2-(Morpholinium-4-yl)ethyl­ammonium sulfate methanol monosolvate

Bi, Y.

doi:10.1107/S1600536810010846

organic compounds

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Volume 66| Part 4| April 2010| Page o951

doi:10.1107/S1600536810010846

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2-(Morpholinium-4-yl)ethylammonium sulfate methanol monosolvate

Ye Bi ^a ^*

^aCollege of Chemistry and Chemical Engineering, Qiqihar University, Qiqihar 161006, People's Republic of China
^*Correspondence e-mail: biyeqqhar@yahoo.com.cn

(Received 20 March 2010; accepted 23 March 2010; online 27 March 2010)

In the title compound, C₆H₁₆N₂O²⁺·SO₄²⁻·CH₃OH, the morpholinium ring of the dication adopts a chair conformation. The crystal structure is stabilized by an extensive three-dimensional network of intermolecular O—H⋯O, N—H⋯O, O—H⋯S and N—H⋯S hydrogen bonds.

Related literature

For supramolecular compounds derived from the self-assembly of inorganic acids with organic amines, see: Xu (2010 ); Akhtar et al. (2010 ); Zhang & Liu (2010 ); Hemamalini & Fun (2010 ); SiMa (2010 ).

Experimental

Crystal data

C₆H₁₆N₂O²⁺·SO₄²⁻·CH₄O
M_r = 260.31
Monoclinic, P 2₁ /c
a = 15.593 (14) Å
b = 8.573 (8) Å
c = 9.483 (9) Å
β = 106.395 (11)°
V = 1216.0 (19) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 298 K
0.20 × 0.18 × 0.18 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.946, T_max = 0.951
5674 measured reflections
2462 independent reflections
1726 reflections with I > 2σ(I)
R_int = 0.049

Refinement

R[F² > 2σ(F²)] = 0.087
wR(F²) = 0.286
S = 1.08
2462 reflections
151 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.62 e Å⁻³
Δρ_min = −0.87 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5⋯O4ⁱ	0.82	1.85	2.659 (6)	172
O5—H5⋯S1ⁱ	0.82	2.92	3.636 (6)	147
N2—H2A⋯O1ⁱⁱ	0.89	2.07	2.914 (5)	158
N2—H2A⋯O3ⁱⁱ	0.89	2.30	3.001 (5)	135
N2—H2A⋯S1ⁱⁱ	0.89	2.68	3.553 (4)	167
N2—H2B⋯O2ⁱⁱⁱ	0.89	2.02	2.898 (5)	168
N2—H2B⋯O3ⁱⁱⁱ	0.89	2.45	3.081 (5)	128
N2—H2B⋯S1ⁱⁱⁱ	0.89	2.72	3.567 (4)	160
N2—H2C⋯O2	0.89	2.18	2.997 (5)	153
N2—H2C⋯O1	0.89	2.23	2.930 (4)	135
N2—H2C⋯S1	0.89	2.71	3.565 (4)	162
N1—H1⋯O2^iv	0.90 (1)	2.01 (3)	2.837 (5)	152 (5)
N1—H1⋯O4^iv	0.90 (1)	2.60 (3)	3.382 (6)	146 (5)
N1—H1⋯S1^iv	0.90 (1)	2.85 (1)	3.738 (4)	172 (5)
Symmetry codes: (i) x, y, z+1; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iv) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810010846/sj2757sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810010846/sj2757Isup2.hkl

checkCIF report

Comment top

Self-assembly of inorganic acids with organic amines readily gives rise to hydrogen-bonded supramolecular compounds (Xu, 2010; Akhtar et al., 2010; Zhang & Liu, 2010; Hemamalini & Fun, 2010; SiMa, 2010). In order to construct a similar supramolecular compound, the title compound was prepared from the reaction of 2-morpholin-4-ylethylamine with sulfuric acid in a methanol solution and its structure is reported here.

The title compound consists of a 2-morpholin-4-ylethylammonium dication, a sulfate dianion, and a methanol molecule (Fig. 1). The crystal structure is stabilized by intermolecular O–H···O, N–H···O, O–H···S, and N–H···S hydrogen bonds (Table 1, Fig. 2).

Related literature top

For supramolecular compounds derived from the self-assembly of inorganic acids with organic amines, see: Xu (2010); Akhtar et al. (2010); Zhang & Liu (2010); Hemamalini & Fun (2010); SiMa (2010).

Experimental top

Equimolar quantities (1.0 mmol each) of 2-morpholin-4-ylethylamine and sulfuric acid were mixed in a methanol solution. The mixture was stirred at room temperature for half an hour to give a colorless solution. After keeping the solution in air for a few days, colorless block-shaped crystals were formed.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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 structure of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. Molecular packing of the title compound, viewed along the a axis. Hydrogen bonds are shown as dashed lines.

2-(Morpholinium-4-yl)ethylammonium sulfate methanol monosolvate top

Crystal data top

C₆H₁₆N₂O²⁺·SO₄²⁻·CH₄O	F(000) = 560
M_r = 260.31	D_x = 1.422 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2104 reflections
a = 15.593 (14) Å	θ = 2.2–27.7°
b = 8.573 (8) Å	µ = 0.28 mm⁻¹
c = 9.483 (9) Å	T = 298 K
β = 106.395 (11)°	Block, colorless
V = 1216.0 (19) Å³	0.20 × 0.18 × 0.18 mm
Z = 4

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	2462 independent reflections
Radiation source: fine-focus sealed tube	1726 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.049
ω scans	θ_max = 27.0°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −19→14
T_min = 0.946, T_max = 0.951	k = −10→10
5674 measured reflections	l = −10→12

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)] = 0.087	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.286	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.1965P)²] where P = (F_o² + 2F_c²)/3
2462 reflections	(Δ/σ)_max < 0.001
151 parameters	Δρ_max = 0.62 e Å⁻³
1 restraint	Δρ_min = −0.87 e Å⁻³

Crystal data top

C₆H₁₆N₂O²⁺·SO₄²⁻·CH₄O	V = 1216.0 (19) Å³
M_r = 260.31	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 15.593 (14) Å	µ = 0.28 mm⁻¹
b = 8.573 (8) Å	T = 298 K
c = 9.483 (9) Å	0.20 × 0.18 × 0.18 mm
β = 106.395 (11)°

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	2462 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1726 reflections with I > 2σ(I)
T_min = 0.946, T_max = 0.951	R_int = 0.049
5674 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.087	1 restraint
wR(F²) = 0.286	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.62 e Å⁻³
2462 reflections	Δρ_min = −0.87 e Å⁻³
151 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 > 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
S1	0.35803 (6)	0.59946 (11)	0.06772 (9)	0.0369 (4)
O1	0.3987 (2)	0.5157 (3)	0.2047 (3)	0.0523 (8)
O2	0.3969 (2)	0.7579 (3)	0.0786 (3)	0.0557 (8)
O3	0.3768 (2)	0.5166 (4)	−0.0531 (3)	0.0574 (9)
O4	0.2617 (2)	0.6167 (5)	0.0429 (5)	0.0772 (11)
O5	0.1552 (3)	0.3688 (5)	1.0088 (7)	0.1071 (18)
H5	0.1834	0.4507	1.0182	0.161*
O6	0.9107 (2)	0.4451 (4)	0.5902 (3)	0.0606 (9)
N1	0.7246 (2)	0.5104 (4)	0.4511 (3)	0.0371 (7)
N2	0.51382 (19)	0.7510 (4)	0.3894 (3)	0.0403 (8)
H2A	0.5402	0.8420	0.3841	0.061*
H2B	0.4754	0.7621	0.4426	0.061*
H2C	0.4846	0.7192	0.2993	0.061*
C1	0.7681 (3)	0.5356 (5)	0.6131 (4)	0.0469 (10)
H1A	0.7247	0.5183	0.6673	0.056*
H1B	0.7893	0.6422	0.6300	0.056*
C2	0.8462 (3)	0.4232 (7)	0.6667 (5)	0.0593 (12)
H2D	0.8736	0.4392	0.7709	0.071*
H2E	0.8242	0.3168	0.6528	0.071*
C3	0.8723 (3)	0.4061 (6)	0.4418 (5)	0.0558 (12)
H3A	0.8513	0.2991	0.4351	0.067*
H3B	0.9174	0.4135	0.3895	0.067*
C4	0.7949 (3)	0.5129 (5)	0.3698 (4)	0.0471 (10)
H4A	0.8168	0.6186	0.3682	0.056*
H4B	0.7684	0.4801	0.2690	0.056*
C5	0.6558 (2)	0.6314 (5)	0.3848 (4)	0.0394 (8)
H5A	0.6304	0.6094	0.2810	0.047*
H5B	0.6841	0.7330	0.3938	0.047*
C6	0.5817 (3)	0.6351 (5)	0.4589 (5)	0.0497 (10)
H6A	0.5542	0.5328	0.4524	0.060*
H6B	0.6065	0.6604	0.5621	0.060*
C7	0.0750 (4)	0.3876 (9)	0.9066 (8)	0.0911 (19)
H7A	0.0295	0.3351	0.9386	0.137*
H7B	0.0778	0.3444	0.8146	0.137*
H7C	0.0611	0.4968	0.8944	0.137*
H1	0.702 (4)	0.413 (3)	0.437 (6)	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0318 (6)	0.0445 (6)	0.0335 (6)	0.0004 (3)	0.0079 (4)	0.0002 (3)
O1	0.0618 (19)	0.0560 (18)	0.0355 (14)	−0.0019 (14)	0.0078 (13)	0.0054 (11)
O2	0.068 (2)	0.0439 (17)	0.0592 (18)	−0.0076 (14)	0.0246 (14)	−0.0018 (12)
O3	0.071 (2)	0.065 (2)	0.0364 (14)	0.0049 (15)	0.0159 (13)	−0.0076 (12)
O4	0.0357 (18)	0.089 (3)	0.107 (3)	0.0122 (15)	0.0190 (18)	0.005 (2)
O5	0.070 (3)	0.081 (3)	0.143 (4)	−0.002 (2)	−0.016 (3)	0.016 (3)
O6	0.0330 (15)	0.092 (2)	0.0519 (17)	0.0065 (15)	0.0046 (12)	−0.0012 (16)
N1	0.0305 (15)	0.0446 (17)	0.0346 (15)	−0.0036 (12)	0.0068 (11)	−0.0012 (12)
N2	0.0317 (16)	0.0509 (19)	0.0376 (15)	−0.0020 (12)	0.0085 (12)	−0.0046 (13)
C1	0.039 (2)	0.067 (3)	0.0326 (18)	0.0013 (18)	0.0064 (14)	0.0002 (16)
C2	0.043 (2)	0.089 (3)	0.039 (2)	0.009 (2)	0.0008 (17)	0.011 (2)
C3	0.036 (2)	0.081 (3)	0.050 (2)	0.0041 (19)	0.0122 (17)	−0.0046 (19)
C4	0.036 (2)	0.068 (3)	0.0380 (18)	−0.0050 (18)	0.0119 (15)	−0.0039 (16)
C5	0.0333 (18)	0.055 (2)	0.0287 (16)	0.0000 (15)	0.0072 (13)	−0.0001 (14)
C6	0.050 (2)	0.059 (2)	0.047 (2)	0.0108 (19)	0.0257 (17)	0.0136 (18)
C7	0.049 (3)	0.108 (5)	0.109 (5)	0.005 (3)	0.011 (3)	0.000 (4)

Geometric parameters (Å, º) top

S1—O3	1.446 (3)	C1—H1A	0.9700
S1—O4	1.461 (4)	C1—H1B	0.9700
S1—O1	1.463 (3)	C2—H2D	0.9700
S1—O2	1.479 (3)	C2—H2E	0.9700
O5—C7	1.358 (7)	C3—C4	1.516 (6)
O5—H5	0.8200	C3—H3A	0.9700
O6—C3	1.405 (5)	C3—H3B	0.9700
O6—C2	1.409 (6)	C4—H4A	0.9700
N1—C5	1.497 (5)	C4—H4B	0.9700
N1—C4	1.508 (5)	C5—C6	1.512 (5)
N1—C1	1.509 (5)	C5—H5A	0.9700
N1—H1	0.899 (10)	C5—H5B	0.9700
N2—C6	1.466 (5)	C6—H6A	0.9700
N2—H2A	0.8900	C6—H6B	0.9700
N2—H2B	0.8900	C7—H7A	0.9600
N2—H2C	0.8900	C7—H7B	0.9600
C1—C2	1.524 (6)	C7—H7C	0.9600

O3—S1—O4	110.5 (2)	H2D—C2—H2E	108.0
O3—S1—O1	109.1 (2)	O6—C3—C4	111.5 (4)
O4—S1—O1	111.2 (2)	O6—C3—H3A	109.3
O3—S1—O2	109.6 (2)	C4—C3—H3A	109.3
O4—S1—O2	107.5 (2)	O6—C3—H3B	109.3
O1—S1—O2	108.85 (17)	C4—C3—H3B	109.3
C7—O5—H5	109.5	H3A—C3—H3B	108.0
C3—O6—C2	108.6 (3)	N1—C4—C3	111.3 (3)
C5—N1—C4	108.3 (3)	N1—C4—H4A	109.4
C5—N1—C1	113.0 (3)	C3—C4—H4A	109.4
C4—N1—C1	109.6 (3)	N1—C4—H4B	109.4
C5—N1—H1	112 (4)	C3—C4—H4B	109.4
C4—N1—H1	104 (4)	H4A—C4—H4B	108.0
C1—N1—H1	109 (4)	N1—C5—C6	111.7 (3)
C6—N2—H2A	109.5	N1—C5—H5A	109.3
C6—N2—H2B	109.5	C6—C5—H5A	109.3
H2A—N2—H2B	109.5	N1—C5—H5B	109.3
C6—N2—H2C	109.5	C6—C5—H5B	109.3
H2A—N2—H2C	109.5	H5A—C5—H5B	107.9
H2B—N2—H2C	109.5	N2—C6—C5	110.8 (3)
N1—C1—C2	109.6 (3)	N2—C6—H6A	109.5
N1—C1—H1A	109.7	C5—C6—H6A	109.5
C2—C1—H1A	109.7	N2—C6—H6B	109.5
N1—C1—H1B	109.7	C5—C6—H6B	109.5
C2—C1—H1B	109.7	H6A—C6—H6B	108.1
H1A—C1—H1B	108.2	O5—C7—H7A	109.5
O6—C2—C1	111.3 (4)	O5—C7—H7B	109.5
O6—C2—H2D	109.4	H7A—C7—H7B	109.5
C1—C2—H2D	109.4	O5—C7—H7C	109.5
O6—C2—H2E	109.4	H7A—C7—H7C	109.5
C1—C2—H2E	109.4	H7B—C7—H7C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O4ⁱ	0.82	1.85	2.659 (6)	172
O5—H5···S1ⁱ	0.82	2.92	3.636 (6)	147
N2—H2A···O1ⁱⁱ	0.89	2.07	2.914 (5)	158
N2—H2A···O3ⁱⁱ	0.89	2.30	3.001 (5)	135
N2—H2A···S1ⁱⁱ	0.89	2.68	3.553 (4)	167
N2—H2B···O2ⁱⁱⁱ	0.89	2.02	2.898 (5)	168
N2—H2B···O3ⁱⁱⁱ	0.89	2.45	3.081 (5)	128
N2—H2B···S1ⁱⁱⁱ	0.89	2.72	3.567 (4)	160
N2—H2C···O2	0.89	2.18	2.997 (5)	153
N2—H2C···O1	0.89	2.23	2.930 (4)	135
N2—H2C···S1	0.89	2.71	3.565 (4)	162
N1—H1···O2^iv	0.90 (1)	2.01 (3)	2.837 (5)	152 (5)
N1—H1···O4^iv	0.90 (1)	2.60 (3)	3.382 (6)	146 (5)
N1—H1···S1^iv	0.90 (1)	2.85 (1)	3.738 (4)	172 (5)

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

Experimental details

Crystal data
Chemical formula	C₆H₁₆N₂O²⁺·SO₄²⁻·CH₄O
M_r	260.31
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	15.593 (14), 8.573 (8), 9.483 (9)
β (°)	106.395 (11)
V (Å³)	1216.0 (19)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.20 × 0.18 × 0.18

Data collection
Diffractometer	Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.946, 0.951
No. of measured, independent and observed [I > 2σ(I)] reflections	5674, 2462, 1726
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.087, 0.286, 1.08
No. of reflections	2462
No. of parameters	151
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.62, −0.87

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), 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
O5—H5···O4ⁱ	0.82	1.85	2.659 (6)	171.5
O5—H5···S1ⁱ	0.82	2.92	3.636 (6)	146.9
N2—H2A···O1ⁱⁱ	0.89	2.07	2.914 (5)	157.9
N2—H2A···O3ⁱⁱ	0.89	2.30	3.001 (5)	135.1
N2—H2A···S1ⁱⁱ	0.89	2.68	3.553 (4)	166.6
N2—H2B···O2ⁱⁱⁱ	0.89	2.02	2.898 (5)	168.0
N2—H2B···O3ⁱⁱⁱ	0.89	2.45	3.081 (5)	128.2
N2—H2B···S1ⁱⁱⁱ	0.89	2.72	3.567 (4)	159.6
N2—H2C···O2	0.89	2.18	2.997 (5)	152.7
N2—H2C···O1	0.89	2.23	2.930 (4)	135.4
N2—H2C···S1	0.89	2.71	3.565 (4)	162.4
N1—H1···O2^iv	0.899 (10)	2.01 (3)	2.837 (5)	152 (5)
N1—H1···O4^iv	0.899 (10)	2.60 (3)	3.382 (6)	146 (5)
N1—H1···S1^iv	0.899 (10)	2.845 (13)	3.738 (4)	172 (5)

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

References

Akhtar, T., Masih, K., Tahir, M. N., Tariq, M. I. & Iqbal, S. (2010). Acta Cryst. E66, o819. Web of Science CSD CrossRef IUCr Journals Google Scholar
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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page o951

doi:10.1107/S1600536810010846

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