N-(2-Methyl-3,6-dinitro­phen­yl)acetamide

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

doi:10.1107/S1600536805034355

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 61| Part 11| November 2005| Pages o3888-o3890

https://doi.org/10.1107/S1600536805034355

N-(2-Methyl-3,6-dinitrophenyl)acetamide

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 17 October 2005; accepted 24 October 2005; online 27 October 2005)

The structure of the title compound, C₉H₉N₃O₅, 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 structure consists of hydrogen-bonded ribbons of molecules stacked along the a axis with the benzene rings parallel by unit-cell translations.

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 ), though (I) was not used in the test. 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.

The sample consisted of large, striated, pale-cream laths. Attempts were made to obtain a roughly isometric sample, but the specimens inevitably splintered freely if any attempt was made to cut them into shorter lengths. One was selected on the basis of its sharp diffraction pattern and relative thickness. Changes in illuminated volume were kept to a minimum by the data collection strategy, and were taken into account (Görbitz, 1999 ) by the multi-scan inter-frame scaling (DENZO/SCALEPACK; Otwinowski & Minor, 1997 ).

The two nitro groups are twisted by almost the same angle from the plane of the benzene ring [C1—C2—N3—O5 = 143.3 (3)° and C9—C8—C11—O12 = −147.9 (3)°]. The almost planar acetamide group is rotated out of the ring plane [C9—C1—N14—C15 = 129.3 (3)°] (Fig. 1).

The structure consists of ribbons of molecules stacked with the benzene rings parallel by unit-cell translations along the a axis, giving an interplanar separation of 3.618 (3) Å (Fig. 2). Molecules in these ribbons are linked together by hydrogen bonds (Fig. 3 and Table 1). Other intermolecular contacts are unexceptional.

Figure 1
The title compound, with atomic displacement parameters drawn at the 50% probability level and the H atoms with arbitary radii.

Figure 2
Projection along the b axis, showing the hydrogen bonding (dotted lines) and the aromatic ring stacking.

Figure 3
Projection along the a axis, showing the hydrogen-bonded (dotted lines) chain, with the benzene rings all on the same side of the c axis.

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

C₉H₉N₃O₅
M_r = 239.19
Monoclinic, P 2₁
a = 4.9309 (2) Å
b = 11.7571 (4) Å
c = 8.7944 (3) Å
β = 99.8608 (14)°
V = 502.31 (3) Å³
Z = 2
D_x = 1.581 Mg m⁻³
Mo Kα radiation
Cell parameters from 939 reflections
θ = 5–27°
μ = 0.13 mm⁻¹
T = 120 K
Lath, pale yellow
0.76 × 0.20 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer
ω scans
Absorption correction: multi-scan(DENZO/SCALEPACK; Otwinowski & Minor, 1997)T_min = 0.80, T_max = 0.99
3452 measured reflections
1188 independent reflections
1188 reflections with I > −10σ(I)
R_int = 0.021
θ_max = 27.5°
h = −6 → 6
k = −15 → 12
l = −11 → 11

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.062
S = 1.09
1188 reflections
154 parameters
H-atom parameters constrained
w = 1/[σ²(F²) + (0.02P)² + 0.13P] where P = [max(F_o²,0) + 2F_c²]/3
(Δ/σ)_max < 0.001
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N14—H7⋯O16ⁱ	0.84	2.13	2.963 (2)	168
Symmetry code: (i) x-1, y, z.

In the absence of significant anomalous scattering, Friedel pairs were merged. 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 in the target range 0.93–98 Å and N—H 0.86 Å) and isotropic displacement parameters [U_iso(H) in the range 1.2–1.5 times U_eq of the parent atom], after which they were refined with riding constraints.

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/S1600536805034355/cf6468sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805034355/cf6468Isup2.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.

N-(2-Methyl-3,6-dinitrophenyl)acetamide top

Crystal data top

C₉H₉N₃O₅	F(000) = 248
M_r = 239.19	D_x = 1.581 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 4.9309 (2) Å	Cell parameters from 939 reflections
b = 11.7571 (4) Å	θ = 5–27°
c = 8.7944 (3) Å	µ = 0.13 mm⁻¹
β = 99.8608 (14)°	T = 120 K
V = 502.31 (3) Å³	Lath, pale-yellow
Z = 2	0.76 × 0.20 × 0.10 mm

Data collection top

Nonius KappaCCD diffractometer	1188 reflections with I > −10σ(I)
Graphite monochromator	R_int = 0.021
ω scans	θ_max = 27.5°, θ_min = 5.2°
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	h = −6→6
T_min = 0.80, T_max = 0.99	k = −15→12
3452 measured reflections	l = −11→11
1188 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)] = 0.024	H-atom parameters constrained
wR(F²) = 0.062	w = 1/[σ²(F²) + (0.02P)² + 0.13P] where P = [max(F_o²,0) + 2F_c²]/3
S = 1.09	(Δ/σ)_max = 0.000205
1188 reflections	Δρ_max = 0.21 e Å⁻³
154 parameters	Δρ_min = −0.17 e Å⁻³
1 restraint

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

	x	y	z	U_iso*/U_eq
C1	0.4948 (3)	0.14319 (14)	0.28928 (18)	0.0111
C2	0.7148 (3)	0.18283 (14)	0.39815 (18)	0.0114
N3	0.8638 (3)	0.10778 (13)	0.51881 (15)	0.0140
O4	0.7326 (3)	0.03921 (12)	0.58113 (14)	0.0219
O5	1.1140 (2)	0.12260 (12)	0.55405 (15)	0.0219
C6	0.8003 (3)	0.29526 (15)	0.40571 (18)	0.0134
C7	0.6540 (3)	0.37335 (15)	0.30692 (19)	0.0139
C8	0.4280 (3)	0.33503 (15)	0.20287 (18)	0.0116
C9	0.3458 (3)	0.22171 (15)	0.18546 (18)	0.0118
C10	0.1222 (3)	0.17863 (15)	0.06026 (19)	0.0159
N11	0.2738 (3)	0.42462 (13)	0.10628 (16)	0.0138
O12	0.4046 (3)	0.50665 (11)	0.07238 (15)	0.0211
O13	0.0249 (2)	0.41328 (11)	0.06852 (15)	0.0196
N14	0.4172 (3)	0.02758 (12)	0.27649 (17)	0.0130
C15	0.5946 (3)	−0.05962 (14)	0.26833 (18)	0.0129
O16	0.8450 (2)	−0.04647 (11)	0.28353 (14)	0.0166
C17	0.4615 (3)	−0.17467 (14)	0.2390 (2)	0.0169
H61	0.9522	0.3189	0.4777	0.0171*
H71	0.7032	0.4511	0.3102	0.0169*
H73	0.2672	−0.1711	0.2518	0.0263*
H72	0.4683	−0.1941	0.1353	0.0281*
H4	0.5585	−0.2301	0.3078	0.0284*
H7	0.2481	0.0118	0.2655	0.0178*
H1	0.1742	0.1034	0.0229	0.0241*
H2	−0.0511	0.1712	0.1004	0.0240*
H3	0.0949	0.2334	−0.0280	0.0238*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0084 (6)	0.0117 (8)	0.0136 (7)	−0.0006 (6)	0.0031 (5)	−0.0001 (6)
C2	0.0089 (7)	0.0124 (8)	0.0129 (7)	0.0016 (6)	0.0016 (5)	0.0019 (6)
N3	0.0133 (6)	0.0144 (7)	0.0136 (6)	0.0012 (6)	−0.0001 (5)	0.0007 (6)
O4	0.0207 (6)	0.0245 (7)	0.0203 (6)	−0.0025 (6)	0.0027 (5)	0.0099 (6)
O5	0.0124 (5)	0.0206 (7)	0.0300 (7)	0.0002 (5)	−0.0045 (5)	0.0049 (6)
C6	0.0111 (7)	0.0141 (8)	0.0144 (7)	−0.0009 (6)	0.0004 (5)	−0.0018 (7)
C7	0.0141 (7)	0.0122 (7)	0.0159 (8)	−0.0014 (6)	0.0040 (6)	−0.0024 (6)
C8	0.0114 (7)	0.0114 (7)	0.0127 (7)	0.0016 (6)	0.0035 (6)	0.0016 (6)
C9	0.0093 (6)	0.0142 (8)	0.0127 (7)	0.0003 (6)	0.0040 (6)	0.0002 (6)
C10	0.0134 (7)	0.0150 (8)	0.0178 (8)	−0.0005 (6)	−0.0014 (6)	−0.0006 (7)
N11	0.0140 (6)	0.0135 (7)	0.0141 (6)	0.0017 (6)	0.0032 (5)	0.0011 (6)
O12	0.0209 (6)	0.0149 (6)	0.0270 (7)	−0.0034 (5)	0.0026 (5)	0.0083 (5)
O13	0.0124 (5)	0.0192 (7)	0.0262 (6)	0.0027 (5)	0.0009 (5)	0.0042 (6)
N14	0.0080 (5)	0.0115 (7)	0.0194 (7)	−0.0012 (5)	0.0020 (5)	−0.0001 (6)
C15	0.0132 (7)	0.0138 (8)	0.0120 (7)	0.0008 (6)	0.0024 (5)	0.0014 (6)
O16	0.0099 (5)	0.0176 (6)	0.0225 (6)	0.0010 (5)	0.0027 (4)	0.0009 (5)
C17	0.0156 (7)	0.0121 (8)	0.0230 (8)	−0.0002 (7)	0.0032 (6)	0.0003 (7)

Geometric parameters (Å, º) top

C1—C2	1.398 (2)	C9—C10	1.506 (2)
C1—C9	1.413 (2)	C10—H1	0.992
C1—N14	1.411 (2)	C10—H2	0.982
C2—N3	1.476 (2)	C10—H3	1.000
C2—C6	1.386 (2)	N11—O12	1.2250 (19)
N3—O4	1.221 (2)	N11—O13	1.2228 (17)
N3—O5	1.2318 (17)	N14—C15	1.358 (2)
C6—C7	1.380 (2)	N14—H7	0.843
C6—H61	0.936	C15—O16	1.2287 (18)
C7—C8	1.390 (2)	C15—C17	1.506 (2)
C7—H71	0.945	C17—H73	0.984
C8—C9	1.393 (2)	C17—H72	0.947
C8—N11	1.479 (2)	C17—H4	0.959

C2—C1—C9	118.77 (15)	C9—C10—H1	110.1
C2—C1—N14	122.93 (15)	C9—C10—H2	109.9
C9—C1—N14	118.29 (14)	H1—C10—H2	109.2
C1—C2—N3	121.71 (15)	C9—C10—H3	109.6
C1—C2—C6	123.02 (15)	H1—C10—H3	109.0
N3—C2—C6	115.20 (14)	H2—C10—H3	109.1
C2—N3—O4	118.72 (13)	C8—N11—O12	117.40 (13)
C2—N3—O5	116.77 (14)	C8—N11—O13	118.15 (14)
O4—N3—O5	124.44 (14)	O12—N11—O13	124.44 (15)
C2—C6—C7	118.84 (15)	C1—N14—C15	124.26 (14)
C2—C6—H61	121.1	C1—N14—H7	118.0
C7—C6—H61	120.0	C15—N14—H7	117.5
C6—C7—C8	118.21 (16)	N14—C15—O16	122.96 (16)
C6—C7—H71	121.4	N14—C15—C17	114.91 (13)
C8—C7—H71	120.4	O16—C15—C17	122.14 (15)
C7—C8—C9	124.57 (15)	C15—C17—H73	110.3
C7—C8—N11	114.99 (15)	C15—C17—H72	107.2
C9—C8—N11	120.43 (13)	H73—C17—H72	108.5
C1—C9—C8	116.39 (14)	C15—C17—H4	110.2
C1—C9—C10	119.16 (15)	H73—C17—H4	110.3
C8—C9—C10	124.37 (15)	H72—C17—H4	110.4

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N14—H7···O16ⁱ	0.84	2.13	2.963 (2)	168

Symmetry code: (i) x−1, y, z.

Acknowledgements

We 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 them, and Professor Anna Arnoldi for help in their retrieval.

References

Altomare, A., Cascarano, G., Giacovazzo, G., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. CrossRef Web of Science IUCr Journals Google Scholar
Betteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, K. & Watkin, D. J. (2003). J. Appl. Cryst. 36, 1487. Web of Science CrossRef IUCr Journals Google Scholar
Demartin, F., Filippini, G., Gavezzotti, A. & Rizzato, S. (2004). Acta Cryst. B60, 609–620. Web of Science CSD CAS Google Scholar
Görbitz, C. H. (1999). Acta Cryst. B55, 1090–1098. Web of Science CSD CrossRef IUCr Journals Google Scholar
Nonius (2001). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Watkin, D. J., Motherwell, W. D. S., Cooper, R. I. & Pantos, S. (2004). Acta Cryst. E60, o2295–o2297. Web of Science CSD CrossRef IUCr Journals Google Scholar
Watkin, D. J., Prout, C. K. & Pearce, L. J. (1996). CAMERON. Chemical Crystallography Laboratory, Oxford, England. Google Scholar

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