Acetone 3-nitro­phenyl­hydrazone, redetermined at 120 K: sheets built from N—H⋯O, C—H⋯O and C—H⋯N hydrogen bonds

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

doi:10.1107/S1600536806020472

organic compounds

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Volume 62| Part 7| July 2006| Pages o2838-o2840

https://doi.org/10.1107/S1600536806020472

Acetone 3-nitrophenylhydrazone, redetermined at 120 K: sheets built from N—H⋯O, C—H⋯O and C—H⋯N hydrogen bonds

Solange M. S. V. Wardell,^a Marcus V. N. de Souza,^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 30 May 2006; accepted 30 May 2006; online 16 June 2006)

Molecules of the title compound, C₉H₁₁N₃O₂, are linked into sheets by a combination of N—H⋯O, C—H⋯O and C—H⋯N hydrogen bonds.

Comment

The structure of the title compound, (I) (Fig. 1), was determined many years ago [Cambridge Structural Database, Version 7.27 (Allen 2002 ) refcode NPHYAC; Menczel, 1969 ], using diffraction data collected at ambient temperature; no H atom coordinates were reported, and the structure was refined only to R = 0.169. We have now redetermined this structure using diffraction data collected at 120 K, and we report here the details of the supramolecular aggregation.

The molecules are linked into sheets by a combination of N—H⋯O, C—H⋯O and C—H⋯N hydrogen bonds (Table 1), and the sheet formation is readily analysed in terms of a hydrogen-bonded dimer as the basic building block. Atoms N1 and C2 in the molecule at (x, y, z) both act as hydrogen-bond donors to atom O31 in the molecule at ( $[{3\over 2}]$ − x, $[{1\over 2}]$ − y, 1 − z), so forming a centrosymmetric dimer centred at (¾, ¼, ½) containing three edge-fused rings, one of R₂²(10) type (Bernstein et al., 1995 ) flanked by two of R₂¹(6) type (Fig. 2).

Atoms C5 in the molecules at (x, y, z) and ( $[3\over2]$ − x, $[{1\over 2}]$ − y, 1 − z), which form the dimer centred at ( $[3\over4]$ , $[1\over4]$ , $[1\over2]$ ), act as hydrogen-bond donors to atoms N2 in the molecules at ( $[3\over2]$ − x, $[{1\over 2}]$ + y, $[3\over2]$ − z) and (x, −y, − $[{1\over 2}]$ + z), which lie in the dimers centred at ( $[3\over4]$ , $[3\over4]$ , 1) and ( $[3\over4]$ , − $[1\over4]$ , 0), respectively. Similarly, atoms N2 at (x, y, z) and ( $[3\over2]$ − x, $[{1\over 2}]$ − y, 1 − z) accept hydrogen bonds from atoms C5 in the molecules at ( $[3\over2]$ − x, − $[{1\over 2}]$ + y, $[3\over2]$ − z) and (x, 1 − y, − $[{1\over 2}]$ + z), which themselves form parts of the dimers centred at ( $[3\over4]$ , − $[1\over4]$ , 1) and ( $[3\over4]$ , $[3\over4]$ , 0), respectively. Hence each dimer is linked by C—H⋯N hydrogen bonds to four other dimers and propagation of these interactions then generates a sheet parallel to (100) (Fig. 3).

This sheet is generated by centres of inversion with x = $[3\over4]$ , and it occupies the domain 0.5 < x < 1.0; a second sheet, related to the first by the C-centring operation, is generated by centres of inversion with x = $[1\over4]$ , and it occupies the domain 0 < x < 0.5; however, there are no direction-specific interactions between adjacent sheets.

Figure 1
A molecule of (I)

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

Figure 2
The molecular structure of (I)

, showing the formation of a centrosymmetric dimer containing three edge-fused hydrogen-bonded (dashed lines) rings. For the sake of clarity, H atoms not involved in the motifs shown have been omitted. The atoms marked with an asterisk (*) are at the symmetry position (1 − x, 1 − y, 1 − z).

Figure 3
A stereoscopic view of part of the crystal structure of (I)

, showing the formation of a hydrogen-bonded (dashed lines) sheet parallel to (100). For the sake of clarity, H atoms not involved in the motifs shown have been omitted.

Experimental

3-Nitrohydrazine hydrochloride (3 mmol) was dissolved in acetone (30 ml) and the solution was then heated under reflux for 1 h. The solution was cooled and the excess solvent was removed under reduced pressure. The resulting solid product, (I), was crystallized from ethanol.

Crystal data

C₉H₁₁N₃O₂
M_r = 193.21
Monoclinic, C 2/c
a = 22.7837 (15) Å
b = 3.8307 (2) Å
c = 21.7292 (13) Å
β = 100.129 (3)°
V = 1866.91 (19) Å³
Z = 8
D_x = 1.375 Mg m⁻³
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 120 (2) K
Lath, colourless
0.20 × 0.06 × 0.02 mm

Data collection

Bruker–Nonius KappaCCD diffractometer
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.977, T_max = 0.998
10187 measured reflections
2117 independent reflections
1392 reflections with I > 2σ(I)
R_int = 0.079
θ_max = 27.5°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.146
S = 1.03
2117 reflections
129 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0576P)² + 1.9052P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O31ⁱ	0.84	2.35	3.144 (2)	158
C2—H2⋯O31ⁱ	0.95	2.49	3.305 (3)	143
C5—H5⋯N2ⁱⁱ	0.95	2.61	3.546 (3)	167
Symmetry codes: (i) $[-x+{\script{3\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

All H atoms were located in difference maps and then treated as riding atoms with distances C—H = 0.95 Å or 0.98 Å and N—H = 0.84 Å, and with U_iso(H) = 1.2U_eq(C,N).

Data collection: COLLECT (Hooft, 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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536806020472/lh2094sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806020472/lh2094Isup2.hkl

Computing details top

Data collection: COLLECT (Hooft, 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).

Acetone 3-nitrophenylhydrazone top

Crystal data top

C₉H₁₁N₃O₂	F(000) = 816
M_r = 193.21	D_x = 1.375 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2405 reflections
a = 22.7837 (15) Å	θ = 2.9–27.5°
b = 3.8307 (2) Å	µ = 0.10 mm⁻¹
c = 21.7292 (13) Å	T = 120 K
β = 100.129 (3)°	Plate, colourless
V = 1866.91 (19) Å³	0.20 × 0.06 × 0.02 mm
Z = 8

Data collection top

Bruker–Nonius KappaCCD diffractometer	2117 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	1392 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.079
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 3.6°
φ and ω scans	h = −19→28
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −4→4
T_min = 0.977, T_max = 0.998	l = −28→28
10187 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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.146	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0576P)² + 1.9052P] where P = (F_o² + 2F_c²)/3
2117 reflections	(Δ/σ)_max < 0.001
129 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

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

	x	y	z	U_iso*/U_eq
C1	0.73046 (9)	0.6977 (5)	0.62467 (9)	0.0208 (5)
C2	0.76687 (9)	0.5776 (6)	0.58397 (9)	0.0219 (5)
C3	0.82780 (9)	0.6216 (6)	0.60016 (9)	0.0222 (5)
N3	0.86561 (8)	0.4855 (5)	0.55769 (8)	0.0247 (4)
O31	0.84193 (7)	0.3164 (5)	0.51155 (7)	0.0349 (4)
O32	0.91943 (7)	0.5383 (5)	0.56931 (7)	0.0379 (5)
C4	0.85489 (9)	0.7812 (6)	0.65520 (10)	0.0248 (5)
C5	0.81809 (10)	0.9004 (6)	0.69488 (10)	0.0261 (5)
C6	0.75668 (9)	0.8622 (5)	0.68035 (9)	0.0231 (5)
N1	0.66953 (7)	0.6555 (5)	0.60836 (8)	0.0252 (4)
N2	0.63415 (8)	0.7306 (5)	0.65204 (8)	0.0240 (4)
C7	0.57836 (10)	0.6671 (6)	0.63644 (10)	0.0259 (5)
C8	0.54023 (10)	0.7472 (7)	0.68419 (11)	0.0343 (6)
C9	0.54904 (9)	0.5192 (6)	0.57486 (10)	0.0279 (5)
H2	0.7501	0.4674	0.5457	0.026*
H4	0.8970	0.8073	0.6652	0.030*
H5	0.8352	1.0110	0.7329	0.031*
H6	0.7323	0.9479	0.7083	0.028*
H1	0.6569	0.5158	0.5792	0.030*
H8A	0.5645	0.8593	0.7205	0.041*
H8B	0.5233	0.5301	0.6973	0.041*
H8C	0.5079	0.9047	0.6660	0.041*
H9A	0.5556	0.6765	0.5411	0.033*
H9B	0.5062	0.4945	0.5744	0.033*
H9C	0.5662	0.2900	0.5688	0.033*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0254 (11)	0.0207 (11)	0.0158 (10)	−0.0018 (9)	0.0018 (8)	0.0009 (8)
C2	0.0276 (11)	0.0217 (11)	0.0154 (10)	−0.0027 (9)	0.0010 (8)	0.0008 (8)
C3	0.0271 (11)	0.0219 (11)	0.0176 (10)	−0.0009 (9)	0.0035 (8)	0.0016 (9)
N3	0.0238 (10)	0.0284 (11)	0.0213 (9)	−0.0023 (8)	0.0025 (7)	−0.0002 (8)
O31	0.0317 (9)	0.0481 (11)	0.0245 (8)	−0.0038 (8)	0.0043 (7)	−0.0110 (8)
O32	0.0213 (8)	0.0539 (12)	0.0382 (10)	−0.0046 (8)	0.0041 (7)	−0.0086 (8)
C4	0.0243 (11)	0.0247 (12)	0.0236 (11)	−0.0048 (9)	−0.0005 (9)	0.0010 (9)
C5	0.0329 (12)	0.0251 (12)	0.0181 (10)	−0.0049 (10)	−0.0021 (9)	−0.0010 (9)
C6	0.0312 (12)	0.0205 (11)	0.0184 (10)	0.0009 (9)	0.0060 (9)	0.0012 (9)
N1	0.0263 (10)	0.0314 (11)	0.0177 (9)	−0.0024 (8)	0.0031 (7)	−0.0074 (8)
N2	0.0266 (10)	0.0271 (10)	0.0185 (9)	0.0028 (8)	0.0049 (7)	0.0000 (8)
C7	0.0294 (12)	0.0258 (12)	0.0221 (11)	0.0044 (10)	0.0037 (9)	0.0032 (9)
C8	0.0318 (13)	0.0422 (15)	0.0296 (12)	0.0024 (11)	0.0075 (10)	−0.0021 (11)
C9	0.0262 (12)	0.0320 (14)	0.0250 (12)	−0.0017 (10)	0.0035 (9)	−0.0026 (10)

Geometric parameters (Å, º) top

C1—N1	1.381 (2)	C6—H6	0.95
C1—C2	1.393 (3)	N1—N2	1.379 (2)
C1—C6	1.401 (3)	N1—H1	0.84
C2—C3	1.381 (3)	N2—C7	1.280 (3)
C2—H2	0.95	C7—C8	1.497 (3)
C3—C4	1.387 (3)	C7—C9	1.498 (3)
C3—N3	1.465 (3)	C8—H8A	0.98
N3—O32	1.224 (2)	C8—H8B	0.98
N3—O31	1.235 (2)	C8—H8C	0.98
C4—C5	1.382 (3)	C9—H9A	0.98
C4—H4	0.95	C9—H9B	0.98
C5—C6	1.387 (3)	C9—H9C	0.98
C5—H5	0.95

N1—C1—C2	118.85 (18)	C1—C6—H6	119.9
N1—C1—C6	122.08 (19)	N2—N1—C1	118.80 (16)
C2—C1—C6	119.06 (19)	N2—N1—H1	119.1
C3—C2—C1	118.82 (19)	C1—N1—H1	117.7
C3—C2—H2	120.6	C7—N2—N1	116.84 (17)
C1—C2—H2	120.6	N2—C7—C8	116.60 (19)
C2—C3—C4	123.2 (2)	N2—C7—C9	125.06 (19)
C2—C3—N3	118.17 (18)	C8—C7—C9	118.34 (19)
C4—C3—N3	118.57 (19)	C7—C8—H8A	109.5
O32—N3—O31	122.21 (18)	C7—C8—H8B	109.5
O32—N3—C3	119.31 (17)	H8A—C8—H8B	109.5
O31—N3—C3	118.47 (17)	C7—C8—H8C	109.5
C5—C4—C3	117.2 (2)	H8A—C8—H8C	109.5
C5—C4—H4	121.4	H8B—C8—H8C	109.5
C3—C4—H4	121.4	C7—C9—H9A	109.5
C4—C5—C6	121.45 (19)	C7—C9—H9B	109.5
C4—C5—H5	119.3	H9A—C9—H9B	109.5
C6—C5—H5	119.3	C7—C9—H9C	109.5
C5—C6—C1	120.26 (19)	H9A—C9—H9C	109.5
C5—C6—H6	119.9	H9B—C9—H9C	109.5

N1—C1—C2—C3	179.65 (19)	C3—C4—C5—C6	0.0 (3)
C6—C1—C2—C3	0.6 (3)	C4—C5—C6—C1	0.5 (3)
C1—C2—C3—C4	−0.2 (3)	N1—C1—C6—C5	−179.77 (19)
C1—C2—C3—N3	178.36 (18)	C2—C1—C6—C5	−0.8 (3)
C2—C3—N3—O32	175.98 (19)	C2—C1—N1—N2	171.33 (18)
C4—C3—N3—O32	−5.4 (3)	C6—C1—N1—N2	−9.7 (3)
C2—C3—N3—O31	−4.9 (3)	C1—N1—N2—C7	−175.71 (19)
C4—C3—N3—O31	173.65 (19)	N1—N2—C7—C8	179.65 (18)
C2—C3—C4—C5	−0.2 (3)	N1—N2—C7—C9	−0.1 (3)
N3—C3—C4—C5	−178.69 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O31ⁱ	0.84	2.35	3.144 (2)	158
C2—H2···O31ⁱ	0.95	2.49	3.305 (3)	143
C5—H5···N2ⁱⁱ	0.95	2.61	3.546 (3)	167

Symmetry codes: (i) −x+3/2, −y+1/2, −z+1; (ii) −x+3/2, y+1/2, −z+3/2.

Acknowledgements

X-ray data were collected at the EPSRC X-ray Crystallographic 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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