)-4-nitrobenzimidoyl cyanide

Rodolfo Moreno-Fuquen,^a ^* Andres C. Garcia,^a Rodrigo Abonia,^a Luz M. Jaramillo-Gómez ^a and Alan R. Kennedy ^b

^aDepartamento de Química - Facultad de Ciencias Naturales y Exactas, Universidad del Valle, A.A. 25360, Santiago de Cali, Colombia, and ^bWestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, Scotland
^*Correspondence e-mail: rodimo26@yahoo.es

Edited by E. R. T. Tiekink, Sunway University, Malaysia (Received 5 February 2016; accepted 24 February 2016; online 27 February 2016)

In the title molecule, C₁₄H₈IN₃O₂, the cyanide group is anti to the iodide substituent of the adjacent benzene ring. The central segment is essentially planar (r.m.s deviation = 0.0341 Å) and it is twisted away from the iodide- and nitro-substituted benzene rings by 69.02 (9) and 15.83 (16)°, respectively. In the crystal, molecules are linked by weak C—H⋯N interactions, leading to C(8) chains along [010].

Keywords: crystal structure; α-iminonitrile; C—H⋯N interactions.

CCDC reference: 1455354

Structure description

The α-iminonitriles are an important class of synthetic products with interesting biological activities (Jursic et al., 2002 ). These compounds are useful precursors for the synthesis of analogues of naturally occurring iminosugars (Ayers & Fleet, 2014 ), amide-functionality formation (Gualtierotti et al., 2012 ), and are frequently found in different natural compounds, pharmaceuticals and polymers. Several methodologies have been developed for the synthesis of α-iminonitriles (Fontaine et al., 2008 ; Gualtierotti et al., 2012; Jursic et al., 2002). In our approach, the (Z)-N-(2-iodophenyl)-4-nitrobenzimidoyl cyanide, (I), was obtained through an oxidative Strecker-type reaction from the imine, previously formed by a condensation reaction of 2-iodoaniline with 4-nitrobenzaldehyde.

A perspective view of the molecule of the title compound, showing the atomic numbering scheme, is given in Fig. 1. The structural parameters of a related ligand, i.e. containing (I) in its backbone, has been reported in an organoruthenium compound (II) (Xiang et al., 2010 ), and can serve as a comparison with (I). A comparison of the bond lengths in the central segment C1/N1/C8/C7/N2/C9 of (I) and (II), shows an elongation in the C1—N1 [1.452 (3) Å] and a shortening in C8—C9 [1.460 (3) Å] in (II). These differences in bond lengths may be due to the formation of bonds with the ruthenium atom via O atoms appended to the backbone. The cyanide group is anti to the o-iodide substituent in the adjacent benzene ring. The central segment C1/N1/C8/C7/N2/C9 is essentially planar, with an r.m.s deviation of 0.0341 Å and it is twisted away from the iodide- and nitro-substituted benzene rings by 69.02 (9) and 15.83 (16)°, respectively.

Figure 1
The molecular structure of (I) with displacement ellipsoids drawn at the 50% probability level.

In the crystal, molecules of (I) are linked by weak intermolecular C—H⋯N interactions, Table 1. These interactions generate C(8) chains of molecules along [010], see Fig. 2.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯N2ⁱ	0.95	2.61	3.485 (4)	153
Symmetry code: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 2
Part of the crystal structure of (I), showing the formation of C(8) chains of molecules along [010]. [Symmetry code: (i) −x, y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ .]

Synthesis and crystallization

A mixture of 2-iodoaniline (100 mg, 0.46 mmol) and 4-nitrobenzaldehyde (69 mg, 0.46 mmol) was heated at 373 K for 1 h in solvent-free conditions until the starting materials were no longer detected by TLC, to afford a yellow solid (in quantitative yield) corresponding to the imine. Then a mixture of imine (100 mg, 0.28 mmol), potassium cyanide (37 mg, 0.57 mmol), silica gel (50 mg) and acetonitrile (5 mL) was stirred at room temperature for 20 h. After the imine was consumed (monitored by TLC), the solvent was evaporated under reduced pressure and the crude product was purified by column chromatography on silica gel using a hexane–dichloromethane mixture (4:1, v/v) as eluent to afford compound (I) [57% yield, orange solid, m.p. 433 (1) K].

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The maximum and minimum residual electron density peaks of 1.42 and 0.84 eÅ⁻³, respectively, were located 0.86 and 0.79 Å from the I1 atom.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₄H₈IN₃O₂
M_r	377.13
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	123
a, b, c (Å)	11.9620 (7), 9.0103 (5), 13.2047 (8)
β (°)	109.893 (6)
V (Å³)	1338.29 (13)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	2.40
Crystal size (mm)	0.25 × 0.25 × 0.18

Data collection
Diffractometer	Oxford Diffraction Xcalibur E
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ )
T_min, T_max	0.850, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6073, 3014, 2602
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.087, 1.07
No. of reflections	3014
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.42, −0.84
Computer programs: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ), SIR92 (Altomare et al., 1994 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ), Mercury (Macrae et al., 2006 ).

Structural data

CCDC reference: 1455354

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314616003151/tk4003sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616003151/tk4003Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616003151/tk4003Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

(Z)-N-(2-Iodophenyl)-4-nitrobenzimidoyl cyanide top

Crystal data top

C₁₄H₈IN₃O₂	D_x = 1.872 Mg m⁻³
M_r = 377.13	Melting point: 433(1) K
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.9620 (7) Å	Cell parameters from 3743 reflections
b = 9.0103 (5) Å	θ = 4.8–28.3°
c = 13.2047 (8) Å	µ = 2.40 mm⁻¹
β = 109.893 (6)°	T = 123 K
V = 1338.29 (13) Å³	Fragment from a large block, orange
Z = 4	0.25 × 0.25 × 0.18 mm
F(000) = 728

Data collection top

Oxford Diffraction Xcalibur E diffractometer	3014 independent reflections
Radiation source: fine-focus sealed tube	2602 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.049
ω scans	θ_max = 27.5°, θ_min = 4.8°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	h = −14→15
T_min = 0.850, T_max = 1.000	k = −11→8
6073 measured reflections	l = −17→16

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.087	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0437P)²] where P = (F_o² + 2F_c²)/3
3014 reflections	(Δ/σ)_max < 0.001
181 parameters	Δρ_max = 1.42 e Å⁻³
0 restraints	Δρ_min = −0.84 e Å⁻³

Special details top

Experimental. IR (FT–IR SHIMADZU IR-Affinity-1 spectrophotometer; KBr): cm^-1, 3072, 2954, 2225 (CN), 1593, 1510 (NO₂), 1340 (NO₂), 1201, 1002. ¹H NMR (400 MHz, CDCl₃) δ: 8.04 (dd, J = 7.9, 1.3 Hz, 2H), 7.54 (btd, J = 7.7, 1.3 Hz, 2H), 7.23 (dd, J = 7.9, 1.4 Hz, 2H), 7.13 (btd, J = 7.7, 1.5 Hz, 2H) ppm. ¹³C NMR (100 MHz, CDCl ₃) δ: 150.4, 149.3, 139.7, 138.2, 138.0, 129.6, 129.5, 129.4, 124.3, 118.5, 110.0, 93.00 ppm. MS (70 eV) m/z (%): 379, 378, 377 (2.4, 18, 100) [M+], 250 (17), 203 (47), 204 (68). Crystals of (I) suitable for single-crystal X-ray diffraction were grown by slow evaporation, at ambient temperature and in air, from a solution in chloroform.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
I1	0.04067 (2)	0.30747 (2)	0.19197 (2)	0.02256 (10)
O1	0.4118 (2)	0.0280 (3)	−0.29485 (18)	0.0305 (6)
O2	0.5255 (2)	0.2000 (3)	−0.1999 (2)	0.0255 (5)
N1	0.2669 (2)	0.1140 (3)	0.1927 (2)	0.0185 (5)
N2	0.1607 (3)	−0.2436 (4)	0.1256 (2)	0.0271 (7)
N3	0.4470 (2)	0.1070 (3)	−0.2146 (2)	0.0199 (6)
C1	0.2371 (3)	0.0802 (3)	0.2856 (2)	0.0164 (6)
C2	0.1477 (3)	0.1590 (3)	0.3068 (2)	0.0172 (6)
C3	0.1250 (3)	0.1364 (4)	0.4016 (2)	0.0190 (6)
H3	0.0627	0.1891	0.4151	0.023*
C4	0.1942 (3)	0.0358 (4)	0.4772 (2)	0.0209 (7)
H4	0.1801	0.0208	0.5430	0.025*
C5	0.2828 (3)	−0.0417 (4)	0.4564 (2)	0.0200 (7)
H5	0.3296	−0.1102	0.5083	0.024*
C6	0.3052 (3)	−0.0219 (4)	0.3611 (3)	0.0199 (7)
H6	0.3662	−0.0770	0.3472	0.024*
C7	0.2035 (3)	−0.1303 (4)	0.1247 (2)	0.0190 (6)
C8	0.2576 (3)	0.0148 (3)	0.1211 (2)	0.0164 (6)
C9	0.3007 (2)	0.0423 (3)	0.0300 (2)	0.0154 (6)
C10	0.2656 (3)	−0.0495 (4)	−0.0605 (2)	0.0179 (6)
H10	0.2106	−0.1277	−0.0657	0.021*
C11	0.3108 (3)	−0.0264 (4)	−0.1428 (2)	0.0202 (7)
H11	0.2864	−0.0866	−0.2056	0.024*
C12	0.3920 (3)	0.0861 (4)	−0.1312 (2)	0.0173 (6)
C13	0.4262 (3)	0.1811 (3)	−0.0439 (3)	0.0172 (6)
H13	0.4802	0.2599	−0.0399	0.021*
C14	0.3799 (3)	0.1588 (3)	0.0377 (2)	0.0180 (6)
H14	0.4020	0.2226	0.0986	0.022*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.02007 (14)	0.02419 (15)	0.02160 (15)	0.00280 (8)	0.00473 (10)	0.00532 (8)
O1	0.0444 (15)	0.0318 (14)	0.0182 (12)	−0.0017 (12)	0.0143 (11)	−0.0027 (10)
O2	0.0223 (12)	0.0294 (14)	0.0269 (13)	−0.0027 (10)	0.0113 (10)	0.0048 (10)
N1	0.0215 (12)	0.0176 (14)	0.0178 (13)	−0.0002 (11)	0.0087 (10)	0.0004 (11)
N2	0.0313 (15)	0.0248 (16)	0.0302 (17)	−0.0088 (14)	0.0169 (13)	−0.0046 (14)
N3	0.0247 (13)	0.0194 (15)	0.0169 (12)	0.0068 (11)	0.0087 (10)	0.0045 (11)
C1	0.0174 (13)	0.0147 (15)	0.0165 (14)	−0.0051 (12)	0.0051 (11)	−0.0040 (12)
C2	0.0181 (14)	0.0161 (15)	0.0158 (15)	−0.0007 (12)	0.0038 (12)	0.0008 (12)
C3	0.0200 (14)	0.0167 (16)	0.0210 (16)	0.0015 (13)	0.0079 (12)	−0.0017 (13)
C4	0.0261 (16)	0.0195 (16)	0.0173 (15)	−0.0023 (13)	0.0074 (13)	−0.0011 (13)
C5	0.0237 (15)	0.0156 (16)	0.0206 (16)	0.0015 (13)	0.0073 (13)	−0.0001 (13)
C6	0.0211 (15)	0.0165 (16)	0.0230 (16)	0.0024 (13)	0.0089 (12)	−0.0020 (13)
C7	0.0209 (14)	0.0253 (18)	0.0123 (14)	0.0020 (14)	0.0077 (12)	−0.0012 (13)
C8	0.0167 (13)	0.0142 (15)	0.0170 (15)	0.0025 (12)	0.0041 (11)	0.0024 (12)
C9	0.0149 (13)	0.0165 (15)	0.0148 (14)	0.0024 (12)	0.0050 (11)	0.0027 (12)
C10	0.0189 (14)	0.0153 (16)	0.0189 (15)	−0.0034 (12)	0.0057 (12)	−0.0031 (12)
C11	0.0228 (15)	0.0186 (16)	0.0168 (15)	0.0011 (13)	0.0036 (12)	−0.0015 (13)
C12	0.0180 (13)	0.0188 (16)	0.0159 (14)	0.0061 (12)	0.0068 (11)	0.0054 (12)
C13	0.0182 (14)	0.0126 (15)	0.0191 (16)	0.0006 (11)	0.0041 (12)	0.0022 (11)
C14	0.0223 (15)	0.0163 (16)	0.0144 (15)	−0.0001 (12)	0.0051 (12)	−0.0003 (12)

Geometric parameters (Å, º) top

I1—C2	2.099 (3)	C5—H5	0.9500
O1—N3	1.226 (3)	C6—H6	0.9500
O2—N3	1.223 (4)	C7—C8	1.466 (4)
N1—C8	1.279 (4)	C8—C9	1.482 (4)
N1—C1	1.421 (4)	C9—C14	1.395 (4)
N2—C7	1.144 (4)	C9—C10	1.395 (4)
N3—C12	1.475 (4)	C10—C11	1.384 (4)
C1—C2	1.390 (4)	C10—H10	0.9500
C1—C6	1.397 (4)	C11—C12	1.376 (4)
C2—C3	1.383 (4)	C11—H11	0.9500
C3—C4	1.393 (4)	C12—C13	1.381 (4)
C3—H3	0.9500	C13—C14	1.382 (4)
C4—C5	1.373 (4)	C13—H13	0.9500
C4—H4	0.9500	C14—H14	0.9500
C5—C6	1.385 (4)

C8—N1—C1	120.2 (3)	N2—C7—C8	178.9 (3)
O2—N3—O1	123.6 (3)	N1—C8—C7	121.9 (3)
O2—N3—C12	118.8 (3)	N1—C8—C9	121.1 (3)
O1—N3—C12	117.5 (3)	C7—C8—C9	117.0 (3)
C2—C1—C6	119.7 (3)	C14—C9—C10	120.5 (3)
C2—C1—N1	120.0 (3)	C14—C9—C8	118.8 (3)
C6—C1—N1	120.0 (3)	C10—C9—C8	120.6 (3)
C3—C2—C1	120.6 (3)	C11—C10—C9	119.9 (3)
C3—C2—I1	119.3 (2)	C11—C10—H10	120.0
C1—C2—I1	120.1 (2)	C9—C10—H10	120.0
C2—C3—C4	119.5 (3)	C12—C11—C10	118.2 (3)
C2—C3—H3	120.2	C12—C11—H11	120.9
C4—C3—H3	120.2	C10—C11—H11	120.9
C5—C4—C3	119.9 (3)	C11—C12—C13	123.1 (3)
C5—C4—H4	120.1	C11—C12—N3	119.2 (3)
C3—C4—H4	120.1	C13—C12—N3	117.6 (3)
C4—C5—C6	121.2 (3)	C12—C13—C14	118.5 (3)
C4—C5—H5	119.4	C12—C13—H13	120.7
C6—C5—H5	119.4	C14—C13—H13	120.7
C5—C6—C1	119.1 (3)	C13—C14—C9	119.6 (3)
C5—C6—H6	120.4	C13—C14—H14	120.2
C1—C6—H6	120.4	C9—C14—H14	120.2

C8—N1—C1—C2	−120.1 (3)	N1—C8—C9—C10	−164.4 (3)
C8—N1—C1—C6	66.2 (4)	C7—C8—C9—C10	15.2 (4)
C6—C1—C2—C3	−0.5 (5)	C14—C9—C10—C11	1.0 (5)
N1—C1—C2—C3	−174.2 (3)	C8—C9—C10—C11	−177.1 (3)
C6—C1—C2—I1	−177.9 (2)	C9—C10—C11—C12	1.3 (5)
N1—C1—C2—I1	8.4 (4)	C10—C11—C12—C13	−3.1 (5)
C1—C2—C3—C4	1.3 (5)	C10—C11—C12—N3	176.3 (3)
I1—C2—C3—C4	178.7 (2)	O2—N3—C12—C11	−174.6 (3)
C2—C3—C4—C5	−1.0 (5)	O1—N3—C12—C11	4.5 (4)
C3—C4—C5—C6	0.0 (5)	O2—N3—C12—C13	4.8 (4)
C4—C5—C6—C1	0.7 (5)	O1—N3—C12—C13	−176.1 (3)
C2—C1—C6—C5	−0.5 (5)	C11—C12—C13—C14	2.4 (5)
N1—C1—C6—C5	173.2 (3)	N3—C12—C13—C14	−176.9 (3)
C1—N1—C8—C7	7.3 (4)	C12—C13—C14—C9	0.0 (5)
C1—N1—C8—C9	−173.1 (3)	C10—C9—C14—C13	−1.7 (5)
N1—C8—C9—C14	17.5 (4)	C8—C9—C14—C13	176.5 (3)
C7—C8—C9—C14	−162.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···N2ⁱ	0.95	2.61	3.485 (4)	153

Symmetry code: (i) −x, y+1/2, −z+1/2.

Acknowledgements

RMF, RA, ACG and LMJ are grateful to Colciencias and the Universidad del Valle, Colombia, for partial financial support.

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