Acetone 2-nitro­phenyl­hydrazone

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

doi:10.1107/S1600536807003509

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 63| Part 2| February 2007| Pages o970-o971

https://doi.org/10.1107/S1600536807003509

Acetone 2-nitrophenylhydrazone

Solange M. S. V. Wardell,^a James L. Wardell,^b John N. Low ^c and Christopher Glidewell ^d ^*

^aInstituto de Tecnologia em Fármacos, Far-Manguinhos, FIOCRUZ, 21041-250 Rio de Janeiro, RJ, Brazil, ^bInstituto de Química, Departamento de Química Inorgânica, Universidade Federal do Rio de Janeiro, CP 68563, 21945-970 Rio de Janeiro, RJ, Brazil, ^cDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and ^dSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland
^*Correspondence e-mail: cg@st-andrews.ac.uk

(Received 22 January 2007; accepted 22 January 2007; online 26 January 2007)

There are no direction-specific interactions between the almost-planar molecules of the title compound, C₉H₁₁N₃O₂.

Comment

We report here the structure of acetone 2-nitrophenylhydrazone, (I) (Fig. 1), whose behaviour differs significantly from that of the isomeric compound acetone 3-nitrophenylhydrazone, (II) (Wardell et al., 2006 ).

The non-H atoms in the molecule of (I) are virtually co-planar, as shown by the key torsion angles (Table 1). There is a short intermolecular N—H⋯O hydrogen bond (Table 2), which may assist in controlling the planar conformation. The bond distances (Table 1) show evidence for a significant contribution from the quinonoid form (Ia). In particular, the bonds C3—C4 and C5—C6 are shorter than the remaining bonds in the ring, while C2—N21 is very short for its type and the N—O bonds are long (Allen et al., 1987 ). In contrast, the bond distances in (II) show no unusual values (Wardell et al., 2006).

Whereas the molecules of (II) are linked into complex sheets by a combination of N—H⋯O, C—H⋯O and C—H⋯N hydrogen bonds, there are no direction-specific intermolecular interactions in the structure of (I). In particular, hydrogen bonds of all types and aromatic π–π stacking interactions are absent.

Figure 1
The molecular structure of compound (I)

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

Experimental

2-Nitrophenylhydrazine (3 mmol) was dissolved in acetone (30 ml) and the solution was heated under reflux for 1 h. The solution was then cooled and excess solvent was removed under reduced pressure. The resulting solid product, (I), was crystallized from ethanol (m.p. 339–341 K).

Crystal data

C₉H₁₁N₃O₂
M_r = 193.21
Monoclinic, P 2₁ /c
a = 3.8451 (2) Å
b = 11.4926 (8) Å
c = 21.3214 (13) Å
β = 92.208 (4)°
V = 941.50 (10) Å³
Z = 4
D_x = 1.363 Mg m⁻³
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 120 (2) K
Needle, orange
0.40 × 0.04 × 0.04 mm

Data collection

Bruker Nonius KappaCCD area-detector diffractometer
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.971, T_max = 0.996
10829 measured reflections
2104 independent reflections
1738 reflections with I > 2σ(I)
R_int = 0.046
θ_max = 27.8°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.153
S = 1.06
2104 reflections
129 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0854P)² + 0.2667P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

C1—C2	1.417 (2)
C2—C3	1.4027 (19)
C3—C4	1.370 (2)
C4—C5	1.398 (2)
C5—C6	1.3772 (19)
C6—C1	1.4100 (19)
C1—N1	1.3637 (17)
N1—N2	1.3799 (17)
N2—C7	1.2877 (18)
C2—N21	1.4387 (18)
N21—O21	1.2513 (16)
N21—O22	1.2267 (17)

C1—C2—N21—O21	−0.3 (2)
C1—C2—N21—O22	178.88 (13)
C2—C1—N1—N2	−175.52 (12)
C1—N1—N2—C7	175.80 (12)
N1—N2—C7—C8	179.80 (12)
N1—N2—C7—C9	0.2 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O21	0.88	1.97	2.6010 (17)	128

All H atoms were located in a difference map and then treated as riding, with C—H distances of 0.95 or 0.98 Å and N—H distances of 0.88 Å, and with U_iso(H) = kU_eq(C,N) where k = 1.5 for methyl groups and 1.2 for all other H.

Data collection: COLLECT (Nonius, 1999 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: FLIPPER (Oszlányi & Sütő, 2004 , 2005 ; Spek, 2003 ); program(s) used to refine structure: OSCAIL (McArdle, 2003 ) and SHELXL97 (Sheldrick, 1997 ); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807003509/lh2298sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807003509/lh2298Isup2.hkl

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: FLIPPER (Oszlányi & Sütő, 2004, 2005; Spek, 2003); program(s) used to refine structure: OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Acetone 2-nitrophenylhydrazone top

Crystal data top

C₉H₁₁N₃O₂	F(000) = 408
M_r = 193.21	D_x = 1.363 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2040 reflections
a = 3.8451 (2) Å	θ = 2.9–27.5°
b = 11.4926 (8) Å	µ = 0.10 mm⁻¹
c = 21.3214 (13) Å	T = 120 K
β = 92.208 (4)°	Plate, orange
V = 941.50 (10) Å³	0.40 × 0.04 × 0.04 mm
Z = 4

Data collection top

Bruker Nonius KappaCCD area-detector diffractometer	2104 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	1738 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.8°, θ_min = 3.4°
φ and ω scans	h = −3→4
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −14→14
T_min = 0.971, T_max = 0.996	l = −27→27
10829 measured reflections

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.153	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0854P)² + 0.2667P] where P = (F_o² + 2F_c²)/3
2104 reflections	(Δ/σ)_max < 0.001
129 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

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

	x	y	z	U_iso*/U_eq
C1	0.3793 (4)	0.68934 (13)	0.08125 (6)	0.0202 (3)
N1	0.5144 (3)	0.63071 (11)	0.13218 (5)	0.0230 (3)
N2	0.5246 (3)	0.51069 (11)	0.13215 (6)	0.0239 (3)
C7	0.6772 (4)	0.46464 (14)	0.18091 (7)	0.0250 (4)
C8	0.6941 (4)	0.33459 (14)	0.18324 (8)	0.0328 (4)
C9	0.8357 (4)	0.53242 (15)	0.23532 (7)	0.0304 (4)
C2	0.3832 (4)	0.81231 (13)	0.07662 (6)	0.0211 (3)
N21	0.5444 (3)	0.88451 (12)	0.12460 (6)	0.0265 (3)
O21	0.6846 (3)	0.83762 (10)	0.17212 (5)	0.0328 (3)
O22	0.5455 (3)	0.99053 (10)	0.11794 (6)	0.0402 (4)
C3	0.2387 (4)	0.86983 (13)	0.02377 (7)	0.0235 (3)
C4	0.0882 (4)	0.80780 (13)	−0.02496 (7)	0.0242 (3)
C5	0.0830 (4)	0.68637 (13)	−0.02143 (7)	0.0236 (3)
C6	0.2246 (4)	0.62841 (13)	0.03000 (6)	0.0221 (3)
H1	0.5953	0.6695	0.1652	0.028*
H8A	0.5712	0.3022	0.1461	0.049*
H8B	0.5843	0.3068	0.2212	0.049*
H8C	0.9380	0.3096	0.1840	0.049*
H9A	0.9952	0.5912	0.2196	0.046*
H9B	0.9643	0.4793	0.2637	0.046*
H9C	0.6509	0.5708	0.2580	0.046*
H3	0.2451	0.9524	0.0218	0.028*
H4	−0.0111	0.8467	−0.0606	0.029*
H5	−0.0203	0.6430	−0.0552	0.028*
H6	0.2179	0.5458	0.0310	0.027*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0194 (8)	0.0240 (8)	0.0176 (7)	0.0006 (5)	0.0030 (5)	0.0011 (5)
N1	0.0290 (7)	0.0222 (7)	0.0175 (6)	−0.0002 (5)	−0.0029 (5)	0.0002 (5)
N2	0.0262 (7)	0.0227 (7)	0.0230 (6)	0.0020 (5)	0.0031 (5)	0.0040 (5)
C7	0.0206 (8)	0.0313 (9)	0.0234 (7)	0.0036 (6)	0.0037 (5)	0.0059 (6)
C8	0.0344 (9)	0.0314 (9)	0.0329 (9)	0.0080 (7)	0.0063 (6)	0.0104 (7)
C9	0.0279 (9)	0.0398 (10)	0.0234 (8)	0.0042 (6)	−0.0026 (6)	0.0066 (6)
C2	0.0210 (8)	0.0243 (8)	0.0181 (7)	−0.0019 (5)	0.0022 (5)	−0.0017 (5)
N21	0.0326 (8)	0.0252 (7)	0.0220 (6)	−0.0041 (5)	0.0030 (5)	−0.0017 (5)
O21	0.0411 (7)	0.0343 (7)	0.0222 (6)	−0.0054 (5)	−0.0076 (5)	−0.0015 (4)
O22	0.0629 (9)	0.0230 (6)	0.0342 (7)	−0.0086 (5)	−0.0040 (6)	−0.0025 (5)
C3	0.0238 (8)	0.0230 (8)	0.0240 (7)	0.0006 (5)	0.0042 (5)	0.0027 (5)
C4	0.0240 (8)	0.0278 (8)	0.0207 (7)	0.0028 (6)	0.0007 (5)	0.0058 (6)
C5	0.0234 (8)	0.0277 (8)	0.0196 (7)	−0.0020 (6)	−0.0012 (5)	−0.0011 (6)
C6	0.0235 (8)	0.0217 (7)	0.0213 (7)	−0.0014 (5)	0.0007 (5)	0.0004 (5)

Geometric parameters (Å, º) top

C1—C2	1.417 (2)	C7—C9	1.507 (2)
C2—C3	1.4027 (19)	N1—H1	0.88
C3—C4	1.370 (2)	C8—H8A	0.98
C4—C5	1.398 (2)	C8—H8B	0.98
C5—C6	1.3772 (19)	C8—H8C	0.98
C6—C1	1.4100 (19)	C9—H9A	0.98
C1—N1	1.3637 (17)	C9—H9B	0.98
N1—N2	1.3799 (17)	C9—H9C	0.98
N2—C7	1.2877 (18)	C3—H3	0.95
C2—N21	1.4387 (18)	C4—H4	0.95
N21—O21	1.2513 (16)	C5—H5	0.95
N21—O22	1.2267 (17)	C6—H6	0.95
C7—C8	1.497 (2)

N1—C1—C6	120.54 (13)	H9A—C9—H9C	109.5
N1—C1—C2	122.93 (12)	H9B—C9—H9C	109.5
C6—C1—C2	116.53 (12)	C3—C2—C1	121.41 (13)
C1—N1—N2	120.23 (11)	C3—C2—N21	116.47 (13)
C1—N1—H1	119.9	C1—C2—N21	122.09 (12)
N2—N1—H1	119.9	O22—N21—O21	121.21 (12)
C7—N2—N1	114.99 (12)	O22—N21—C2	119.59 (12)
N2—C7—C8	117.07 (14)	O21—N21—C2	119.19 (13)
N2—C7—C9	124.58 (14)	C4—C3—C2	120.45 (14)
C8—C7—C9	118.35 (13)	C4—C3—H3	119.8
C7—C8—H8A	109.5	C2—C3—H3	119.8
C7—C8—H8B	109.5	C3—C4—C5	119.03 (13)
H8A—C8—H8B	109.5	C3—C4—H4	120.5
C7—C8—H8C	109.5	C5—C4—H4	120.5
H8A—C8—H8C	109.5	C6—C5—C4	121.31 (13)
H8B—C8—H8C	109.5	C6—C5—H5	119.3
C7—C9—H9A	109.5	C4—C5—H5	119.3
C7—C9—H9B	109.5	C5—C6—C1	121.26 (14)
H9A—C9—H9B	109.5	C5—C6—H6	119.4
C7—C9—H9C	109.5	C1—C6—H6	119.4

C1—C2—N21—O21	−0.3 (2)	C6—C1—C2—N21	−177.67 (12)
C1—C2—N21—O22	178.88 (13)	C3—C2—N21—O22	0.8 (2)
C6—C1—N1—N2	4.88 (19)	C3—C2—N21—O21	−178.37 (13)
C2—C1—N1—N2	−175.52 (12)	C1—C2—C3—C4	0.2 (2)
C1—N1—N2—C7	175.80 (12)	N21—C2—C3—C4	178.23 (12)
N1—N2—C7—C8	179.80 (12)	C2—C3—C4—C5	−0.4 (2)
N1—N2—C7—C9	0.2 (2)	C3—C4—C5—C6	0.2 (2)
N1—C1—C2—C3	−179.34 (13)	C4—C5—C6—C1	0.2 (2)
C6—C1—C2—C3	0.28 (19)	N1—C1—C6—C5	179.15 (13)
N1—C1—C2—N21	2.7 (2)	C2—C1—C6—C5	−0.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O21	0.88	1.97	2.6010 (17)	128

Acknowledgements

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

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CSD CrossRef Web of Science Google Scholar
Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada. Google Scholar
McArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland. Google Scholar
Nonius (1999). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Oszlányi, G. & Sütő, A. (2004). Acta Cryst. A60, 134–141. Web of Science CrossRef IUCr Journals Google Scholar
Oszlányi, G. & Sütő, A. (2005). Acta Cryst. A61, 147–152. Web of Science CrossRef IUCr Journals 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
Sheldrick, G. M. (1997). SHELXL97. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany. Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wardell, S. M. S. V., de Souza, M. V. N., Wardell, J. L., Low, J. N. & Glidewell, C. (2006). Acta Cryst. E62, o2838–o2840. Web of Science CSD CrossRef IUCr Journals Google Scholar

© International Union of Crystallography. Prior permission is not required to reproduce short quotations, tables and figures from this article, provided the original authors and source are cited. For more information, click here.