2-[(tert-But­oxy­carbonyl­amino)­oxy]acetic acid

Abstract

The title compound, C₇H₁₃NO₅, was prepared by the condensation of O-(carb­oxy­meth­yl)hydroxyl­amine and (Boc)₂O (Boc = but­oxy­carbon­yl).In the crystal, mol­ecules are linked by weak inter­molecular N—H⋯O hydrogen bonds.

Related literature

For applications and structural studies of N-Boc-O-(carb­oxy­meth­yl)hydroxyl­amine, see: Vandersse et al. (2003 ▶); Deroo et al., 2003 ▶.

Experimental

Crystal data

• C₇H₁₃NO₅

• M _r = 191.18

• Monoclinic,

• a = 5.9973 (5) Å

• b = 10.1292 (13) Å

• c = 15.6445 (17) Å

• β = 90.570 (1)°

• V = 950.32 (18) ų

• Z = 4

• Mo Kα radiation

• μ = 0.11 mm⁻¹

• T = 298 K

• 0.43 × 0.33 × 0.31 mm

Data collection

• Siemens SMART CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.953, T _max = 0.966

• 4733 measured reflections

• 1670 independent reflections

• 1073 reflections with I > 2σ(I)

• R _int = 0.062

Refinement

• R[F ² > 2σ(F ²)] = 0.068

• wR(F ²) = 0.210

• S = 1.00

• 1670 reflections

• 126 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.48 e Å⁻³

• Δρ_min = −0.44 e Å⁻³

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811031990/lx2198Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2i	0.92 (5)	2.50 (5)	3.413 (4)	174 (4)

Symmetry code: (i) .

supplementary crystallographic information

Comment

N–(tert–Butoxycarbonyl)–O– (carboxymethyl)hydroxylamine is an important building block having a broad spectrum of applications in the biochemical fields (Vandersse et al., 2003; Deroo et al., 2003). As a contribution in this filed, we report here the crystal structure of the title compound.

The molecular structure of title compound is shown in Fig. 1. The crystal packing (Fig. 2) is stabilized by weak intermolecular N—H···O hydrogen bonds between the amine H atom and the O atom of the hydroxy group (Table, N1—H1···O2ⁱ).

Experimental

(Boc)₂O (21.8 g, 0.10 mol) was added to a stirred solution of O–(carboxymethyl)hydroxylamine (9.1 g, 0.10 mol) in dioxane. The mixture was stirred at 303 K for 2 h. Then mixture was concentrated and purified by crystallization from MeOH. Single crystals suitable for X–ray diffraction were prepared by slow evaporation of a solution of the title compound in MeOH at room temperature.

Refinement

All H atoms were placed geometrically and treated as riding on their parent atoms, with C—H = 0.93–0.96 Å, N—H = 0.86 Å and U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C) for methyl H atoms.

Figures

Fig. 1.

The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are presented as a small spheres of arbitrary radius.

Fig. 2.

A view of the N—H···O interactions (dotted lines) in the crystal structure of the title compound.

Crystal data

C7H13NO5	F(000) = 408
Mr = 191.18	Dx = 1.336 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1234 reflections
a = 5.9973 (5) Å	θ = 2.4–22.0°
b = 10.1292 (13) Å	µ = 0.11 mm−1
c = 15.6445 (17) Å	T = 298 K
β = 90.570 (1)°	Block, colorless
V = 950.32 (18) Å3	0.43 × 0.33 × 0.31 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	1670 independent reflections
Radiation source: fine-focus sealed tube	1073 reflections with I > 2σ(I)
graphite	Rint = 0.062
φ and ω scans	θmax = 25.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→7
Tmin = 0.953, Tmax = 0.966	k = −9→12
4733 measured reflections	l = −18→18

Refinement

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)] = 0.068	Hydrogen site location: difference Fourier map
wR(F2) = 0.210	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ2(Fo2) + (0.112P)2 + 0.8197P] where P = (Fo2 + 2Fc2)/3
1670 reflections	(Δ/σ)max < 0.001
126 parameters	Δρmax = 0.48 e Å−3
0 restraints	Δρmin = −0.44 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
N1	0.6083 (5)	0.1502 (3)	0.0709 (2)	0.0435 (8)
O1	0.8143 (4)	0.3814 (3)	−0.00926 (18)	0.0496 (8)
O2	1.1753 (4)	0.3574 (3)	0.02405 (19)	0.0520 (8)
H2	1.2247	0.3245	0.0682	0.078*
O3	0.7431 (4)	0.1152 (2)	0.00116 (15)	0.0437 (7)
O4	0.3937 (4)	0.0832 (3)	0.17426 (16)	0.0444 (7)
O5	0.6762 (5)	−0.0506 (3)	0.13138 (17)	0.0521 (8)
C1	0.9751 (6)	0.3117 (4)	0.0088 (2)	0.0370 (9)
C2	0.9609 (6)	0.1647 (4)	0.0151 (2)	0.0416 (9)
H2A	1.0601	0.1258	−0.0265	0.050*
H2B	1.0122	0.1375	0.0715	0.050*
C3	0.5677 (6)	0.0477 (4)	0.1261 (2)	0.0374 (9)
C4	0.3312 (6)	0.0044 (4)	0.2499 (2)	0.0376 (9)
C5	0.1486 (8)	0.0912 (5)	0.2878 (3)	0.0669 (13)
H5A	0.2111	0.1745	0.3047	0.100*
H5B	0.0867	0.0481	0.3368	0.100*
H5C	0.0334	0.1053	0.2458	0.100*
C6	0.2369 (8)	−0.1253 (5)	0.2217 (3)	0.0641 (13)
H6A	0.1142	−0.1105	0.1830	0.096*
H6B	0.1858	−0.1734	0.2706	0.096*
H6C	0.3502	−0.1754	0.1934	0.096*
C7	0.5264 (7)	−0.0085 (5)	0.3105 (3)	0.0609 (13)
H7A	0.6414	−0.0598	0.2841	0.091*
H7B	0.4792	−0.0515	0.3619	0.091*
H7C	0.5832	0.0777	0.3242	0.091*
H1	0.488 (8)	0.201 (5)	0.055 (3)	0.073 (15)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
N1	0.0441 (19)	0.0384 (18)	0.0481 (18)	0.0007 (15)	0.0160 (15)	0.0042 (15)
O1	0.0395 (15)	0.0400 (16)	0.0693 (18)	−0.0018 (12)	−0.0014 (13)	0.0117 (14)
O2	0.0406 (16)	0.0477 (17)	0.0673 (19)	−0.0051 (13)	−0.0115 (13)	0.0054 (14)
O3	0.0464 (15)	0.0420 (16)	0.0431 (15)	−0.0094 (12)	0.0127 (12)	−0.0056 (12)
O4	0.0411 (15)	0.0457 (16)	0.0467 (15)	0.0067 (12)	0.0124 (12)	0.0116 (12)
O5	0.0501 (16)	0.0496 (17)	0.0569 (17)	0.0137 (14)	0.0129 (13)	0.0108 (14)
C1	0.039 (2)	0.039 (2)	0.0332 (18)	−0.0018 (17)	0.0045 (15)	0.0012 (15)
C2	0.039 (2)	0.037 (2)	0.049 (2)	−0.0025 (16)	0.0072 (16)	0.0003 (17)
C3	0.0346 (19)	0.038 (2)	0.040 (2)	−0.0018 (17)	0.0060 (16)	0.0007 (17)
C4	0.0320 (19)	0.046 (2)	0.0347 (19)	−0.0039 (16)	0.0068 (15)	0.0084 (15)
C5	0.059 (3)	0.082 (4)	0.059 (3)	0.010 (3)	0.019 (2)	0.008 (2)
C6	0.068 (3)	0.059 (3)	0.065 (3)	−0.017 (2)	0.006 (2)	0.009 (2)
C7	0.047 (2)	0.082 (4)	0.053 (3)	−0.007 (2)	−0.002 (2)	0.015 (2)

Geometric parameters (Å, °)

N1—C3	1.374 (5)	C4—C6	1.496 (6)
N1—O3	1.410 (4)	C4—C7	1.505 (6)
N1—H1	0.92 (5)	C4—C5	1.529 (6)
O1—C1	1.226 (4)	C5—H5A	0.9600
O2—C1	1.306 (4)	C5—H5B	0.9600
O2—H2	0.8200	C5—H5C	0.9600
O3—C2	1.414 (4)	C6—H6A	0.9600
O4—C3	1.342 (4)	C6—H6B	0.9600
O4—C4	1.479 (4)	C6—H6C	0.9600
O5—C3	1.192 (4)	C7—H7A	0.9600
C1—C2	1.496 (5)	C7—H7B	0.9600
C2—H2A	0.9700	C7—H7C	0.9600
C2—H2B	0.9700
C3—N1—O3	113.8 (3)	O4—C4—C5	100.9 (3)
C3—N1—H1	117 (3)	C6—C4—C5	110.4 (3)
O3—N1—H1	113 (3)	C7—C4—C5	111.1 (4)
C1—O2—H2	109.5	C4—C5—H5A	109.5
N1—O3—C2	109.1 (3)	C4—C5—H5B	109.5
C3—O4—C4	120.6 (3)	H5A—C5—H5B	109.5
O1—C1—O2	123.9 (4)	C4—C5—H5C	109.5
O1—C1—C2	122.9 (3)	H5A—C5—H5C	109.5
O2—C1—C2	113.2 (3)	H5B—C5—H5C	109.5
O3—C2—C1	113.3 (3)	C4—C6—H6A	109.5
O3—C2—H2A	108.9	C4—C6—H6B	109.5
C1—C2—H2A	108.9	H6A—C6—H6B	109.5
O3—C2—H2B	108.9	C4—C6—H6C	109.5
C1—C2—H2B	108.9	H6A—C6—H6C	109.5
H2A—C2—H2B	107.7	H6B—C6—H6C	109.5
O5—C3—O4	127.7 (3)	C4—C7—H7A	109.5
O5—C3—N1	125.1 (3)	C4—C7—H7B	109.5
O4—C3—N1	107.1 (3)	H7A—C7—H7B	109.5
O4—C4—C6	109.7 (3)	C4—C7—H7C	109.5
O4—C4—C7	110.4 (3)	H7A—C7—H7C	109.5
C6—C4—C7	113.5 (4)	H7B—C7—H7C	109.5
C3—N1—O3—C2	−103.9 (3)	O3—N1—C3—O5	19.7 (5)
N1—O3—C2—C1	−70.1 (4)	O3—N1—C3—O4	−163.5 (3)
O1—C1—C2—O3	−2.1 (5)	C3—O4—C4—C6	−69.9 (4)
O2—C1—C2—O3	178.3 (3)	C3—O4—C4—C7	56.0 (4)
C4—O4—C3—O5	7.1 (6)	C3—O4—C4—C5	173.6 (3)
C4—O4—C3—N1	−169.7 (3)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2i	0.92 (5)	2.50 (5)	3.413 (4)	174 (4)

Symmetry codes: (i) x−1, y, z.