(2S*)-2-Ammonio-3-(1H-indol-3-yl)propionate pyridine-2,4-dicarboxylic acid ethanol solvate.

In the title compound, C(11)H(12)N(2)O(2)·C(7)H(5)NO(4)·C(2)H(6)O, the (2S*)-2-amino-3-(1H-indol-3-yl)propionic acid is present in the zwitterionic form. In the crystal structure, 2-amino-3-(1H-indol-3-yl)propionic acid mol-ecules and pyridine-2,4-dicarb-oxylic acid mol-ecules are linked through strong inter-molecular O-H⋯O and N-H⋯O hydrogen bonds, forming layers parallel to (100). The layers are linked through the ethanol mol-ecules via somewhat weaker inter-molecular O-H⋯O and N-H⋯O hydrogen bonds, forming thus a three-dimensional network. Weak C-H⋯O and N-H⋯N hydrogen bonding and π-π inter-actions between the aromatic rings are also present.

Related literature

For supra­molecular structures with imino, carboxyl­ate and pyridine groups inter­connected via inter­molecular hydrogen bonds, see: Broker & Tiekink (2010 ▶); Hemamalini & Fun (2010 ▶); Narimani & Yamin (2010 ▶); Pourayoubi et al. (2010 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶). For hydrogen bonding, see: Desiraju & Steiner (1999 ▶).

Experimental

Crystal data

C11H12N2O2·C7H5NO4·C2H6O

M = 417.41

Triclinic,

a = 7.0320 (14) Å

b = 7.7590 (16) Å

c = 9.5800 (19) Å

α = 85.44 (3)°

β = 81.89 (3)°

γ = 71.84 (3)°

V = 491.34 (19) Å3

Z = 1

Mo Kα radiation

μ = 0.11 mm−1

T = 298 K

0.27 × 0.23 × 0.22 mm

Data collection

Bruker SMART 1000 CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.971, T max = 0.977

4115 measured reflections

2092 independent reflections

1815 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.109

S = 1.02

2092 reflections

285 parameters

6 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.18 e Å−3

Δρmin = −0.22 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810014017/fb2190sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810014017/fb2190Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C11H12N2O2·C7H5NO4·C2H6O	Z = 1
Mr = 417.41	F(000) = 220
Triclinic, P1	Dx = 1.411 Mg m−3
Hall symbol: P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.0320 (14) Å	Cell parameters from 1200 reflections
b = 7.7590 (16) Å	θ = 2.7–24.0°
c = 9.5800 (19) Å	µ = 0.11 mm−1
α = 85.44 (3)°	T = 298 K
β = 81.89 (3)°	Block, colourless
γ = 71.84 (3)°	0.27 × 0.23 × 0.22 mm
V = 491.34 (19) Å3

Bruker SMART 1000 CCD diffractometer	2092 independent reflections
Radiation source: fine-focus sealed tube	1815 reflections with I > 2σ(I)
graphite	Rint = 0.024
ω scans	θmax = 27.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
Tmin = 0.971, Tmax = 0.977	k = −9→9
4115 measured reflections	l = −12→12

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)] = 0.045	Hydrogen site location: difference Fourier map
wR(F2) = 0.109	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0628P)2] where P = (Fo2 + 2Fc2)/3
2092 reflections	(Δ/σ)max < 0.001
285 parameters	Δρmax = 0.18 e Å−3
6 restraints	Δρmin = −0.21 e Å−3
78 constraints

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.

	x	y	z	Uiso*/Ueq
O1	0.2726 (4)	0.7005 (3)	0.5137 (3)	0.0503 (7)
H1	0.276 (7)	0.635 (7)	0.439 (6)	0.075*
O2	0.1776 (6)	0.9447 (4)	0.3743 (3)	0.0725 (10)
O3	0.2236 (5)	0.7586 (4)	1.0219 (3)	0.0560 (8)
O4	0.1597 (5)	1.0309 (3)	1.1063 (2)	0.0509 (7)
H4	0.175 (7)	0.970 (6)	1.187 (3)	0.076*
O5	0.5693 (4)	0.2870 (4)	1.3453 (3)	0.0522 (7)
O6	0.2941 (4)	0.5149 (4)	1.3097 (3)	0.0554 (8)
O7	0.9134 (4)	0.3938 (4)	0.3005 (3)	0.0601 (8)
H7	0.831 (6)	0.332 (6)	0.301 (6)	0.090*
N1	0.1492 (4)	1.1892 (3)	0.8482 (3)	0.0316 (6)
N2	0.5947 (4)	0.2711 (4)	0.6481 (3)	0.0396 (7)
H2A	0.582 (7)	0.304 (6)	0.5569 (17)	0.059*
N3	0.2260 (4)	0.3869 (3)	1.0847 (3)	0.0304 (6)
H3A	0.2096	0.5039	1.0629	0.046*
H3B	0.1305	0.3763	1.1534	0.046*
H3C	0.2174	0.3316	1.0090	0.046*
C1	0.1801 (5)	1.0105 (4)	0.8599 (3)	0.0274 (6)
C2	0.2031 (5)	0.9032 (4)	0.7466 (3)	0.0288 (7)
H2	0.2292	0.7783	0.7597	0.035*
C3	0.1866 (5)	0.9845 (4)	0.6140 (3)	0.0302 (7)
C4	0.1478 (5)	1.1699 (5)	0.6004 (3)	0.0362 (8)
H4A	0.1329	1.2299	0.5128	0.043*
C5	0.1316 (5)	1.2645 (4)	0.7195 (3)	0.0346 (7)
H5	0.1068	1.3895	0.7090	0.042*
C6	0.2122 (5)	0.8722 (5)	0.4871 (3)	0.0400 (8)
C7	0.1919 (5)	0.9201 (4)	1.0033 (3)	0.0329 (7)
C8	0.6594 (5)	0.0930 (5)	0.8419 (3)	0.0311 (7)
C9	0.6549 (5)	0.0934 (5)	0.6954 (3)	0.0341 (7)
C10	0.7065 (6)	−0.0663 (5)	0.6231 (4)	0.0451 (9)
H10	0.7036	−0.0642	0.5263	0.054*
C11	0.7617 (6)	−0.2262 (5)	0.6995 (5)	0.0502 (10)
H11	0.7968	−0.3349	0.6535	0.060*
C12	0.7666 (6)	−0.2308 (6)	0.8447 (5)	0.0510 (10)
H12	0.8051	−0.3420	0.8938	0.061*
C13	0.7152 (5)	−0.0727 (5)	0.9160 (4)	0.0402 (8)
H13	0.7178	−0.0767	1.0130	0.048*
C14	0.6009 (5)	0.2784 (4)	0.8802 (3)	0.0314 (7)
C15	0.5622 (5)	0.3797 (5)	0.7600 (4)	0.0354 (7)
H15	0.5194	0.5059	0.7544	0.043*
C16	0.5926 (5)	0.3425 (5)	1.0252 (3)	0.0368 (8)
H16A	0.5705	0.4726	1.0191	0.044*
H16B	0.7223	0.2856	1.0590	0.044*
C17	0.4276 (5)	0.3016 (4)	1.1330 (3)	0.0303 (7)
H17	0.4531	0.1699	1.1423	0.036*
C18	0.4303 (5)	0.3726 (5)	1.2774 (3)	0.0349 (7)
C19	0.7449 (10)	0.7082 (7)	0.2595 (6)	0.0880 (18)
H19A	0.6650	0.6699	0.2022	0.132*
H19B	0.8566	0.7329	0.2008	0.132*
H19C	0.6635	0.8162	0.3066	0.132*
C20	0.8210 (7)	0.5635 (6)	0.3650 (5)	0.0608 (11)
H20A	0.9183	0.5939	0.4129	0.073*
H20B	0.7101	0.5543	0.4350	0.073*

	U11	U22	U33	U12	U13	U23
O1	0.0771 (19)	0.0433 (16)	0.0285 (13)	−0.0102 (14)	−0.0109 (12)	−0.0145 (11)
O2	0.128 (3)	0.066 (2)	0.0212 (13)	−0.0198 (19)	−0.0207 (15)	−0.0064 (13)
O3	0.105 (2)	0.0348 (14)	0.0324 (14)	−0.0252 (15)	−0.0166 (14)	0.0061 (11)
O4	0.100 (2)	0.0418 (15)	0.0188 (11)	−0.0313 (15)	−0.0099 (13)	0.0001 (10)
O5	0.0589 (17)	0.0725 (19)	0.0293 (13)	−0.0211 (14)	−0.0158 (12)	−0.0036 (13)
O6	0.0627 (18)	0.0611 (18)	0.0423 (16)	−0.0106 (14)	−0.0094 (13)	−0.0298 (13)
O7	0.0569 (18)	0.0624 (19)	0.0623 (19)	−0.0243 (14)	0.0092 (15)	−0.0139 (15)
N1	0.0417 (15)	0.0273 (14)	0.0255 (13)	−0.0086 (11)	−0.0053 (11)	−0.0044 (11)
N2	0.0477 (17)	0.0486 (18)	0.0227 (14)	−0.0155 (14)	−0.0048 (12)	0.0021 (13)
N3	0.0396 (15)	0.0306 (14)	0.0244 (13)	−0.0147 (12)	−0.0020 (10)	−0.0080 (10)
C1	0.0315 (15)	0.0293 (15)	0.0226 (14)	−0.0100 (12)	−0.0040 (11)	−0.0028 (12)
C2	0.0369 (16)	0.0255 (15)	0.0235 (15)	−0.0069 (13)	−0.0046 (12)	−0.0063 (12)
C3	0.0294 (16)	0.0399 (18)	0.0219 (14)	−0.0090 (14)	−0.0053 (12)	−0.0062 (13)
C4	0.047 (2)	0.0393 (19)	0.0226 (16)	−0.0142 (16)	−0.0075 (14)	0.0034 (14)
C5	0.0436 (18)	0.0273 (16)	0.0329 (17)	−0.0100 (14)	−0.0083 (14)	0.0030 (13)
C6	0.050 (2)	0.046 (2)	0.0230 (18)	−0.0117 (17)	−0.0045 (15)	−0.0066 (15)
C7	0.0490 (19)	0.0331 (19)	0.0219 (15)	−0.0177 (15)	−0.0084 (13)	−0.0028 (13)
C8	0.0297 (16)	0.0371 (17)	0.0276 (15)	−0.0126 (13)	0.0003 (12)	−0.0050 (13)
C9	0.0324 (17)	0.0437 (19)	0.0283 (16)	−0.0144 (15)	−0.0017 (13)	−0.0053 (15)
C10	0.051 (2)	0.056 (2)	0.0306 (18)	−0.0194 (18)	0.0049 (15)	−0.0206 (17)
C11	0.046 (2)	0.044 (2)	0.061 (3)	−0.0128 (18)	0.0051 (19)	−0.022 (2)
C12	0.051 (2)	0.038 (2)	0.059 (3)	−0.0112 (17)	0.0027 (19)	−0.0013 (18)
C13	0.043 (2)	0.040 (2)	0.0339 (18)	−0.0092 (16)	−0.0002 (14)	0.0002 (16)
C14	0.0327 (17)	0.0356 (17)	0.0255 (15)	−0.0096 (14)	0.0001 (12)	−0.0075 (13)
C15	0.0391 (18)	0.0355 (18)	0.0319 (17)	−0.0134 (15)	0.0004 (14)	−0.0025 (14)
C16	0.0455 (19)	0.0410 (19)	0.0288 (17)	−0.0209 (15)	0.0004 (14)	−0.0071 (14)
C17	0.0397 (17)	0.0310 (16)	0.0241 (15)	−0.0147 (13)	−0.0050 (12)	−0.0051 (12)
C18	0.0426 (19)	0.046 (2)	0.0233 (15)	−0.0229 (16)	−0.0025 (13)	−0.0059 (14)
C19	0.122 (5)	0.070 (4)	0.056 (3)	−0.013 (3)	−0.001 (3)	0.002 (3)
C20	0.061 (3)	0.074 (3)	0.046 (2)	−0.023 (2)	0.0042 (19)	−0.013 (2)

O1—C6	1.282 (5)	C5—H5	0.9300
O1—H1	0.90 (5)	C8—C13	1.390 (5)
O2—C6	1.199 (4)	C8—C9	1.408 (5)
O3—C7	1.205 (4)	C8—C14	1.430 (5)
O4—C7	1.310 (4)	C9—C10	1.389 (5)
O4—H4	0.875 (11)	C10—C11	1.364 (6)
O5—C18	1.235 (4)	C10—H10	0.9300
O6—C18	1.242 (4)	C11—C12	1.393 (6)
O7—C20	1.422 (5)	C11—H11	0.9300
O7—H7	0.855 (11)	C12—C13	1.374 (5)
N1—C5	1.326 (4)	C12—H12	0.9300
N1—C1	1.333 (4)	C13—H13	0.9300
N2—C15	1.367 (4)	C14—C15	1.352 (5)
N2—C9	1.370 (5)	C14—C16	1.500 (4)
N2—H2A	0.899 (11)	C15—H15	0.9300
N3—C17	1.488 (4)	C16—C17	1.534 (4)
N3—H3A	0.8900	C16—H16A	0.9700
N3—H3B	0.8900	C16—H16B	0.9700
N3—H3C	0.8900	C17—C18	1.534 (4)
C1—C2	1.381 (4)	C17—H17	0.9800
C1—C7	1.493 (4)	C19—C20	1.472 (7)
C2—C3	1.376 (4)	C19—H19A	0.9600
C2—H2	0.9300	C19—H19B	0.9600
C3—C4	1.377 (5)	C19—H19C	0.9600
C3—C6	1.509 (4)	C20—H20A	0.9700
C4—C5	1.378 (5)	C20—H20B	0.9700
C4—H4A	0.9300
C6—O1—H1	113 (3)	C10—C11—C12	121.7 (4)
C7—O4—H4	110 (3)	C10—C11—H11	119.2
C20—O7—H7	112 (4)	C12—C11—H11	119.2
C5—N1—C1	116.2 (3)	C13—C12—C11	120.7 (4)
C15—N2—C9	108.7 (3)	C13—C12—H12	119.6
C15—N2—H2A	128 (3)	C11—C12—H12	119.6
C9—N2—H2A	123 (3)	C12—C13—C8	119.4 (3)
C17—N3—H3A	109.5	C12—C13—H13	120.3
C17—N3—H3B	109.5	C8—C13—H13	120.3
H3A—N3—H3B	109.5	C15—C14—C8	106.3 (3)
C17—N3—H3C	109.5	C15—C14—C16	128.1 (3)
H3A—N3—H3C	109.5	C8—C14—C16	125.6 (3)
H3B—N3—H3C	109.5	C14—C15—N2	110.7 (3)
N1—C1—C2	123.8 (3)	C14—C15—H15	124.7
N1—C1—C7	118.4 (3)	N2—C15—H15	124.7
C2—C1—C7	117.8 (3)	C14—C16—C17	114.1 (3)
C3—C2—C1	118.8 (3)	C14—C16—H16A	108.7
C3—C2—H2	120.6	C17—C16—H16A	108.7
C1—C2—H2	120.6	C14—C16—H16B	108.7
C2—C3—C4	118.3 (3)	C17—C16—H16B	108.7
C2—C3—C6	120.5 (3)	H16A—C16—H16B	107.6
C4—C3—C6	121.2 (3)	N3—C17—C18	109.6 (3)
C3—C4—C5	118.5 (3)	N3—C17—C16	110.3 (3)
C3—C4—H4A	120.7	C18—C17—C16	110.3 (3)
C5—C4—H4A	120.7	N3—C17—H17	108.8
N1—C5—C4	124.3 (3)	C18—C17—H17	108.8
N1—C5—H5	117.8	C16—C17—H17	108.8
C4—C5—H5	117.8	O5—C18—O6	127.7 (3)
O2—C6—O1	125.9 (3)	O5—C18—C17	117.1 (3)
O2—C6—C3	120.3 (3)	O6—C18—C17	115.1 (3)
O1—C6—C3	113.8 (3)	C20—C19—H19A	109.5
O3—C7—O4	123.2 (3)	C20—C19—H19B	109.5
O3—C7—C1	122.3 (3)	H19A—C19—H19B	109.5
O4—C7—C1	114.5 (3)	C20—C19—H19C	109.5
C13—C8—C9	118.6 (3)	H19A—C19—H19C	109.5
C13—C8—C14	134.3 (3)	H19B—C19—H19C	109.5
C9—C8—C14	107.1 (3)	O7—C20—C19	111.0 (4)
N2—C9—C10	130.7 (3)	O7—C20—H20A	109.4
N2—C9—C8	107.2 (3)	C19—C20—H20A	109.4
C10—C9—C8	122.1 (3)	O7—C20—H20B	109.4
C11—C10—C9	117.6 (3)	C19—C20—H20B	109.4
C11—C10—H10	121.2	H20A—C20—H20B	108.0
C9—C10—H10	121.2

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3C···N1i	0.89	2.15	3.032 (4)	170
N3—H3B···O7ii	0.89	1.90	2.787 (4)	171
N3—H3A···O3	0.89	2.01	2.894 (4)	170
N2—H2A···O5iii	0.90 (1)	2.06 (2)	2.922 (4)	161 (4)
O7—H7···O5iii	0.86 (1)	1.96 (3)	2.762 (4)	155 (5)
O1—H1···O6iii	0.90 (5)	1.58 (6)	2.479 (3)	177 (5)
O4—H4···O2iv	0.88 (1)	1.79 (2)	2.611 (3)	155 (5)
C20—H20A···O6v	0.97	2.59	3.200 (6)	122

Cg···Cg	distance	Cg···Cg	distance
Cg1···Cg3i	3.665 (2)	Cg2···Cg3i	3.722 (2)
Cg1···Cg3ii	3.683 (2)	Cg2···Cg3ii	3.701 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3C⋯N1i	0.89	2.15	3.032 (4)	170
N3—H3B⋯O7ii	0.89	1.90	2.787 (4)	171
N3—H3A⋯O3	0.89	2.01	2.894 (4)	170
N2—H2A⋯O5iii	0.90 (1)	2.06 (2)	2.922 (4)	161 (4)
O7—H7⋯O5iii	0.86 (1)	1.96 (3)	2.762 (4)	155 (5)
O1—H1⋯O6iii	0.90 (5)	1.58 (6)	2.479 (3)	177 (5)
O4—H4⋯O2iv	0.88 (1)	1.79 (2)	2.611 (3)	155 (5)
C20—H20A⋯O6v	0.97	2.59	3.200 (6)	122

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

Table 2

π–π inter­actions (Å)

Cg1, Cg2 and Cg3 are the centroids of the N2,C9,C8,C14,C15 (pyrrole), C8–C13 (benzene) and N1,C1–C5 (pyridine) rings, respectively.

Cg1⋯Cg3i	3.665 (2)	Cg2⋯Cg3i	3.722 (2)
Cg1⋯Cg3ii	3.683 (2)	Cg2⋯Cg3ii	3.701 (2)

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