Crystal structure of l-tryptophan-fumaric acid-water (1/1/1).

In the title compound, C11H12N2O2·C4H4O4·H2O, the l-tryp-to-phan mol-ecule crystallized as a zwitterion, together with a neutral fumaric acid mol-ecule and a water solvent mol-ecule. In the crystal, the three components are linked by a series of N-H⋯O, O-H⋯O and C-H⋯O hydrogen bonds, forming slabs lying parallel to (001). The slabs are connected by O-H⋯O hydrogen bonds, involving inversion-related fumaric acid groups, leading to the formation of a three-dimensional structure.

Related literature

For literature on the UV spectroscopy of proteins, see: Demchenko (1986 ▸). For the different polymorphic forms of fumaric acid, see: Reis & Schneider (1928 ▸); Yardley (1925 ▸); Bednowitz & Post (1966 ▸). For the nonlinear optical properties of organic mol­ecules, see: Chemla & Zyss (1987 ▸); Zyss & Ledoux (1994 ▸); Zyss & Nicoud (1996 ▸). For the common conformations of l-tryptophan, see: Bye et al. (1973 ▸); Bakke & Mostad (1980 ▸). The bond lengths and angles in l-trypophan, see, for example: Gorbitz (2006 ▸); Gorbitz et al. (2012 ▸), and for fumaric acid, see: Goswami et al. (1999 ▸). For the crystal structure of l-tryptophan formic acid solvate, see: Hubschle et al. (2002 ▸). For details of the Cambridge Structural Database, see: Groom & Allen (2014 ▸).

Experimental

Crystal data

C11H12N2O2·C4H4O4·H2O

M = 338.31

Monoclinic,

a = 11.3928 (8) Å

b = 6.6476 (4) Å

c = 21.4219 (13) Å

β = 95.801 (3)°

V = 1614.07 (18) Å3

Z = 4

Mo Kα radiation

μ = 0.11 mm−1

T = 296 K

0.30 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▸) T min = 0.898, T max = 0.978

10737 measured reflections

3157 independent reflections

2731 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.084

S = 1.04

3157 reflections

242 parameters

4 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.18 e Å−3

Δρmin = −0.15 e Å−3

Data collection: APEX2 (Bruker, 2004 ▸); cell refinement: APEX2 and SAINT (Bruker, 2004 ▸); data reduction: SAINT and XPREP (Bruker, 2004 ▸); program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸) and Mercury (Macrae et al., 2008 ▸); software used to prepare material for publication: SHELXL2014 and PLATON (Spek, 2009 ▸).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S205698901501484X/su5176sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S205698901501484X/su5176Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S205698901501484X/su5176Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S205698901501484X/su5176fig1.tif

The mol­ecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 40% probability level.

Click here for additional data file.

a . DOI: 10.1107/S205698901501484X/su5176fig2.tif

The crystal packing of the title compound, viewed along the a axis. The hydrogen bonds are shown as dashed lines (see Table 1 for details).

Click here for additional data file.

b . DOI: 10.1107/S205698901501484X/su5176fig3.tif

The crystal packing of the title compound, viewed along the b axis. The hydrogen bonds are shown as dashed lines (see Table 1 for details).

CCDC reference: 1417535

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

C11H12N2O2·C4H4O4·H2O	F(000) = 712
Mr = 338.31	Dx = 1.392 Mg m−3
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
a = 11.3928 (8) Å	Cell parameters from 5033 reflections
b = 6.6476 (4) Å	θ = 2.8–27.9°
c = 21.4219 (13) Å	µ = 0.11 mm−1
β = 95.801 (3)°	T = 296 K
V = 1614.07 (18) Å3	Block, colourless
Z = 4	0.30 × 0.20 × 0.20 mm

Bruker Kappa APEXII CCD diffractometer	2731 reflections with I > 2σ(I)
Radiation source: Sealed X-ray tube	Rint = 0.025
ω and φ scan	θmax = 26.0°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −14→14
Tmin = 0.898, Tmax = 0.978	k = −8→8
10737 measured reflections	l = −26→26
3157 independent reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.084	w = 1/[σ2(Fo2) + (0.0458P)2 + 0.2154P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
3157 reflections	Δρmax = 0.18 e Å−3
242 parameters	Δρmin = −0.15 e Å−3
4 restraints	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0069 (11)

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.

	x	y	z	Uiso*/Ueq
N1	0.75082 (19)	0.1813 (4)	0.77433 (10)	0.0380 (5)
H1	0.825 (3)	0.191 (5)	0.7735 (13)	0.047 (8)*
N2	0.5095 (2)	0.4264 (3)	0.91895 (10)	0.0276 (5)
H2A	0.472 (3)	0.534 (5)	0.9350 (15)	0.056 (10)*
H2B	0.563 (3)	0.476 (5)	0.8921 (14)	0.049 (8)*
H2C	0.554 (3)	0.365 (4)	0.9546 (15)	0.047 (9)*
O1	0.24153 (16)	0.1425 (3)	0.89730 (8)	0.0483 (5)
O2	0.35274 (17)	0.2275 (3)	0.98224 (8)	0.0485 (6)
O3	0.50562 (13)	0.6533 (3)	0.80307 (7)	0.0334 (4)
O4	0.69014 (13)	0.6700 (3)	0.77851 (7)	0.0381 (4)
H4O	0.7050	0.6615	0.8167	0.057*
O5	0.63962 (18)	0.6937 (5)	0.54724 (8)	0.0706 (7)
H5O	0.6080	0.6855	0.5112	0.106*
O6	0.45352 (18)	0.6884 (4)	0.57018 (8)	0.0595 (6)
O7	0.37013 (19)	0.7265 (3)	0.97085 (11)	0.0532 (6)
H7A	0.304 (2)	0.705 (5)	0.9880 (16)	0.080*
H7B	0.382 (3)	0.852 (4)	0.9713 (18)	0.080*
C1	0.3327 (2)	0.2159 (3)	0.92463 (10)	0.0263 (5)
C2	0.4263 (2)	0.2860 (3)	0.88365 (10)	0.0244 (5)
H2	0.3876	0.3556	0.8468	0.029*
C3	0.4928 (2)	0.1034 (4)	0.86179 (12)	0.0328 (6)
H3A	0.5345	0.0401	0.8983	0.039*
H3B	0.4354	0.0073	0.8432	0.039*
C4	0.5792 (2)	0.1458 (4)	0.81563 (11)	0.0302 (5)
C5	0.6979 (2)	0.1602 (4)	0.82805 (11)	0.0357 (6)
H5	0.7379	0.1562	0.8681	0.043*
C6	0.6657 (2)	0.1816 (4)	0.72436 (11)	0.0333 (6)
C7	0.6742 (2)	0.1930 (5)	0.66020 (12)	0.0445 (7)
H7	0.7471	0.2041	0.6445	0.053*
C8	0.5720 (3)	0.1874 (5)	0.62093 (12)	0.0508 (7)
H8	0.5756	0.1951	0.5778	0.061*
C9	0.4630 (2)	0.1705 (5)	0.64405 (13)	0.0507 (7)
H9	0.3951	0.1677	0.6160	0.061*
C10	0.4529 (2)	0.1579 (5)	0.70688 (11)	0.0417 (6)
H10	0.3792	0.1472	0.7216	0.050*
C11	0.5557 (2)	0.1615 (4)	0.74880 (11)	0.0312 (5)
C13	0.57628 (19)	0.6648 (4)	0.76415 (10)	0.0286 (5)
C14	0.5377 (2)	0.6733 (4)	0.69680 (10)	0.0365 (6)
H14	0.4570	0.6672	0.6848	0.044*
C15	0.6070 (2)	0.6888 (5)	0.65258 (11)	0.0418 (7)
H15	0.6880	0.6994	0.6632	0.050*
C16	0.5603 (2)	0.6899 (5)	0.58582 (11)	0.0447 (7)

	U11	U22	U33	U12	U13	U23
N1	0.0245 (11)	0.0520 (14)	0.0381 (12)	0.0037 (12)	0.0067 (9)	−0.0028 (12)
N2	0.0274 (12)	0.0345 (12)	0.0219 (11)	−0.0020 (9)	0.0072 (9)	0.0000 (9)
O1	0.0374 (11)	0.0818 (15)	0.0254 (9)	−0.0268 (11)	0.0019 (7)	−0.0006 (10)
O2	0.0441 (11)	0.0834 (16)	0.0183 (9)	−0.0273 (11)	0.0045 (7)	−0.0019 (9)
O3	0.0300 (9)	0.0449 (10)	0.0260 (8)	−0.0024 (9)	0.0056 (7)	0.0031 (8)
O4	0.0278 (9)	0.0651 (11)	0.0216 (8)	−0.0034 (10)	0.0026 (6)	0.0003 (10)
O5	0.0548 (13)	0.133 (2)	0.0237 (9)	−0.0004 (17)	0.0058 (9)	−0.0012 (15)
O6	0.0464 (12)	0.1044 (17)	0.0265 (9)	0.0027 (13)	−0.0027 (8)	0.0012 (12)
O7	0.0511 (13)	0.0543 (13)	0.0578 (13)	0.0096 (11)	0.0227 (10)	0.0010 (11)
C1	0.0249 (12)	0.0323 (13)	0.0220 (11)	−0.0021 (10)	0.0034 (10)	−0.0003 (10)
C2	0.0250 (13)	0.0331 (12)	0.0149 (11)	0.0015 (10)	0.0011 (9)	0.0015 (9)
C3	0.0399 (15)	0.0318 (13)	0.0275 (13)	0.0034 (11)	0.0073 (12)	−0.0007 (10)
C4	0.0304 (12)	0.0315 (12)	0.0295 (12)	0.0041 (12)	0.0074 (9)	−0.0047 (11)
C5	0.0371 (14)	0.0387 (13)	0.0312 (13)	0.0068 (13)	0.0029 (10)	−0.0028 (12)
C6	0.0327 (13)	0.0365 (13)	0.0317 (12)	0.0040 (12)	0.0076 (10)	−0.0033 (12)
C7	0.0416 (15)	0.0558 (17)	0.0384 (14)	0.0055 (15)	0.0158 (12)	−0.0013 (14)
C8	0.0600 (19)	0.0640 (19)	0.0291 (13)	0.0095 (18)	0.0084 (13)	0.0003 (15)
C9	0.0446 (16)	0.0678 (19)	0.0374 (14)	0.0066 (17)	−0.0071 (12)	−0.0061 (16)
C10	0.0301 (13)	0.0578 (16)	0.0373 (14)	0.0054 (15)	0.0033 (11)	−0.0047 (15)
C11	0.0286 (12)	0.0331 (12)	0.0323 (12)	0.0049 (12)	0.0056 (9)	−0.0043 (12)
C13	0.0286 (12)	0.0313 (12)	0.0257 (11)	−0.0016 (12)	0.0024 (9)	0.0003 (11)
C14	0.0328 (13)	0.0500 (15)	0.0263 (12)	−0.0002 (14)	0.0002 (10)	−0.0013 (14)
C15	0.0339 (14)	0.0630 (18)	0.0278 (13)	0.0024 (15)	−0.0002 (11)	−0.0004 (14)
C16	0.0429 (16)	0.0637 (19)	0.0279 (13)	0.0031 (16)	0.0053 (11)	−0.0018 (15)

N1—C5	1.359 (3)	C3—H3A	0.9700
N1—C6	1.370 (3)	C3—H3B	0.9700
N1—H1	0.85 (3)	C4—C5	1.355 (3)
N2—C2	1.482 (3)	C4—C11	1.433 (3)
N2—H2A	0.92 (4)	C5—H5	0.9300
N2—H2B	0.94 (3)	C6—C7	1.390 (3)
N2—H2C	0.96 (3)	C6—C11	1.413 (3)
O1—C1	1.240 (3)	C7—C8	1.366 (4)
O2—C1	1.235 (3)	C7—H7	0.9300
O3—C13	1.219 (3)	C8—C9	1.387 (4)
O4—C13	1.303 (3)	C8—H8	0.9300
O4—H4O	0.8200	C9—C10	1.365 (4)
O5—C16	1.285 (3)	C9—H9	0.9300
O5—H5O	0.8200	C10—C11	1.401 (3)
O6—C16	1.229 (3)	C10—H10	0.9300
O7—H7A	0.88 (2)	C13—C14	1.466 (3)
O7—H7B	0.85 (2)	C14—C15	1.297 (3)
C1—C2	1.521 (3)	C14—H14	0.9300
C2—C3	1.529 (3)	C15—C16	1.475 (3)
C2—H2	0.9800	C15—H15	0.9300
C3—C4	1.491 (3)
C5—N1—C6	108.8 (2)	N1—C5—H5	124.4
C5—N1—H1	123.6 (19)	N1—C6—C7	131.2 (2)
C6—N1—H1	127.6 (19)	N1—C6—C11	107.1 (2)
C2—N2—H2A	113 (2)	C7—C6—C11	121.7 (2)
C2—N2—H2B	109.4 (19)	C8—C7—C6	117.9 (2)
H2A—N2—H2B	108 (3)	C8—C7—H7	121.1
C2—N2—H2C	113.4 (17)	C6—C7—H7	121.1
H2A—N2—H2C	105 (2)	C7—C8—C9	121.4 (2)
H2B—N2—H2C	108 (2)	C7—C8—H8	119.3
C13—O4—H4O	109.5	C9—C8—H8	119.3
C16—O5—H5O	109.5	C10—C9—C8	121.6 (3)
H7A—O7—H7B	107 (3)	C10—C9—H9	119.2
O2—C1—O1	123.9 (2)	C8—C9—H9	119.2
O2—C1—C2	119.2 (2)	C9—C10—C11	118.9 (2)
O1—C1—C2	116.79 (19)	C9—C10—H10	120.6
N2—C2—C1	110.35 (18)	C11—C10—H10	120.6
N2—C2—C3	110.2 (2)	C10—C11—C6	118.6 (2)
C1—C2—C3	109.37 (19)	C10—C11—C4	134.3 (2)
N2—C2—H2	109.0	C6—C11—C4	107.1 (2)
C1—C2—H2	109.0	O3—C13—O4	123.4 (2)
C3—C2—H2	109.0	O3—C13—C14	121.5 (2)
C4—C3—C2	115.7 (2)	O4—C13—C14	115.07 (19)
C4—C3—H3A	108.4	C15—C14—C13	125.3 (2)
C2—C3—H3A	108.4	C15—C14—H14	117.4
C4—C3—H3B	108.4	C13—C14—H14	117.4
C2—C3—H3B	108.4	C14—C15—C16	121.5 (2)
H3A—C3—H3B	107.4	C14—C15—H15	119.3
C5—C4—C11	105.8 (2)	C16—C15—H15	119.3
C5—C4—C3	126.6 (2)	O6—C16—O5	124.5 (2)
C11—C4—C3	127.4 (2)	O6—C16—C15	121.0 (2)
C4—C5—N1	111.1 (2)	O5—C16—C15	114.6 (2)
C4—C5—H5	124.4
O2—C1—C2—N2	−21.1 (3)	C8—C9—C10—C11	−0.3 (5)
O1—C1—C2—N2	161.6 (2)	C9—C10—C11—C6	1.1 (4)
O2—C1—C2—C3	100.3 (3)	C9—C10—C11—C4	−177.8 (3)
O1—C1—C2—C3	−77.0 (3)	N1—C6—C11—C10	179.9 (3)
N2—C2—C3—C4	−64.7 (3)	C7—C6—C11—C10	−1.5 (4)
C1—C2—C3—C4	173.8 (2)	N1—C6—C11—C4	−0.9 (3)
C2—C3—C4—C5	101.2 (3)	C7—C6—C11—C4	177.6 (3)
C2—C3—C4—C11	−84.9 (3)	C5—C4—C11—C10	180.0 (3)
C11—C4—C5—N1	−0.7 (3)	C3—C4—C11—C10	5.1 (5)
C3—C4—C5—N1	174.2 (2)	C5—C4—C11—C6	1.0 (3)
C6—N1—C5—C4	0.1 (3)	C3—C4—C11—C6	−173.9 (2)
C5—N1—C6—C7	−177.9 (3)	O3—C13—C14—C15	178.9 (3)
C5—N1—C6—C11	0.5 (3)	O4—C13—C14—C15	−1.3 (4)
N1—C6—C7—C8	179.2 (3)	C13—C14—C15—C16	178.1 (3)
C11—C6—C7—C8	1.0 (4)	C14—C15—C16—O6	4.4 (5)
C6—C7—C8—C9	−0.1 (5)	C14—C15—C16—O5	−175.9 (3)
C7—C8—C9—C10	−0.3 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3i	0.85 (3)	2.11 (3)	2.912 (3)	158 (3)
N2—H2A···O7	0.92 (4)	1.94 (4)	2.845 (3)	170 (3)
N2—H2B···O1ii	0.94 (3)	2.30 (3)	3.085 (3)	140 (2)
N2—H2B···O3	0.94 (3)	2.28 (3)	2.901 (3)	123 (2)
N2—H2C···O2iii	0.96 (3)	1.87 (3)	2.832 (3)	174 (3)
O4—H4O···O1ii	0.82	1.74	2.559 (2)	178
O5—H5O···O6iv	0.82	1.81	2.630 (3)	174
O7—H7A···O1v	0.88 (2)	2.60 (3)	3.261 (3)	133 (3)
O7—H7A···O2v	0.88 (2)	1.97 (2)	2.824 (3)	165 (3)
O7—H7B···O2vi	0.85 (2)	2.53 (3)	3.347 (3)	162 (3)
C3—H3B···O3vii	0.97	2.66	3.255 (3)	120
C5—H5···O7i	0.93	2.58	3.491 (3)	166

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N1H1O3i	0.85(3)	2.11(3)	2.912(3)	158(3)
N2H2AO7	0.92(4)	1.94(4)	2.845(3)	170(3)
N2H2BO1ii	0.94(3)	2.30(3)	3.085(3)	140(2)
N2H2BO3	0.94(3)	2.28(3)	2.901(3)	123(2)
N2H2CO2iii	0.96(3)	1.87(3)	2.832(3)	174(3)
O4H4OO1ii	0.82	1.74	2.559(2)	178
O5H5OO6iv	0.82	1.81	2.630(3)	174
O7H7AO1v	0.88(2)	2.60(3)	3.261(3)	133(3)
O7H7AO2v	0.88(2)	1.97(2)	2.824(3)	165(3)
O7H7BO2vi	0.85(2)	2.53(3)	3.347(3)	162(3)
C3H3BO3vii	0.97	2.66	3.255(3)	120
C5H5O7i	0.93	2.58	3.491(3)	166

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