(R,S)-3-Carb­oxy-2-(isoquinolinium-2-yl)propanoate monohydrate

Stilinović, V.; Frkanec, L.; Kaitner, B.

doi:10.1107/S1600536810018428

organic compounds

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Volume 66| Part 6| June 2010| Page o1427

https://doi.org/10.1107/S1600536810018428

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(R,S)-3-Carboxy-2-(isoquinolinium-2-yl)propanoate monohydrate

Vladimir Stilinović,^a Leo Frkanec ^b and Branko Kaitner ^a ^*

^aLaboratory of General and Inorganic Chemistry, Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102 A, HR-10000 Zagreb, Croatia, and ^bDepartment of Organic Chemistry and Biochemistry, Ruder Bošković Institute, PO Box 180, HR-10002 Zagreb, Croatia
^*Correspondence e-mail: kaitner@chem.pmf.hr

(Received 15 April 2010; accepted 18 May 2010; online 22 May 2010)

The title compound, C₁₃H₁₁NO₄·H₂O, is a monohydrate of a betaine exhibiting a positively charged N-substituted isoquinoline group and a deprotonated carboxyl group. In the crystal, molecules are connected via short O—H⋯O hydrogen bonds between protonated and deprotonated carboxyl groups into chains of either R or S enantiomers along [001]. These chains are additionally connected by hydrogen bonding between water molecules and the deprotonated carboxy groups of neighbouring molecules.

Related literature

For the structure of a co-crystal of a quinoline derivative betaine, see: Szafran et al. (2002 ) and for the structure of a 4-dithiocarboxylisoquinoline betaine, see: Matthews et al. (1973 ). For possible applications of isoquinoline derivatives, see: Katritsky & Pozharskii (2000 ). For the preparation of the title compound, see: Flett & Gardner (1952 ).

Experimental

Crystal data

C₁₃H₁₁NO₄·H₂O
M_r = 263.24
Monoclinic, P c
a = 10.1030 (15) Å
b = 8.0706 (8) Å
c = 7.8911 (10) Å
β = 104.282 (14)°
V = 623.53 (14) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 295 K
0.43 × 0.19 × 0.17 mm

Data collection

Oxford Diffraction Xcalibur CCD diffractometer
7142 measured reflections
1659 independent reflections
994 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.076
wR(F²) = 0.222
S = 1.02
1659 reflections
178 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H1⋯O2	0.86 (6)	2.05 (6)	2.851 (7)	156 (6)
O5—H2⋯O2ⁱ	0.86 (6)	2.08 (7)	2.874 (7)	153 (6)
O4—H4⋯O1ⁱⁱ	0.82	1.70	2.518 (7)	172
Symmetry codes: (i) $[x, -y+2, z+{\script{1\over 2}}]$ ; (ii) x, y, z-1.

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ), PLATON (Spek, 2009 ) and PARST (Nardelli, 1995 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810018428/im2195sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810018428/im2195Isup2.hkl

checkCIF report

Comment top

Isoquinoline derivatives are of interest in synthesizing new fungicides, insecticides, textile assistants, corrosion inhibitors, dye stabilizers, and pharmaceuticals (Katritsky & Pozharskii, 2000) The molecular structure of I is given in Figure 1. The molecule of 3-carboxy-2-isoquinolinium-2-ylpropanoate is a betaine, i.e. a zwitterion containing a quaternary nitrogen atom and a deprotonated carboxyl group. It is the first betaine derived from isoquinoline to be structurally characterised, the only two similar compounds being a quinoline derivative (Szafran et al., 2002) and a 4-dithiocarboxylisoquinoline derivative (Matthews et al., 1973)

The compound crystallises in the space group Pc with two formula units per unit cell. Molecules of 3-carboxy-2-isoquinolinium-2-ylpropanoate are connected via strong hydrogen bonds between protonated and deprotonated carboxyl groups (O4—H4···O1 2.518 (7) Å, (x, y, -1+z)) along the c axis. Water molecules bridge two deprotonated carboxyl groups of neighbouring molecules along chains (O5—H2···O2 2.874 (7) Å, (x, 2- y, 1/2 + z) and O5—H1···O2 2.851 (7) Å). Chains consist of either R or S enantiomers and each chain is interconnected by water molecules to a neighbouring chain in which the molecules are of opposite chirality, thus forming double chains about the glide plane.

Related literature top

For the structure of a co-crystal of a quinoline derivative betaine, see: Szafran et al. (2002) and for the structure of a 4-dithiocarboxylisoquinoline betaine, see: Matthews et al. (1973). For possible applications of isoquinoline derivatives, see: Katritsky & Pozharskii (2000). For the preparation of the title compound, see: Flett & Gardner (1952).

Experimental top

The title compound (I) was prepared according to a method described earlier (Flett & Gardner, 1952). Separate solutions are prepared of isoquinoline (1.17 ml; 10 mmol) and maleic acid (1.16 g; 10 mmol) in anhydrous ether. Upon mixing, isoquinolinium maleate precipitates. This precipitate is separated by filtration, washed, and dried. It is then rapidly heated to its melting point at 103 °C and held at this temperature for a few minutes. Rapid conversion to the betaine takes place. The betaine is then purified by dissolving it in hot water and treatment with animal charcoal. The solution was set aside for the formation of crystals, yield is 79 %. Crystals suitable for crystallographic study were grown from a solution of (I) in water by slow evaporation at room temperature.

Structure description top

For the structure of a co-crystal of a quinoline derivative betaine, see: Szafran et al. (2002) and for the structure of a 4-dithiocarboxylisoquinoline betaine, see: Matthews et al. (1973). For possible applications of isoquinoline derivatives, see: Katritsky & Pozharskii (2000). For the preparation of the title compound, see: Flett & Gardner (1952).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 1999), PLATON (Spek, 2009) and PARST (Nardelli, 1995).

Figures top

	Fig. 1. View of (I) with the atom labeling scheme. Displacement ellipsoids of are shown at 30% probability. Hydrogen atoms are shown as spheres of arbitrary radii.
	Fig. 2. Crystal packing of (I) viewed along the x axis.

(R,S)-3-Carboxy-2-(isoquinolin-2-ium-2-yl)propanoate monohydrate top

Crystal data top

C₁₃H₁₁NO₄·H₂O	F(000) = 276
M_r = 263.24	D_x = 1.402 Mg m⁻³
Monoclinic, Pc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P -2yc	Cell parameters from 275 reflections
a = 10.1030 (15) Å	θ = 4.6–52.0°
b = 8.0706 (8) Å	µ = 0.11 mm⁻¹
c = 7.8911 (10) Å	T = 295 K
β = 104.282 (14)°	Prism, colourless
V = 623.53 (14) Å³	0.43 × 0.19 × 0.17 mm
Z = 2

Data collection top

Oxford Diffraction Xcalibur CCD diffractometer	994 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.054
Graphite monochromator	θ_max = 29°, θ_min = 3.9°
ω scan	h = −13→13
7142 measured reflections	k = −11→11
1659 independent reflections	l = −10→10

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)] = 0.076	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.222	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.1361P)²] where P = (F_o² + 2F_c²)/3
1659 reflections	(Δ/σ)_max < 0.001
178 parameters	Δρ_max = 0.38 e Å⁻³
6 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₃H₁₁NO₄·H₂O	V = 623.53 (14) Å³
M_r = 263.24	Z = 2
Monoclinic, Pc	Mo Kα radiation
a = 10.1030 (15) Å	µ = 0.11 mm⁻¹
b = 8.0706 (8) Å	T = 295 K
c = 7.8911 (10) Å	0.43 × 0.19 × 0.17 mm
β = 104.282 (14)°

Data collection top

Oxford Diffraction Xcalibur CCD diffractometer	994 reflections with I > 2σ(I)
7142 measured reflections	R_int = 0.054
1659 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.076	6 restraints
wR(F²) = 0.222	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.38 e Å⁻³
1659 reflections	Δρ_min = −0.23 e Å⁻³
178 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
O5	0.9214 (4)	0.9884 (8)	0.9683 (6)	0.0817 (17)
H1	0.865 (6)	0.928 (9)	0.895 (8)	0.085*
H2	0.885 (7)	1.014 (11)	1.052 (7)	0.086*
O3	0.5000 (5)	0.8301 (5)	0.0404 (6)	0.0581 (12)
O1	0.5719 (5)	0.7025 (7)	0.6870 (6)	0.0664 (14)
O4	0.6768 (5)	0.6788 (6)	0.0104 (6)	0.0576 (12)
H4	0.6439	0.6955	−0.094	0.086*
C2	0.5675 (6)	0.8088 (7)	0.4031 (6)	0.0340 (11)
H2A	0.5661	0.9273	0.3756	0.041*
N1	0.4242 (5)	0.7538 (5)	0.3583 (6)	0.0375 (10)
C4	0.6005 (6)	0.7514 (6)	0.1025 (7)	0.0372 (12)
C1	0.6317 (6)	0.7933 (7)	0.6011 (7)	0.0384 (12)
O2	0.7403 (5)	0.8672 (6)	0.6568 (6)	0.0584 (12)
C12	0.2584 (7)	0.5400 (7)	0.3023 (7)	0.0448 (13)
C3	0.6546 (6)	0.7251 (7)	0.2928 (7)	0.0415 (13)
H3A	0.7469	0.7684	0.3277	0.05*
H3B	0.6589	0.6071	0.3167	0.05*
C13	0.3918 (7)	0.5934 (7)	0.3442 (8)	0.0446 (13)
H13	0.4616	0.5153	0.3632	0.054*
C7	0.1528 (8)	0.6561 (9)	0.2716 (11)	0.0632 (18)
C6	0.1918 (8)	0.8250 (10)	0.287 (2)	0.115 (5)
H6	0.1246	0.9064	0.2687	0.137*
C10	0.0902 (11)	0.3265 (12)	0.251 (2)	0.121 (5)
H10	0.0679	0.2145	0.2447	0.146*
C8	0.0157 (8)	0.6063 (11)	0.2240 (15)	0.088 (3)
H8	−0.0545	0.6839	0.1992	0.105*
C11	0.2251 (9)	0.3727 (10)	0.2954 (16)	0.093 (3)
H11	0.2935	0.2928	0.3209	0.112*
C9	−0.0115 (9)	0.4417 (12)	0.2152 (14)	0.089 (3)
H9	−0.102	0.4065	0.184	0.107*
C5	0.3220 (8)	0.8692 (9)	0.3285 (14)	0.083 (3)
H5	0.3444	0.9812	0.3373	0.099*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O5	0.058 (3)	0.088 (4)	0.093 (4)	0.004 (3)	0.009 (3)	−0.029 (3)
O3	0.070 (3)	0.058 (3)	0.044 (2)	0.011 (3)	0.010 (2)	0.012 (2)
O1	0.087 (4)	0.088 (3)	0.0270 (19)	−0.019 (3)	0.020 (2)	0.006 (2)
O4	0.074 (3)	0.068 (3)	0.032 (2)	0.004 (2)	0.0153 (19)	−0.004 (2)
C2	0.050 (3)	0.035 (3)	0.0162 (18)	−0.003 (2)	0.0079 (19)	0.0013 (18)
N1	0.049 (3)	0.030 (2)	0.031 (2)	0.0015 (19)	0.0078 (18)	−0.0013 (17)
C4	0.045 (3)	0.036 (3)	0.030 (3)	−0.011 (2)	0.008 (2)	−0.013 (2)
C1	0.040 (3)	0.042 (3)	0.034 (3)	0.000 (2)	0.009 (2)	0.002 (2)
O2	0.056 (3)	0.077 (3)	0.037 (2)	−0.020 (2)	0.0025 (18)	0.002 (2)
C12	0.045 (3)	0.047 (3)	0.039 (3)	−0.004 (3)	0.003 (2)	0.004 (2)
C3	0.048 (3)	0.043 (3)	0.029 (3)	0.000 (3)	0.002 (2)	0.007 (2)
C13	0.049 (4)	0.035 (3)	0.048 (3)	0.002 (3)	0.007 (3)	0.003 (2)
C7	0.043 (4)	0.054 (4)	0.090 (5)	0.003 (3)	0.013 (3)	−0.012 (3)
C6	0.037 (5)	0.043 (4)	0.244 (15)	0.004 (3)	−0.002 (6)	−0.030 (6)
C10	0.066 (6)	0.059 (5)	0.215 (15)	−0.022 (4)	−0.010 (7)	0.032 (7)
C8	0.039 (4)	0.073 (5)	0.142 (8)	−0.008 (4)	0.006 (4)	−0.010 (6)
C11	0.067 (6)	0.042 (4)	0.152 (9)	−0.010 (4)	−0.008 (6)	−0.001 (5)
C9	0.047 (5)	0.085 (6)	0.126 (8)	−0.029 (4)	0.003 (4)	−0.006 (5)
C5	0.045 (4)	0.034 (3)	0.157 (8)	0.008 (3)	0.004 (4)	−0.024 (4)

Geometric parameters (Å, º) top

O5—H1	0.86 (6)	C12—C7	1.396 (9)
O5—H2	0.86 (6)	C3—H3A	0.97
O3—C4	1.195 (7)	C3—H3B	0.97
O1—C1	1.250 (7)	C13—H13	0.93
O4—C4	1.320 (7)	C7—C8	1.402 (11)
O4—H4	0.82	C7—C6	1.416 (11)
C2—N1	1.471 (7)	C6—C5	1.324 (11)
C2—C3	1.538 (7)	C6—H6	0.93
C2—C1	1.543 (6)	C10—C9	1.364 (13)
C2—H2A	0.98	C10—C11	1.372 (12)
N1—C13	1.333 (7)	C10—H10	0.93
N1—C5	1.368 (8)	C8—C9	1.354 (12)
C4—C3	1.481 (7)	C8—H8	0.93
C1—O2	1.231 (7)	C11—H11	0.93
C12—C13	1.375 (8)	C9—H9	0.93
C12—C11	1.389 (10)	C5—H5	0.93

H1—O5—H2	109 (7)	H3A—C3—H3B	107.8
C4—O4—H4	109.5	N1—C13—C12	122.0 (5)
N1—C2—C3	113.5 (4)	N1—C13—H13	119
N1—C2—C1	111.2 (4)	C12—C13—H13	119
C3—C2—C1	112.4 (4)	C12—C7—C8	121.1 (7)
N1—C2—H2A	106.4	C12—C7—C6	116.5 (7)
C3—C2—H2A	106.4	C8—C7—C6	122.3 (7)
C1—C2—H2A	106.4	C5—C6—C7	121.3 (7)
C13—N1—C5	119.2 (6)	C5—C6—H6	119.3
C13—N1—C2	121.3 (5)	C7—C6—H6	119.3
C5—N1—C2	119.5 (5)	C9—C10—C11	121.2 (8)
O3—C4—O4	124.2 (5)	C9—C10—H10	119.4
O3—C4—C3	123.8 (5)	C11—C10—H10	119.4
O4—C4—C3	112.0 (5)	C9—C8—C7	118.0 (8)
O2—C1—O1	126.7 (5)	C9—C8—H8	121
O2—C1—C2	116.0 (5)	C7—C8—H8	121
O1—C1—C2	117.2 (5)	C10—C11—C12	119.3 (8)
C13—C12—C11	121.9 (6)	C10—C11—H11	120.3
C13—C12—C7	119.5 (6)	C12—C11—H11	120.3
C11—C12—C7	118.6 (7)	C8—C9—C10	121.7 (8)
C4—C3—C2	113.0 (4)	C8—C9—H9	119.2
C4—C3—H3A	109	C10—C9—H9	119.2
C2—C3—H3A	109	C6—C5—N1	121.4 (7)
C4—C3—H3B	109	C6—C5—H5	119.3
C2—C3—H3B	109	N1—C5—H5	119.3

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H1···O2	0.86 (6)	2.05 (6)	2.851 (7)	156 (6)
O5—H2···O2ⁱ	0.86 (6)	2.08 (7)	2.874 (7)	153 (6)
O4—H4···O1ⁱⁱ	0.82	1.70	2.518 (7)	172

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₁NO₄·H₂O
M_r	263.24
Crystal system, space group	Monoclinic, Pc
Temperature (K)	295
a, b, c (Å)	10.1030 (15), 8.0706 (8), 7.8911 (10)
β (°)	104.282 (14)
V (Å³)	623.53 (14)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.43 × 0.19 × 0.17

Data collection
Diffractometer	Oxford Diffraction Xcalibur CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7142, 1659, 994
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.682

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.076, 0.222, 1.02
No. of reflections	1659
No. of parameters	178
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.23

Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006), WinGX (Farrugia, 1999), PLATON (Spek, 2009) and PARST (Nardelli, 1995).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H1···O2	0.86 (6)	2.05 (6)	2.851 (7)	156 (6)
O5—H2···O2ⁱ	0.86 (6)	2.08 (7)	2.874 (7)	153 (6)
O4—H4···O1ⁱⁱ	0.82	1.70	2.518 (7)	172

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

Acknowledgements

The authors would like to thank the Ministry of Science, Education and Sport, Republic of Croatia, for financial support of this work through grant Nos. 119–1193079-3069, 119–1191342-2960 and 098–0982904-29121.

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