organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

Meth­yl aceto­acetate at 150 K

aChemical Crystallography Laboratory, Chemistry Research Laboratory, Mansfield Road, Oxford University, Oxford OX1 3TA, England
*Correspondence e-mail: howard.shallard-brown@lmh.ox.ac.uk

(Received 20 May 2005; accepted 3 June 2005; online 9 July 2005)

The crystal structure of meth­yl acetoacetate, C5H8O3, at 150 K contains discrete mol­ecules.

Comment

Many of the esters and ketones used in the flavours and fragrances industry are liquid at room temperature, meaning that in the past crystalline derivatives have had to be prepared for X-ray analysis. As part of a programme to systematize in situ crystal growth from liquids, we have examined a range of commercially available chemicals. Low-mol­ecular-weight organic ketones are liquid at room temperature. Mol­ecules of meth­yl acetoacetate, (I)[link], exist as discrete entities in the crystal structure at 150 K, with no strong inter­molecular inter­actions.

[Scheme 1]
[Figure 1]
Figure 1
The title compound, with displacement ellipsoids drawn at the 50% probability level. H atoms are of arbitrary radii.
[Figure 2]
Figure 2
The crystal structure, viewed down the a axis.
[Figure 3]
Figure 3
The crystal structure, viewed down the b axis.

Experimental

A 3 mm column of the title material, which is a liquid at room temperature, was sealed in a 0.3 mm Lindemann tube. The Lindemann tube was not precisely parallel to the φ axis. A single crystal of the compound was grown by keeping the sample under a stream of nitro­gen gas (Oxford Cryostream 600) at 180 K and slowly moving a small liquid zone, created by a micro-heating coil, up and down the sample. Once a suitable approximately single-crystal specimen had been obtained, the main data collection was carried out at 150 K. Because not all the data were collected with the Lindemann tube perpendicular to the X-ray beam, the multi-scan corrections applied by DENZO/SCALEPACK (Otwinowski & Minor, 1997[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.]) also contain contributions due to changes in the illuminated volume of the cylindrical sample, which affects the value of Tmin/Tmax.

Crystal data
  • C5H8O3

  • Mr = 116.12

  • Monoclinic, P 121 /c 1

  • a = 6.0018 (2) Å

  • b = 8.0384 (3) Å

  • c = 12.4802 (3) Å

  • β = 95.5132 (17)°

  • V = 599.32 (3) Å3

  • Z = 4

  • Dx = 1.287 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 1392 reflections

  • θ = 5–27°

  • μ = 0.11 mm−1

  • T = 150 K

  • Cylinder, colourless

  • 0.70 × 0.30 × 0.30 mm

Data collection
  • Nonius KappaCCD diffractometer

  • ω scans

  • Absorption correction: multi-scan(DENZO/SCALEPACK; Otwinowski & Minor, 1997[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.])Tmin = 0.68, Tmax = 0.95

  • 2531 measured reflections

  • 1343 independent reflections

  • 1184 reflections with I > 2σ(I)

  • Rint = 0.022

  • θmax = 27.5°

  • h = −7 → 7

  • k = −10 → 10

  • l = −16 → 16

Refinement
  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.036

  • wR(F2) = 0.095

  • S = 1.01

  • 1343 reflections

  • 106 parameters

  • Only H-atom coordinates refined

  • w = 1/[σ2(F) + 0.04 + 0.19P] where P = [max(Fo2, 0) + 2Fc2]/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.25 e Å−3

  • Δρmin = −0.22 e Å−3

Table 1
Selected geometric parameters (Å, °)[link]

C1—C2 1.5001 (15)
C1—O6 1.3328 (14)
C1—O8 1.1997 (14)
C2—C3 1.5191 (15)
C3—O4 1.2118 (13)
C3—C5 1.4920 (15)
O6—C7 1.4458 (14)
C2—C1—O6 111.96 (9)
C2—C1—O8 124.51 (11)
O6—C1—O8 123.53 (10)
C1—C2—C3 112.28 (9)
C2—C3—O4 121.15 (10)
C2—C3—C5 115.27 (9)
O4—C3—C5 123.58 (10)
C1—O6—C7 116.27 (9)

All H atoms were located in a difference map. Alternative positions were clearly visible for the disordered H atoms on C7, whose site occupancy factors were set to 0.5. The H atoms were then repositioned geometrically and refined with soft restraints on the bond lengths and angles to regularize their geometry, with C—H = 0.97–1.01 Å, and Uiso(H) = 1.2Ueq(C), after which the restraints were removed.

Data collection: COLLECT (Nonius, 1997[Nonius (1997). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997[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.]); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994[Altomare, A., Cascarano, G., Giacovazzo, G., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435.]); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003[Betteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, K. & Watkin, D. J. (2003). J. Appl. Cryst. 36, 1487.]); molecular graphics: CAMERON (Watkin et al., 1996[Watkin, D. J., Prout, C. K. & Pearce, L. J. (1996). CAMERON. Chemical Crystallography Laboratory, Oxford, England.]); software used to prepare material for publication: CRYSTALS.

Supporting information


Comment top

Many of the esters and ketones used in the flavours and fragrances industry are liquid at room temperature, meaning that in the past crystalline derivatives have had to be prepared for X-ray analysis. As part of a programme to systematize in situ crystal growth from liquids, we have examined a range of commercially available chemicals. Low-molecular-weight organic ketones are liquid at room temperature. Molecules of methyl acetoacetate exist as discrete entities in the crystal structure at 150 K, with no strong intermolecular interactions.

Experimental top

A 3 mm column of the title material, which is a liquid at room temperature, was sealed in a 0.3 mm Lindemann tube. The Lindemann tube was not precisely parallel to the ϕ axis. A single-crystal of the compound was grown by keeping the sample under a stream of nitrogen gas (Oxford Cryostream 600) at 180 K and slowly moving a small liquid zone, created by a micro-heating coil, up and down the sample. Once a suitable approximately single-crystal specimen had been obtained, the main data collection was carried out at 150 K. Because not all the data were collected with the Lindemann tube perpendicular to the X-ray beam, the multi-scan corrections applied by DENZO/SCALEPACK (Otwinowski & Minor, 1997) also contain contributions due to changes in the illuminated volume of the cylindrical sample, which affects the value of Tmin/Tmax.

Refinement top

All H atoms were located in a difference map. Alternative positions were clearly visible for the disordered hydrogen atoms on C7, whose site occupation numbers were set to 0.5. The hydrogen atoms were then repositioned geometrically and refined with soft restraints on the bond lengths and angles to regularize their geometry, with C—H = 0.97–1.01 Å, and U(H) = 1.2Ueq(C), after which the restaints were removed.

Computing details top

Data collection: COLLECT (Nonius, 1997); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: CRYSTALS.

Figures top
[Figure 1] Fig. 1. The title compound, with displacement ellipsoids drawn at the 50% probability level. H atoms are of arbitrary radii.
[Figure 2] Fig. 2. The crystal structure, viewed down the a axis.
[Figure 3] Fig. 3. The crystal structure, viewed down the b axis.
(I) top
Crystal data top
C5H8O3F(000) = 248
Mr = 116.12Dx = 1.287 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 6.0018 (2) ÅCell parameters from 1392 reflections
b = 8.0384 (3) Åθ = 5–27°
c = 12.4802 (3) ŵ = 0.11 mm1
β = 95.5132 (17)°T = 150 K
V = 599.32 (3) Å3Cylinder, colourless
Z = 40.70 × 0.30 × 0.30 × 0.30 (radius) mm
Data collection top
Nonius KappaCCD
diffractometer
1184 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.022
ω scansθmax = 27.5°, θmin = 5.5°
Absorption correction: multi-scan
(DENZO/SCALEPACK; Otwinowski & Minor, 1997)
h = 77
Tmin = 0.68, Tmax = 0.95k = 1010
2531 measured reflectionsl = 1616
1343 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036Only H-atom coordinates refined
wR(F2) = 0.095 w = 1/[σ2(F) + 0.04 + 0.19P]
where P = (max(Fo2, 0) + 2Fc2)/3
S = 1.01(Δ/σ)max = 0.000179
1343 reflectionsΔρmax = 0.25 e Å3
106 parametersΔρmin = 0.22 e Å3
34 restraints
Crystal data top
C5H8O3V = 599.32 (3) Å3
Mr = 116.12Z = 4
Monoclinic, P21/cMo Kα radiation
a = 6.0018 (2) ŵ = 0.11 mm1
b = 8.0384 (3) ÅT = 150 K
c = 12.4802 (3) Å0.70 × 0.30 × 0.30 × 0.30 (radius) mm
β = 95.5132 (17)°
Data collection top
Nonius KappaCCD
diffractometer
1343 independent reflections
Absorption correction: multi-scan
(DENZO/SCALEPACK; Otwinowski & Minor, 1997)
1184 reflections with I > 2σ(I)
Tmin = 0.68, Tmax = 0.95Rint = 0.022
2531 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.03634 restraints
wR(F2) = 0.095Only H-atom coordinates refined
S = 1.01Δρmax = 0.25 e Å3
1343 reflectionsΔρmin = 0.22 e Å3
106 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
C10.98275 (18)0.27935 (14)0.16468 (9)0.0295
C20.8961 (2)0.29879 (15)0.27279 (9)0.0326
C30.71045 (17)0.42745 (13)0.27155 (8)0.0266
O40.68130 (14)0.52847 (11)0.19950 (7)0.0377
C50.5717 (2)0.41962 (18)0.36442 (10)0.0374
O61.15380 (13)0.38125 (11)0.15274 (6)0.0336
C71.2470 (2)0.3743 (2)0.05022 (10)0.0447
O80.90835 (17)0.18382 (13)0.09654 (8)0.0499
H210.839 (2)0.1936 (17)0.2936 (10)0.0468*
H221.014 (2)0.3354 (17)0.3247 (11)0.0469*
H510.472 (3)0.5128 (19)0.3641 (12)0.0651*
H520.489 (3)0.3144 (18)0.3609 (12)0.0660*
H530.669 (2)0.418 (2)0.4325 (11)0.0652*
H711.382 (4)0.438 (4)0.056 (2)0.0803*0.5000
H721.138 (4)0.411 (4)0.0067 (17)0.0792*0.5000
H731.281 (5)0.259 (2)0.037 (2)0.0794*0.5000
H741.366 (4)0.295 (3)0.054 (2)0.0796*0.5000
H751.307 (5)0.485 (3)0.040 (2)0.0798*0.5000
H761.131 (4)0.348 (4)0.0065 (17)0.0794*0.5000
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0310 (5)0.0281 (5)0.0297 (5)0.0021 (4)0.0038 (4)0.0019 (4)
C20.0367 (6)0.0318 (6)0.0303 (6)0.0053 (5)0.0082 (4)0.0072 (4)
C30.0264 (5)0.0263 (5)0.0266 (5)0.0032 (4)0.0006 (4)0.0000 (4)
O40.0381 (5)0.0357 (5)0.0392 (5)0.0039 (4)0.0035 (3)0.0119 (4)
C50.0353 (6)0.0451 (7)0.0326 (6)0.0034 (5)0.0082 (5)0.0002 (5)
O60.0342 (4)0.0409 (5)0.0266 (4)0.0062 (3)0.0067 (3)0.0018 (3)
C70.0391 (7)0.0651 (9)0.0316 (6)0.0047 (6)0.0119 (5)0.0002 (6)
O80.0563 (6)0.0516 (6)0.0426 (5)0.0191 (5)0.0090 (4)0.0136 (4)
Geometric parameters (Å, º) top
C1—C21.5001 (15)C5—H520.978 (14)
C1—O61.3328 (14)C5—H530.983 (13)
C1—O81.1997 (14)O6—C71.4458 (14)
C2—C31.5191 (15)C7—H710.958 (18)
C2—H210.957 (13)C7—H720.965 (18)
C2—H220.960 (13)C7—H730.970 (18)
C3—O41.2118 (13)C7—H740.957 (18)
C3—C51.4920 (15)C7—H750.973 (18)
C5—H510.958 (14)C7—H760.969 (18)
C2—C1—O6111.96 (9)H51—C5—H53109.4 (12)
C2—C1—O8124.51 (11)H52—C5—H53106.4 (12)
O6—C1—O8123.53 (10)C1—O6—C7116.27 (9)
C1—C2—C3112.28 (9)O6—C7—H71108.2 (14)
C1—C2—H21108.4 (8)O6—C7—H72110.3 (15)
C3—C2—H21108.9 (8)H71—C7—H72113.4 (16)
C1—C2—H22110.0 (8)O6—C7—H73107.2 (14)
C3—C2—H22107.0 (8)H71—C7—H73109.5 (16)
H21—C2—H22110.4 (11)H72—C7—H73108.0 (16)
C2—C3—O4121.15 (10)O6—C7—H74109.6 (15)
C2—C3—C5115.27 (9)O6—C7—H75105.2 (15)
O4—C3—C5123.58 (10)H74—C7—H75109.3 (16)
C3—C5—H51111.0 (9)O6—C7—H76110.0 (15)
C3—C5—H52108.6 (9)H74—C7—H76111.9 (16)
H51—C5—H52111.2 (11)H75—C7—H76110.6 (16)
C3—C5—H53110.0 (9)

Experimental details

Crystal data
Chemical formulaC5H8O3
Mr116.12
Crystal system, space groupMonoclinic, P21/c
Temperature (K)150
a, b, c (Å)6.0018 (2), 8.0384 (3), 12.4802 (3)
β (°) 95.5132 (17)
V3)599.32 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.11
Crystal size (mm)0.70 × 0.30 × 0.30 × 0.30 (radius)
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(DENZO/SCALEPACK; Otwinowski & Minor, 1997)
Tmin, Tmax0.68, 0.95
No. of measured, independent and
observed [I > 2σ(I)] reflections
2531, 1343, 1184
Rint0.022
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.095, 1.01
No. of reflections1343
No. of parameters106
No. of restraints34
H-atom treatmentOnly H-atom coordinates refined
Δρmax, Δρmin (e Å3)0.25, 0.22

Computer programs: COLLECT (Nonius, 1997), DENZO/SCALEPACK (Otwinowski & Minor, 1997), DENZO/SCALEPACK, SIR92 (Altomare et al., 1994), CRYSTALS (Betteridge et al., 2003), CAMERON (Watkin et al., 1996), CRYSTALS.

Selected geometric parameters (Å, º) top
C1—C21.5001 (15)C3—O41.2118 (13)
C1—O61.3328 (14)C3—C51.4920 (15)
C1—O81.1997 (14)O6—C71.4458 (14)
C2—C31.5191 (15)
C2—C1—O6111.96 (9)C2—C3—O4121.15 (10)
C2—C1—O8124.51 (11)C2—C3—C5115.27 (9)
O6—C1—O8123.53 (10)O4—C3—C5123.58 (10)
C1—C2—C3112.28 (9)C1—O6—C7116.27 (9)
 

References

First citationAltomare, A., Cascarano, G., Giacovazzo, G., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. CrossRef Web of Science IUCr Journals
First citationBetteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, K. & Watkin, D. J. (2003). J. Appl. Cryst. 36, 1487. Web of Science CrossRef IUCr Journals
First citationNonius (1997). COLLECT. Nonius BV, Delft, The Netherlands.
First citationOtwinowski, 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.
First citationWatkin, D. J., Prout, C. K. & Pearce, L. J. (1996). CAMERON. Chemical Crystallography Laboratory, Oxford, England.

© 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.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds