2-[(2-Hy­droxy­eth­yl)aza­nium­yl]ethanaminium oxalate monohydrate

Jin, Y.

doi:10.1107/S1600536811056157

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page o337

doi:10.1107/S1600536811056157

Open

access

2-[(2-Hydroxyethyl)azaniumyl]ethanaminium oxalate monohydrate

Yu Jin ^a ^*

^aOrdered Matter Science Research Center, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: jinyunihao@yahoo.cn

(Received 28 December 2011; accepted 29 December 2011; online 11 January 2012)

In the title hydrated molecular salt, C₄H₁₄N₂O²⁺·C₂O₄²⁻·H₂O, the oxalate dianion is almost planar (r.m.s. deviation = 0.020 Å). In the crystal, the components are linked by N—H⋯O(water), N—H⋯O(oxalate) O—H(ammonium)⋯O(oxalate), O—H(water)⋯O(oxalate) and O—H(water)⋯O(ammonium) hydrogen bonds, thereby forming a complex three-dimensional packing motif.

Related literature

For related structures, see: Sakai et al. (2003 ); Kolitsch (2004 ); Cotton et al. (1996 ); Barnes (2003 ).

Experimental

Crystal data

C₄H₁₄N₂O²⁺·C₂O₄²⁻·H₂O
M_r = 212.21
Monoclinic, P 2₁
a = 5.7311 (11) Å
b = 13.136 (3) Å
c = 6.7373 (13) Å
β = 102.52 (3)°
V = 495.16 (17) Å³
Z = 2
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 293 K
0.3 × 0.3 × 0.2 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.489, T_max = 1.000
5068 measured reflections
2261 independent reflections
1853 reflections with I > 2σ(I)
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.086
S = 0.97
2261 reflections
135 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1Wⁱ	0.89	1.96	2.823 (2)	164
N1—H1B⋯O3ⁱⁱ	0.89	2.12	2.8769 (19)	143
N1—H1B⋯O4ⁱⁱ	0.89	2.11	2.818 (2)	136
N1—H1F⋯O2	0.89	1.82	2.707 (2)	172
N2—H2A⋯O4ⁱⁱⁱ	0.90	1.80	2.688 (2)	170
N2—H2D⋯O5^iv	0.90	2.16	2.862 (2)	134
N2—H2D⋯O2^iv	0.90	2.00	2.773 (2)	143
O1—H1C⋯O3^v	0.82	1.94	2.736 (2)	163
O1W—H2W⋯O5^iv	0.84 (1)	1.91 (1)	2.753 (2)	178 (2)
O1W—H1W⋯O1^vi	0.84 (1)	2.27 (3)	2.968 (2)	141 (4)
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+1]$ ; (ii) x, y, z-1; (iii) x+1, y, z-1; (iv) x+1, y, z; (v) $[-x+2, y+{\script{1\over 2}}, -z+1]$ ; (vi) x-1, y, z.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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 I, global. DOI: 10.1107/S1600536811056157/hb6584sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811056157/hb6584Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811056157/hb6584Isup3.cml

checkCIF report

Comment top

Several crystal structures of oxalate have been reported previously (Sakai et al., 2003; Kolitsch, 2004; Cotton et al., 1996). As an extension of research, we report here the synthesis and the crystal structure of the title complex, (C₄H₁₄N₂O)²⁺.(C₂O₄)^2-.H₂O.

In the crystal synthesized by Barnes, amine salts with oxalic acid contain the monohydrogenoxalate ion (Barnes, 2003), while the crystal reported here, oxalic acid reacts with alcohol amine to give crystals of the fully deprotonated C₂O₄^2- salt as the monohydrate.

The (locally) centrosymmetric anion and one cation are shown in Fig. 1 with the hydrogen bonds listed in Table 1. The water molecules in the compound serve as a connection, i.e., two protonated cations are connected to a water molecule through N—H···O (water) and O—H (water)···O (ammonium) hydrogen-bonds and one anion is linked to the same water molecule via O—H (water)···O (oxalate) hydrogen bonding interactions, the components are further held by O—H (ammonium)···O (oxalate), O—H (water)···O (oxalate) and O—H (water)···O (ammonium) hydrogen-bonding interactions, and thus forms a three-dimensional structure. (Fig.2)

Related literature top

For related structures, see: Sakai et al. (2003); Kolitsch (2004); Cotton et al. (1996); Barnes (2003).

Experimental top

A mixture of C₄H₁₂N₂O (104.15 mg, 1.00 mmol), C₂H₂O₄ (90.04 mg, 1.00 mmol) and distilled water (5 ml) was stirred a few minutes at room temperature, giving a clear transparent solution. After evaporation for several days, colorless blocks of the title compound were obtained in about 82% yield and filtered and washed with distilled water.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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. Molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. Crystal structure of the title compound with view along the a axis. Intermolecular interactions are shown as dashed lines.

2-[(2-Hydroxyethyl)azaniumyl]ethanaminium oxalate monohydrate top

Crystal data top

C₄H₁₄N₂O²⁺·C₂O₄²⁻·H₂O	F(000) = 228
M_r = 212.21	D_x = 1.423 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 3450 reflections
a = 5.7311 (11) Å	θ = 6.2–55.3°
b = 13.136 (3) Å	µ = 0.13 mm⁻¹
c = 6.7373 (13) Å	T = 293 K
β = 102.52 (3)°	Block, colorless
V = 495.16 (17) Å³	0.3 × 0.3 × 0.2 mm
Z = 2

Data collection top

Rigaku Mercury CCD diffractometer	2261 independent reflections
Radiation source: fine-focus sealed tube	1853 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
ω scans	θ_max = 27.5°, θ_min = 3.1°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −7→7
T_min = 0.489, T_max = 1.000	k = −16→16
5068 measured reflections	l = −8→8

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.086	H atoms treated by a mixture of independent and constrained refinement
S = 0.97	w = 1/[σ²(F_o²) + (0.0314P)²] where P = (F_o² + 2F_c²)/3
2261 reflections	(Δ/σ)_max < 0.001
135 parameters	Δρ_max = 0.22 e Å⁻³
3 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₄H₁₄N₂O²⁺·C₂O₄²⁻·H₂O	V = 495.16 (17) Å³
M_r = 212.21	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 5.7311 (11) Å	µ = 0.13 mm⁻¹
b = 13.136 (3) Å	T = 293 K
c = 6.7373 (13) Å	0.3 × 0.3 × 0.2 mm
β = 102.52 (3)°

Data collection top

Rigaku Mercury CCD diffractometer	2261 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1853 reflections with I > 2σ(I)
T_min = 0.489, T_max = 1.000	R_int = 0.046
5068 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	3 restraints
wR(F²) = 0.086	H atoms treated by a mixture of independent and constrained refinement
S = 0.97	Δρ_max = 0.22 e Å⁻³
2261 reflections	Δρ_min = −0.25 e Å⁻³
135 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
C1	1.1138 (4)	0.63105 (16)	0.1821 (3)	0.0342 (5)
H1D	1.1520	0.5976	0.0648	0.041*
H1E	1.0764	0.7017	0.1467	0.041*
C2	0.9023 (4)	0.58091 (12)	0.2350 (3)	0.0290 (4)
H2B	0.8808	0.6071	0.3644	0.035*
H2C	0.7607	0.5980	0.1328	0.035*
C3	0.6935 (4)	0.41905 (13)	0.2318 (3)	0.0256 (4)
H3A	0.5915	0.4347	0.1007	0.031*
H3B	0.6171	0.4452	0.3365	0.031*
C4	0.7217 (4)	0.30554 (15)	0.2545 (3)	0.0284 (5)
H4A	0.8062	0.2791	0.1555	0.034*
H4B	0.8127	0.2888	0.3895	0.034*
C5	0.2891 (3)	0.33640 (13)	0.6829 (2)	0.0213 (4)
C6	0.1213 (3)	0.39951 (13)	0.7871 (3)	0.0234 (4)
H1W	0.472 (5)	0.541 (3)	0.636 (3)	0.117 (14)*
H2W	0.702 (3)	0.522 (2)	0.723 (3)	0.057 (9)*
N1	0.4808 (3)	0.26039 (11)	0.2219 (2)	0.0244 (4)
H1A	0.4931	0.1931	0.2351	0.037*
H1B	0.3992	0.2758	0.0975	0.037*
H1F	0.4048	0.2851	0.3134	0.037*
N2	0.9269 (3)	0.46896 (11)	0.2484 (2)	0.0210 (3)
H2A	0.9948	0.4465	0.1480	0.025*
H2D	1.0235	0.4521	0.3678	0.025*
O1	1.3118 (3)	0.62633 (11)	0.3457 (2)	0.0453 (4)
H1C	1.4124	0.6679	0.3285	0.068*
O2	0.2737 (3)	0.35255 (12)	0.49926 (18)	0.0391 (4)
O3	0.4216 (3)	0.27372 (10)	0.78762 (18)	0.0320 (3)
O4	0.1307 (3)	0.38042 (10)	0.96855 (18)	0.0333 (3)
O5	−0.0084 (3)	0.46250 (12)	0.6815 (2)	0.0429 (4)
O1W	0.5752 (3)	0.54801 (12)	0.7448 (2)	0.0425 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0382 (13)	0.0278 (9)	0.0369 (10)	−0.0049 (9)	0.0084 (9)	0.0046 (8)
C2	0.0263 (11)	0.0223 (9)	0.0374 (10)	0.0008 (8)	0.0044 (8)	0.0020 (8)
C3	0.0216 (11)	0.0251 (9)	0.0314 (10)	−0.0002 (8)	0.0081 (8)	−0.0009 (7)
C4	0.0241 (11)	0.0250 (9)	0.0375 (11)	0.0007 (9)	0.0102 (9)	−0.0023 (8)
C5	0.0188 (10)	0.0222 (8)	0.0227 (8)	−0.0017 (7)	0.0045 (7)	0.0004 (7)
C6	0.0231 (11)	0.0248 (9)	0.0220 (8)	−0.0004 (8)	0.0039 (8)	−0.0028 (7)
N1	0.0279 (10)	0.0218 (7)	0.0242 (7)	−0.0011 (7)	0.0071 (7)	0.0015 (6)
N2	0.0213 (9)	0.0226 (7)	0.0192 (7)	0.0018 (7)	0.0047 (6)	0.0004 (6)
O1	0.0344 (9)	0.0474 (9)	0.0505 (9)	−0.0138 (8)	0.0015 (7)	0.0129 (7)
O2	0.0393 (10)	0.0576 (10)	0.0234 (7)	0.0198 (8)	0.0138 (6)	0.0067 (6)
O3	0.0358 (9)	0.0320 (7)	0.0290 (7)	0.0148 (7)	0.0086 (6)	0.0043 (5)
O4	0.0371 (9)	0.0424 (8)	0.0234 (6)	0.0127 (7)	0.0128 (6)	0.0031 (6)
O5	0.0495 (11)	0.0490 (8)	0.0305 (7)	0.0281 (8)	0.0091 (7)	0.0080 (7)
O1W	0.0448 (11)	0.0345 (8)	0.0478 (10)	0.0076 (8)	0.0091 (8)	−0.0079 (7)

Geometric parameters (Å, º) top

C1—O1	1.402 (2)	C5—O3	1.233 (2)
C1—C2	1.489 (3)	C5—O2	1.239 (2)
C1—H1D	0.9700	C5—C6	1.548 (3)
C1—H1E	0.9700	C6—O5	1.230 (2)
C2—N2	1.478 (2)	C6—O4	1.238 (2)
C2—H2B	0.9700	N1—H1A	0.8900
C2—H2C	0.9700	N1—H1B	0.8900
C3—N2	1.472 (2)	N1—H1F	0.8900
C3—C4	1.504 (3)	N2—H2A	0.9000
C3—H3A	0.9700	N2—H2D	0.9000
C3—H3B	0.9700	O1—H1C	0.8200
C4—N1	1.475 (3)	O1W—H1W	0.838 (10)
C4—H4A	0.9700	O1W—H2W	0.841 (10)
C4—H4B	0.9700

O1—C1—C2	110.75 (16)	C3—C4—H4B	110.1
O1—C1—H1D	109.5	H4A—C4—H4B	108.4
C2—C1—H1D	109.5	O3—C5—O2	125.95 (17)
O1—C1—H1E	109.5	O3—C5—C6	117.66 (14)
C2—C1—H1E	109.5	O2—C5—C6	116.37 (15)
H1D—C1—H1E	108.1	O5—C6—O4	126.77 (19)
N2—C2—C1	112.53 (17)	O5—C6—C5	117.06 (15)
N2—C2—H2B	109.1	O4—C6—C5	116.18 (14)
C1—C2—H2B	109.1	C4—N1—H1A	109.5
N2—C2—H2C	109.1	C4—N1—H1B	109.5
C1—C2—H2C	109.1	H1A—N1—H1B	109.5
H2B—C2—H2C	107.8	C4—N1—H1F	109.5
N2—C3—C4	110.98 (15)	H1A—N1—H1F	109.5
N2—C3—H3A	109.4	H1B—N1—H1F	109.5
C4—C3—H3A	109.4	C3—N2—C2	111.45 (14)
N2—C3—H3B	109.4	C3—N2—H2A	109.3
C4—C3—H3B	109.4	C2—N2—H2A	109.3
H3A—C3—H3B	108.0	C3—N2—H2D	109.3
N1—C4—C3	107.88 (16)	C2—N2—H2D	109.3
N1—C4—H4A	110.1	H2A—N2—H2D	108.0
C3—C4—H4A	110.1	C1—O1—H1C	109.5
N1—C4—H4B	110.1	H1W—O1W—H2W	106 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1Wⁱ	0.89	1.96	2.823 (2)	164
N1—H1B···O3ⁱⁱ	0.89	2.12	2.8769 (19)	143
N1—H1B···O4ⁱⁱ	0.89	2.11	2.818 (2)	136
N1—H1F···O2	0.89	1.82	2.707 (2)	172
N2—H2A···O4ⁱⁱⁱ	0.90	1.80	2.688 (2)	170
N2—H2D···O5^iv	0.90	2.16	2.862 (2)	134
N2—H2D···O2^iv	0.90	2.00	2.773 (2)	143
O1—H1C···O3^v	0.82	1.94	2.736 (2)	163
O1W—H2W···O5^iv	0.84 (1)	1.91 (1)	2.753 (2)	178 (2)
O1W—H1W···O1^vi	0.84 (1)	2.27 (3)	2.968 (2)	141 (4)

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

Experimental details

Crystal data
Chemical formula	C₄H₁₄N₂O²⁺·C₂O₄²⁻·H₂O
M_r	212.21
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	293
a, b, c (Å)	5.7311 (11), 13.136 (3), 6.7373 (13)
β (°)	102.52 (3)
V (Å³)	495.16 (17)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.3 × 0.3 × 0.2

Data collection
Diffractometer	Rigaku Mercury CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.489, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5068, 2261, 1853
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.086, 0.97
No. of reflections	2261
No. of parameters	135
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.25

Computer programs: CrystalClear (Rigaku, 2005), 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
N1—H1A···O1Wⁱ	0.89	1.96	2.823 (2)	164
N1—H1B···O3ⁱⁱ	0.89	2.12	2.8769 (19)	143
N1—H1B···O4ⁱⁱ	0.89	2.11	2.818 (2)	136
N1—H1F···O2	0.89	1.82	2.707 (2)	172
N2—H2A···O4ⁱⁱⁱ	0.90	1.80	2.688 (2)	170
N2—H2D···O5^iv	0.90	2.16	2.862 (2)	134
N2—H2D···O2^iv	0.90	2.00	2.773 (2)	143
O1—H1C···O3^v	0.82	1.94	2.736 (2)	163
O1W—H2W···O5^iv	0.841 (10)	1.912 (10)	2.753 (2)	178 (2)
O1W—H1W···O1^vi	0.838 (10)	2.27 (3)	2.968 (2)	141 (4)

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

Acknowledgements

The author thanks the Ordered Matter Science Research Center, Southeast University, for support.

References

Barnes, J. C. (2003). Acta Cryst. E59, o931–o933. Web of Science CSD CrossRef IUCr Journals Google Scholar
Cotton, F. A., Daniels, L. M., Shang, M., Llusar, R. & Schwotzer, W. (1996). Acta Cryst. C52, 835–838. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Kolitsch, U. (2004). Acta Cryst. C60, m129–m133. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sakai, K., Akiyama, N., Mizota, M., Yokokawa, K. & Yokoyama, Y. (2003). Acta Cryst. E59, m408–m410. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar