Hydrogen-bond inter­actions in morpholinium bromide

Padayachy, K.; Mgcima, Z.; Fernandes, M.A.; Marques, H.M.; Sousa, A.S. de

doi:10.1107/S1600536811035598

organic compounds

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Volume 67| Part 10| October 2011| Page o2594

https://doi.org/10.1107/S1600536811035598

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Hydrogen-bond interactions in morpholinium bromide

Kamentheren Padayachy,^a Zolani Mgcima,^a Manuel A. Fernandes,^a Helder M. Marques ^a and Alvaro S. de Sousa ^a ^*

^aSchool of Chemistry, Molecular Sciences Institute, University of the Witwatersrand, Private Bag 3, Wits 2050, Johannesburg, South Africa
^*Correspondence e-mail: Alvaro.DeSousa@wits.ac.za

(Received 11 August 2011; accepted 1 September 2011; online 14 September 2011)

In the title compound, C₄H₁₀NO⁺·Br⁻, which was synthesized by dehydration of diethanolamine with HBr, morpholinium and bromide ions are linked into chains by N—H⋯Br hydrogen bonds describing a C₂¹(4) graph-set motif. Weaker bifurcated N—H⋯Br interactions join centrosymmetrically related chains through alternating binary graph-set R₄²(8) and R₂²(4) motifs, to form ladders along [100]. In addition, C—H⋯O interactions between centrosymmetric morpholinium cations link ladders, via [R^2_2] (8) motifs, to yield sheets parallel to (101), which in turn are crosslinked by weak C—H⋯O interactions, related across a glide plane, to form a three-dimensional network.

Related literature

For the structures of related morpholinium salts, see: Loehlin & Okasako (2007 ); Mafud et al. (2011 ); Swaminathan et al. (1976 ); Koroniak et al. (2000 ); Turnbull (1997 ); Mazur et al. (2007 ); Yao (2010 ); Christensen et al. (1993 ). For the synthesis, see: Pettit et al. (1964 ). For the graph-set analysis, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₄H₁₀NO⁺·Br⁻
M_r = 168.04
Monoclinic, P 2₁ /c
a = 6.1247 (2) Å
b = 10.3063 (3) Å
c = 10.1141 (3) Å
β = 100.312 (2)°
V = 628.12 (3) Å³
Z = 4
Mo Kα radiation
μ = 6.44 mm⁻¹
T = 173 K
0.40 × 0.20 × 0.09 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: integration (face indexed absorption corrections carried out with XPREP; Sheldrick, 2008 ) T_min = 0.183, T_max = 0.595
11662 measured reflections
1516 independent reflections
1314 reflections with I > 2σ(I)
R_int = 0.210

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.100
S = 1.03
1516 reflections
64 parameters
H-atom parameters constrained
Δρ_max = 1.07 e Å⁻³
Δρ_min = −1.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Br1	0.92	2.52	3.331 (2)	148
N1—H1A⋯Br1ⁱ	0.92	2.89	3.389 (2)	115
N1—H1B⋯Br1ⁱⁱ	0.92	2.40	3.292 (2)	164
C4—H4A⋯O1ⁱⁱⁱ	0.99	2.52	3.366 (4)	143
C1—H1C⋯O1^iv	0.99	2.59	3.498 (4)	152
Symmetry codes: (i) -x+1, -y, -z; (ii) x-1, y, z; (iii) -x+1, -y, -z+1; (iv) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005 ); cell refinement: APEX2; data reduction: SAINT-Plus (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and WinGX (Farrugia, 1997 ); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536811035598/lr2027sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811035598/lr2027Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811035598/lr2027Isup3.cml

checkCIF report

Comment top

The structures and hydrogen bonding of several salts of morpholinium and its derivatives have been reported (Loehlin & Okasako, 2007; Mafud et al., 2011; Swaminathan et al., 1976; Koroniak et al., 2000 ; Turnbull, 1997; Mazur et al., 2007; Yao, 2010; Christensen et al., 1993). The title compound, morpholinium bromide, contains a single quaternary nitrogen donor (Figure1) and weak N-H···Br interactions are observable in the crystal structure. The morpholinium and bromide ions are joined into chains along the a-axis through N-H···Br hydrogen bonds in a motif of graph set C₂¹(4). Chains are joined to form ladders by weak, bifurcated N-H···Br interactions at ammonium hydrogen, H1A, (Figure 2). Alternating ring motifs R₄²(8) and R₂²(4) describe the binary graph-set for ladders along [100]. Weak C4-H4A···O1 interactions between centrosymmetric morpholinium cations link ladders,via R₂²(8) motifs, to yield sheets parallel to the ac plane, which in turn are weakly joined by C1-H1C···O1 interactions (Figure 3) across a glide plane perpendicular to [010], glide component (0, 0, 0.5), to form a three dimensional network.

Related literature top

For the structures of related morpholinium salts, see: Loehlin & Okasako (2007); Mafud et al. (2011); Swaminathan et al. (1976); Koroniak et al. (2000); Turnbull (1997); Mazur et al. (2007); Yao (2010); Christensen et al. (1993). For the synthesis, see: Pettit et al. (1964). For the graph-set analysis, see: Bernstein et al. (1995).

Experimental top

Morpholinium Bromide was obtained as the minor product of the synthesis reported by Pettit et al. (1964). Diethanolamine (12 g, 0.114 mol) was added, with cooling, to 100 mL of 48% HBr. The reaction vessel was fitted with a Vigreaux column and Dean-Stark apparatus and the solution heated collecting approximately 70 mL of water through azeotropic distillation. The remaining HBr was removed under reduced pressure to yield viscous orange oil that crystallized upon cooling. The pure crystalline sample product was obtained by several recrystallisations from an ethanol-diethyl ether solution.

¹H(D₂O, 300 MHz) 3.667 (4H, t, CH₂NH), 3.779 (4H, t, CH₂O).

Structure description top

For the structures of related morpholinium salts, see: Loehlin & Okasako (2007); Mafud et al. (2011); Swaminathan et al. (1976); Koroniak et al. (2000); Turnbull (1997); Mazur et al. (2007); Yao (2010); Christensen et al. (1993). For the synthesis, see: Pettit et al. (1964). For the graph-set analysis, see: Bernstein et al. (1995).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT-Plus (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and WinGX (Farrugia, 1997); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON, (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of (1), showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Ring motifs (a) R₂²(4) and (b) R₄²(8) arising from intermolecular N-H···Br, and (c) R₂²(8) from C-H···O interactions, in sheets parallel to the ac plane. [symmetry codes: (i) 1-x,-y,-z; (ii) x-1,y,z; (iii) 1-x, -y,1-z;]
	Fig. 3. Intermolecular C1-H1C···O1 interactions linking sheets into a three dimensional network.

morpholinium bromide top

Crystal data top

C₄H₁₀NO⁺·Br⁻	F(000) = 336
M_r = 168.04	D_x = 1.777 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5677 reflections
a = 6.1247 (2) Å	θ = 2.9–28.3°
b = 10.3063 (3) Å	µ = 6.44 mm⁻¹
c = 10.1141 (3) Å	T = 173 K
β = 100.312 (2)°	Needle, colourless
V = 628.12 (3) Å³	0.40 × 0.20 × 0.09 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	1516 independent reflections
Radiation source: fine-focus sealed tube	1314 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.210
φ and ω scans	θ_max = 28.0°, θ_min = 2.9°
Absorption correction: integration (face indexed absorption corrections carried out with XPREP; Sheldrick, 2008)	h = −8→8
T_min = 0.183, T_max = 0.595	k = −13→13
11662 measured reflections	l = −13→13

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.100	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0518P)²] where P = (F_o² + 2F_c²)/3
1516 reflections	(Δ/σ)_max = 0.002
64 parameters	Δρ_max = 1.07 e Å⁻³
0 restraints	Δρ_min = −1.38 e Å⁻³

Crystal data top

C₄H₁₀NO⁺·Br⁻	V = 628.12 (3) Å³
M_r = 168.04	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.1247 (2) Å	µ = 6.44 mm⁻¹
b = 10.3063 (3) Å	T = 173 K
c = 10.1141 (3) Å	0.40 × 0.20 × 0.09 mm
β = 100.312 (2)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	1516 independent reflections
Absorption correction: integration (face indexed absorption corrections carried out with XPREP; Sheldrick, 2008)	1314 reflections with I > 2σ(I)
T_min = 0.183, T_max = 0.595	R_int = 0.210
11662 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.100	H-atom parameters constrained
S = 1.03	Δρ_max = 1.07 e Å⁻³
1516 reflections	Δρ_min = −1.38 e Å⁻³
64 parameters

Special details top

Experimental. Intensity data were collected on a Bruker APEX II CCD area detector diffractometer with graphite monochromated Mo Kα radiation (50 kV, 30 mA) using the APEX 2 (Bruker, 2005) data collection software. The collection method involved ω-scans of width 0.5° and 512 x 512 bit data frames. Data reduction was carried out using the program SAINT-Plus (Bruker, 2005). The crystal structure was solved by direct methods using SHELXTL (Sheldrick, 2008). Non-hydrogen atoms were first refined isotropically followed by anisotropic refinement by full matrix least-squares calculations based on F² using SHELXTL.

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
Br1	0.74904 (4)	0.11971 (3)	0.07284 (3)	0.02454 (16)
O1	0.2489 (4)	0.10940 (17)	0.4694 (3)	0.0263 (5)
N1	0.2813 (4)	0.0830 (2)	0.1937 (2)	0.0199 (5)
H1A	0.3739	0.0758	0.1318	0.024*
H1B	0.1372	0.0808	0.1480	0.024*
C1	0.3228 (5)	0.2082 (3)	0.2657 (3)	0.0243 (6)
H1C	0.2788	0.2807	0.2024	0.029*
H1D	0.4831	0.2170	0.3026	0.029*
C4	0.3199 (5)	−0.0280 (3)	0.2893 (3)	0.0246 (6)
H4A	0.4801	−0.0347	0.3272	0.029*
H4B	0.2732	−0.1098	0.2410	0.029*
C2	0.1926 (5)	0.2149 (3)	0.3781 (3)	0.0273 (6)
H2A	0.2241	0.2980	0.4268	0.033*
H2B	0.0319	0.2119	0.3404	0.033*
C3	0.1915 (5)	−0.0094 (3)	0.4004 (3)	0.0272 (6)
H3A	0.0308	−0.0095	0.3628	0.033*
H3B	0.2221	−0.0824	0.4646	0.033*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0153 (2)	0.0332 (2)	0.0242 (2)	−0.00109 (9)	0.00118 (14)	−0.00764 (10)
O1	0.0358 (13)	0.0301 (11)	0.0127 (10)	0.0010 (8)	0.0031 (9)	0.0004 (7)
N1	0.0159 (11)	0.0289 (11)	0.0147 (11)	0.0018 (8)	0.0021 (9)	−0.0013 (8)
C1	0.0259 (14)	0.0220 (13)	0.0238 (14)	−0.0055 (10)	0.0014 (11)	0.0010 (10)
C4	0.0274 (14)	0.0238 (14)	0.0213 (14)	0.0042 (10)	0.0014 (11)	−0.0004 (10)
C2	0.0336 (16)	0.0246 (14)	0.0225 (15)	0.0050 (11)	0.0018 (13)	−0.0047 (11)
C3	0.0340 (15)	0.0245 (14)	0.0230 (14)	−0.0033 (11)	0.0053 (12)	0.0037 (11)

Geometric parameters (Å, º) top

O1—C3	1.422 (3)	C1—H1D	0.9900
O1—C2	1.428 (3)	C4—C3	1.495 (4)
N1—C1	1.481 (3)	C4—H4A	0.9900
N1—C4	1.490 (3)	C4—H4B	0.9900
N1—H1A	0.9200	C2—H2A	0.9900
N1—H1B	0.9200	C2—H2B	0.9900
C1—C2	1.502 (4)	C3—H3A	0.9900
C1—H1C	0.9900	C3—H3B	0.9900

C3—O1—C2	109.1 (2)	N1—C4—H4B	109.6
C1—N1—C4	110.9 (2)	C3—C4—H4B	109.6
C1—N1—H1A	109.5	H4A—C4—H4B	108.1
C4—N1—H1A	109.5	O1—C2—C1	110.8 (2)
C1—N1—H1B	109.5	O1—C2—H2A	109.5
C4—N1—H1B	109.5	C1—C2—H2A	109.5
H1A—N1—H1B	108.1	O1—C2—H2B	109.5
N1—C1—C2	110.1 (2)	C1—C2—H2B	109.5
N1—C1—H1C	109.6	H2A—C2—H2B	108.1
C2—C1—H1C	109.6	O1—C3—C4	111.3 (2)
N1—C1—H1D	109.6	O1—C3—H3A	109.4
C2—C1—H1D	109.6	C4—C3—H3A	109.4
H1C—C1—H1D	108.1	O1—C3—H3B	109.4
N1—C4—C3	110.2 (2)	C4—C3—H3B	109.4
N1—C4—H4A	109.6	H3A—C3—H3B	108.0
C3—C4—H4A	109.6

C4—N1—C1—C2	−52.4 (3)	N1—C1—C2—O1	57.9 (3)
C1—N1—C4—C3	52.1 (3)	C2—O1—C3—C4	62.3 (3)
C3—O1—C2—C1	−62.4 (3)	N1—C4—C3—O1	−57.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Br1	0.92	2.52	3.331 (2)	148
N1—H1A···Br1ⁱ	0.92	2.89	3.389 (2)	115
N1—H1B···Br1ⁱⁱ	0.92	2.40	3.292 (2)	164
C4—H4A···O1ⁱⁱⁱ	0.99	2.52	3.366 (4)	143
C1—H1C···O1^iv	0.99	2.59	3.498 (4)	152

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

Experimental details

Crystal data
Chemical formula	C₄H₁₀NO⁺·Br⁻
M_r	168.04
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	6.1247 (2), 10.3063 (3), 10.1141 (3)
β (°)	100.312 (2)
V (Å³)	628.12 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	6.44
Crystal size (mm)	0.40 × 0.20 × 0.09

Data collection
Diffractometer	Bruker APEXII CCD area-detector
Absorption correction	Integration (face indexed absorption corrections carried out with XPREP; Sheldrick, 2008)
T_min, T_max	0.183, 0.595
No. of measured, independent and observed [I > 2σ(I)] reflections	11662, 1516, 1314
R_int	0.210
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.100, 1.03
No. of reflections	1516
No. of parameters	64
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.07, −1.38

Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and WinGX (Farrugia, 1997), SHELXTL (Sheldrick, 2008) and PLATON, (Spek, 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Br1	0.92	2.52	3.331 (2)	148
N1—H1A···Br1ⁱ	0.92	2.89	3.389 (2)	115
N1—H1B···Br1ⁱⁱ	0.92	2.40	3.292 (2)	164
C4—H4A···O1ⁱⁱⁱ	0.99	2.52	3.366 (4)	143
C1—H1C···O1^iv	0.99	2.59	3.498 (4)	152

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

Acknowledgements

This work was supported by the National Research Foundation (South Africa).

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