3-Iodo-2,6-dinitro­toluene

Watkin, D.J.; Motherwell, W.D.S.; Cooper, R.I.; Pantos, S.; Steadman, O.I.

doi:10.1107/S1600536805024864

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 61| Part 9| September 2005| Pages o2836-o2838

https://doi.org/10.1107/S1600536805024864

3-Iodo-2,6-dinitrotoluene

David J. Watkin,^a ^* W. D. S. Motherwell,^b Richard I. Cooper,^a Stefan Pantos ^a and Oliver I. Steadman ^a

^aChemical Crystallography, Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA, England, and ^bCambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, England
^*Correspondence e-mail: david.watkin@chem.ox.ac.uk

(Received 29 July 2005; accepted 3 August 2005; online 12 August 2005)

The structure of the title compound, C₇H₅IN₂O₄, was determined as one of a group of five related compounds, in order to assess its suitability as a test material for the 2004 Cambridge Crystallographic Data Centre `Blind Structure Prediction Test'. The crystal structure consists of columns of nearly planar molecules stacked parallel to the a axis, with an interplanar spacing of 3.478 (3) Å.

Comment

The structure of the title material, (I), was determined as part of the preparations for the 2004 Cambridge Crystallographic Data Centre `Blind Structure Prediction Tests' (Watkin et al., 2004 ), although it was not used in the test.

The sample consisted of chunky opaque pale-cream flakes. Attempts were made to obtain a roughly isometric sample, but the specimens had a tendency to crush. A suitable fragment was chosen on the basis of its sharp diffraction pattern and data were initially collected at 263 K, because of the fragililty of the material. A further data set was then collected on the same crystal at 110 K without any problems, and which gave essentially the same structure.

The methyl atom H71 is almost coplanar with the benzene group [H71—C7—C6—C5 = −165 (1)°], as are the I and N atoms (deviations of 0.02, 0.06 and 0.07 Å, respectively). The two nitro groups are rotated out of the plane of the benzene group [O12—N11—C1—C2 = 98.0 (3)° and O9—N8—C5—C4 = −42.9 (3)°] (Fig. 1). Except for the O atoms, the atomic displacement parameters conform to a rigid group (R_TLS = 0.09), with the principal axis of libration at 80 (1)° to the normal to the plane through the C atoms.

The structure of (I) consists of columns of molecules stacked along the a axis, with an interplanar separation of 3.780 (3) Å (Fig. 2). There are no hydrogen bonds (Fig. 3) and the only exceptionally short intermolecular contacts between the columns are from atom I14 to atoms O12 and O13 in an adjacent molecule [3.368 (3) and 3.481 (3) Å, respectively].

Figure 1
A view of the molecule of (I)

, with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitary radii.

Figure 2
Diagram showing a column of molecules viewed end-on, parallel to the a axis.

Figure 3
Diagram showing a column of molecules viewed approximately perpendicular to the column axis and parallel to the plane of the benzene group.

Experimental

The material was from a collection of nitrotoluene derivatives synthesized by Wilhelm Koerner about a century ago and retrieved from a depository at the University of Milan (Demartin et al., 2004 ). Details of the preparation and crystallization are unknown.

Crystal data

C₇H₅IN₂O₄
M_r = 308.03
Monoclinic, P 2₁ /c
a = 11.0997 (5) Å
b = 6.9493 (3) Å
c = 12.3296 (5) Å
β = 92.084 (2)°
V = 950.42 (7) Å³
Z = 4
D_x = 2.153 Mg m⁻³
Mo Kα radiation
Cell parameters from 3027 reflections
θ = 5–27°
μ = 3.36 mm⁻¹
T = 110 K
Block, pale yellow
0.15 × 0.10 × 0.10 mm

Data collection

Nonius KappaCCD area-detector diffractometer
ω scans
Absorption correction: multi-scan(DENZO/SCALEPACK; Otwinowski & Minor, 1997 )T_min = 0.65, T_max = 0.71
9545 measured reflections
2140 independent reflections
2140 reflections with I > 10σ(I)
R_int = 0.033
θ_max = 27.5°
h = −13 → 14
k = −7 → 9
l = −16 → 15

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.067
S = 0.89
2140 reflections
142 parameters
Only H-atom coordinates refined
w = 1/[σ²(F²) + (0.01P)²] where P = (max(F_o²,0) + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.89 e Å⁻³
Δρ_min = −0.95 e Å⁻³

Table 1
Selected contact distances (Å)

I14⋯O12ⁱ	3.368 (3)
I14⋯O13ⁱ	3.481 (3)
Symmetry code: (i) $[-x+1, y-{\script{1\over 2}}, -z-{\script{1\over 2}}]$ .

The H atoms were all located in a difference map, but those attached to C atoms were repositioned geometrically. The H atoms were initially refined with soft restraints on the bond lengths and angles to regularize their geometry (C—H distances in the range 0.93–0.98 Å) and displacement parameters [U_iso(H) in the range 1.2–1.5 times U_eq of the parent atom], after which they were refined freely.

Data collection: COLLECT (Nonius, 2001 ).; cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ); molecular graphics: CAMERON (Watkin et al., 1996 ); software used to prepare material for publication: CRYSTALS.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536805024864/lh6482sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805024864/lh6482Isup2.hkl

Computing details top

Data collection: COLLECT (Nonius, 2001).; cell refinement: DENZO/SCALEPACK; data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: CRYSTALS.

3-Iodo-2,6-dinitrotoluene top

Crystal data top

C₇H₅IN₂O₄	F(000) = 584
M_r = 308.03	D_x = 2.153 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.0997 (5) Å	Cell parameters from 3027 reflections
b = 6.9493 (3) Å	θ = 5–27°
c = 12.3296 (5) Å	µ = 3.36 mm⁻¹
β = 92.084 (2)°	T = 110 K
V = 950.42 (7) Å³	Block, pale yellow
Z = 4	0.15 × 0.10 × 0.10 mm

Data collection top

Nonius KappaCCD area-detector diffractometer	2140 reflections with I > −10σ(I)
Graphite monochromator	R_int = 0.033
ω scans	θ_max = 27.5°, θ_min = 5.5°
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	h = −13→14
T_min = 0.65, T_max = 0.71	k = −7→9
9545 measured reflections	l = −16→15
2140 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.051	Only H-atom coordinates refined
wR(F²) = 0.067	w = 1/[σ²(F²) + (0.01P)²] where P = (max(F_o²,0) + 2F_c²)/3
S = 0.89	(Δ/σ)_max = 0.001
2140 reflections	Δρ_max = 0.89 e Å⁻³
142 parameters	Δρ_min = −0.95 e Å⁻³
11 restraints

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

	x	y	z	U_iso*/U_eq
C1	0.7256 (3)	1.0278 (5)	−0.0381 (2)	0.0350
C2	0.6582 (3)	0.8596 (5)	−0.0365 (3)	0.0381
C3	0.6803 (4)	0.7314 (6)	0.0480 (3)	0.0477
C4	0.7626 (4)	0.7760 (6)	0.1292 (3)	0.0486
C5	0.8268 (3)	0.9455 (6)	0.1241 (3)	0.0416
C6	0.8125 (3)	1.0783 (5)	0.0406 (3)	0.0391
C7	0.8804 (4)	1.2631 (7)	0.0358 (4)	0.0572
N8	0.9112 (4)	0.9825 (5)	0.2160 (3)	0.0618
O9	0.8761 (3)	0.9482 (6)	0.3070 (2)	0.0911
O10	1.0102 (4)	1.0444 (6)	0.1978 (3)	0.1055
N11	0.6986 (3)	1.1659 (5)	−0.1261 (2)	0.0434
O12	0.6341 (3)	1.3010 (4)	−0.1076 (3)	0.0704
O13	0.7396 (3)	1.1356 (4)	−0.2142 (2)	0.0702
I14	0.52258 (2)	0.80126 (4)	−0.153334 (18)	0.0502
H31	0.636 (3)	0.629 (5)	0.048 (3)	0.0500*
H41	0.773 (3)	0.703 (5)	0.182 (3)	0.0500*
H71	0.850 (3)	1.344 (4)	−0.012 (3)	0.0500*
H72	0.878 (3)	1.324 (4)	0.097 (2)	0.0500*
H73	0.950 (3)	1.247 (5)	0.015 (3)	0.0500*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0412 (19)	0.033 (2)	0.0303 (16)	0.0084 (16)	−0.0046 (14)	0.0002 (14)
C2	0.0430 (19)	0.039 (2)	0.0321 (17)	0.0039 (16)	−0.0023 (14)	−0.0055 (15)
C3	0.055 (2)	0.037 (2)	0.050 (2)	−0.0004 (18)	−0.0030 (19)	0.0050 (19)
C4	0.061 (3)	0.045 (3)	0.039 (2)	0.010 (2)	−0.0067 (19)	0.0072 (18)
C5	0.044 (2)	0.048 (2)	0.0325 (17)	0.0105 (17)	−0.0068 (15)	−0.0023 (17)
C6	0.0399 (19)	0.037 (2)	0.0404 (18)	0.0049 (17)	−0.0030 (15)	−0.0008 (17)
C7	0.059 (3)	0.059 (3)	0.053 (3)	−0.010 (2)	−0.011 (2)	−0.001 (2)
N8	0.068 (3)	0.058 (2)	0.057 (2)	0.018 (2)	−0.0292 (19)	−0.0046 (19)
O9	0.115 (3)	0.114 (3)	0.0426 (17)	0.033 (2)	−0.0262 (18)	−0.0150 (19)
O10	0.074 (2)	0.132 (4)	0.106 (3)	−0.018 (2)	−0.052 (2)	0.020 (3)
N11	0.0502 (18)	0.042 (2)	0.0371 (17)	−0.0017 (15)	−0.0105 (14)	0.0016 (14)
O12	0.084 (2)	0.057 (2)	0.069 (2)	0.0286 (18)	−0.0030 (17)	0.0139 (16)
O13	0.109 (2)	0.066 (2)	0.0362 (15)	0.0065 (18)	0.0056 (15)	0.0074 (14)
I14	0.05144 (18)	0.05178 (19)	0.04654 (17)	−0.00438 (13)	−0.01050 (11)	−0.00924 (12)

Geometric parameters (Å, º) top

C1—C2	1.388 (5)	C5—N8	1.467 (5)
C1—C6	1.389 (5)	C6—C7	1.491 (6)
C1—N11	1.471 (4)	C7—H71	0.87 (3)
C2—C3	1.386 (5)	C7—H72	0.86 (3)
C2—I14	2.085 (3)	C7—H73	0.83 (3)
C3—C4	1.365 (6)	N8—O9	1.224 (4)
C3—H31	0.87 (3)	N8—O10	1.208 (5)
C4—C5	1.379 (5)	N11—O12	1.208 (4)
C4—H41	0.83 (3)	N11—O13	1.211 (4)
C5—C6	1.388 (5)

I14···O12ⁱ	3.368 (3)	I14···O13ⁱ	3.481 (3)

C2—C1—C6	124.3 (3)	C1—C6—C5	114.1 (3)
C2—C1—N11	117.7 (3)	C1—C6—C7	121.9 (3)
C6—C1—N11	117.9 (3)	C5—C6—C7	123.9 (3)
C1—C2—C3	118.1 (3)	C6—C7—H71	113 (2)
C1—C2—I14	122.0 (2)	C6—C7—H72	111 (2)
C3—C2—I14	119.9 (3)	H71—C7—H72	104 (3)
C2—C3—C4	120.0 (4)	C6—C7—H73	112 (2)
C2—C3—H31	116 (3)	H71—C7—H73	103 (3)
C4—C3—H31	124 (3)	H72—C7—H73	113 (3)
C3—C4—C5	119.6 (4)	C5—N8—O9	117.2 (4)
C3—C4—H41	120 (3)	C5—N8—O10	118.6 (4)
C5—C4—H41	120 (3)	O9—N8—O10	124.2 (4)
C4—C5—C6	123.8 (3)	C1—N11—O12	118.3 (3)
C4—C5—N8	115.6 (3)	C1—N11—O13	118.3 (3)
C6—C5—N8	120.6 (4)	O12—N11—O13	123.3 (3)

Symmetry code: (i) −x+1, y−1/2, −z−1/2.

Acknowledgements

The authors thank Professor Angelo Gavezzotti for obtaining the samples, Professor Lucio Merlini, Director of the Dipartmento di Scienze Molecolari Agroalimentari of the University of Milan, for generously donating the samples, and Professor Anna Arnoldi for help in the retrieval of the crystals.

References

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