A re-examination of supra­molecular aggregation in two polymorphs of acetone 2,4-dinitro­phenyl­hydrazone

The structure of the triclinic polymorph of acetone 2,4-dinitrophenylhydrazone, C₉H₁₀N₄O₄, has been redetermined from diffraction data collected at 120 (2) K; the mol­ecules are linked by C-H...O hydrogen bonds into centrosymmetric R₂²(10) dimers which are themselves linked into a chain by an aromatic [pi]-[pi] stacking inter­action. In the monoclinic polymorph, which crystallizes with Z' = 2 in the space group P2₁/n, one type of mol­ecule forms dimers exactly as in the triclinic polymorph, while the other forms C(6) chains.

Computing details

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 2,4-dinitrophenylhydrazone

Crystal data

C9H10N4O4	Z = 2
Mr = 238.21	F(000) = 248
Triclinic, P1	Dx = 1.514 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.0932 (3) Å	Cell parameters from 2396 reflections
b = 8.2032 (4) Å	θ = 2.2–27.6°
c = 10.0526 (4) Å	µ = 0.12 mm^−1
α = 66.613 (2)°	T = 120 K
β = 88.822 (3)°	Plate, yellow
γ = 77.387 (3)°	0.40 × 0.40 × 0.02 mm
V = 522.49 (4) Å^3

Data collection

Bruker–Nonius KappaCCD diffractometer	2393 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	1957 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
Detector resolution: 9.091 pixels mm^-1	θmax = 27.6°, θmin = 2.2°
φ & ω scans	h = −9→8
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −10→10
Tmin = 0.964, Tmax = 0.998	l = −13→13
12000 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.117	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.082P)^2 + 0.0909P] where P = (Fo^2 + 2Fc^2)/3
2393 reflections	(Δ/σ)max < 0.001
156 parameters	Δρmax = 0.28 e Å^−3
0 restraints	Δρmin = −0.34 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O21	0.79883 (13)	0.43025 (14)	0.35357 (10)	0.0264 (2)
O22	0.68045 (14)	0.47172 (13)	0.14315 (10)	0.0269 (2)
O41	0.14892 (16)	0.23433 (16)	0.08958 (10)	0.0335 (3)
O42	−0.00269 (13)	0.09926 (13)	0.27652 (10)	0.0243 (2)
N1	0.63130 (15)	0.27688 (14)	0.58865 (11)	0.0183 (2)
N2	0.60008 (15)	0.21548 (15)	0.73545 (11)	0.0192 (3)
N12	0.67715 (15)	0.41367 (15)	0.27552 (12)	0.0196 (3)
N14	0.12470 (16)	0.18034 (15)	0.21951 (12)	0.0204 (3)
C1	0.50745 (17)	0.26031 (16)	0.49651 (13)	0.0161 (3)
C2	0.52596 (17)	0.32171 (16)	0.34472 (13)	0.0161 (3)
C3	0.40033 (17)	0.29639 (17)	0.25365 (13)	0.0173 (3)
C4	0.25470 (17)	0.21064 (17)	0.31336 (13)	0.0167 (3)
C5	0.22706 (18)	0.15232 (17)	0.46174 (14)	0.0179 (3)
C6	0.35066 (17)	0.17739 (17)	0.55101 (13)	0.0184 (3)
C11	0.72963 (18)	0.22764 (17)	0.81669 (14)	0.0198 (3)
C12	0.7005 (2)	0.1620 (2)	0.97499 (15)	0.0279 (3)
C13	0.90674 (18)	0.29973 (19)	0.76374 (15)	0.0236 (3)
H1	0.7452	0.3232	0.5534	0.022*
H3	0.4153	0.3377	0.1522	0.021*
H5	0.1233	0.0957	0.5003	0.021*
H6	0.3309	0.1384	0.6517	0.022*
H12A	0.5738	0.1311	0.9922	0.042*
H12B	0.7059	0.2583	1.0083	0.042*
H12C	0.8026	0.0536	1.0286	0.042*
H13A	0.9932	0.2165	0.7291	0.035*
H13B	0.9743	0.3090	0.8436	0.035*
H13C	0.8682	0.4206	0.6840	0.035*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O21	0.0217 (5)	0.0343 (6)	0.0269 (5)	−0.0139 (4)	0.0016 (4)	−0.0124 (4)
O22	0.0305 (5)	0.0307 (6)	0.0186 (5)	−0.0133 (4)	0.0070 (4)	−0.0061 (4)
O41	0.0415 (6)	0.0465 (7)	0.0160 (5)	−0.0225 (5)	−0.0001 (4)	−0.0096 (5)
O42	0.0233 (5)	0.0269 (5)	0.0258 (5)	−0.0131 (4)	0.0008 (4)	−0.0099 (4)
N1	0.0181 (5)	0.0226 (6)	0.0155 (5)	−0.0064 (4)	0.0007 (4)	−0.0080 (4)
N2	0.0208 (5)	0.0209 (6)	0.0166 (5)	−0.0054 (4)	0.0006 (4)	−0.0080 (4)
N12	0.0190 (5)	0.0195 (5)	0.0205 (6)	−0.0058 (4)	0.0030 (4)	−0.0075 (4)
N14	0.0222 (6)	0.0202 (6)	0.0189 (6)	−0.0060 (4)	−0.0011 (4)	−0.0073 (5)
C1	0.0154 (6)	0.0142 (6)	0.0183 (6)	−0.0013 (5)	−0.0005 (5)	−0.0072 (5)
C2	0.0151 (6)	0.0145 (6)	0.0182 (6)	−0.0036 (5)	0.0025 (5)	−0.0059 (5)
C3	0.0189 (6)	0.0161 (6)	0.0154 (6)	−0.0024 (5)	0.0015 (5)	−0.0057 (5)
C4	0.0175 (6)	0.0164 (6)	0.0169 (6)	−0.0038 (5)	−0.0022 (5)	−0.0071 (5)
C5	0.0167 (6)	0.0171 (6)	0.0188 (6)	−0.0049 (5)	0.0016 (5)	−0.0058 (5)
C6	0.0188 (6)	0.0196 (6)	0.0158 (6)	−0.0045 (5)	0.0020 (5)	−0.0062 (5)
C11	0.0207 (6)	0.0176 (6)	0.0215 (7)	−0.0016 (5)	−0.0021 (5)	−0.0095 (5)
C12	0.0296 (7)	0.0357 (8)	0.0217 (7)	−0.0092 (6)	−0.0002 (5)	−0.0139 (6)
C13	0.0202 (6)	0.0272 (7)	0.0265 (7)	−0.0063 (5)	−0.0019 (5)	−0.0135 (6)

Geometric parameters (Å, º)

C1—N1	1.3542 (15)	C2—C3	1.3931 (17)
C1—C6	1.4174 (17)	C2—N12	1.4523 (16)
C1—C2	1.4176 (17)	N12—O22	1.2241 (14)
N1—N2	1.3876 (15)	N12—O21	1.2421 (14)
N1—H1	0.9687	C3—C4	1.3707 (17)
N2—C11	1.2872 (16)	C3—H3	0.95
C11—C12	1.4899 (19)	C4—C5	1.3982 (17)
C11—C13	1.5028 (18)	C4—N14	1.4574 (15)
C12—H12A	0.98	N14—O41	1.2233 (14)
C12—H12B	0.98	N14—O42	1.2353 (14)
C12—H12C	0.98	C5—C6	1.3688 (17)
C13—H13A	0.98	C5—H5	0.95
C13—H13B	0.98	C6—H6	0.95
C13—H13C	0.98
N1—C1—C6	119.92 (11)	C3—C2—C1	121.76 (11)
N1—C1—C2	123.20 (11)	C3—C2—N12	116.26 (11)
C6—C1—C2	116.88 (11)	C1—C2—N12	121.98 (10)
C1—N1—N2	119.23 (10)	O22—N12—O21	122.43 (10)
C1—N1—H1	120.2	O22—N12—C2	119.14 (10)
N2—N1—H1	120.4	O21—N12—C2	118.43 (10)
C11—N2—N1	115.35 (11)	C4—C3—C2	118.65 (11)
N2—C11—C12	116.60 (12)	C4—C3—H3	120.7
N2—C11—C13	124.89 (12)	C2—C3—H3	120.7
C12—C11—C13	118.51 (11)	C3—C4—C5	121.73 (11)
C11—C12—H12A	109.5	C3—C4—N14	119.10 (11)
C11—C12—H12B	109.5	C5—C4—N14	119.17 (11)
H12A—C12—H12B	109.5	O41—N14—O42	123.72 (11)
C11—C12—H12C	109.5	O41—N14—C4	118.46 (10)
H12A—C12—H12C	109.5	O42—N14—C4	117.81 (10)
H12B—C12—H12C	109.5	C6—C5—C4	119.50 (11)
C11—C13—H13A	109.5	C6—C5—H5	120.2
C11—C13—H13B	109.5	C4—C5—H5	120.2
H13A—C13—H13B	109.5	C5—C6—C1	121.43 (11)
C11—C13—H13C	109.5	C5—C6—H6	119.3
H13A—C13—H13C	109.5	C1—C6—H6	119.3
H13B—C13—H13C	109.5
C6—C1—N1—N2	−1.35 (17)	C1—C2—C3—C4	0.40 (18)
C2—C1—N1—N2	178.96 (10)	N12—C2—C3—C4	−179.86 (11)
C1—N1—N2—C11	176.60 (11)	C2—C3—C4—C5	1.47 (18)
N1—N2—C11—C12	−179.76 (10)	C2—C3—C4—N14	−178.84 (10)
N1—N2—C11—C13	−0.70 (18)	C3—C4—N14—O41	−0.69 (18)
N1—C1—C2—C3	177.53 (11)	C5—C4—N14—O41	179.00 (11)
C6—C1—C2—C3	−2.16 (17)	C3—C4—N14—O42	178.46 (11)
N1—C1—C2—N12	−2.19 (18)	C5—C4—N14—O42	−1.84 (17)
C6—C1—C2—N12	178.12 (10)	C3—C4—C5—C6	−1.47 (19)
C3—C2—N12—O22	3.83 (17)	N14—C4—C5—C6	178.85 (11)
C1—C2—N12—O22	−176.44 (11)	C4—C5—C6—C1	−0.44 (19)
C3—C2—N12—O21	−176.12 (11)	N1—C1—C6—C5	−177.53 (11)
C1—C2—N12—O21	3.62 (18)	C2—C1—C6—C5	2.17 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O21	0.97	1.91	2.5994 (15)	125
C5—H5···O42^i	0.95	2.45	3.2660 (16)	144

Symmetry code: (i) −x, −y, −z+1.