Morpholin-4-ium hydrogen tartrate

Liu, M.-L.

doi:10.1107/S1600536811055759

organic compounds

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Volume 68| Part 2| February 2012| Page o289

doi:10.1107/S1600536811055759

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Morpholin-4-ium hydrogen tartrate

Ming-Liang Liu ^a ^*

^aOrdered Matter Science Research Center, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: jgsdxlml@163.com

(Received 22 December 2011; accepted 26 December 2011; online 7 January 2012)

In the title molecular salt, C₄H₁₀NO⁺·C₄H₅O₆⁻, the morpholinium cation adopts a chair conformation. The conformation of the C—C—C—C backbone of the monotartrate anion is close to anti [torsion angle = 173.18 (17)°], which is supported by two intramolecular O—H⋯O hydrogen bonds. In the crystal, the components are linked by N—H—O and O—H—O hydrogen bonds, generating (001) sheets.

Related literature

For a related structure, see: Ruble et al. (1976 ).

Experimental

Crystal data

C₄H₁₀NO⁺·C₄H₅O₆⁻
M_r = 237.21
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.2601 (15) Å
b = 9.1716 (18) Å
c = 16.283 (3) Å
V = 1084.2 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 293 K
0.36 × 0.32 × 0.28 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.954, T_max = 0.966
8960 measured reflections
1903 independent reflections
1747 reflections with I > 2σ(I)
R_int = 0.060

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.097
S = 1.17
1903 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2ⁱ	0.90	2.05	2.918 (3)	162
N1—H1B⋯O2ⁱⁱ	0.90	1.95	2.790 (3)	154
O1—H1⋯O2	0.82	2.09	2.600 (2)	120
O1—H1⋯O4ⁱⁱⁱ	0.82	2.40	3.068 (2)	139
O5—H5⋯O3^iv	0.82	1.73	2.529 (2)	165
O6—H6⋯O4	0.82	2.20	2.674 (2)	117
O6—H6⋯O1^v	0.82	2.24	2.996 (2)	153
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+1, z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) x+1, y, z; (v) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811055759/hb6576sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811055759/hb6576Isup2.hkl

checkCIF report

Related literature top

For a related structure, see: Ruble et al. (1976).

Experimental top

0.87 g (0.01 mol) of morpholine was firstly dissolved in 30 ml of ethanol, to which 1.50 g (0.01 mol) of tartaric acid was added at ambient temperature. Colourless blocks were obtained by the slow evaporation of the above solution after 3 days in air.

The dielectric constant of the compound as a function of temperature indicates that the permittivity is basically temperature-independent (ε = C/(T–T₀)), suggesting that this compound is not ferroelectric or there may be no distinct phase transition occurring within the measured temperature (below the melting point).

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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids.
	Fig. 2. Crystal structure of the title compound with view along the b axis. Intermolecular interactions are shown as dashed lines.

Morpholin-4-ium hydrogen tartrate top

Crystal data top

C₄H₁₀NO⁺·C₄H₅O₆⁻	F(000) = 504
M_r = 237.21	D_x = 1.453 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1903 reflections
a = 7.2601 (15) Å	θ = 3.4–26.4°
b = 9.1716 (18) Å	µ = 0.13 mm⁻¹
c = 16.283 (3) Å	T = 293 K
V = 1084.2 (4) Å³	Block, colourless
Z = 4	0.36 × 0.32 × 0.28 mm

Data collection top

Rigaku Mercury2 diffractometer	1747 reflections with I > \2s(I)
Radiation source: fine-focus sealed tube	R_int = 0.060
Graphite monochromator	θ_max = 25°, θ_min = 3.1°
ω scans	h = −8→8
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −10→10
T_min = 0.954, T_max = 0.966	l = −19→19
8960 measured reflections	3 standard reflections every 180 reflections
1903 independent reflections	intensity decay: none

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.097	H-atom parameters constrained
S = 1.17	w = 1/[σ²(F_o²) + (0.0363P)² + 0.0989P] where P = (F_o² + 2F_c²)/3
1903 reflections	(Δ/σ)_max = 0.095
146 parameters	Δρ_max = 0.14 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₄H₁₀NO⁺·C₄H₅O₆⁻	V = 1084.2 (4) Å³
M_r = 237.21	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.2601 (15) Å	µ = 0.13 mm⁻¹
b = 9.1716 (18) Å	T = 293 K
c = 16.283 (3) Å	0.36 × 0.32 × 0.28 mm

Data collection top

Rigaku Mercury2 diffractometer	1747 reflections with I > \2s(I)
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	R_int = 0.060
T_min = 0.954, T_max = 0.966	3 standard reflections every 180 reflections
8960 measured reflections	intensity decay: none
1903 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.097	H-atom parameters constrained
S = 1.17	Δρ_max = 0.14 e Å⁻³
1903 reflections	Δρ_min = −0.20 e Å⁻³
146 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
O7	0.3787 (3)	0.3058 (2)	0.55071 (10)	0.0542 (5)
N1	0.4758 (3)	0.4978 (2)	0.68097 (11)	0.0426 (5)
H1A	0.4382	0.4480	0.7256	0.051*
H1B	0.5249	0.5827	0.6979	0.051*
C1	0.3161 (4)	0.5269 (3)	0.62661 (15)	0.0510 (7)
H1C	0.3541	0.5882	0.5811	0.061*
H1D	0.2210	0.5780	0.6570	0.061*
C2	0.2413 (4)	0.3847 (3)	0.59447 (15)	0.0508 (7)
H2A	0.1973	0.3262	0.6400	0.061*
H2B	0.1378	0.4039	0.5584	0.061*
C3	0.5307 (4)	0.2735 (3)	0.60333 (15)	0.0519 (7)
H3A	0.6219	0.2178	0.5731	0.062*
H3B	0.4885	0.2143	0.6490	0.062*
C4	0.6178 (4)	0.4113 (3)	0.63583 (16)	0.0504 (7)
H4A	0.7186	0.3871	0.6725	0.060*
H4B	0.6668	0.4684	0.5907	0.060*
O1	0.4383 (2)	0.75847 (19)	0.31549 (10)	0.0494 (5)
H1	0.3531	0.7781	0.2843	0.074*
O2	0.08530 (19)	0.71085 (17)	0.31349 (8)	0.0358 (4)
O3	0.08075 (18)	0.60421 (18)	0.43779 (9)	0.0394 (4)
O4	0.73405 (19)	0.46475 (19)	0.31136 (9)	0.0418 (4)
O5	0.73379 (19)	0.58152 (19)	0.43315 (9)	0.0410 (4)
H5	0.8459	0.5815	0.4269	0.062*
O6	0.3670 (2)	0.44104 (19)	0.31002 (10)	0.0474 (5)
H6	0.4483	0.4105	0.2796	0.071*
C5	0.6557 (3)	0.5186 (2)	0.36993 (13)	0.0312 (5)
C6	0.4477 (3)	0.5161 (3)	0.37717 (12)	0.0304 (5)
H6A	0.4145	0.4652	0.4280	0.036*
C7	0.3714 (3)	0.6722 (2)	0.38132 (13)	0.0304 (5)
H7	0.4082	0.7168	0.4335	0.036*
C8	0.1603 (3)	0.6624 (2)	0.37789 (13)	0.0284 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O7	0.0728 (12)	0.0500 (12)	0.0397 (9)	0.0035 (11)	−0.0084 (9)	−0.0083 (9)
N1	0.0568 (12)	0.0357 (12)	0.0351 (10)	−0.0088 (10)	0.0062 (9)	−0.0021 (9)
C1	0.0662 (17)	0.0440 (17)	0.0427 (13)	0.0129 (14)	0.0084 (12)	0.0050 (12)
C2	0.0513 (15)	0.0540 (18)	0.0472 (14)	0.0009 (14)	−0.0056 (12)	0.0016 (12)
C3	0.0590 (16)	0.0467 (18)	0.0499 (15)	0.0103 (14)	−0.0012 (13)	−0.0094 (13)
C4	0.0462 (15)	0.0577 (18)	0.0472 (14)	−0.0024 (14)	0.0061 (12)	−0.0044 (13)
O1	0.0317 (8)	0.0551 (12)	0.0614 (11)	−0.0088 (8)	0.0021 (8)	0.0244 (9)
O2	0.0332 (8)	0.0366 (9)	0.0377 (8)	0.0004 (7)	−0.0087 (7)	0.0026 (7)
O3	0.0229 (8)	0.0569 (11)	0.0384 (8)	−0.0009 (7)	0.0019 (7)	0.0068 (8)
O4	0.0298 (8)	0.0526 (11)	0.0429 (9)	0.0040 (8)	0.0065 (7)	−0.0073 (8)
O5	0.0211 (7)	0.0579 (11)	0.0441 (9)	0.0001 (7)	0.0015 (7)	−0.0070 (8)
O6	0.0299 (8)	0.0554 (11)	0.0568 (10)	0.0005 (8)	0.0002 (8)	−0.0227 (9)
C5	0.0257 (10)	0.0330 (13)	0.0349 (11)	0.0021 (10)	0.0013 (9)	0.0033 (10)
C6	0.0255 (10)	0.0337 (13)	0.0318 (11)	−0.0008 (10)	0.0023 (8)	−0.0002 (10)
C7	0.0244 (10)	0.0323 (13)	0.0344 (11)	−0.0025 (10)	−0.0003 (8)	0.0031 (10)
C8	0.0255 (10)	0.0245 (12)	0.0351 (11)	0.0000 (10)	−0.0015 (9)	−0.0034 (10)

Geometric parameters (Å, º) top

O7—C2	1.423 (3)	C4—H4B	0.9700
O7—C3	1.428 (3)	O1—C7	1.418 (2)
N1—C1	1.483 (3)	O1—H1	0.8203
N1—C4	1.494 (3)	O2—C8	1.263 (2)
N1—H1A	0.9006	O3—C8	1.253 (2)
N1—H1B	0.8996	O4—C5	1.216 (2)
C1—C2	1.507 (4)	O5—C5	1.309 (2)
C1—H1C	0.9700	O5—H5	0.8200
C1—H1D	0.9700	O6—C6	1.419 (2)
C2—H2A	0.9700	O6—H6	0.8198
C2—H2B	0.9700	C5—C6	1.515 (3)
C3—C4	1.510 (4)	C6—C7	1.536 (3)
C3—H3A	0.9700	C6—H6A	0.9800
C3—H3B	0.9700	C7—C8	1.536 (3)
C4—H4A	0.9700	C7—H7	0.9800

C2—O7—C3	110.29 (17)	N1—C4—H4A	109.9
C1—N1—C4	109.97 (18)	C3—C4—H4A	109.9
C1—N1—H1A	109.6	N1—C4—H4B	109.9
C4—N1—H1A	109.7	C3—C4—H4B	109.9
C1—N1—H1B	109.7	H4A—C4—H4B	108.3
C4—N1—H1B	109.7	C7—O1—H1	109.4
H1A—N1—H1B	108.2	C5—O5—H5	109.4
N1—C1—C2	109.5 (2)	C6—O6—H6	109.5
N1—C1—H1C	109.8	O4—C5—O5	126.37 (18)
C2—C1—H1C	109.8	O4—C5—C6	121.5 (2)
N1—C1—H1D	109.8	O5—C5—C6	112.16 (18)
C2—C1—H1D	109.8	O6—C6—C5	111.03 (17)
H1C—C1—H1D	108.2	O6—C6—C7	109.70 (17)
O7—C2—C1	111.2 (2)	C5—C6—C7	110.44 (18)
O7—C2—H2A	109.4	O6—C6—H6A	108.5
C1—C2—H2A	109.4	C5—C6—H6A	108.5
O7—C2—H2B	109.4	C7—C6—H6A	108.5
C1—C2—H2B	109.4	O1—C7—C6	111.28 (16)
H2A—C2—H2B	108.0	O1—C7—C8	110.32 (17)
O7—C3—C4	111.1 (2)	C6—C7—C8	107.67 (18)
O7—C3—H3A	109.4	O1—C7—H7	109.2
C4—C3—H3A	109.4	C6—C7—H7	109.2
O7—C3—H3B	109.4	C8—C7—H7	109.2
C4—C3—H3B	109.4	O3—C8—O2	126.69 (18)
H3A—C3—H3B	108.0	O3—C8—C7	117.18 (18)
N1—C4—C3	109.1 (2)	O2—C8—C7	116.10 (19)

C4—N1—C1—C2	56.0 (3)	O5—C5—C6—C7	61.0 (2)
C3—O7—C2—C1	60.4 (3)	O6—C6—C7—O1	−70.5 (2)
N1—C1—C2—O7	−58.4 (3)	C5—C6—C7—O1	52.2 (2)
C2—O7—C3—C4	−60.4 (3)	O6—C6—C7—C8	50.5 (2)
C1—N1—C4—C3	−55.9 (3)	C5—C6—C7—C8	173.18 (17)
O7—C3—C4—N1	58.0 (3)	O1—C7—C8—O3	−171.64 (18)
O4—C5—C6—O6	1.9 (3)	C6—C7—C8—O3	66.7 (2)
O5—C5—C6—O6	−177.08 (17)	O1—C7—C8—O2	10.1 (3)
O4—C5—C6—C7	−120.0 (2)	C6—C7—C8—O2	−111.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.90	2.05	2.918 (3)	162
N1—H1B···O2ⁱⁱ	0.90	1.95	2.790 (3)	154
O1—H1···O2	0.82	2.09	2.600 (2)	120
O1—H1···O4ⁱⁱⁱ	0.82	2.40	3.068 (2)	139
O5—H5···O3^iv	0.82	1.73	2.529 (2)	165
O6—H6···O4	0.82	2.20	2.674 (2)	117
O6—H6···O1^v	0.82	2.24	2.996 (2)	153

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

Experimental details

Crystal data
Chemical formula	C₄H₁₀NO⁺·C₄H₅O₆⁻
M_r	237.21
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	7.2601 (15), 9.1716 (18), 16.283 (3)
V (Å³)	1084.2 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.36 × 0.32 × 0.28

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.954, 0.966
No. of measured, independent and observed [I > \2s(I)] reflections	8960, 1903, 1747
R_int	0.060
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.097, 1.17
No. of reflections	1903
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.20

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···O2ⁱ	0.90	2.05	2.918 (3)	162
N1—H1B···O2ⁱⁱ	0.90	1.95	2.790 (3)	154
O1—H1···O2	0.82	2.09	2.600 (2)	120
O1—H1···O4ⁱⁱⁱ	0.82	2.40	3.068 (2)	139
O5—H5···O3^iv	0.82	1.73	2.529 (2)	165
O6—H6···O4	0.82	2.20	2.674 (2)	117
O6—H6···O1^v	0.82	2.24	2.996 (2)	153

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

Acknowledgements

The author thanks an anonymous advisor from the Ordered Matter Science Research Centre, Southeast University, for great help in the revision of this paper.

References

Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Ruble, J. R., Hite, G. & Soares, J. R. (1976). Acta Cryst. B32, 136–140. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar