3-(4-Iodo­phen­yl)penta­nedi­nitrile

Nanpo, Y.; Okuno, T.

doi:10.1107/S2414314619002827

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 4| Part 2| February 2019| x190282

https://doi.org/10.1107/S2414314619002827

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3-(4-Iodophenyl)pentanedinitrile

Yuuki Nanpo ^a and Tsunehisa Okuno ^a ^*

^aFaculty of Systems Engineering, Wakayama University, Sakaedani, Wakayama, 640-8510, Japan
^*Correspondence e-mail: okuno@wakayama-u.ac.jp

Edited by S. Parkin, University of Kentucky, USA (Received 4 February 2019; accepted 25 February 2019; online 28 February 2019)

In the title pentanedinitrile derivative, C₁₁H₉IN₂, the iodophenyl group is connected at the 3-position. The central propylene chain of the pentanedinitrile moiety contains one gauche conformation as a result of steric repulsion with the phenyl ring. Intermolecular close contacts in the crystal comprise a weak Csp³—H⋯N hydrogen bond and a C—I⋯N halogen bond.

Keywords: crystal structure; pentanedinitrile,glutaronitrile; hydrogen bond; halogen bond.

CCDC reference: 1899183

Structure description

The title compound, C₁₁H₉IN₂, is a pentanedinitrile (glutaronitrile) derivative, in which the iodophenyl group is connected at the 3-position. Pentanedinitrile derivatives are used as precursors in the synthesis of 2,6-diaminopyridines, which are used as raw materials for insecticides (Kato et al., 1989 ).

The title compound (Fig. 1) was obtained in a condensation reaction between 4-iodebenzaldehyde and cyanoacetic acid. The central propylene chain of the pentanedinitrile group contains one gauche conformation where the torsion angle of C1—C2—C3—C4 is 161.3 (9)°. Similarly, the conformations of related compounds (see e.g. Al-Arab et al., 1988 ; Lorente et al., 1995 ; Percino et al., 2014 ) also do not show all-anti conformations. In the title compound, steric repulsion between the C1—N1 cyano group and the phenyl ring is thought to result in the gauche conformation.

Figure 1
The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level, with H atoms shown as small spheres.

In the crystal, intermolecular halogen bonds are formed between inversion-related molecules to give a dimeric structure (Fig. 2), where the distance of C—I⋯Nⁱ [symmetry code: (i) −x + 1, −y, −z + 1] is 3.369 (7) Å and the C—I⋯Nⁱ angle is 166.2 (2)°. Here, the intermolecular distance is shorter by 4.6% than the sum of the van der Waals radii of the nitrogen and iodine atoms, such that this halogen bond is classified as a weak interaction. Pairs of weak intermolecular Csp³—H⋯N1ⁱⁱ hydrogen bonds also form between inversion-related dimers (Fig. 2, Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4B⋯N1ⁱ	0.99	2.61	3.387 (12)	135
Symmetry code: (i) -x, -y, -z.

Figure 2
A view of the intermolecular interactions in the title compound [symmetry codes:(i) −x + 1, −y, −z + 1; (ii) −x, −y, −z].

Synthesis and crystallization

A solution of 4-iodobenzaldehyde (1.0 g, 4.3 mmol) and cyanoacetic acid (0.73 g, 8.6 mmol) in acetonitrile (30 ml) was refluxed overnight with piperidine (0.22 ml) as a basic catalyst. The solution was condensed using a rotary evaporator, and the residual yellowish oil was dissolved in chloroform (90 ml). The solution was washed with HCl_aq (1.0 M) and water. It was dried over Na₂SO₄ and condensed under reduced pressure. The residue was purified by recrystallization from a hexane-ethanol (v:v = 7:1) solution to give 3-(4-iodophenyl)pentanedinitrile in a yield of 41% (0.52 g).

1H NMR (400 MHz): δ 7.73 (d, J = 8.4 Hz, 2H), 7.19 (d, J = 8.4 Hz, 2H), 3.39 (m, 1H), 2.91 (d, J = 7.4 Hz, 4H)

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₁H₉IN₂
M_r	296.11
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	93
a, b, c (Å)	6.508 (4), 10.524 (6), 16.047 (10)
β (°)	90.507 (10)
V (Å³)	1099.0 (11)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	2.88
Crystal size (mm)	0.15 × 0.10 × 0.02

Data collection
Diffractometer	Rigaku Saturn724+
Absorption correction	Numerical (NUMABS; Rigaku, 1999 )
T_min, T_max	0.744, 0.944
No. of measured, independent and observed [F² > 2.0σ(F²)] reflections	7204, 1920, 1618
R_int	0.065
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.068, 0.095, 1.21
No. of reflections	1920
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.02, −0.83
Computer programs: CrystalClear (Rigaku, 2008 ), SIR92 (Altomare et al., 1994 ), SHELXL2013 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ) and CrystalStructure (Rigaku, 2014 ).

Structural data

CCDC reference: 1899183

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314619002827/pk4025sup1.cif

Supporting information file. DOI: https://doi.org/10.1107/S2414314619002827/pk4025Isup2.cml

checkCIF report

Computing details top

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: CrystalStructure (Rigaku, 2014).

3-(4-Iodophenyl)pentanedinitrile top

Crystal data top

C₁₁H₉IN₂	F(000) = 568.00
M_r = 296.11	D_x = 1.790 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71075 Å
a = 6.508 (4) Å	Cell parameters from 2574 reflections
b = 10.524 (6) Å	θ = 2.5–25.0°
c = 16.047 (10) Å	µ = 2.88 mm⁻¹
β = 90.507 (10)°	T = 93 K
V = 1099.0 (11) Å³	Prism, colorless
Z = 4	0.15 × 0.10 × 0.02 mm

Data collection top

Rigaku Saturn724+ diffractometer	1618 reflections with F² > 2.0σ(F²)
Detector resolution: 7.111 pixels mm^-1	R_int = 0.065
ω scans	θ_max = 25.0°, θ_min = 3.1°
Absorption correction: numerical (NUMABS; Rigaku, 1999)	h = −7→6
T_min = 0.744, T_max = 0.944	k = −12→12
7204 measured reflections	l = −18→19
1920 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.095	H-atom parameters constrained
S = 1.21	w = 1/[σ²(F_o²) + (0.P)² + 7.5421P] where P = (F_o² + 2F_c²)/3
1920 reflections	(Δ/σ)_max = 0.001
127 parameters	Δρ_max = 1.02 e Å⁻³
0 restraints	Δρ_min = −0.83 e Å⁻³
Primary atom site location: structure-invariant direct methods

Special details top

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 sigma(F²) is used only for calculating R-factor (gt).

The C-bound H atoms were placed at ideal positions and were refined as riding on their parent C atoms. U_iso(H) values of the H atoms were set at 1.2U_eq(parent atom for C).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
I1	0.77853 (9)	0.16532 (6)	0.51640 (4)	0.0351 (2)
N1	0.2457 (12)	0.0590 (8)	−0.0356 (5)	0.045 (2)
N2	0.0921 (11)	−0.2452 (7)	0.2869 (4)	0.0362 (19)
C1	0.2949 (14)	0.0783 (8)	0.0303 (6)	0.035 (2)
C2	0.3609 (14)	0.1037 (8)	0.1178 (5)	0.035 (2)
C3	0.3499 (13)	−0.0126 (9)	0.1745 (5)	0.034 (2)
C4	0.1348 (14)	−0.0614 (9)	0.1804 (5)	0.041 (2)
C5	0.1166 (12)	−0.1689 (9)	0.2395 (5)	0.0301 (19)
C6	0.4440 (13)	0.0237 (8)	0.2588 (5)	0.030 (2)
C7	0.6281 (12)	−0.0277 (8)	0.2834 (5)	0.030 (2)
C8	0.7244 (13)	0.0096 (9)	0.3576 (5)	0.032 (2)
C9	0.6311 (12)	0.0997 (8)	0.4067 (5)	0.0248 (19)
C10	0.4428 (13)	0.1489 (9)	0.3852 (5)	0.035 (2)
C11	0.3499 (13)	0.1095 (8)	0.3110 (5)	0.034 (2)
H2A	0.2728	0.1714	0.1411	0.0425*
H2B	0.50393	0.13561	0.11769	0.0425*
H3	0.43663	−0.08104	0.14959	0.0402*
H4A	0.04378	0.00848	0.19859	0.0497*
H4B	0.08771	−0.08939	0.12454	0.0497*
H7	0.69157	−0.08991	0.24927	0.0363*
H8	0.85222	−0.02667	0.37399	0.0389*
H10	0.37682	0.20873	0.42025	0.0416*
H11	0.21879	0.14254	0.29604	0.0412*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.0355 (3)	0.0376 (3)	0.0322 (3)	0.0030 (3)	−0.0112 (2)	−0.0077 (3)
N1	0.041 (5)	0.064 (6)	0.030 (5)	0.002 (4)	0.000 (4)	0.002 (4)
N2	0.040 (5)	0.040 (5)	0.029 (4)	−0.017 (4)	0.000 (3)	0.001 (4)
C1	0.036 (5)	0.020 (5)	0.047 (6)	0.009 (4)	0.008 (5)	0.005 (4)
C2	0.046 (6)	0.032 (5)	0.028 (5)	0.000 (4)	0.003 (4)	0.006 (4)
C3	0.039 (5)	0.039 (5)	0.023 (4)	−0.001 (4)	−0.005 (4)	0.006 (4)
C4	0.047 (6)	0.051 (6)	0.025 (5)	−0.006 (5)	−0.004 (4)	0.007 (4)
C5	0.037 (5)	0.033 (5)	0.020 (4)	−0.011 (5)	−0.007 (4)	−0.007 (4)
C6	0.044 (6)	0.025 (5)	0.021 (4)	−0.004 (4)	−0.007 (4)	0.002 (4)
C7	0.032 (5)	0.035 (5)	0.024 (5)	−0.002 (4)	0.011 (4)	−0.001 (4)
C8	0.029 (5)	0.038 (5)	0.030 (5)	−0.004 (4)	−0.005 (4)	0.003 (4)
C9	0.031 (5)	0.022 (4)	0.020 (4)	−0.001 (4)	−0.009 (4)	−0.002 (4)
C10	0.035 (5)	0.032 (5)	0.037 (5)	0.003 (4)	−0.013 (4)	0.002 (4)
C11	0.029 (5)	0.035 (5)	0.039 (5)	−0.008 (4)	−0.020 (4)	0.005 (4)

Geometric parameters (Å, º) top

I1—C9	2.113 (8)	C9—C10	1.371 (11)
N1—C1	1.120 (12)	C10—C11	1.393 (12)
N2—C5	1.118 (11)	C2—H2A	0.990
C1—C2	1.489 (13)	C2—H2B	0.990
C2—C3	1.526 (12)	C3—H3	1.000
C3—C4	1.495 (12)	C4—H4A	0.990
C3—C6	1.529 (11)	C4—H4B	0.990
C4—C5	1.482 (13)	C7—H7	0.950
C6—C7	1.369 (12)	C8—H8	0.950
C6—C11	1.379 (12)	C10—H10	0.950
C7—C8	1.398 (11)	C11—H11	0.950
C8—C9	1.378 (12)

N1—C1—C2	179.8 (9)	C3—C2—H2A	108.805
C1—C2—C3	113.8 (7)	C3—C2—H2B	108.800
C2—C3—C4	111.2 (7)	H2A—C2—H2B	107.673
C2—C3—C6	107.9 (7)	C2—C3—H3	108.068
C4—C3—C6	113.4 (7)	C4—C3—H3	108.070
C3—C4—C5	112.6 (7)	C6—C3—H3	108.068
N2—C5—C4	175.0 (9)	C3—C4—H4A	109.087
C3—C6—C7	119.9 (7)	C3—C4—H4B	109.085
C3—C6—C11	121.6 (7)	C5—C4—H4A	109.082
C7—C6—C11	118.5 (7)	C5—C4—H4B	109.080
C6—C7—C8	121.3 (8)	H4A—C4—H4B	107.844
C7—C8—C9	119.0 (8)	C6—C7—H7	119.373
I1—C9—C8	120.1 (6)	C8—C7—H7	119.368
I1—C9—C10	119.0 (6)	C7—C8—H8	120.514
C8—C9—C10	120.9 (7)	C9—C8—H8	120.523
C9—C10—C11	118.9 (8)	C9—C10—H10	120.539
C6—C11—C10	121.4 (8)	C11—C10—H10	120.550
C1—C2—H2A	108.800	C6—C11—H11	119.287
C1—C2—H2B	108.802	C10—C11—H11	119.285

C1—C2—C3—C4	−61.3 (9)	C3—C6—C11—C10	−175.6 (7)
C1—C2—C3—C6	173.8 (6)	C7—C6—C11—C10	3.2 (12)
C2—C3—C4—C5	−176.1 (6)	C11—C6—C7—C8	−2.9 (12)
C2—C3—C6—C7	−110.6 (8)	C6—C7—C8—C9	0.1 (12)
C2—C3—C6—C11	68.2 (9)	C7—C8—C9—I1	−177.0 (6)
C4—C3—C6—C7	125.8 (8)	C7—C8—C9—C10	2.6 (12)
C4—C3—C6—C11	−55.4 (10)	I1—C9—C10—C11	177.3 (5)
C6—C3—C4—C5	−54.3 (9)	C8—C9—C10—C11	−2.3 (12)
C3—C6—C7—C8	175.9 (7)	C9—C10—C11—C6	−0.7 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4B···N1ⁱ	0.99	2.61	3.387 (12)	135

Symmetry code: (i) −x, −y, −z.

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