2-Iodo-4-nitro-N-(trifluoro­acet­yl)aniline: sheets built from iodo–nitro and nitro–nitro inter­actions

Garden, S.J.; Wardell, J.L.; Low, J.N.; Skakle, J.M.S.; Glidewell, C.

doi:10.1107/S1600536806029072

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 62| Part 9| September 2006| Pages o3762-o3764

https://doi.org/10.1107/S1600536806029072

2-Iodo-4-nitro-N-(trifluoroacetyl)aniline: sheets built from iodo–nitro and nitro–nitro interactions

Simon J. Garden,^a James L. Wardell,^a John N. Low,^b Janet M. S. Skakle ^b and Christopher Glidewell ^c ^*

^aInstituto de Química, Departamento de Química Inorgânica, Universidade Federal do Rio de Janeiro, CP 68563, 21945-970 Rio de Janeiro, RJ, Brazil, ^bDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and ^cSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland
^*Correspondence e-mail: cg@st-andrews.ac.uk

(Received 5 July 2006; accepted 26 July 2006; online 9 August 2006)

In the title compound, C₈H₄F₃IN₂O₃, the molecules are linked into sheets by a combination of a nearly symmetrical three-centre iodo–nitro interaction and a dipolar nitro–nitro interaction. Hydrogen bonds are absent from the structure.

Comment

We have recently reported the supramolecular structures of a range of iodonitroanilines, which exhibit a wide variety of intermolecular interactions including hydrogen bonds, iodo–nitro interactions and aromatic π–π stacking interactions (Garden et al., 2001 , 2002 , 2004 , 2005 ; McWilliam et al., 2001 ). Continuing this study, we now report the structure of 2-iodo-4-nitro-N-(trifluoroacetyl)aniline, (I) (Fig. 1).

With the exception of the trifluoromethyl group, the molecule of (I) is approximately planar, as shown by the key torsion angles (Table 1); the bond distances and inter-bond angles show no unusual values.

The molecules of (I) are linked by a nearly symmetrical three-centre iodo–nitro interaction. Atom I2 in the molecule at (x, y, z) makes contacts with both nitro atoms O41 and O42 in the molecule at (− $[{1\over 2}]$ + x, $[{3\over 2}]$ − y, − $[{1\over 2}]$ + z), with geometric parameters I2⋯O41ⁱ = 3.3853 (16) Å, I2⋯O42ⁱ = 3.4159 (18) Å, C2—I2⋯O41ⁱ = 158.24 (6)°, C2—I2⋯O42ⁱ = 155.32 (6)° and O41ⁱ⋯I2⋯O42ⁱ = 37.06 (4)° [symmetry code: (i) − $[{1\over 2}]$ + x, $[{3\over 2}]$ − y, − $[{1\over 2}]$ + z]. Propagation of this interaction then produces a C(6)C(6)[R₂¹(4)] chain of rings (Bernstein et al., 1995 ; Starbuck et al., 1999 ) running parallel to the [101] direction and generated by the n-glide plane at y = $[{3 \over 4}]$ (Fig. 2).

Two chains of this type, which are related to one another by inversion and which are thus anti-parallel, pass through each unit cell. The [101] chains are linked into sheets by a dipolar nitro–nitro interaction. Nitro atom O41 in the molecule at (x, y, z) makes a short dipolar contact with nitro atom N4 in the molecule at ( $[{3\over 2}]$ − x, $[{1\over 2}]$ + y, $[{3\over 2}]$ − z), with geometric parameters O41⋯N4ⁱⁱ = 2.872 (2) Å and N4—O41⋯N4ⁱⁱ = 148.26 (14)° [symmetry code: (ii) $[{3\over 2}]$ − x, $[{1\over 2}]$ + y, $[{3\over 2}]$ − z]. Propagation of this interaction, which resembles the type I (perpendicular) carbonyl–carbonyl interaction (Allen et al., 1998 ), produces a C(2) chain running parallel to the [010] direction and generated by the 2₁ screw axis along ( $[{3 \over 4}]$ , y, $[{3 \over 4}]$ ) (Fig. 3).

The combination of [101] and [010] chains generates a sheet parallel to (10 $[\overline{1}]$ ), but there are no direction-specific interactions between adjacent sheets; in particular, hydrogen bonds of all types and aromatic π–π stacking interactions are absent from the structure of (I). The absence of any participation by the amide group in any significant intermolecular interactions is unexpected.

Figure 1
The molecular structure of compound (I)

, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 2
Part of the crystal structure of compound (I)

, showing the formation of a chain of rings along the [101] direction. For the sake of clarity, H atoms have all been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (− $[{1\over 2}]$ + x, $[{3\over 2}]$ − y, − $[{1\over 2}]$ + z) and ( $[{1\over 2}]$ + x, $[{3\over 2}]$ − y, $[{1\over 2}]$ + z), respectively.

Figure 3
Part of the crystal structure of compound (I)

, showing the formation of a chain along the [010] direction. For the sake of clarity, H atoms have all been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions ( $[{3\over 2}]$ − x, $[{1\over 2}]$ + y, $[{3\over 2}]$ − z) and ( $[{3\over 2}]$ − x, − $[{1\over 2}]$ + y, $[{3\over 2}]$ − z), respectively.

Experimental

2-Iodo-4-nitro-N-(trifluoroacetyl)aniline was prepared according to a published method (Latham & Stanforth, 1997 ) and recrystallized from ethanol (m.p. 399–400 K).

Crystal data

C₈H₄F₃IN₂O₃
M_r = 360.03
Monoclinic, P 2₁ /n
a = 14.6372 (3) Å
b = 5.0029 (2) Å
c = 15.2723 (3) Å
β = 110.318 (2)°
V = 1048.78 (5) Å³
Z = 4
D_x = 2.280 Mg m⁻³
Mo Kα radiation
μ = 3.10 mm⁻¹
T = 120 (2) K
Block, yellow
0.30 × 0.20 × 0.20 mm

Data collection

Nonius KappaCCD diffractometer
φ and ω scans
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997 ) T_min = 0.425, T_max = 0.536
13862 measured reflections
2402 independent reflections
2214 reflections with I > 2σ(I)
R_int = 0.050
θ_max = 27.5°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.021
wR(F²) = 0.050
S = 1.14
2402 reflections
154 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0133P)² + 1.0182P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.62 e Å⁻³
Δρ_min = −0.83 e Å⁻³

Table 1
Selected torsion angles (°)

C2—C1—N1—C11	164.14 (19)
C1—N1—C11—C12	−178.11 (18)
C3—C4—N4—O41	4.7 (3)

All H atoms were located in difference maps and then treated as riding, with C—H = 0.95 Å, N—H = 0.88 Å and U_iso(H) = 1.2U_eq(C,N).

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

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536806029072/rn2011sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806029072/rn2011Isup2.hkl

Computing details top

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

2-iodo-4-nitro-N-(trifluoroacetyl)aniline top

Crystal data top

C₈H₄F₃IN₂O₃	F(000) = 680
M_r = 360.03	D_x = 2.280 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2402 reflections
a = 14.6372 (3) Å	θ = 3.0–27.5°
b = 5.0029 (2) Å	µ = 3.10 mm⁻¹
c = 15.2723 (3) Å	T = 120 K
β = 110.318 (2)°	Block, yellow
V = 1048.78 (5) Å³	0.30 × 0.20 × 0.20 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	2402 independent reflections
Radiation source: fine-focus sealed X-ray tube	2214 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.050
φ and ω scans	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997)	h = −19→18
T_min = 0.425, T_max = 0.536	k = −6→6
13862 measured reflections	l = −19→19

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)] = 0.021	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.050	H-atom parameters constrained
S = 1.14	w = 1/[σ²(F_o²) + (0.0133P)² + 1.0182P] where P = (F_o² + 2F_c²)/3
2402 reflections	(Δ/σ)_max = 0.001
154 parameters	Δρ_max = 0.62 e Å⁻³
0 restraints	Δρ_min = −0.83 e Å⁻³

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

	x	y	z	U_iso*/U_eq
C1	0.41248 (14)	0.3324 (4)	0.68419 (13)	0.0136 (4)
C2	0.46717 (14)	0.5180 (4)	0.65374 (12)	0.0132 (4)
C3	0.56627 (14)	0.5485 (4)	0.70208 (13)	0.0157 (4)
C4	0.60949 (14)	0.3870 (4)	0.77944 (13)	0.0158 (4)
C5	0.55859 (17)	0.1934 (4)	0.80803 (15)	0.0187 (4)
C6	0.45995 (16)	0.1672 (4)	0.76057 (14)	0.0177 (4)
N1	0.31119 (13)	0.3194 (4)	0.63785 (12)	0.0148 (3)
C11	0.25016 (14)	0.1210 (4)	0.64240 (13)	0.0152 (4)
O11	0.27013 (11)	−0.0869 (3)	0.68607 (10)	0.0210 (3)
C12	0.14369 (16)	0.1693 (4)	0.57965 (15)	0.0180 (4)
F1	0.11944 (10)	−0.0034 (3)	0.50804 (9)	0.0278 (3)
F2	0.08382 (9)	0.1259 (3)	0.62684 (9)	0.0274 (3)
F3	0.12630 (9)	0.4152 (3)	0.54381 (10)	0.0269 (3)
I2	0.402878 (9)	0.74612 (2)	0.532577 (8)	0.01443 (7)
N4	0.71340 (13)	0.4257 (4)	0.83326 (12)	0.0199 (4)
O41	0.75675 (11)	0.6106 (3)	0.81166 (11)	0.0288 (4)
O42	0.75250 (14)	0.2737 (3)	0.89876 (13)	0.0293 (4)
H3	0.6035	0.6762	0.6828	0.019*
H5	0.5910	0.0805	0.8595	0.022*
H6	0.4239	0.0361	0.7798	0.021*
H1	0.2844	0.4559	0.6017	0.018*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0157 (9)	0.0122 (9)	0.0130 (8)	−0.0006 (8)	0.0050 (7)	−0.0015 (7)
C2	0.0163 (9)	0.0122 (9)	0.0107 (8)	0.0016 (7)	0.0044 (7)	−0.0002 (7)
C3	0.0160 (9)	0.0176 (10)	0.0142 (9)	−0.0014 (8)	0.0061 (7)	−0.0014 (7)
C4	0.0138 (9)	0.0166 (9)	0.0149 (9)	0.0008 (8)	0.0026 (7)	−0.0036 (7)
C5	0.0222 (11)	0.0175 (9)	0.0147 (9)	0.0031 (9)	0.0044 (8)	0.0019 (8)
C6	0.0215 (10)	0.0151 (9)	0.0154 (9)	−0.0022 (9)	0.0048 (8)	0.0012 (8)
N1	0.0136 (8)	0.0131 (7)	0.0175 (8)	−0.0009 (7)	0.0053 (7)	0.0023 (7)
C11	0.0158 (9)	0.0151 (10)	0.0172 (9)	−0.0015 (8)	0.0087 (7)	−0.0026 (7)
O11	0.0215 (7)	0.0149 (7)	0.0269 (8)	−0.0020 (6)	0.0091 (6)	0.0038 (6)
C12	0.0173 (10)	0.0172 (10)	0.0199 (10)	−0.0037 (9)	0.0070 (8)	−0.0003 (9)
F1	0.0294 (7)	0.0271 (7)	0.0224 (6)	−0.0056 (6)	0.0034 (5)	−0.0084 (5)
F2	0.0174 (6)	0.0378 (8)	0.0303 (7)	−0.0064 (6)	0.0126 (5)	0.0008 (6)
F3	0.0183 (6)	0.0202 (6)	0.0376 (7)	−0.0003 (5)	0.0039 (5)	0.0059 (6)
I2	0.01406 (9)	0.01624 (10)	0.01339 (9)	0.00049 (4)	0.00527 (6)	0.00346 (4)
N4	0.0169 (8)	0.0241 (9)	0.0156 (8)	0.0002 (7)	0.0017 (7)	−0.0032 (7)
O41	0.0199 (8)	0.0331 (9)	0.0274 (8)	−0.0092 (7)	0.0006 (6)	0.0005 (7)
O42	0.0215 (9)	0.0359 (10)	0.0232 (9)	0.0055 (7)	−0.0017 (7)	0.0069 (6)

Geometric parameters (Å, º) top

C1—C6	1.401 (3)	C6—H6	0.95
C1—N1	1.405 (3)	N1—C11	1.353 (3)
C1—C2	1.406 (3)	N1—H1	0.88
C2—C3	1.389 (3)	C11—O11	1.215 (2)
C2—I2	2.0982 (18)	C11—C12	1.539 (3)
C3—C4	1.389 (3)	C12—F2	1.332 (2)
C3—H3	0.95	C12—F3	1.335 (3)
C4—C5	1.382 (3)	C12—F1	1.341 (2)
C4—N4	1.469 (2)	N4—O42	1.228 (2)
C5—C6	1.379 (3)	N4—O41	1.230 (2)
C5—H5	0.95

C6—C1—N1	121.56 (18)	C1—C6—H6	119.7
C6—C1—C2	119.34 (18)	C11—N1—C1	127.44 (18)
N1—C1—C2	119.09 (17)	C11—N1—H1	116.3
C3—C2—C1	120.40 (17)	C1—N1—H1	116.3
C3—C2—I2	118.36 (14)	O11—C11—N1	128.23 (19)
C1—C2—I2	121.21 (14)	O11—C11—C12	118.34 (18)
C2—C3—C4	118.13 (18)	N1—C11—C12	113.37 (17)
C2—C3—H3	120.9	F2—C12—F3	107.75 (18)
C4—C3—H3	120.9	F2—C12—F1	107.37 (17)
C5—C4—C3	122.69 (19)	F3—C12—F1	107.51 (17)
C5—C4—N4	118.85 (18)	F2—C12—C11	110.60 (17)
C3—C4—N4	118.47 (18)	F3—C12—C11	114.07 (17)
C6—C5—C4	118.80 (19)	F1—C12—C11	109.30 (17)
C6—C5—H5	120.6	O42—N4—O41	123.11 (18)
C4—C5—H5	120.6	O42—N4—C4	118.25 (18)
C5—C6—C1	120.5 (2)	O41—N4—C4	118.64 (17)
C5—C6—H6	119.7

C6—C1—C2—C3	−3.8 (3)	C2—C1—N1—C11	164.14 (19)
N1—C1—C2—C3	175.52 (18)	C1—N1—C11—O11	−1.1 (3)
C6—C1—C2—I2	174.30 (15)	C1—N1—C11—C12	−178.11 (18)
N1—C1—C2—I2	−6.4 (2)	O11—C11—C12—F2	50.4 (3)
C1—C2—C3—C4	1.4 (3)	N1—C11—C12—F2	−132.29 (19)
I2—C2—C3—C4	−176.70 (14)	O11—C11—C12—F3	171.99 (18)
C2—C3—C4—C5	2.0 (3)	N1—C11—C12—F3	−10.7 (3)
C2—C3—C4—N4	−177.50 (17)	O11—C11—C12—F1	−67.6 (2)
C3—C4—C5—C6	−3.0 (3)	N1—C11—C12—F1	109.71 (19)
N4—C4—C5—C6	176.49 (18)	C5—C4—N4—O42	4.1 (3)
C4—C5—C6—C1	0.6 (3)	C3—C4—N4—O42	−176.38 (19)
N1—C1—C6—C5	−176.51 (19)	C5—C4—N4—O41	−174.9 (2)
C2—C1—C6—C5	2.7 (3)	C3—C4—N4—O41	4.7 (3)
C6—C1—N1—C11	−16.6 (3)

Acknowledgements

X-ray data were collected at the EPSRC National X-ray Crystallography Service, University of Southampton, England; the authors thank the staff of the Service for all their help and advice. JLW thanks CNPq and FAPERJ for financial support.

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