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The mol­ecules of 2-cyano-4-iodo­acetanilide, C9H7IN2O, are linked by N-H...N and C-H...O hydrogen bonds into chains of alternating R22(12) and R22(14) rings.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107026492/sk3136sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107026492/sk3136Isup2.hkl
Contains datablock I

CCDC reference: 655509

Comment top

We report here the molecular and supramolecular structure of 2-cyano-4-iodoacetanilide, (I) (Fig. 1), and we compare the structure of (I) with that of the simpler analogue 2-cyanoacetanilide, (II), for which we have re-interpreted the recently published structure (Arslan et al., 2005). The present study is a continuation of our extended programme on the supramolecular structures of substituted iodoaniline derivatives (Ferguson et al., 2005; Garden et al., 2002, 2004, 2005, 2006; Garden, Glidewell et al., 2001; Glidewell et al., 2004; McWilliam et al., 2001).

In (I), the C6—C1—N1, C1—N1—C11 and N1—C11—O1 angles are all significantly larger than 120° (Table 1), suggesting that the short intramolecular contact H6···O1 (Table 2) may be repulsive rather than attractive. Despite this, the molecule of (I) is almost planar, as indicated by the leading torsion angles, and it is thus possible that the overall molecular conformation results from a balance between repulsive intramolecular contacts and attractive intermolecular hydrogen bonds. The remaining bond lengths and angles show no unusual features

Two intermolecular hydrogen bonds link the molecules of (I) into chains of fused rings. Atoms N1 and C5 in the molecule at (x, y, z) acts as hydrogen-bond donors, respectively, to atoms N2 in the molecule at (2 - x, 1 - y, 1 - z) and O1 in the molecule at (-x, 2 - y, 1 - z). Propagation by inversion of these two interactions generates a chain of rings running parallel to the [210] direction, with centrosymmetric R22(12) rings containing N—H···N hydrogen bonds and centred at (2n + 1, 1/2 - n, 1/2) (where n represents zero or an integer) alternating with centrosymmetric R22(14) rings containing C—H···O hydrogen bonds and centred at (2n, 1 - n, 1/2) (where n represents zero or an integer) (Fig. 2).

The structure of the related compound (II) has recently been reported (Arslan et al., 2005). The structure was described as forming sheets parallel to (100) generated by a combination of N—H···N and C—H···O hydrogen bonds. The formation of a two-dimensional supramolecular structure in space group P212121 is somewhat unexpected, and re-analysis of the published structure shows that the hydrogen-bonded structure of compound (II) is, in fact, three dimensional. The N—H···N and C—H···O hydrogen bonds, acting individually, form chains running parallel to the [100] and [010] directions, of C(6) and C(8) types, respectively, while in combination they form a C22(10) chain running parallel to the [001] direction, so completing the three-dimensional framework. The original report on (II) (Arslan et al., 2005) showed the structure in projection along [100], and the published packing diagram appears to show the formation of R22(12) rings containing pairs of N—H···N hydrogen bonds, when in fact this hydrogen bond forms C(6) chains along the direction of the projection and thus normal to the plane of the supposed hydrogen-bonded sheet.

Although the iodine substituent in (I) plays no direct role in the supramolecular aggregation, its presence leads to an entirely different supramolecular structure in (I) as compared with (II), even though the structures of (I) and (II) are each built from the combination of one N—H···N hydrogen bond and one C—H···O hydrogen bond.

Related literature top

For related literature, see: Arslan et al. (2005); Ferguson et al. (2005); Garden et al. (2002, 2004, 2005, 2006); Garden, Glidewell, Low, McWilliam, Pinto, Skakle, Torres & Wardell (2001); Garden, Torres, Melo, Lima, Pinto & Lima (2001); Glidewell et al. (2004); Harris et al. (1992); McWilliam et al. (2001).

Experimental top

Compound (I) was prepared by the acetylation of 2-amino-5-iodobenzonitrile, prepared as follows. K(ICl2) (Garden, Torres et al., 2001) (3 ml of a 2 mol dm-3 solution in water) was added to a methanol solution (15 ml) of 2-aminobenzonitrile (0.510 g, 5.0 mmol). The reaction mixture was stirred at room temperature. After 2 h, the product had precipitated and the benzonitrile substrate had been completely consumed. The reaction mixture was diluted with water (50 ml) and the product was collected by filtration and dried in air (yield 93%). Recrystallization from aqueous ethanol (97:3 v/v) gave pale-brown plates [m.p. 356–357 K; literature (Harris et al., 1992) 358 K]. NMR (CDCl3): δ (H) 6.20 (2H, s, NH2), 6.62 (1H, d, J = 8.8 Hz), 7.52 (1H, dd, J = 8.8 and 2.0 Hz), 7.65 (1H, d, J = 2.0 Hz); δ (C): 74.9, 96.0, 116.8, 117.8, 139.7, 142.2, 151.2. IR (KBr disk, cm-1): 3456, 3359, 2224, 1643, 1552, 1483, 1402, 1155, 899, 820. The foregoing product (0.500 g, 2.0 mmol) was treated with acetic anhydride (1 ml) and acetic acid (2 ml). The reaction mixture was warmed gently for a few minutes then hydrolyzed with water (20 ml). The product (I) was collected by filtration and recrystallized from aqueous ethanol (97:3 v/v) (yield 79%, m.p. 449–451 K). NMR (CDCl3): δ(H) 2.27 (3H, s, CH3), 7.69 (1H, br, s, NH), 7.85 (1H, dd, J = 10 and 1.9 Hz, H-5), 7.87 (1H, d, J = 1.9 Hz, H-3), 8.19 (1H, d, J = 10 Hz, H-6); δ(C) 24.4, 85.5, 103.2, 114.5, 122.4, 139.7, 139.9, 142.7, 168.2. IR (KBr disk, cm-1): 3344, 3054, 2225, 1689, 1577, 1516, 1383, 1369, 1295, 1258, 1182, 1122, 884, 842.

Refinement top

Crystals of compound (I) are triclinic; the space group P1 was selected and confirmed by the subsequent structure analysis. All H atoms were located in difference maps and then treated as riding atoms in geometrically idealized positions, with C—H distances of 0.95 (aromatic) or 0.98 Å (methyl), N—H distances of 0.86 Å, and Uiso(H) = kUeq(C,N), where k = 1.5 for the methyl groups and k = 1.2 for all other H atoms.

Computing details top

Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures top
[Figure 1] Fig. 1. The molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. A stereoview of part of the crystal structure of (I), showing a chain of alternating R22(12) and R22(14) rings running parallel to [210]. For the sake of clarity, H atoms not involved in the motifs shown have been omitted.
2-cyano-4-iodoacetanilide top
Crystal data top
C9H7IN2OZ = 2
Mr = 286.07F(000) = 272
Triclinic, P1Dx = 1.994 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 4.6657 (2) ÅCell parameters from 2160 reflections
b = 9.4172 (4) Åθ = 3.4–27.5°
c = 11.6841 (4) ŵ = 3.32 mm1
α = 109.7520 (17)°T = 120 K
β = 98.598 (2)°Plate, colourless
γ = 90.926 (2)°0.24 × 0.06 × 0.02 mm
V = 476.51 (3) Å3
Data collection top
Bruker–Nonius KappaCCD
diffractometer
2160 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode2047 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.038
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.4°
ϕ & ω scansh = 66
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1212
Tmin = 0.503, Tmax = 0.937l = 1515
7314 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.027Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.058H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2)P)2 + 1.164P]
where P = (Fo2 + 2Fc2)/3
2160 reflections(Δ/σ)max = 0.001
119 parametersΔρmax = 0.56 e Å3
0 restraintsΔρmin = 0.49 e Å3
Crystal data top
C9H7IN2Oγ = 90.926 (2)°
Mr = 286.07V = 476.51 (3) Å3
Triclinic, P1Z = 2
a = 4.6657 (2) ÅMo Kα radiation
b = 9.4172 (4) ŵ = 3.32 mm1
c = 11.6841 (4) ÅT = 120 K
α = 109.7520 (17)°0.24 × 0.06 × 0.02 mm
β = 98.598 (2)°
Data collection top
Bruker–Nonius KappaCCD
diffractometer
2160 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
2047 reflections with I > 2σ(I)
Tmin = 0.503, Tmax = 0.937Rint = 0.038
7314 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0270 restraints
wR(F2) = 0.058H-atom parameters constrained
S = 1.04Δρmax = 0.56 e Å3
2160 reflectionsΔρmin = 0.49 e Å3
119 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.4745 (6)0.7510 (3)0.4281 (3)0.0158 (5)
N10.5835 (5)0.7571 (3)0.5479 (2)0.0181 (5)
C110.4614 (6)0.8221 (3)0.6515 (3)0.0187 (6)
O10.2268 (5)0.8773 (3)0.6482 (2)0.0253 (5)
C120.6356 (7)0.8183 (4)0.7689 (3)0.0235 (6)
C20.5777 (6)0.6477 (3)0.3278 (3)0.0171 (6)
C210.7918 (6)0.5453 (3)0.3466 (3)0.0195 (6)
N20.9606 (6)0.4631 (3)0.3599 (3)0.0265 (6)
C30.4760 (6)0.6388 (3)0.2069 (3)0.0197 (6)
C40.2682 (6)0.7335 (3)0.1854 (3)0.0191 (6)
I40.10582 (5)0.72195 (2)0.005121 (18)0.02832 (8)
C50.1651 (6)0.8377 (3)0.2832 (3)0.0197 (6)
C60.2676 (6)0.8468 (3)0.4032 (3)0.0180 (6)
H10.74190.71360.55490.022*
H12A0.57020.89370.83930.035*
H12B0.84180.84140.77000.035*
H12C0.60870.71750.77430.035*
H30.54900.56840.14010.024*
H50.02340.90320.26780.024*
H60.19620.91920.46940.022*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0115 (13)0.0173 (13)0.0169 (14)0.0006 (10)0.0013 (10)0.0052 (11)
N10.0117 (12)0.0225 (13)0.0191 (12)0.0059 (9)0.0019 (9)0.0061 (10)
C110.0181 (15)0.0173 (14)0.0227 (15)0.0014 (11)0.0060 (12)0.0082 (12)
O10.0218 (11)0.0302 (12)0.0297 (12)0.0115 (9)0.0115 (9)0.0145 (10)
C120.0252 (16)0.0284 (16)0.0196 (15)0.0033 (13)0.0062 (12)0.0104 (13)
C20.0141 (14)0.0142 (13)0.0217 (15)0.0015 (10)0.0017 (11)0.0051 (11)
C210.0190 (15)0.0186 (14)0.0200 (15)0.0007 (11)0.0037 (11)0.0055 (12)
N20.0255 (15)0.0234 (14)0.0305 (15)0.0072 (11)0.0045 (11)0.0087 (12)
C30.0205 (15)0.0188 (14)0.0180 (14)0.0030 (11)0.0028 (11)0.0042 (11)
C40.0194 (15)0.0201 (14)0.0172 (14)0.0020 (11)0.0000 (11)0.0070 (11)
I40.03228 (14)0.03270 (13)0.02011 (12)0.00763 (9)0.00067 (9)0.01112 (9)
C50.0170 (14)0.0172 (14)0.0251 (15)0.0042 (11)0.0013 (12)0.0082 (12)
C60.0145 (14)0.0169 (13)0.0216 (15)0.0044 (10)0.0030 (11)0.0052 (11)
Geometric parameters (Å, º) top
C1—N11.397 (4)C2—C31.394 (4)
C1—C61.398 (4)C2—C211.444 (4)
C1—C21.402 (4)C21—N21.144 (4)
N1—C111.371 (4)C3—C41.380 (4)
N1—H10.86C3—H30.95
C11—O11.220 (4)C4—C51.386 (4)
C11—C121.498 (4)C4—I42.095 (3)
C12—H12A0.98C5—C61.385 (4)
C12—H12B0.98C5—H50.95
C12—H12C0.98C6—H60.95
C6—C1—N1122.5 (3)C3—C2—C21117.7 (3)
N1—C1—C2119.8 (2)C1—C2—C21120.7 (3)
C6—C1—C2117.6 (3)N2—C21—C2179.1 (3)
C1—N1—C11126.8 (2)C4—C3—C2119.3 (3)
C11—N1—H1118.5C4—C3—H3120.3
C1—N1—H1114.7C2—C3—H3120.3
N1—C11—O1122.6 (3)C3—C4—C5120.2 (3)
O1—C11—C12122.4 (3)C3—C4—I4120.5 (2)
N1—C11—C12115.0 (3)C5—C4—I4119.3 (2)
C11—C12—H12A109.5C6—C5—C4120.3 (3)
C11—C12—H12B109.5C6—C5—H5119.8
H12A—C12—H12B109.5C4—C5—H5119.8
C11—C12—H12C109.5C5—C6—C1120.9 (3)
H12A—C12—H12C109.5C5—C6—H6119.5
H12B—C12—H12C109.5C1—C6—H6119.5
C3—C2—C1121.6 (3)
C6—C1—N1—C1118.5 (4)C21—C2—C3—C4179.1 (3)
C2—C1—N1—C11162.9 (3)C2—C3—C4—C50.9 (4)
C1—N1—C11—O13.8 (5)C2—C3—C4—I4179.2 (2)
C1—N1—C11—C12177.0 (3)C3—C4—C5—C60.6 (4)
N1—C1—C2—C3179.5 (3)I4—C4—C5—C6179.5 (2)
C6—C1—C2—C30.8 (4)C4—C5—C6—C10.5 (4)
N1—C1—C2—C211.2 (4)N1—C1—C6—C5179.8 (3)
C6—C1—C2—C21179.9 (3)C2—C1—C6—C51.1 (4)
C1—C2—C3—C40.2 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N2i0.862.543.309 (4)149
C5—H5···O1ii0.952.383.214 (4)147
C6—H6···O10.952.242.815 (4)118
Symmetry codes: (i) x+2, y+1, z+1; (ii) x, y+2, z+1.

Experimental details

Crystal data
Chemical formulaC9H7IN2O
Mr286.07
Crystal system, space groupTriclinic, P1
Temperature (K)120
a, b, c (Å)4.6657 (2), 9.4172 (4), 11.6841 (4)
α, β, γ (°)109.7520 (17), 98.598 (2), 90.926 (2)
V3)476.51 (3)
Z2
Radiation typeMo Kα
µ (mm1)3.32
Crystal size (mm)0.24 × 0.06 × 0.02
Data collection
DiffractometerBruker–Nonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.503, 0.937
No. of measured, independent and
observed [I > 2σ(I)] reflections
7314, 2160, 2047
Rint0.038
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.027, 0.058, 1.04
No. of reflections2160
No. of parameters119
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.56, 0.49

Computer programs: COLLECT (Nonius, 1999), DENZO (Otwinowski & Minor, 1997) and COLLECT, DENZO and COLLECT, OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997), OSCAIL and SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).

Selected bond angles (º) top
C6—C1—N1122.5 (3)N1—C11—O1122.6 (3)
C1—N1—C11126.8 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N2i0.862.543.309 (4)149
C5—H5···O1ii0.952.383.214 (4)147
C6—H6···O10.952.242.815 (4)118
Symmetry codes: (i) x+2, y+1, z+1; (ii) x, y+2, z+1.
 

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