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The structure of the triclinic polymorph of acetone 2,4-dinitrophenylhydrazone, C
9H
10N
4O
4, 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
-
stacking interaction. In the monoclinic polymorph, which crystallizes with
Z' = 2 in the space group
P2
1/
n, one type of molecule forms dimers exactly as in the triclinic polymorph, while the other forms
C(6) chains.
Supporting information
CCDC reference: 645575
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
top
Crystal data top
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) Å3 | |
Data collection top
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 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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.117 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.082P)2 + 0.0909P] where P = (Fo2 + 2Fc2)/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 (Å2) top | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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) top
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···O42i | 0.95 | 2.45 | 3.2660 (16) | 144 |
Symmetry code: (i) −x, −y, −z+1. |
Hydrogen bond parameters (Å, °)
for polymorphs (I) at 120 K and (II) at 150 K topPolymorph | D-H···A | | D-H | H···A | D···A | D-H···A |
(I) | N1-H1···O21 | | 0.97 | 1.91 | 2.5994 (15) | 125 |
| C5-H5···O42i | | 0.95 | 2.45 | 3.2660 (16) | 144 |
(II) | N1-H1···O1 | | 0.88 | 1.95 | 2.592 (3) | 129 |
| N5-H11···O5 | | 0.88 | 1.98 | 2.618 (3) | 129 |
| C4-H3···O4ii | | 0.95 | 2.40 | 3.281 (4) | 154 |
| C14-H14···O8iii | | 0.95 | 2.42 | 3.279 (4) | 150 |
Original atom-numbering for polymorph (II). Symmetry
codes: (i) -x, -y, -z + 1; (ii) -x - 2, -y + 1, -z;
(iii) -x - 1/2, y - 1/2, -z + 1/2. |
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