Crystal structure of morpholin-4-ium cinnamate.

In the anhydrous salt formed from the reaction of morpholine with cinnamic acid, C4H10NO(+)·C9H7O2 (-), the acid side chain in the trans-cinnamate anion is significantly rotated out of the benzene plane [C-C-C- C torsion angle = 158.54 (17)°]. In the crystal, one of the the aminium H atoms is involved in an asymmetric three-centre cation-anion N-H⋯(O,O') R 1 (2)(4) hydrogen-bonding inter-action with the two carboxyl-ate O-atom acceptors of the anion. The second aminium-H atom forms an inter-species N-H⋯Ocarboxyl-ate hydrogen bond. The result of the hydrogen bonding is the formation of a chain structure extending along [100]. Chains are linked by C-H⋯O inter-actions, forming a supra-molecular layer parallel to (01-1).

Related literature

For background on morpholine compounds and the structure of an aliphatic morpholine salt, see: Kelley et al. (2013 ▸). For the structures of analogous morpholinate salts of some aromatic acid analogues, see: Chumakov et al. (2006 ▸); Ishida et al. (2001a ▸,b ▸,c ▸); Smith & Lynch (2015 ▸).

Experimental

Crystal data

C4H10NO+·C9H7O2 −

M = 235.27

Triclinic,

a = 5.7365 (7) Å

b = 9.7526 (10) Å

c = 11.7760 (11) Å

α = 103.270 (8)°

β = 93.468 (9)°

γ = 105.493 (10)°

V = 612.69 (12) Å3

Z = 2

Mo Kα radiation

μ = 0.09 mm−1

T = 200 K

0.52 × 0.24 × 0.05 mm

Data collection

Oxford Diffraction Gemini-S CCD-detector diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014 ▸) T min = 0.965, T max = 0.990

4253 measured reflections

2393 independent reflections

1860 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.100

S = 1.01

2393 reflections

160 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.15 e Å−3

Δρmin = −0.15 e Å−3

Data collection: CrysAlis PRO (Agilent, 2014 ▸); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸) within WinGX (Farrugia, 2012 ▸); molecular graphics: PLATON (Spek, 2009 ▸); software used to prepare material for publication: PLATON.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015019179/tk5397sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015019179/tk5397Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015019179/tk5397Isup3.cml

Click here for additional data file.

B A . DOI: 10.1107/S2056989015019179/tk5397fig1.tif

The atom-numbering scheme and the mol­ecular conformation of the morpholinium anion (B) and the cinnamate cation (A) in the title salt, with displacement ellipsoids drawn at the 40% probability level. The cation–anion hydrogen bonds are shown as dashed lines.

Click here for additional data file.

a . DOI: 10.1107/S2056989015019179/tk5397fig2.tif

The one-dimensional hydrogen-bonded polymeric structure extending along a. For symmetry codes, see Table 1.

CCDC reference: 1430629

Additional supporting information: crystallographic information; 3D view; checkCIF report

C4H10NO+·C9H7O2−	Z = 2
Mr = 235.27	F(000) = 252
Triclinic, P1	Dx = 1.281 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.7365 (7) Å	Cell parameters from 1133 reflections
b = 9.7526 (10) Å	θ = 3.6–28.4°
c = 11.7760 (11) Å	µ = 0.09 mm−1
α = 103.270 (8)°	T = 200 K
β = 93.468 (9)°	Plate, colourless
γ = 105.493 (10)°	0.52 × 0.24 × 0.05 mm
V = 612.69 (12) Å3

Oxford Diffraction Gemini-S CCD-detector diffractometer	2393 independent reflections
Radiation source: Enhance (Mo) X-ray source	1860 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
Detector resolution: 16.077 pixels mm-1	θmax = 26.0°, θmin = 3.2°
ω scans	h = −6→7
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −12→12
Tmin = 0.965, Tmax = 0.990	l = −14→14
4253 measured reflections

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ2(Fo2) + (0.0429P)2 + 0.0676P] where P = (Fo2 + 2Fc2)/3
2393 reflections	(Δ/σ)max < 0.001
160 parameters	Δρmax = 0.15 e Å−3
2 restraints	Δρmin = −0.15 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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.

	x	y	z	Uiso*/Ueq
O13A	0.72059 (18)	0.32720 (13)	0.51574 (9)	0.0370 (4)
O14A	0.50422 (18)	0.43517 (12)	0.63746 (10)	0.0323 (4)
C1A	0.0669 (3)	0.04440 (16)	0.29775 (13)	0.0256 (5)
C2A	−0.1554 (3)	0.00183 (17)	0.34093 (15)	0.0299 (5)
C3A	−0.3583 (3)	−0.09424 (18)	0.26731 (16)	0.0365 (6)
C4A	−0.3450 (3)	−0.14842 (18)	0.14947 (16)	0.0388 (6)
C5A	−0.1258 (3)	−0.10770 (18)	0.10580 (15)	0.0384 (6)
C6A	0.0789 (3)	−0.01381 (17)	0.17959 (14)	0.0321 (5)
C11A	0.2852 (3)	0.14762 (17)	0.37395 (14)	0.0262 (5)
C12A	0.2907 (3)	0.24300 (17)	0.47379 (14)	0.0276 (5)
C13A	0.5213 (3)	0.34254 (17)	0.54714 (13)	0.0258 (5)
O4B	1.2058 (2)	0.63511 (13)	0.93100 (10)	0.0398 (4)
N1B	1.0764 (2)	0.48489 (14)	0.68969 (11)	0.0253 (4)
C2B	1.0246 (3)	0.40701 (18)	0.78354 (14)	0.0310 (5)
C3B	1.2089 (3)	0.48633 (18)	0.89057 (14)	0.0354 (6)
C5B	1.2676 (3)	0.71057 (18)	0.84191 (15)	0.0355 (6)
C6B	1.0875 (3)	0.64183 (17)	0.73241 (14)	0.0298 (5)
H2A	−0.16720	0.03930	0.42160	0.0360*
H3A	−0.50810	−0.12330	0.29790	0.0440*
H4A	−0.48570	−0.21320	0.09880	0.0470*
H5A	−0.11570	−0.14440	0.02480	0.0460*
H6A	0.22990	0.01130	0.14920	0.0390*
H11A	0.43820	0.14510	0.34830	0.0310*
H12A	0.14000	0.24890	0.50070	0.0330*
H11B	1.227 (3)	0.4752 (17)	0.6663 (13)	0.0300*
H12B	0.951 (3)	0.4376 (17)	0.6261 (12)	0.0300*
H21B	1.03230	0.30470	0.75550	0.0370*
H22B	0.85830	0.40330	0.80370	0.0370*
H31B	1.17210	0.43540	0.95390	0.0420*
H32B	1.37370	0.48430	0.87120	0.0420*
H51B	1.43250	0.70830	0.82290	0.0430*
H52B	1.27130	0.81480	0.87160	0.0430*
H61B	0.92430	0.65020	0.74950	0.0360*
H62B	1.13770	0.69400	0.67100	0.0360*

	U11	U22	U33	U12	U13	U23
O13A	0.0181 (6)	0.0508 (8)	0.0320 (7)	0.0093 (5)	−0.0013 (5)	−0.0075 (6)
O14A	0.0217 (6)	0.0368 (7)	0.0304 (6)	0.0073 (5)	−0.0001 (5)	−0.0048 (5)
C1A	0.0255 (8)	0.0211 (8)	0.0289 (9)	0.0061 (7)	−0.0022 (7)	0.0063 (7)
C2A	0.0265 (8)	0.0251 (9)	0.0334 (9)	0.0043 (7)	−0.0008 (7)	0.0035 (7)
C3A	0.0259 (9)	0.0273 (9)	0.0516 (12)	0.0036 (7)	−0.0029 (8)	0.0075 (8)
C4A	0.0375 (10)	0.0242 (9)	0.0453 (11)	0.0036 (8)	−0.0174 (8)	0.0026 (8)
C5A	0.0522 (11)	0.0299 (10)	0.0279 (9)	0.0099 (9)	−0.0062 (8)	0.0026 (8)
C6A	0.0349 (9)	0.0279 (9)	0.0312 (9)	0.0069 (8)	0.0013 (7)	0.0065 (7)
C11A	0.0213 (8)	0.0277 (9)	0.0294 (9)	0.0065 (7)	0.0021 (6)	0.0080 (7)
C12A	0.0191 (8)	0.0311 (9)	0.0303 (9)	0.0072 (7)	0.0019 (6)	0.0039 (7)
C13A	0.0213 (8)	0.0295 (9)	0.0261 (9)	0.0076 (7)	0.0007 (6)	0.0064 (7)
O4B	0.0518 (8)	0.0356 (7)	0.0241 (6)	0.0068 (6)	−0.0002 (5)	0.0001 (5)
N1B	0.0185 (6)	0.0305 (8)	0.0222 (7)	0.0066 (6)	−0.0013 (5)	−0.0007 (6)
C2B	0.0287 (8)	0.0269 (9)	0.0361 (10)	0.0057 (7)	0.0024 (7)	0.0085 (8)
C3B	0.0402 (10)	0.0363 (10)	0.0286 (9)	0.0101 (8)	−0.0011 (7)	0.0088 (8)
C5B	0.0380 (10)	0.0257 (9)	0.0351 (10)	0.0009 (8)	0.0011 (8)	0.0032 (8)
C6B	0.0296 (9)	0.0280 (9)	0.0321 (9)	0.0082 (7)	0.0045 (7)	0.0085 (7)

O13A—C13A	1.258 (2)	C2A—H2A	0.9500
O14A—C13A	1.2553 (19)	C3A—H3A	0.9500
O4B—C3B	1.425 (2)	C4A—H4A	0.9500
O4B—C5B	1.424 (2)	C5A—H5A	0.9500
N1B—C2B	1.480 (2)	C6A—H6A	0.9500
N1B—C6B	1.480 (2)	C11A—H11A	0.9500
N1B—H11B	0.944 (18)	C12A—H12A	0.9500
N1B—H12B	0.943 (15)	C2B—C3B	1.503 (2)
C1A—C6A	1.390 (2)	C5B—C6B	1.501 (2)
C1A—C2A	1.396 (2)	C2B—H21B	0.9900
C1A—C11A	1.471 (2)	C2B—H22B	0.9900
C2A—C3A	1.381 (2)	C3B—H31B	0.9900
C3A—C4A	1.382 (3)	C3B—H32B	0.9900
C4A—C5A	1.382 (3)	C5B—H51B	0.9900
C5A—C6A	1.382 (2)	C5B—H52B	0.9900
C11A—C12A	1.314 (2)	C6B—H61B	0.9900
C12A—C13A	1.493 (2)	C6B—H62B	0.9900
C3B—O4B—C5B	109.75 (12)	C1A—C6A—H6A	120.00
C2B—N1B—C6B	111.05 (12)	C12A—C11A—H11A	117.00
C6B—N1B—H11B	110.9 (10)	C1A—C11A—H11A	117.00
C2B—N1B—H12B	107.7 (10)	C11A—C12A—H12A	118.00
H11B—N1B—H12B	109.8 (14)	C13A—C12A—H12A	118.00
C2B—N1B—H11B	107.0 (10)	N1B—C2B—C3B	109.50 (14)
C6B—N1B—H12B	110.3 (10)	O4B—C3B—C2B	110.91 (14)
C2A—C1A—C11A	121.67 (14)	O4B—C5B—C6B	111.36 (14)
C6A—C1A—C11A	120.00 (15)	N1B—C6B—C5B	109.46 (14)
C2A—C1A—C6A	118.33 (15)	N1B—C2B—H21B	110.00
C1A—C2A—C3A	120.55 (16)	N1B—C2B—H22B	110.00
C2A—C3A—C4A	120.46 (17)	C3B—C2B—H21B	110.00
C3A—C4A—C5A	119.55 (16)	C3B—C2B—H22B	110.00
C4A—C5A—C6A	120.21 (16)	H21B—C2B—H22B	108.00
C1A—C6A—C5A	120.88 (16)	O4B—C3B—H31B	109.00
C1A—C11A—C12A	126.79 (16)	O4B—C3B—H32B	109.00
C11A—C12A—C13A	123.45 (16)	C2B—C3B—H31B	109.00
O13A—C13A—O14A	123.98 (15)	C2B—C3B—H32B	109.00
O13A—C13A—C12A	118.14 (14)	H31B—C3B—H32B	108.00
O14A—C13A—C12A	117.87 (15)	O4B—C5B—H51B	109.00
C1A—C2A—H2A	120.00	O4B—C5B—H52B	109.00
C3A—C2A—H2A	120.00	C6B—C5B—H51B	109.00
C4A—C3A—H3A	120.00	C6B—C5B—H52B	109.00
C2A—C3A—H3A	120.00	H51B—C5B—H52B	108.00
C3A—C4A—H4A	120.00	N1B—C6B—H61B	110.00
C5A—C4A—H4A	120.00	N1B—C6B—H62B	110.00
C6A—C5A—H5A	120.00	C5B—C6B—H61B	110.00
C4A—C5A—H5A	120.00	C5B—C6B—H62B	110.00
C5A—C6A—H6A	120.00	H61B—C6B—H62B	108.00
C3B—O4B—C5B—C6B	61.19 (17)	C1A—C2A—C3A—C4A	−0.7 (3)
C5B—O4B—C3B—C2B	−61.29 (17)	C2A—C3A—C4A—C5A	1.0 (3)
C2B—N1B—C6B—C5B	54.09 (17)	C3A—C4A—C5A—C6A	0.2 (3)
C6B—N1B—C2B—C3B	−54.46 (17)	C4A—C5A—C6A—C1A	−1.8 (3)
C2A—C1A—C6A—C5A	2.1 (2)	C1A—C11A—C12A—C13A	178.94 (15)
C6A—C1A—C11A—C12A	158.54 (17)	C11A—C12A—C13A—O13A	−5.0 (2)
C11A—C1A—C6A—C5A	−178.16 (16)	C11A—C12A—C13A—O14A	175.97 (16)
C2A—C1A—C11A—C12A	−21.7 (3)	N1B—C2B—C3B—O4B	57.95 (17)
C6A—C1A—C2A—C3A	−0.8 (2)	O4B—C5B—C6B—N1B	−57.43 (18)
C11A—C1A—C2A—C3A	179.41 (16)

D—H···A	D—H	H···A	D···A	D—H···A
N1B—H11B···O14Ai	0.94 (2)	1.77 (2)	2.7052 (17)	170 (2)
N1B—H12B···O13A	0.94 (2)	1.73 (2)	2.6643 (17)	172 (2)
N1B—H12B···O14A	0.94 (2)	2.57 (2)	3.1868 (17)	123 (1)
C4A—H4A···O4Bii	0.95	2.46	3.393 (2)	167
C11A—H11A···O13A	0.95	2.48	2.812 (2)	101
C6B—H62B···O13Aiii	0.99	2.37	3.234 (2)	145

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N1BH11BO14A i	0.94(2)	1.77(2)	2.7052(17)	170(2)
N1BH12BO13A	0.94(2)	1.73(2)	2.6643(17)	172(2)
N1BH12BO14A	0.94(2)	2.57(2)	3.1868(17)	123(1)
C4AH4AO4B ii	0.95	2.46	3.393(2)	167
C6BH62BO13A iii	0.99	2.37	3.234(2)	145

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