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ISSN: 2056-9890

A low-temperature determination of butyramide

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aDepartment of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, England
*Correspondence e-mail: d.a.tocher@ucl.ac.uk

(Received 9 May 2005; accepted 27 May 2005; online 10 June 2005)

The low-temperature structure determination of butyramide, C4H9NO, obtained as part of a experimental polymorph screen on adenine, is reported here. Each molecule takes part in four hydrogen bonds to form a three-dimensional ribbon structure.

Comment

The title compound, (I)[link], is one of the n-aliphatic amides and has recently been studied as a possible agent for growth inhibition of human neuroblastoma cell lines (Rocchi et al., 1998[Rocchi, P., Ferreri, A. M., Magrini, E. & Perocco, P. (1998). Anticancer Res. 18, 1099-1103.]) and inhibitory effects on DNA synthesis on hepatoma cells (Lea et al., 1993[Lea, M. A., Xiao, Q., Sadhukhan, A., Sharma, S. & Newmark, H. L. (1993). Anticancer Res. 13, 145-150.]).

[Scheme 1]

The powder diffractogram data for (I)[link] were reported in 1950 (Matthews et al., 1950[Matthews, F. W., Warren, G. G. & Michell, J. H. (1950). Anal. Chem. 22, 514-519.]), as part of a study on derivatives of fatty acids, and the unit cell was determined five years later (Turner & Lingafelter, 1955[Turner, J. D. & Lingafelter, E. C. (1955). Acta Cryst. 8, 549-550.]) using Weissenberg photographs, to give a = 9.94 Å, b = 5.79 Å, c = 10.02 Å and β = 100.9°. Examination of the systematic absences showed the space group to be P21/a; however, no atomic coordinates were published. We have solved and refined the crystal structure of butyramide at 150 K, to give a final R value of 0.041. There is a 12° difference in the β angle between the two determinations. In (I)[link], the bond lengths and angles are within expected values (Allen et al., 1987[Allen, F. H., Kennard, O. & Watson, D. G. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-18.]), with the C—C bond lengths in the range 1.5057 (18)–1.515 (2) Å and with N1—C1 and O2—C1 bond lengths of 1.3257 (15) and 1.2395 (13) Å, respectively. There is a relative twist of the carbon chain from planarity, with torsion angles C1—C2—C3—C4 and N1—C1—C2—C3 of 177.41 (21) and 151.62 (12)°, respectively. The packing consists of centrosymmetric dimers, linked through a pair of N—H⋯O hydrogen bonds [2.9470 (15) Å]. The other amine H atom is used to hydrogen bond to an adjacent dimer unit which is approximately perpendicular (73°), through an N—H⋯O hydrogen bond [2.8496 (14) Å], resulting in the formation of a three-dimensional criss-crossed ribbon structure (Fig. 2[link]).

[Figure 1]
Figure 1
View of (I)[link], showing the atom labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2]
Figure 2
The packing in (I)[link], showing the butyramide dimer unit which forms a hydrogen-bonded (dashed lines) criss-cross ribbon motif.

Experimental

As part of an experimental polymorph screen on adenine, (I)[link] was obtained from a 0.3 M aqueous solution of (I)[link], to which approximately 0.15 g of adenine was added, and which was stirred on a hotplate at 303 K for 3 d. This solution was filtered, then evaporated at room temperature (10 ml solution, in 75 × 25 mm vessels) in an attempt to crystallize adenine, as it has been found that the solubility of purine and pyrimidine bases increases in aqueous amide solutions (Herskovits & Bowen, 1974[Herskovits, T. T. & Bowen, J. J. (1974). Biochemistry, 13, 5474-5483.]). Colourless block-like crystals of (I)[link] were formed after a number of days.

Crystal data
  • C4H9NO

  • Mr = 87.12

  • Monoclinic, P 21 /c

  • a = 9.814 (3) Å

  • b = 5.9232 (17) Å

  • c = 9.701 (3) Å

  • β = 112.070 (4)°

  • V = 522.6 (3) Å3

  • Z = 4

  • Dx = 1.107 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 1237 reflections

  • θ = 2.2–25.4°

  • μ = 0.08 mm−1

  • T = 150 (2) K

  • Block, colourless

  • 0.38 × 0.20 × 0.16 mm

Data collection
  • Bruker SMART APEX diffractometer

  • ω scans

  • Absorption correction: multi-scan(SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.])Tmin = 0.971, Tmax = 0.987

  • 4321 measured reflections

  • 1244 independent reflections

  • 993 reflections with I > 2σ(I)

  • Rint = 0.021

  • θmax = 28.3°

  • h = −13 → 12

  • k = −7 → 7

  • l = −12 → 12

Refinement
  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.041

  • wR(F2) = 0.111

  • S = 1.01

  • 1244 reflections

  • 91 parameters

  • All H-atom parameters refined

  • w = 1/[σ2(Fo2) + (0.064P)2 + 0.0651P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.19 e Å−3

  • Δρmin = −0.12 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)[link]

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1⋯O2i 0.92 (2) 2.03 (2) 2.9470 (15) 176 (1)
N1—H2⋯O2ii 0.89 (2) 1.98 (2) 2.8496 (14) 168 (1)
Symmetry codes: (i) -x+1, -y, -z+1; (ii) [x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}].

H atoms were refined independently with an isotropic model.

Data collection: SMART (Bruker, 2000[Bruker (2000). SMART, SAINT and SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT; data reduction: SAINT (Bruker, 2000[Bruker (2000). SMART, SAINT and SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990[Sheldrick, G. M. (1990). Acta Cryst. A46, 467-473.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXL97. University of Göttingen, Germany.]); molecular graphics: SHELXTL (Bruker, 2000[Bruker (2000). SMART, SAINT and SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.]) and MERCURY (Bruno et al., 2002[Bruno, I. J., Cole, J. C., Edgington, P. R., Kessler, M. K., Macrae, C. F., McCabe, P., Pearson, J. & Taylor, R. (2002). Acta Cryst. B58, 389-397.]); software used to prepare material for publication: SHELXL97.

Supporting information


Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000) and Mercury (Bruno et al., 2002); software used to prepare material for publication: SHELXL97.

Butyramide top
Crystal data top
C4H9NOF(000) = 192
Mr = 87.12Dx = 1.107 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 9.814 (3) ÅCell parameters from 1237 reflections
b = 5.9232 (17) Åθ = 2.2–25.4°
c = 9.701 (3) ŵ = 0.08 mm1
β = 112.070 (4)°T = 150 K
V = 522.6 (3) Å3Plate, colourless
Z = 40.38 × 0.20 × 0.16 mm
Data collection top
Bruker SMART APEX
diffractometer
1244 independent reflections
Radiation source: fine-focus sealed tube993 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.021
ω rotation with narrow frames scansθmax = 28.3°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1312
Tmin = 0.971, Tmax = 0.987k = 77
4321 measured reflectionsl = 1212
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.111All H-atom parameters refined
S = 1.01 w = 1/[σ2(Fo2) + (0.064P)2 + 0.0651P]
where P = (Fo2 + 2Fc2)/3
1244 reflections(Δ/σ)max < 0.001
91 parametersΔρmax = 0.19 e Å3
0 restraintsΔρmin = 0.12 e Å3
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O20.62317 (10)0.21606 (15)0.61392 (8)0.0388 (3)
N10.58606 (12)0.13501 (19)0.37696 (10)0.0327 (3)
C10.65020 (13)0.25241 (19)0.50094 (11)0.0300 (3)
C20.76164 (15)0.4276 (2)0.50031 (14)0.0370 (3)
C30.77563 (15)0.6237 (2)0.60348 (16)0.0387 (3)
C40.89354 (17)0.7892 (3)0.60401 (19)0.0457 (4)
H10.5216 (15)0.022 (3)0.3760 (14)0.042 (4)*
H20.6058 (15)0.164 (2)0.2966 (16)0.037 (3)*
H30.7428 (17)0.475 (3)0.4012 (17)0.055 (4)*
H40.860 (2)0.344 (3)0.5341 (19)0.061 (5)*
H50.680 (2)0.701 (3)0.5663 (18)0.054 (4)*
H60.7966 (16)0.564 (2)0.7050 (18)0.050 (4)*
H70.8744 (19)0.845 (3)0.506 (2)0.063 (5)*
H80.898 (2)0.914 (3)0.664 (2)0.070 (5)*
H90.9914 (18)0.716 (3)0.6376 (16)0.049 (4)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O20.0579 (6)0.0422 (5)0.0254 (4)0.0114 (4)0.0263 (4)0.0053 (3)
N10.0456 (6)0.0368 (6)0.0222 (5)0.0047 (5)0.0202 (4)0.0012 (4)
C10.0398 (6)0.0317 (6)0.0240 (5)0.0024 (5)0.0183 (5)0.0006 (4)
C20.0475 (7)0.0403 (7)0.0297 (6)0.0074 (6)0.0218 (5)0.0019 (5)
C30.0383 (7)0.0353 (7)0.0453 (8)0.0003 (5)0.0190 (6)0.0028 (5)
C40.0435 (8)0.0382 (8)0.0549 (9)0.0031 (6)0.0179 (7)0.0013 (7)
Geometric parameters (Å, º) top
O2—C11.2395 (13)C2—H41.022 (18)
N1—C11.3257 (15)C3—C41.515 (2)
N1—H10.919 (16)C3—H50.985 (18)
N1—H20.887 (15)C3—H60.993 (16)
C1—C21.5091 (17)C4—H70.954 (18)
C2—C31.5057 (18)C4—H80.93 (2)
C2—H30.950 (16)C4—H90.990 (16)
C1—N1—H1118.8 (8)C2—C3—C4112.36 (11)
C1—N1—H2120.7 (9)C2—C3—H5106.1 (9)
H1—N1—H2120.5 (13)C4—C3—H5109.0 (9)
O2—C1—N1121.64 (11)C2—C3—H6108.5 (9)
O2—C1—C2121.28 (10)C4—C3—H6110.7 (9)
N1—C1—C2117.05 (10)H5—C3—H6110.0 (13)
C3—C2—C1114.40 (10)C3—C4—H7110.9 (11)
C3—C2—H3112.4 (10)C3—C4—H8111.5 (11)
C1—C2—H3109.9 (10)H7—C4—H8107.2 (16)
C3—C2—H4108.6 (10)C3—C4—H9111.3 (9)
C1—C2—H4105.5 (10)H7—C4—H9106.4 (14)
H3—C2—H4105.5 (13)H8—C4—H9109.4 (14)
O2—C1—C2—C330.35 (18)C1—C2—C3—C4177.41 (12)
N1—C1—C2—C3151.62 (12)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O2i0.919 (16)2.030 (16)2.9470 (15)175.9 (13)
N1—H2···O2ii0.887 (15)1.976 (15)2.8496 (14)167.9 (13)
Symmetry codes: (i) x+1, y, z+1; (ii) x, y+1/2, z1/2.
 

Acknowledgements

This research was supported by the EPSRC in funding a studentship for TCL. The authors acknowledge the Research Councils UK Basic Technology Programme for supporting `Control and Prediction of the Organic Solid State'. For more information on this work, please visit https://www.cposs.org.uk.

References

First citationAllen, F. H., Kennard, O. & Watson, D. G. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–18.  CrossRef Google Scholar
First citationBruker (2000). SMART, SAINT and SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationBruno, I. J., Cole, J. C., Edgington, P. R., Kessler, M. K., Macrae, C. F., McCabe, P., Pearson, J. & Taylor, R. (2002). Acta Cryst. B58, 389–397.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationHerskovits, T. T. & Bowen, J. J. (1974). Biochemistry, 13, 5474–5483.  CrossRef CAS PubMed Web of Science Google Scholar
First citationLea, M. A., Xiao, Q., Sadhukhan, A., Sharma, S. & Newmark, H. L. (1993). Anticancer Res. 13, 145–150.  CAS PubMed Web of Science Google Scholar
First citationMatthews, F. W., Warren, G. G. & Michell, J. H. (1950). Anal. Chem. 22, 514–519.  CrossRef CAS Web of Science Google Scholar
First citationRocchi, P., Ferreri, A. M., Magrini, E. & Perocco, P. (1998). Anticancer Res. 18, 1099–1103.  Web of Science CAS PubMed Google Scholar
First citationSheldrick, G. M. (1990). Acta Cryst. A46, 467–473.  CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (1997). SHELXL97. University of Göttingen, Germany.  Google Scholar
First citationTurner, J. D. & Lingafelter, E. C. (1955). Acta Cryst. 8, 549–550.  CSD CrossRef CAS IUCr Journals Web of Science Google Scholar

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