(S)-2-Oxotetra­hydro­furan-3-aminium bromide

Sandifer, J.D.; Fronczek, F.R.; Watkins, S.F.

doi:10.1107/S1600536812032552

organic compounds

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ISSN: 2056-9890

Volume 68| Part 8| August 2012| Page o2539

https://doi.org/10.1107/S1600536812032552

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(S)-2-Oxotetrahydrofuran-3-aminium bromide¹

Jace D. Sandifer,^a Frank R. Fronczek ^a ^* and Steven F. Watkins ^a

^aDepartment of Chemistry, Louisiana State University, Baton Rouge, LA 70803-1804, USA
^*Correspondence e-mail: ffroncz@lsu.edu

(Received 11 July 2012; accepted 17 July 2012; online 25 July 2012)

In the title HBr salt of (S)-homoserine lactone, C₄H₈NO₂⁺·Br⁻, the five-membered ring has an envelope conformation, with the –CH₂– C atom adjacent to the N-substituted C atom at the flap position. The four-atom mean plane (r.m.s. deviation = 0.005 Å) of the envelope forms a dihedral angle of 32.12 (9)° with the three-atom flap plane. The distorted square-pyramidal coordination about the anion involves five surrounding cations, with the square base defined by three N—H⋯Br hydrogen bonds [Br⋯N = 3.3046 (10), 3.3407 (12) and 3.3644 (13) Å] and near-contact with an H atom attached to C [Br⋯C = 3.739 (1) Å]. Another Br⋯C contact of 3.427 (1) Å defines the apex. There is also an N—H⋯O hydrogen bond present linking the cations.

Related literature

For related crystal structures, see: Bocelli & Grenier-Loustalot (1981 ); Papaioannou et al. (1990 ). For the synthesis of the title compound, see: Armstrong (1948 ); Cowell (1996 ). For the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

C₄H₈NO₂⁺·Br⁻
M_r = 182.02
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.1425 (1) Å
b = 9.4196 (2) Å
c = 11.0394 (3) Å
V = 638.74 (2) Å³
Z = 4
Mo Kα radiation
μ = 6.35 mm⁻¹
T = 90 K
0.25 × 0.25 × 0.22 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997 ) T_min = 0.300, T_max = 0.336
4072 measured reflections
4072 independent reflections
3915 reflections with I > 2σ(I)
R_int = 0

Refinement

R[F² > 2σ(F²)] = 0.022
wR(F²) = 0.049
S = 1.07
4072 reflections
76 parameters
H-atom parameters constrained
Δρ_max = 0.68 e Å⁻³
Δρ_min = −0.74 e Å⁻³
Absolute structure: Flack (1983 ) and Hooft et al. (2008 ), with 1724 Friedel pairs
Flack parameter: 0.030 (7)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Br1ⁱ	0.91	2.47	3.3407 (12)	161
N1—H1B⋯Br1ⁱⁱ	0.91	2.41	3.3046 (10)	168
N1—H1C⋯Br1ⁱⁱⁱ	0.91	2.51	3.3644 (13)	157
N1—H1C⋯O1ⁱⁱⁱ	0.91	2.5	3.0050 (14)	115
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y, z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, -y, z+{\script{1\over 2}}]$ .

Data collection: COLLECT (Nonius, 2000 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SIR2002 (Burla et al., 2003 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: IDEAL (Gould et al., 1988 ) and WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812032552/zq2176sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812032552/zq2176Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812032552/zq2176Isup3.cml

checkCIF report

Comment top

The structure of the racemate of title compound I was determined at 295 K by Bocelli & Grenier-Loustalot (1981; BAKHAW, Allen, 2002); the geometries of the cation in BAKHAW and I are similar, as characterized by least-squares fit of all non-hydrogen atoms in the cation (δ_r.m.s. = 0.025; Gould et al., 1988). In addition, the envelope flap angles are similar (31.0° versus 32.6°). The racemate at 295 K has a volume per formula unit of 162.3 Å³, whereas pure enantiomer I at 90 K has a volume per formula unit of 159.7 Å³, a decrease of about 1.6%.

The chloride analog of I (TADTAT; Papaioannou et al., 1990) crystallizes in the same space group as I and with similar lattice constants, but the geometries of the cation differ slightly (δ_r.m.s. = 0.094), and the envelope flap angles also differ: 17.58° versus 32.6°.

There are no intramolecular H-bonds in I. However, all three H-atoms of the ammonium group participate in intermolecular H-bonding to form a three-dimensional network. These H atoms bond to three different anions [N···Br = 3.3046 (10), 3.3407 (12) and 3.3644 (13) Å] and to an ether oxygen: N···O1 = 3.0050 (14) Å.

Related literature top

For related crystal structures, see: Bocelli & Grenier-Loustalot (1981); Papaioannou et al. (1990). For the synthesis of the title compound, see: Armstrong (1948); Cowell (1996). For the Cambridge Structural Database, see: Allen (2002).

Experimental top

The earliest preparation of racemic and enantiomerically pure homoserine lactones was reported by Armstrong (1948). Cowell recrystallized I from methanol and provided the crystal used for data collection (Cowell, 1996).

Structure description top

For related crystal structures, see: Bocelli & Grenier-Loustalot (1981); Papaioannou et al. (1990). For the synthesis of the title compound, see: Armstrong (1948); Cowell (1996). For the Cambridge Structural Database, see: Allen (2002).

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: IDEAL (Gould et al., 1988) and WinGX (Farrugia, 1999).

Figures top

Fig. 1. View of the title compound (50% probability displacement ellipsoids)

(S)-2-Oxotetrahydrofuran-3-aminium bromide top

Crystal data top

C₄H₈NO₂⁺·Br⁻	D_x = 1.893 Mg m⁻³
M_r = 182.02	Melting point: 514 K
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2320 reflections
a = 6.1425 (1) Å	θ = 2.6–41.2°
b = 9.4196 (2) Å	µ = 6.35 mm⁻¹
c = 11.0394 (3) Å	T = 90 K
V = 638.74 (2) Å³	Prism, colourless
Z = 4	0.25 × 0.25 × 0.22 mm
F(000) = 360

Data collection top

Nonius KappaCCD diffractometer	4072 independent reflections
Radiation source: sealed tube	3915 reflections with I > 2σ(I)
Horizonally mounted graphite crystal monochromator	R_int = 0
Detector resolution: 9 pixels mm^-1	θ_max = 40.8°, θ_min = 2.8°
CCD rotation images, thick slices scans	h = −11→11
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	k = −16→17
T_min = 0.300, T_max = 0.336	l = −20→20
4072 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.022	w = 1/[σ²(F_o²) + (0.0124P)² + 0.6239P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.049	(Δ/σ)_max = 0.001
S = 1.07	Δρ_max = 0.68 e Å⁻³
4072 reflections	Δρ_min = −0.74 e Å⁻³
76 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0198 (9)
0 constraints	Absolute structure: Flack (1983) and Hooft et al. (2008), with 1724 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.030 (7)
Secondary atom site location: difference Fourier map

Crystal data top

C₄H₈NO₂⁺·Br⁻	V = 638.74 (2) Å³
M_r = 182.02	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.1425 (1) Å	µ = 6.35 mm⁻¹
b = 9.4196 (2) Å	T = 90 K
c = 11.0394 (3) Å	0.25 × 0.25 × 0.22 mm

Data collection top

Nonius KappaCCD diffractometer	4072 independent reflections
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	3915 reflections with I > 2σ(I)
T_min = 0.300, T_max = 0.336	R_int = 0
4072 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.022	H-atom parameters constrained
wR(F²) = 0.049	Δρ_max = 0.68 e Å⁻³
S = 1.07	Δρ_min = −0.74 e Å⁻³
4072 reflections	Absolute structure: Flack (1983) and Hooft et al. (2008), with 1724 Friedel pairs
76 parameters	Absolute structure parameter: 0.030 (7)
0 restraints

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.

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

	x	y	z	U_iso*/U_eq
Br1	0.398524 (19)	−0.035758 (13)	−0.012904 (11)	0.00918 (3)
C1	0.73144 (19)	−0.01395 (12)	0.23546 (12)	0.00862 (18)
C2	0.64286 (18)	0.13091 (12)	0.27008 (11)	0.00776 (17)
H2	0.505	0.1494	0.2246	0.009*
C3	0.8183 (2)	0.23236 (13)	0.22670 (12)	0.01110 (19)
H3A	0.9319	0.2468	0.2891	0.013*
H3B	0.7564	0.3254	0.2032	0.013*
C4	0.9071 (3)	0.15234 (14)	0.11731 (11)	0.01289 (19)
H4A	0.8245	0.1772	0.0433	0.015*
H4B	1.0626	0.1752	0.1042	0.015*
N1	0.5994 (2)	0.13823 (11)	0.40235 (9)	0.00966 (14)
H1A	0.4755	0.0892	0.4197	0.014*
H1B	0.5828	0.2305	0.4249	0.014*
H1C	0.7131	0.0994	0.4435	0.014*
O1	0.87958 (17)	0.00107 (10)	0.14696 (9)	0.01107 (15)
O2	0.68198 (18)	−0.12734 (10)	0.27816 (10)	0.01255 (16)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.00741 (4)	0.00830 (4)	0.01182 (4)	−0.00006 (4)	−0.00068 (3)	0.00165 (3)
C1	0.0080 (4)	0.0070 (5)	0.0109 (4)	−0.0001 (3)	−0.0007 (3)	−0.0011 (3)
C2	0.0082 (4)	0.0052 (4)	0.0099 (4)	0.0006 (3)	0.0002 (3)	−0.0001 (3)
C3	0.0133 (5)	0.0066 (4)	0.0134 (5)	−0.0012 (4)	0.0025 (4)	0.0011 (3)
C4	0.0159 (5)	0.0101 (4)	0.0126 (4)	−0.0012 (5)	0.0040 (5)	0.0010 (3)
N1	0.0093 (3)	0.0084 (3)	0.0112 (4)	−0.0007 (4)	0.0026 (4)	−0.0013 (3)
O1	0.0120 (4)	0.0086 (3)	0.0126 (3)	0.0003 (3)	0.0033 (3)	−0.0017 (3)
O2	0.0132 (4)	0.0063 (3)	0.0181 (4)	−0.0017 (3)	−0.0006 (3)	0.0009 (3)

Geometric parameters (Å, º) top

C1—O2	1.2063 (15)	C3—H3B	0.99
C1—O1	1.3427 (16)	C4—O1	1.4717 (16)
C1—C2	1.5179 (17)	C4—H4A	0.99
C2—N1	1.4861 (16)	C4—H4B	0.99
C2—C3	1.5178 (17)	N1—H1A	0.91
C2—H2	1	N1—H1B	0.91
C3—C4	1.5244 (18)	N1—H1C	0.91
C3—H3A	0.99

O2—C1—O1	123.25 (12)	C4—C3—H3B	111.6
O2—C1—C2	127.40 (12)	H3A—C3—H3B	109.4
O1—C1—C2	109.35 (10)	O1—C4—C3	105.16 (10)
O2—C1—Br1	96.27 (8)	O1—C4—H4A	110.7
O1—C1—Br1	80.12 (7)	C3—C4—H4A	110.7
C2—C1—Br1	92.37 (7)	O1—C4—H4B	110.7
N1—C2—C1	110.70 (10)	C3—C4—H4B	110.7
N1—C2—C3	114.11 (10)	H4A—C4—H4B	108.8
C1—C2—C3	103.42 (10)	C2—N1—H1A	109.5
N1—C2—H2	109.5	C2—N1—H1B	109.5
C1—C2—H2	109.5	H1A—N1—H1B	109.5
C3—C2—H2	109.5	C2—N1—H1C	109.5
C2—C3—C4	101.11 (10)	H1A—N1—H1C	109.5
C2—C3—H3A	111.6	H1B—N1—H1C	109.5
C4—C3—H3A	111.6	C1—O1—C4	109.98 (10)
C2—C3—H3B	111.6

O2—C1—C2—N1	35.80 (17)	C1—C2—C3—C4	31.16 (13)
O1—C1—C2—N1	−144.09 (10)	C2—C3—C4—O1	−31.04 (14)
Br1—C1—C2—N1	135.54 (8)	O2—C1—O1—C4	−178.50 (13)
O2—C1—C2—C3	158.41 (13)	C2—C1—O1—C4	1.40 (14)
O1—C1—C2—C3	−21.48 (13)	Br1—C1—O1—C4	90.45 (9)
Br1—C1—C2—C3	−101.84 (8)	C3—C4—O1—C1	19.30 (15)
N1—C2—C3—C4	151.48 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Br1ⁱ	0.91	2.47	3.3407 (12)	161
N1—H1B···Br1ⁱⁱ	0.91	2.41	3.3046 (10)	168
N1—H1C···Br1ⁱⁱⁱ	0.91	2.51	3.3644 (13)	157
N1—H1C···O1ⁱⁱⁱ	0.91	2.5	3.0050 (14)	115

Symmetry codes: (i) −x+1/2, −y, z+1/2; (ii) −x+1, y+1/2, −z+1/2; (iii) −x+3/2, −y, z+1/2.

Experimental details

Crystal data
Chemical formula	C₄H₈NO₂⁺·Br⁻
M_r	182.02
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	90
a, b, c (Å)	6.1425 (1), 9.4196 (2), 11.0394 (3)
V (Å³)	638.74 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	6.35
Crystal size (mm)	0.25 × 0.25 × 0.22

Data collection
Diffractometer	Nonius KappaCCD
Absorption correction	Multi-scan (SCALEPACK; Otwinowski & Minor, 1997)
T_min, T_max	0.300, 0.336
No. of measured, independent and observed [I > 2σ(I)] reflections	4072, 4072, 3915
R_int	0
(sin θ/λ)_max (Å⁻¹)	0.918

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.049, 1.07
No. of reflections	4072
No. of parameters	76
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.68, −0.74
Absolute structure	Flack (1983) and Hooft et al. (2008), with 1724 Friedel pairs
Absolute structure parameter	0.030 (7)

Computer programs: COLLECT (Nonius, 2000), SCALEPACK (Otwinowski & Minor, 1997), DENZO (Otwinowski & Minor, 1997) and SCALEPACK, SIR2002 (Burla et al., 2003), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), IDEAL (Gould et al., 1988) and WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Br1ⁱ	0.91	2.47	3.3407 (12)	161
N1—H1B···Br1ⁱⁱ	0.91	2.41	3.3046 (10)	168
N1—H1C···Br1ⁱⁱⁱ	0.91	2.51	3.3644 (13)	157.4
N1—H1C···O1ⁱⁱⁱ	0.91	2.5	3.0050 (14)	115.1

Symmetry codes: (i) −x+1/2, −y, z+1/2; (ii) −x+1, y+1/2, −z+1/2; (iii) −x+3/2, −y, z+1/2.

Footnotes

¹CAS 15295-77-9.

Acknowledgements

The purchase of the diffractometer was made possible by Grant No. LEQSF(1999–2000)-ESH-TR-13, administered by the Louisiana Board of Regents.

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