Acetone (2,6-dichloro­benzo­yl)hydrazone: chains of π-stacked hydrogen-bonded dimers

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

doi:10.1107/S1600536806020691

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 62| Part 7| July 2006| Pages o2841-o2843

https://doi.org/10.1107/S1600536806020691

Acetone (2,6-dichlorobenzoyl)hydrazone: chains of π-stacked hydrogen-bonded dimers

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 31 May 2006; accepted 31 May 2006; online 14 June 2006)

In the title compound, C₁₀H₁₀Cl₂N₂O, the aryl ring is almost orthogonal to the rest of the molecule. Molecules are linked into centrosymmetric dimers by N—H⋯O hydrogen bonds, and these dimers are linked into chains by a single π–π stacking interaction.

Comment

We report here the molecular and supramolecular structure of the title compound, (I) (Fig. 1). Apart from the dichlorophenyl ring, the non-H atoms are nearly coplanar, as shown by the leading torsion angles (Table 1). The aryl ring is almost orthogonal to the rest of the molecule, with a dihedral angle of 82.5 (2)° between the aryl ring and the mean plane through the rest of the non-H atoms. This is a consequence of the repulsive interactions between the lone pairs of electrons on the two Cl atoms and those on atoms N2 and O7.

The molecules are linked by paired N—H⋯O hydrogen bonds (Table 2) into cyclic centrosymmetric R₂²(8) (Bernstein et al., 1995 ) dimers (Fig. 2), and these dimers are linked into chains by a single aromatic π–π stacking interaction. The aryl rings of the molecules at (x, y, z) and (1 − x, 2 − y, −z) are strictly parallel, with an interplanar spacing of 3.593 (2) Å. The ring-centroid separation is 3.695 (2) Å, corresponding to a ring offset of 0.862 (2) Å. Propagation by inversion of this interaction then links the hydrogen-bonded dimers into a π-stacked chain running parallel to the [01 $[\overline{1}]$ ] direction (Fig. 3), but there are no direction-specific interactions between adjacent chains.

Figure 1
A molecule of compound (I)

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

Figure 2
The molecular structure of compound (I)

, showing the formation of a hydrogen-bonded (dashed lines) R₂²(8) dimer. For the sake of clarity, H atoms bonded to C atoms have been omitted. 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 compound (I)

, showing the formation of a π-stacked chain of hydrogen-bonded (dashed lines) dimers along [01 $[\overline{1}]$ ]. For the sake of clarity, H atoms bonded to C atoms have been omitted.

Experimental

2,6-Dichlorobenzoylhydrazine (3 mmol) was dissolved in acetone (30 ml) and the solution was heated under reflux for 1 h. The solution was then cooled and the excess solvent was removed under reduced pressure. The resulting solid product, (I), was crystallized from ethanol.

Crystal data

C₁₀H₁₀Cl₂N₂O
M_r = 245.10
Triclinic, $[P \overline 1]$
a = 7.4980 (3) Å
b = 8.1320 (2) Å
c = 9.7759 (3) Å
α = 71.609 (2)°
β = 80.822 (2)°
γ = 89.033 (2)°
V = 558.03 (3) Å³
Z = 2
D_x = 1.459 Mg m⁻³
Mo Kα radiation
μ = 0.56 mm⁻¹
T = 120 (2) K
Lath, colourless
0.42 × 0.10 × 0.08 mm

Data collection

Bruker Nonius KappaCCD area-detector diffractometer
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.822, T_max = 0.957
13458 measured reflections
2568 independent reflections
1970 reflections with I > 2σ(I)
R_int = 0.045
θ_max = 27.6°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.096
S = 1.03
2568 reflections
138 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0449P)² + 0.2175P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Selected torsion angles (°)

C2—C1—C7—N1	101.4 (2)
C1—C7—N1—N2	−2.8 (2)
C7—N1—N2—C8	175.32 (16)
N1—N2—C8—C9	178.37 (15)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O7ⁱ	0.85	2.09	2.9232 (18)	169
Symmetry code: (i) -x+1, -y+1, -z+1.

All atoms were located in difference maps and then treated as riding atoms, with C—H = 0.95 (aromatic) or 0.98 Å (methyl) and N—H = 0.85 Å, and with U_iso(H) = kU_eq(C,N), where k = 1.5 for the methyl groups and k = 1.2 for all other H atoms.

Data collection: COLLECT (Nonius, 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/S1600536806020691/lh2095sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806020691/lh2095Isup2.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: 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 (2,6-dichlorobenzoyl)hydrazone top

Crystal data top

C₁₀H₁₀Cl₂N₂O	Z = 2
M_r = 245.10	F(000) = 252
Triclinic, P1	D_x = 1.459 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4980 (3) Å	Cell parameters from 2540 reflections
b = 8.1320 (2) Å	θ = 2.9–27.5°
c = 9.7759 (3) Å	µ = 0.56 mm⁻¹
α = 71.609 (2)°	T = 120 K
β = 80.822 (2)°	Lath, colourless
γ = 89.033 (2)°	0.42 × 0.10 × 0.08 mm
V = 558.03 (3) Å³

Data collection top

Bruker Nonius KappaCCD area-detector diffractometer	2568 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	1970 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.6°, θ_min = 3.8°
φ and ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −10→10
T_min = 0.822, T_max = 0.957	l = −12→12
13458 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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0449P)² + 0.2175P] where P = (F_o² + 2F_c²)/3
2568 reflections	(Δ/σ)_max = 0.001
138 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

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

	x	y	z	U_iso*/U_eq
C1	0.6756 (2)	0.8506 (2)	0.18118 (17)	0.0197 (4)
C2	0.7648 (2)	0.8102 (2)	0.06043 (19)	0.0225 (4)
Cl2	0.80670 (8)	0.59432 (6)	0.07718 (5)	0.03773 (16)
C3	0.8217 (3)	0.9350 (3)	−0.07220 (19)	0.0276 (4)
C4	0.7856 (3)	1.1063 (3)	−0.0867 (2)	0.0306 (5)
C5	0.6953 (3)	1.1521 (2)	0.0295 (2)	0.0273 (4)
C6	0.6420 (2)	1.0247 (2)	0.16195 (19)	0.0213 (4)
Cl6	0.52761 (7)	1.08133 (6)	0.30856 (5)	0.03135 (15)
N1	0.6983 (2)	0.67279 (18)	0.43117 (15)	0.0213 (3)
N2	0.8638 (2)	0.75866 (19)	0.41427 (16)	0.0221 (3)
C7	0.6030 (2)	0.7097 (2)	0.32012 (18)	0.0213 (4)
O7	0.46049 (18)	0.63126 (16)	0.33026 (13)	0.0288 (3)
C8	0.9384 (2)	0.7238 (2)	0.52866 (19)	0.0217 (4)
C9	1.1187 (3)	0.8105 (3)	0.5128 (2)	0.0304 (4)
C10	0.8629 (3)	0.6040 (2)	0.6766 (2)	0.0284 (4)
H3	0.8847	0.9037	−0.1522	0.036*
H4	0.8234	1.1935	−0.1777	0.040*
H5	0.6699	1.2699	0.0187	0.035*
H1	0.6567	0.5918	0.5083	0.026*
H9A	1.1539	0.8857	0.4118	0.039*
H9B	1.2092	0.7222	0.5374	0.039*
H9C	1.1109	0.8802	0.5789	0.039*
H10A	0.7368	0.6313	0.7031	0.037*
H10B	0.9338	0.6181	0.7484	0.037*
H10C	0.8683	0.4840	0.6753	0.037*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0177 (9)	0.0220 (9)	0.0171 (9)	−0.0042 (7)	−0.0063 (7)	−0.0011 (7)
C2	0.0221 (9)	0.0238 (9)	0.0205 (9)	0.0013 (7)	−0.0077 (7)	−0.0035 (7)
Cl2	0.0544 (4)	0.0293 (3)	0.0310 (3)	0.0131 (2)	−0.0103 (2)	−0.0106 (2)
C3	0.0254 (10)	0.0374 (11)	0.0163 (9)	−0.0007 (8)	−0.0030 (7)	−0.0032 (8)
C4	0.0299 (11)	0.0314 (10)	0.0212 (9)	−0.0071 (8)	−0.0045 (8)	0.0053 (8)
C5	0.0280 (10)	0.0203 (9)	0.0290 (10)	−0.0041 (8)	−0.0096 (8)	0.0014 (8)
C6	0.0194 (9)	0.0233 (9)	0.0211 (9)	−0.0035 (7)	−0.0052 (7)	−0.0055 (7)
Cl6	0.0327 (3)	0.0336 (3)	0.0308 (3)	0.0005 (2)	−0.0033 (2)	−0.0155 (2)
N1	0.0221 (8)	0.0220 (7)	0.0151 (7)	−0.0069 (6)	−0.0035 (6)	0.0015 (6)
N2	0.0204 (8)	0.0244 (8)	0.0199 (8)	−0.0060 (6)	−0.0028 (6)	−0.0045 (6)
C7	0.0231 (9)	0.0224 (9)	0.0164 (8)	−0.0028 (7)	−0.0039 (7)	−0.0027 (7)
O7	0.0276 (7)	0.0296 (7)	0.0225 (7)	−0.0123 (6)	−0.0085 (6)	0.0038 (5)
C8	0.0237 (9)	0.0212 (9)	0.0211 (9)	−0.0002 (7)	−0.0043 (7)	−0.0076 (7)
C9	0.0245 (10)	0.0362 (11)	0.0303 (10)	−0.0058 (8)	−0.0063 (8)	−0.0090 (9)
C10	0.0303 (11)	0.0317 (10)	0.0214 (9)	−0.0040 (8)	−0.0101 (8)	−0.0031 (8)

Geometric parameters (Å, º) top

C1—C2	1.391 (2)	N1—N2	1.395 (2)
C1—C6	1.392 (2)	N1—H1	0.8475
C1—C7	1.502 (2)	N2—C8	1.280 (2)
C2—C3	1.379 (2)	C7—O7	1.228 (2)
C2—Cl2	1.7387 (18)	C8—C10	1.493 (2)
C3—C4	1.382 (3)	C8—C9	1.498 (2)
C3—H3	0.95	C9—H9A	0.98
C4—C5	1.379 (3)	C9—H9B	0.98
C4—H4	0.95	C9—H9C	0.98
C5—C6	1.383 (2)	C10—H10A	0.98
C5—H5	0.95	C10—H10B	0.98
C6—Cl6	1.7360 (18)	C10—H10C	0.98
N1—C7	1.347 (2)

C2—C1—C6	116.86 (15)	N2—N1—H1	122.3
C2—C1—C7	120.72 (15)	C8—N2—N1	115.92 (14)
C6—C1—C7	122.13 (16)	O7—C7—N1	121.67 (15)
C3—C2—C1	122.47 (17)	O7—C7—C1	120.05 (15)
C3—C2—Cl2	118.67 (15)	N1—C7—C1	118.27 (15)
C1—C2—Cl2	118.86 (13)	N2—C8—C10	126.04 (16)
C2—C3—C4	118.84 (18)	N2—C8—C9	117.10 (16)
C2—C3—H3	120.6	C10—C8—C9	116.85 (16)
C4—C3—H3	120.6	C8—C9—H9A	109.5
C5—C4—C3	120.68 (17)	C8—C9—H9B	109.5
C5—C4—H4	119.7	H9A—C9—H9B	109.5
C3—C4—H4	119.7	C8—C9—H9C	109.5
C4—C5—C6	119.33 (17)	H9A—C9—H9C	109.5
C4—C5—H5	120.3	H9B—C9—H9C	109.5
C6—C5—H5	120.3	C8—C10—H10A	109.5
C5—C6—C1	121.81 (17)	C8—C10—H10B	109.5
C5—C6—Cl6	119.56 (14)	H10A—C10—H10B	109.5
C1—C6—Cl6	118.62 (13)	C8—C10—H10C	109.5
C7—N1—N2	120.40 (14)	H10A—C10—H10C	109.5
C7—N1—H1	117.2	H10B—C10—H10C	109.5

C2—C1—C7—N1	101.4 (2)	C4—C5—C6—C1	−0.6 (3)
C1—C7—N1—N2	−2.8 (2)	C4—C5—C6—Cl6	−179.81 (14)
C7—N1—N2—C8	175.32 (16)	C2—C1—C6—C5	−0.3 (3)
N1—N2—C8—C9	178.37 (15)	C7—C1—C6—C5	−174.12 (16)
C6—C1—C2—C3	1.3 (3)	C2—C1—C6—Cl6	178.92 (13)
C7—C1—C2—C3	175.21 (17)	C7—C1—C6—Cl6	5.1 (2)
C6—C1—C2—Cl2	−178.85 (13)	N2—N1—C7—O7	177.13 (16)
C7—C1—C2—Cl2	−5.0 (2)	C2—C1—C7—O7	−78.5 (2)
C1—C2—C3—C4	−1.4 (3)	C6—C1—C7—O7	95.0 (2)
Cl2—C2—C3—C4	178.78 (14)	C6—C1—C7—N1	−85.1 (2)
C2—C3—C4—C5	0.4 (3)	N1—N2—C8—C10	−1.3 (3)
C3—C4—C5—C6	0.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O7ⁱ	0.85	2.09	2.9232 (18)	169

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

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

References

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