N-(2-Aza­niumyleth­yl)carbamate monohydrate

Shao, B.; Wang, H.-B.

doi:10.1107/S1600536811044850

organic compounds

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Volume 67| Part 12| December 2011| Page o3201

https://doi.org/10.1107/S1600536811044850

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N-(2-Azaniumylethyl)carbamate monohydrate

Bo Shao ^a and Hai-Bin Wang ^b ^*

^aCollege of Biology and Environmental Engineering, Zhejiang Shuren University, Hangzhou 310015, People's Republic of China, and ^bCollege of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China
^*Correspondence e-mail: zgdwhb@sina.com

(Received 29 July 2011; accepted 26 October 2011; online 5 November 2011)

In the crystal structure of the title compound, C₃H₈N₂O₂·H₂O, the organic molecule exists as zwitterion with the carboxyl group deprotonated and the amino group protonated. In the crystal, the components are linked by O—H⋯O and N—H⋯O hydrogen bonds.

Related literature

CO₂ readily reacts with amines to yied carbamates, see: Brown & Gray (1982 ); Dell'Amico et al. (2003); Jing et al. (2007 ). For N-(2-ammonioethyl)carbamate (AECM), a reactive product of ethylenediamine with CO₂, see: Garbauskas et al. (1983 ); Antsyshkina et al. (2007 ). For standard bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₃H₈N₂O₂·H₂O
M_r = 122.13
Monoclinic, P 2₁ /c
a = 8.0301 (6) Å
b = 8.7842 (7) Å
c = 8.1748 (6) Å
β = 98.889 (1)°
V = 569.71 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 293 K
0.35 × 0.34 × 0.30 mm

Data collection

Bruker APEX area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.945, T_max = 0.966
2877 measured reflections
1002 independent reflections
960 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.093
S = 1.04
1002 reflections
82 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯O1	0.80 (3)	1.92 (3)	2.708 (2)	170 (3)
O3—H3B⋯O2ⁱ	0.86 (3)	1.92 (3)	2.773 (2)	171 (3)
N1—H1C⋯O3ⁱⁱ	0.89	1.89	2.767 (2)	167
N1—H1D⋯O2ⁱⁱⁱ	0.89	1.91	2.775 (2)	163
N1—H1E⋯O1^iv	0.89	1.95	2.798 (2)	158
N2—H2⋯O2^v	0.86	2.43	3.278 (2)	167
C2—H2A⋯O1^vi	0.97	2.56	3.499 (2)	163
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) x, y, z-1; (iii) -x+2, -y+1, -z; (iv) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (v) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (vi) -x+1, -y+1, -z.

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536811044850/nc2244sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811044850/nc2244Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811044850/nc2244Isup3.cml

checkCIF report

Comment top

It has been known for decades that CO₂ readily reacts with amines to yied carbamates (Brown & Gray 1982; Dell'Amico et al. 2003; Jing et al. 2007). N-(2-ammonioethyl)carbamate (AECM), a reactive product of ethylenediamine with CO₂, was reported previously (Garbauskas et al. 1983; Antsyshkina et al. 2007). Recently, AECM hydrate, (I) (Scheme 1, Table 1), is prepared from ethylenediamine as starting material in our lab, and its structure is studied hereafter.

In (I), AECM molecule exists as zwitterion, the molecule is linked with the water molecule by an O3—H3A^···O1 hydrogen bond (Fig. 1, Table 2). The N1 atom is protonated, showing as the center of positive charge. The negative charge is concentrated on the O2 atom of the COO^_ fragment and is somewhat delocalized: the C3—O1 and C3—N2 bonds are slightly elongated, and the N2—C2 bond is shortened compared to standard values of 1.21, 1.334 and 1.454 Å, respectively (Allen et al. 1987). The torsion angle of N1—C1—C2—N2 [46.21 (18)%] is much smaller than that observed in the one of Garbauskas' polymorphs (175.6%), and is smaller than those observed in the second polymorph (66.6% in Antsyshkina's case, 65.5% in Garbauskas' case).

There are many hydrogen bonds in the crystal (Fig. 1, Table 2), playing important role in restraining the AECM comformation, and in building the crystal.

Related literature top

CO₂ readily reacts with amines to yied carbamates, see: Brown & Gray (1982); Dell'Amico et al. (2003); Jing et al. (2007). For N-(2-ammonioethyl)carbamate (AECM), a reactive product of ethylenediamine with CO₂, see: Garbauskas et al. (1983); Antsyshkina et al. (2007). For standard bond lengths, see: Allen et al. (1987).

Experimental top

Ethylenediamine (10.1 ml) was dissolved in xylenol (25.2 ml), forming clear solution with stirring, afterwards, the resulting solution was exposed in the air for two month at room temperature. With the reaction deepened, the system separated into two layers gradually. Upper layer was yellowish and pasty, and lower layer was colorless and clear. Crystals of (I) (6.9 g) were at the bottom of the lower lay. Analysis: Cald. for (I) (%): C 29.50, H 8.25, N 22.94; found: C 29.45, H 8.31, N 22.90. IR Spectrum (KBr, cm^-1): 3289(s), 2964(m), 2214(w), 1673(m), 1601(s), 1492(s), 1381(s), 1332(s), 1210(w), 1146(m), 1050(w), 1029(w), 1010(w), 887(w), 861(w), 821(m), 725(m), 646(w), 555(m). ¹H NMR (500 MHz, D2O) δ/p.p.m.: 3.20 (t, 2 H, J = 5.95), 2.97 (t, 2H, J = 5.95).

Structure description top

There are many hydrogen bonds in the crystal (Fig. 1, Table 2), playing important role in restraining the AECM comformation, and in building the crystal.

CO₂ readily reacts with amines to yied carbamates, see: Brown & Gray (1982); Dell'Amico et al. (2003); Jing et al. (2007). For N-(2-ammonioethyl)carbamate (AECM), a reactive product of ethylenediamine with CO₂, see: Garbauskas et al. (1983); Antsyshkina et al. (2007). For standard bond lengths, see: Allen et al. (1987).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Crystal structure of (I) with labeling and displacemant ellipsoids drawn at the 40% probability level. Intermolecular hydrogen bonding is shown as a dashed line.
	Fig. 2. The crystal packing of (I) viewed down the b axis. Hydrogen bonds are drawn as dashed lines.

N-(2-Azaniumylethyl)carbamate monohydrate top

Crystal data top

C₃H₈N₂O₂·H₂O	F(000) = 264.0
M_r = 122.13	D_x = 1.424 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 358 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.0301 (6) Å	Cell parameters from 1358 reflections
b = 8.7842 (7) Å	θ = 2.4–18.3°
c = 8.1748 (6) Å	µ = 0.12 mm⁻¹
β = 98.889 (1)°	T = 293 K
V = 569.71 (7) Å³	Block, colorless
Z = 4	0.35 × 0.34 × 0.30 mm

Data collection top

Bruker APEX area-detector diffractometer	1002 independent reflections
Radiation source: fine-focus sealed tube	960 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
φ and ω scan	θ_max = 25.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −9→9
T_min = 0.945, T_max = 0.966	k = −10→10
2877 measured reflections	l = −9→6

Refinement top

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0545P)² + 0.1863P] where P = (F_o² + 2F_c²)/3
1002 reflections	(Δ/σ)_max < 0.001
82 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₃H₈N₂O₂·H₂O	V = 569.71 (7) Å³
M_r = 122.13	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.0301 (6) Å	µ = 0.12 mm⁻¹
b = 8.7842 (7) Å	T = 293 K
c = 8.1748 (6) Å	0.35 × 0.34 × 0.30 mm
β = 98.889 (1)°

Data collection top

Bruker APEX area-detector diffractometer	1002 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	960 reflections with I > 2σ(I)
T_min = 0.945, T_max = 0.966	R_int = 0.016
2877 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.21 e Å⁻³
1002 reflections	Δρ_min = −0.27 e Å⁻³
82 parameters

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

	x	y	z	U_iso*/U_eq
O3	0.79493 (17)	0.47441 (13)	0.42240 (14)	0.0480 (4)
H3A	0.788 (2)	0.472 (2)	0.326 (3)	0.050 (5)*
H3B	0.844 (3)	0.391 (3)	0.466 (3)	0.069 (6)*
O2	0.91742 (12)	0.29983 (10)	0.06003 (11)	0.0324 (3)
O1	0.75733 (13)	0.50450 (10)	0.08899 (11)	0.0325 (3)
N1	0.82463 (13)	0.69023 (12)	−0.32825 (13)	0.0270 (3)
H1D	0.9110	0.6736	−0.2480	0.041*
H1E	0.8288	0.7855	−0.3644	0.041*
H1C	0.8303	0.6260	−0.4114	0.041*
N2	0.76650 (14)	0.40847 (12)	−0.16430 (13)	0.0265 (3)
H2	0.8216	0.3547	−0.2257	0.032*
C3	0.81591 (15)	0.40494 (13)	0.00256 (15)	0.0235 (3)
C2	0.62537 (16)	0.49851 (15)	−0.24347 (16)	0.0280 (3)
H2A	0.5340	0.4898	−0.1790	0.034*
H2B	0.5862	0.4560	−0.3521	0.034*
C1	0.66425 (16)	0.66607 (15)	−0.26316 (16)	0.0288 (3)
H1A	0.5729	0.7126	−0.3380	0.035*
H1B	0.6709	0.7161	−0.1566	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O3	0.0844 (9)	0.0333 (6)	0.0250 (6)	0.0148 (6)	0.0046 (6)	−0.0027 (5)
O2	0.0397 (5)	0.0250 (5)	0.0294 (5)	0.0052 (4)	−0.0050 (4)	0.0000 (4)
O1	0.0459 (6)	0.0274 (5)	0.0252 (5)	0.0038 (4)	0.0084 (4)	−0.0035 (4)
N1	0.0343 (6)	0.0222 (5)	0.0239 (5)	−0.0015 (4)	0.0022 (4)	0.0029 (4)
N2	0.0349 (6)	0.0236 (6)	0.0213 (6)	0.0056 (4)	0.0050 (4)	0.0001 (4)
C3	0.0279 (6)	0.0183 (6)	0.0243 (6)	−0.0041 (5)	0.0044 (5)	0.0003 (5)
C2	0.0273 (6)	0.0297 (7)	0.0263 (7)	−0.0017 (5)	0.0018 (5)	0.0038 (5)
C1	0.0316 (7)	0.0263 (7)	0.0283 (7)	0.0062 (5)	0.0036 (5)	0.0023 (5)

Geometric parameters (Å, º) top

O3—H3A	0.78 (2)	N2—C3	1.3608 (16)
O3—H3B	0.88 (3)	N2—C2	1.4499 (16)
O2—C3	1.2725 (15)	N2—H2	0.8600
O1—C3	1.2603 (15)	C2—C1	1.5184 (18)
N1—C1	1.4828 (16)	C2—H2A	0.9700
N1—H1D	0.8900	C2—H2B	0.9700
N1—H1E	0.8900	C1—H1A	0.9700
N1—H1C	0.8900	C1—H1B	0.9700

H3A—O3—H3B	110 (2)	N2—C2—C1	114.63 (10)
C1—N1—H1D	109.5	N2—C2—H2A	108.6
C1—N1—H1E	109.5	C1—C2—H2A	108.6
H1D—N1—H1E	109.5	N2—C2—H2B	108.6
C1—N1—H1C	109.5	C1—C2—H2B	108.6
H1D—N1—H1C	109.5	H2A—C2—H2B	107.6
H1E—N1—H1C	109.5	N1—C1—C2	112.39 (10)
C3—N2—C2	123.13 (10)	N1—C1—H1A	109.1
C3—N2—H2	118.4	C2—C1—H1A	109.1
C2—N2—H2	118.4	N1—C1—H1B	109.1
O1—C3—O2	124.74 (11)	C2—C1—H1B	109.1
O1—C3—N2	118.03 (11)	H1A—C1—H1B	107.9
O2—C3—N2	117.23 (11)

C2—N2—C3—O1	−13.44 (17)	C3—N2—C2—C1	79.98 (15)
C2—N2—C3—O2	165.99 (11)	N2—C2—C1—N1	46.09 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O1	0.80 (3)	1.92 (3)	2.708 (2)	170 (3)
O3—H3B···O2ⁱ	0.86 (3)	1.92 (3)	2.773 (2)	171 (3)
N1—H1C···O3ⁱⁱ	0.89	1.89	2.767 (2)	167
N1—H1D···O2ⁱⁱⁱ	0.89	1.91	2.775 (2)	163
N1—H1E···O1^iv	0.89	1.95	2.798 (2)	158
N2—H2···O2^v	0.86	2.43	3.278 (2)	167
C2—H2A···O1^vi	0.97	2.56	3.499 (2)	163

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

Experimental details

Crystal data
Chemical formula	C₃H₈N₂O₂·H₂O
M_r	122.13
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.0301 (6), 8.7842 (7), 8.1748 (6)
β (°)	98.889 (1)
V (Å³)	569.71 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.35 × 0.34 × 0.30

Data collection
Diffractometer	Bruker APEX area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.945, 0.966
No. of measured, independent and observed [I > 2σ(I)] reflections	2877, 1002, 960
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.093, 1.04
No. of reflections	1002
No. of parameters	82
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.27

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O1	0.80 (3)	1.92 (3)	2.708 (2)	170 (3)
O3—H3B···O2ⁱ	0.86 (3)	1.92 (3)	2.773 (2)	171 (3)
N1—H1C···O3ⁱⁱ	0.89	1.89	2.767 (2)	167.1
N1—H1D···O2ⁱⁱⁱ	0.89	1.91	2.775 (2)	162.7
N1—H1E···O1^iv	0.89	1.95	2.798 (2)	158.2
N2—H2···O2^v	0.86	2.43	3.278 (2)	167.2
C2—H2A···O1^vi	0.97	2.56	3.499 (2)	163.1

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

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CSD CrossRef Web of Science Google Scholar
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Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dell'Amico, D. B., Calderazzo, F., Labella, L., Marchetti, F. & Pampaloni, G. (2003). Chem. Rev. 103, 3857–3898. Web of Science PubMed Google Scholar
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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 12| December 2011| Page o3201

https://doi.org/10.1107/S1600536811044850

Open

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