n-Butyl acetate

Shallard-Brown, H.A.; Watkin, D.J.; Cowley, A.R.

doi:10.1107/S1600536805000371

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 61| Part 3| March 2005| Pages o561-o562

https://doi.org/10.1107/S1600536805000371

n-Butyl acetate

Howard A. Shallard-Brown,^a ^* David J. Watkin ^a and Andrew R. Cowley ^a

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

(Received 16 December 2004; accepted 5 January 2005; online 5 February 2005)

The title compound, C₆H₁₂O₂, was prepared by a modified zone-refinement method at 150 K and consists of discrete molecules in van der Waals contact.

Comment

Many of the esters and ketones used in the flavours and fragrances industry are liquid at room temperature; thus, 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 esters are liquid at room temperature. To date, only the crystal structure of methyl acetate has been determined (Barrow et al., 1981 ). It was shown that the molecules of methyl acetate exist as discrete entities, without any strong intermolecular contacts. n-Butyl acetate, (I), was examined because it has a melting point suitable for our trials. The crystal structure is similar to that of methyl acetate, consisting of discrete molecules in van der Waals contact. The most evident feature is the pairwise parallel butyl residues related by a crystallographic centre of symmetry. The open packing of the structure is reflected in its low density of 1.09 Mg m⁻³.

Figure 1
The title compound, with displacement ellipsoids drawn at the 50% probability level. H atoms are of arbitrary radii.

Figure 2
A packing diagram, viewed along the a axis, showing the parallel pairing of the butyl groups.

Experimental

A 3 mm column of the title material, which is a liquid at room temperature, was sealed in a 0.2 mm Lindemann tube, which was not accurately parallel to the φ axis. A single crystal of the compound was grown by keeping the compound under a cold nitrogen gas stream at 150 K (a little below its melting point), 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 this temperature. 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 illuminated volume of the cylindrical sample; this is reflected in the ratio T_min/T_max.

Crystal data

C₆H₁₂O₂
M_r = 116.16
Triclinic, P $[\bar{1}]$
a = 4.7272 (1) Å
b = 7.6955 (3) Å
c = 10.1387 (4) Å
α = 100.7426 (13)°
β = 96.0038 (15)°
γ = 99.3371 (18)°
V = 354.09 (2) Å³
Z = 2
D_x = 1.089 Mg m⁻³
Mo Kα radiation
Cell parameters from 1476 reflections
θ = 5–27°
μ = 0.08 mm⁻¹
T = 150 K
Cylinder, colourless
0.80 × 0.20 × 0.20 mm

Data collection

Nonius KappaCCD diffractometer
ω scans
Absorption correction: multi-scan(DENZO/SCALEPACK; Otwinowski & Minor, 1997)T_min = 0.33, T_max = 0.98
5958 measured reflections
1585 independent reflections
1194 reflections with I > 2σ(I)
R_int = 0.035
θ_max = 27.4°
h = −6 → 5
k = −9 → 9
l = −13 → 13

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.104
S = 0.97
1585 reflections
73 parameters
H-atom parameters constrained
w = 1/[σ²(F) + 0.045 + 0.061P] where P = [max(F_o²,0) + 2F_c²]/3
(Δ/σ)_max < 0.0001
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

C1—O2	1.3411 (14)
C1—O7	1.2037 (14)
C1—C8	1.4981 (17)
O2—C3	1.4571 (14)
C3—C4	1.5096 (16)
C4—C5	1.5192 (17)
C5—C6	1.5189 (18)

O2—C1—O7	123.27 (11)
O2—C1—C8	111.16 (10)
O7—C1—C8	125.57 (11)
C1—O2—C3	115.87 (9)
O2—C3—C4	107.14 (9)
C3—C4—C5	113.98 (10)
C4—C5—C6	112.59 (11)

All H atoms were located in a difference map, but those attached to C atoms were repositioned geometrically. The H atoms were initially refined with soft restraints on the bond lengths and angles to regularize their geometry (C—H = 0.97–1.01 Å), after which they were refined with riding constraints and with U_iso(H) = 1.2U_eq(C).

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536805000371/cf6393sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805000371/cf6393Isup2.hkl

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.

n-Butyl acetate top

Crystal data top

C₆H₁₂O₂	Z = 2
M_r = 116.16	F(000) = 128
Triclinic, P1	D_x = 1.089 Mg m⁻³
a = 4.7272 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.6955 (3) Å	Cell parameters from 1476 reflections
c = 10.1387 (4) Å	θ = 5–27°
α = 100.7426 (13)°	µ = 0.08 mm⁻¹
β = 96.0038 (15)°	T = 150 K
γ = 99.3371 (18)°	Cylinder, colourless
V = 354.09 (2) Å³	0.80 × 0.20 × 0.20 mm

Data collection top

Nonius KappaCCD diffractometer	1194 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ω scans	θ_max = 27.4°, θ_min = 5.1°
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	h = −6→5
T_min = 0.33, T_max = 0.98	k = −9→9
5958 measured reflections	l = −13→13
1585 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.104	w = 1/[σ²(F) + 0.045 + 0.061P] where P = [max(F_o²,0) + 2F_c²]/3
S = 0.97	(Δ/σ)_max = 0.0002
1585 reflections	Δρ_max = 0.19 e Å⁻³
73 parameters	Δρ_min = −0.31 e Å⁻³
0 restraints

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

	x	y	z	U_iso*/U_eq
C1	0.4329 (2)	0.19532 (15)	0.61673 (12)	0.0319
O2	0.65680 (17)	0.30569 (11)	0.69916 (8)	0.0339
C3	0.8300 (3)	0.43555 (16)	0.63810 (12)	0.0346
C4	1.0599 (3)	0.54983 (16)	0.74868 (12)	0.0343
C5	0.9433 (3)	0.67482 (17)	0.85537 (13)	0.0391
C6	1.1774 (3)	0.77932 (18)	0.96950 (14)	0.0473
O7	0.37156 (19)	0.20225 (12)	0.49981 (9)	0.0425
C8	0.2750 (3)	0.06562 (18)	0.68942 (14)	0.0422
H31	0.7054	0.5128	0.6039	0.0396*
H32	0.9191	0.3691	0.5635	0.0386*
H41	1.1621	0.4712	0.7951	0.0409*
H42	1.2056	0.6241	0.7048	0.0407*
H51	0.7923	0.6020	0.8923	0.0463*
H52	0.8546	0.7619	0.8135	0.0456*
H61	1.0958	0.8659	1.0380	0.0562*
H62	1.2725	0.6978	1.0129	0.0569*
H63	1.3283	0.8469	0.9317	0.0556*
H81	0.0981	0.0075	0.6299	0.0492*
H82	0.2414	0.1286	0.7779	0.0492*
H83	0.3985	−0.0178	0.6998	0.0499*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0323 (6)	0.0278 (6)	0.0334 (7)	0.0043 (5)	0.0010 (5)	0.0040 (5)
O2	0.0365 (5)	0.0326 (5)	0.0297 (5)	−0.0025 (4)	0.0006 (3)	0.0092 (4)
C3	0.0359 (6)	0.0347 (6)	0.0330 (6)	−0.0005 (5)	0.0047 (5)	0.0123 (5)
C4	0.0310 (6)	0.0349 (7)	0.0361 (7)	0.0018 (5)	0.0024 (5)	0.0096 (5)
C5	0.0390 (7)	0.0339 (7)	0.0432 (7)	0.0028 (5)	0.0060 (6)	0.0078 (6)
C6	0.0593 (9)	0.0387 (8)	0.0385 (7)	0.0000 (6)	0.0018 (6)	0.0051 (6)
O7	0.0461 (5)	0.0411 (5)	0.0350 (5)	−0.0011 (4)	−0.0061 (4)	0.0092 (4)
C8	0.0460 (7)	0.0353 (7)	0.0410 (7)	−0.0034 (6)	0.0044 (6)	0.0072 (6)

Geometric parameters (Å, º) top

C1—O2	1.3411 (14)	C5—C6	1.5189 (18)
C1—O7	1.2037 (14)	C5—H51	0.983
C1—C8	1.4981 (17)	C5—H52	0.983
O2—C3	1.4571 (14)	C6—H61	1.021
C3—C4	1.5096 (16)	C6—H62	0.971
C3—H31	0.984	C6—H63	0.968
C3—H32	1.002	C8—H81	0.967
C4—C5	1.5192 (17)	C8—H82	0.978
C4—H41	0.988	C8—H83	0.948
C4—H42	1.015

O2—C1—O7	123.27 (11)	C4—C5—H51	108.3
O2—C1—C8	111.16 (10)	C6—C5—H51	109.8
O7—C1—C8	125.57 (11)	C4—C5—H52	109.8
C1—O2—C3	115.87 (9)	C6—C5—H52	108.1
O2—C3—C4	107.14 (9)	H51—C5—H52	108.2
O2—C3—H31	109.0	C5—C6—H61	111.2
C4—C3—H31	109.1	C5—C6—H62	110.7
O2—C3—H32	109.0	H61—C6—H62	111.4
C4—C3—H32	111.0	C5—C6—H63	109.1
H31—C3—H32	111.3	H61—C6—H63	109.3
C3—C4—C5	113.98 (10)	H62—C6—H63	104.9
C3—C4—H41	109.5	C1—C8—H81	106.2
C5—C4—H41	107.8	C1—C8—H82	110.4
C3—C4—H42	108.1	H81—C8—H82	113.2
C5—C4—H42	109.2	C1—C8—H83	105.1
H41—C4—H42	108.1	H81—C8—H83	110.9
C4—C5—C6	112.59 (11)	H82—C8—H83	110.7

References

Altomare, 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 Google Scholar
Barrow, M. J., Cradock, S., Ebsworth, E. A. V. & Rankin, D. W. H. (1981). J. Chem. Soc. Dalton Trans. 16, 1988–1993. CSD CrossRef Web of Science Google Scholar
Betteridge, 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 Google Scholar
Nonius (1997). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
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. Google Scholar
Watkin, D. J., Prout, C. K. & Pearce, L. J. (1996). CAMERON. Chemical Crystallography Laboratory, Oxford, England. Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 61| Part 3| March 2005| Pages o561-o562

https://doi.org/10.1107/S1600536805000371

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

n-Butyl acetate

Comment

Experimental

Crystal data

Data collection

Refinement

Supporting information

References

organic compounds