Morpholin-4-ium hydrogen tartrate

Abstract

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,

• a = 7.2601 (15) Å

• b = 9.1716 (18) Å

• c = 16.283 (3) Å

• V = 1084.2 (4) ų

• 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[F ² > 2σ(F ²)] = 0.044

• wR(F ²) = 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

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.

Supplementary Material

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—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⋯O3iv	0.82	1.73	2.529 (2)	165
O6—H6⋯O4	0.82	2.20	2.674 (2)	117
O6—H6⋯O1v	0.82	2.24	2.996 (2)	153

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .

supplementary crystallographic information

Experimental

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).

Refinement

The absolute structure is indeterminate based on the present model. H atoms were placed in calculated positions (N—H = 0.89 Å; C—H = 0.93Å for Csp² atoms and C—H = 0.96Å and 0.97Å for Csp³ atoms), assigned fixed U_iso values [U_iso = 1.2Ueq(Csp²) and 1.5Ueq(Csp³,N)] and allowed to ride.

Figures

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.

Crystal data

C4H10NO+·C4H5O6−	F(000) = 504
Mr = 237.21	Dx = 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

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

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.097	H-atom parameters constrained
S = 1.17	w = 1/[σ2(Fo2) + (0.0363P)2 + 0.0989P] where P = (Fo2 + 2Fc2)/3
1903 reflections	(Δ/σ)max = 0.095
146 parameters	Δρmax = 0.14 e Å−3
0 restraints	Δρmin = −0.20 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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···O3iv	0.82	1.73	2.529 (2)	165
O6—H6···O4	0.82	2.20	2.674 (2)	117
O6—H6···O1v	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.