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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 71| Part 9| September 2015| Pages o661-o662
https://doi.org/10.1107/S205698901501484X

Crystal structure of L-tryptophan–fumaric acid–water (1/1/1)

CROSSMARK_Color_square_no_text.svg
M. Lydia Caroline,a* S. Kumaresan,a P. G. Aravindan,b M. Peer Mohamedc and G. Mania

aPG & Research Department of Physics, Arignar Anna Govt. Arts College, Cheyyar 604 407, Tamil Nadu, India, bThiru.Vi.Ka. Govt Arts College, Thiruvarur 610 003, Tamilnadu, India, and cDepartment of Physics, C. Abdul Hakeem College, Melvisharam 632 509, Tamil Nadu, India
*Correspondence e-mail: lydiacaroline2006@yahoo.co.in

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 21 July 2015; accepted 7 August 2015; online 15 August 2015)

In the title compound, C11H12N2O2·C4H4O4·H2O, the L-tryp­to­phan mol­ecule crystallized as a zwitterion, together with a neutral fumaric acid mol­ecule and a water solvent mol­ecule. 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.

CCDC reference: 1417535

Similar articles

1. Related literature

For literature on the UV spectroscopy of proteins, see: Demchenko (1986[Demchenko, A. P. (1986). In Ultraviolet Spectroscopy of Proteins. Berlin: Springer.]). For the different polymorphic forms of fumaric acid, see: Reis & Schneider (1928[Reis, A. & Schneider, E. (1928). Z. Kristallogr. 68, 543-545.]); Yardley (1925[Yardley, J. (1925). J. Chem. Soc. Trans. 127, 2207-2219.]); Bednowitz & Post (1966[Bednowitz, A. L. & Post, B. (1966). Acta Cryst. 21, 566-571.]). For the nonlinear optical properties of organic mol­ecules, see: Chemla & Zyss (1987[Chemla, D. S. & Zyss, J. (1987). In Nonlinear optical properties of organic molecules and crystals, Vol. 1-2. Orlando, New York: Academic Press.]); Zyss & Ledoux (1994[Zyss, J. & Ledoux, I. (1994). Chem. Rev. 94, 77-105.]); Zyss & Nicoud (1996[Zyss, J. & Nicoud, J. F. (1996). Curr. Opin. Solid State Mater. Sci. 1, 533-546.]). For the common conformations of L-tryptophan, see: Bye et al. (1973[Bye, E., Mostad, A., Rømming, C., Husebye, S., Klaeboe, P. & Swahn, C. (1973). Acta Chem. Scand. 27, 471-484.]); Bakke & Mostad (1980[Bakke, O., Mostad, A., Grynfarb, M., Bartfai, T. & Enzell, C. R. (1980). Acta Chem. Scand. 34b, 559-570.]). The bond lengths and angles in L-trypophan, see, for example: Gorbitz (2006[Görbitz, C. H. (2006). Acta Cryst. C62, o328-o330.]); Gorbitz et al. (2012[Görbitz, C. H., Törnroos, K. W. & Day, G. M. (2012). Acta Cryst. B68, 549-557.]), and for fumaric acid, see: Goswami et al. (1999[Goswami, S., Mahapatra, A. K., Nigam, G. D., Chinnakali, K., Fun, H.-K. & Razak, I. A. (1999). Acta Cryst. C55, 583-585.]). For the crystal structure of L-tryptophan formic acid solvate, see: Hubschle et al. (2002[Hübschle, C. B., Dittrich, B. & Luger, P. (2002). Acta Cryst. C58, o540-o542.]). For details of the Cambridge Structural Database, see: Groom & Allen (2014[Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662-671.]).

[Scheme 1]

2. Experimental

2.1. Crystal data

  • C11H12N2O2·C4H4O4·H2O

  • Mr = 338.31

  • Monoclinic, C 2

  • 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

2.2. Data collection

  • Bruker Kappa APEXII CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2004[Bruker (2004). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.898, Tmax = 0.978

  • 10737 measured reflections

  • 3157 independent reflections

  • 2731 reflections with I > 2σ(I)

  • Rint = 0.025

2.3. Refinement

  • R[F2 > 2σ(F2)] = 0.034

  • wR(F2) = 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

Table 1
Hydrogen-bond geometry (Å, °)

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
Symmetry codes: (i) [x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]; (ii) [x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]; (iii) -x+1, y, -z+2; (iv) -x+1, y, -z+1; (v) [-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+2]; (vi) x, y+1, z; (vii) x, y-1, z.

Data collection: APEX2 (Bruker, 2004[Bruker (2004). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: APEX2 and SAINT (Bruker, 2004[Bruker (2004). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT and XPREP (Bruker, 2004[Bruker (2004). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); program(s) used to solve structure: SIR92 (Altomare et al., 1994[Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435.]); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]) and Mercury (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]); software used to prepare material for publication: SHELXL2014 and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information

CCDC reference: 1417535

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S205698901501484X/su5176sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698901501484X/su5176Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S205698901501484X/su5176Isup3.cml

checkCIF report


Comment top

Natural aromatic amino acids, particularly tryptophan, have near UV absorption and emission properties which are utilized extensively in solution phase investigations of structure-function relationships (Demchenko, 1986). Fumaric acid is known to exist in two different polymorphic forms viz. cis and trans ( Reis & Schneider, 1928; Yardley, 1925; Bednowitz & Post, 1966).

In conjunction with our ongoing work on non-linear optical organic crystals among the 20 naturally occurring amino acids, we have directed our inter­est to tryptophan (Trp), one of the essential amino acids for humans. The non-linear optical properties of organic molecules and crystals have been reviewed by Zyss (Chemla & Zyss, 1987; Zyss & Ledoux, 1994; Zyss & Nicoud, 1996). For similar properties and most the common confirmations of L-tryptophan have been reported (Bye et al., 1973; Bakke & Mostad, 1980). Compared with other amino acids, there are less than 30 tryptophan structures listed in the Cambridge Structural Database (Groom & Allen, 2014), due to the difficulty of obtaining good optical quality crystals; as noted by (Hubschle et al., 2002) who studied the crystal structure of L-tryptophan formic acid solvate. We successfully obtained good quality hard golden-yellow single crystals of L-tryptophan fumaric acid monohydrate, and we report herein on its synthesis and crystal structure.

In the title compound, Fig. 1, L-tryptophan is zwitterionic, as are most amino acids in the solid state, and fumaric acid is neutral. The bond lengths and angles in L-trypophan and fumaric acid are similar to those reported previously (Gorbitz, 2006; Gorbitz et al., 2012; Goswami et al., 1999).

In the crystal, the three components are linked by a series of O—H···O, N—H···O and C—H···O hydrogen bonds forming slabs lying parallel to (001); Table 1 and Fig. 2. 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; Table 1 and Fig. 3.

Synthesis and crystallization top

An aqueous solution of L-tryptophan and fumaric acid in a 1:1 stoichiometric ratio was stirred at room temperature for 6 h. The resulting yellow solution was filtered and kept in a Petri dish. Yellow prismatic-shaped hard crystals suitable for X-ray analysis were obtained over a period of 5 days.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. The N-bound, acid and water H atoms were located in a difference Fourier map. The NH and NH3 H atoms were freely refined. The water H atoms were refined with distance restraints: O—H = 0.86 (2) Å, H···H = 1.388 (20) Å with Uiso(H) = 1.5Ueq(O). The acid (OH) H atoms and the C-bound H atoms were included in calculated positions and treated as riding atoms: Uiso(H) = 1.5Ueq(O,C) for OH and methyl H atoms and 1.2Ueq(C) for other H atoms.

Related literature top

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).

Structure description top

Natural aromatic amino acids, particularly tryptophan, have near UV absorption and emission properties which are utilized extensively in solution phase investigations of structure-function relationships (Demchenko, 1986). Fumaric acid is known to exist in two different polymorphic forms viz. cis and trans ( Reis & Schneider, 1928; Yardley, 1925; Bednowitz & Post, 1966).

In conjunction with our ongoing work on non-linear optical organic crystals among the 20 naturally occurring amino acids, we have directed our inter­est to tryptophan (Trp), one of the essential amino acids for humans. The non-linear optical properties of organic molecules and crystals have been reviewed by Zyss (Chemla & Zyss, 1987; Zyss & Ledoux, 1994; Zyss & Nicoud, 1996). For similar properties and most the common confirmations of L-tryptophan have been reported (Bye et al., 1973; Bakke & Mostad, 1980). Compared with other amino acids, there are less than 30 tryptophan structures listed in the Cambridge Structural Database (Groom & Allen, 2014), due to the difficulty of obtaining good optical quality crystals; as noted by (Hubschle et al., 2002) who studied the crystal structure of L-tryptophan formic acid solvate. We successfully obtained good quality hard golden-yellow single crystals of L-tryptophan fumaric acid monohydrate, and we report herein on its synthesis and crystal structure.

In the title compound, Fig. 1, L-tryptophan is zwitterionic, as are most amino acids in the solid state, and fumaric acid is neutral. The bond lengths and angles in L-trypophan and fumaric acid are similar to those reported previously (Gorbitz, 2006; Gorbitz et al., 2012; Goswami et al., 1999).

In the crystal, the three components are linked by a series of O—H···O, N—H···O and C—H···O hydrogen bonds forming slabs lying parallel to (001); Table 1 and Fig. 2. 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; Table 1 and Fig. 3.

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).

Synthesis and crystallization top

An aqueous solution of L-tryptophan and fumaric acid in a 1:1 stoichiometric ratio was stirred at room temperature for 6 h. The resulting yellow solution was filtered and kept in a Petri dish. Yellow prismatic-shaped hard crystals suitable for X-ray analysis were obtained over a period of 5 days.

Refinement details top

Crystal data, data collection and structure refinement details are summarized in Table 2. The N-bound, acid and water H atoms were located in a difference Fourier map. The NH and NH3 H atoms were freely refined. The water H atoms were refined with distance restraints: O—H = 0.86 (2) Å, H···H = 1.388 (20) Å with Uiso(H) = 1.5Ueq(O). The acid (OH) H atoms and the C-bound H atoms were included in calculated positions and treated as riding atoms: Uiso(H) = 1.5Ueq(O,C) for OH and methyl H atoms and 1.2Ueq(C) for other H atoms.

Computing details top

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 (Sheldrick, 2015) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 40% probability level.
[Figure 2] Fig. 2. 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).
[Figure 3] Fig. 3. 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).
L-Tryptophan–fumaric acid–water (1/1/1) top
Crystal data top
C11H12N2O2·C4H4O4·H2OF(000) = 712
Mr = 338.31Dx = 1.392 Mg m−3
Monoclinic, C2Mo Kα radiation, λ = 0.71073 Å
a = 11.3928 (8) ÅCell parameters from 5033 reflections
b = 6.6476 (4) Åθ = 2.8–27.9°
c = 21.4219 (13) ŵ = 0.11 mm−1
β = 95.801 (3)°T = 296 K
V = 1614.07 (18) Å3Block, colourless
Z = 40.30 × 0.20 × 0.20 mm
Data collection top
Bruker Kappa APEXII CCD
diffractometer		2731 reflections with I > 2σ(I)
Radiation source: Sealed X-ray tubeRint = 0.025
ω and φ scanθmax = 26.0°, θmin = 2.9°
Absorption correction: multi-scan
(SADABS; Bruker, 2004)		h = −14→14
Tmin = 0.898, Tmax = 0.978k = −8→8
10737 measured reflectionsl = −26→26
3157 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.034H 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 reflectionsΔρmax = 0.18 e Å−3
242 parametersΔρmin = −0.15 e Å−3
4 restraintsExtinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0069 (11)
Crystal data top
C11H12N2O2·C4H4O4·H2OV = 1614.07 (18) Å3
Mr = 338.31Z = 4
Monoclinic, C2Mo Kα radiation
a = 11.3928 (8) ŵ = 0.11 mm−1
b = 6.6476 (4) ÅT = 296 K
c = 21.4219 (13) Å0.30 × 0.20 × 0.20 mm
β = 95.801 (3)°
Data collection top
Bruker Kappa APEXII CCD
diffractometer		3157 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2004)		2731 reflections with I > 2σ(I)
Tmin = 0.898, Tmax = 0.978Rint = 0.025
10737 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0344 restraints
wR(F2) = 0.084H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.18 e Å−3
3157 reflectionsΔρmin = −0.15 e Å−3
242 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.75082 (19)0.1813 (4)0.77433 (10)0.0380 (5)
H10.825 (3)0.191 (5)0.7735 (13)0.047 (8)*
N20.5095 (2)0.4264 (3)0.91895 (10)0.0276 (5)
H2A0.472 (3)0.534 (5)0.9350 (15)0.056 (10)*
H2B0.563 (3)0.476 (5)0.8921 (14)0.049 (8)*
H2C0.554 (3)0.365 (4)0.9546 (15)0.047 (9)*
O10.24153 (16)0.1425 (3)0.89730 (8)0.0483 (5)
O20.35274 (17)0.2275 (3)0.98224 (8)0.0485 (6)
O30.50562 (13)0.6533 (3)0.80307 (7)0.0334 (4)
O40.69014 (13)0.6700 (3)0.77851 (7)0.0381 (4)
H4O0.70500.66150.81670.057*
O50.63962 (18)0.6937 (5)0.54724 (8)0.0706 (7)
H5O0.60800.68550.51120.106*
O60.45352 (18)0.6884 (4)0.57018 (8)0.0595 (6)
O70.37013 (19)0.7265 (3)0.97085 (11)0.0532 (6)
H7A0.304 (2)0.705 (5)0.9880 (16)0.080*
H7B0.382 (3)0.852 (4)0.9713 (18)0.080*
C10.3327 (2)0.2159 (3)0.92463 (10)0.0263 (5)
C20.4263 (2)0.2860 (3)0.88365 (10)0.0244 (5)
H20.38760.35560.84680.029*
C30.4928 (2)0.1034 (4)0.86179 (12)0.0328 (6)
H3A0.53450.04010.89830.039*
H3B0.43540.00730.84320.039*
C40.5792 (2)0.1458 (4)0.81563 (11)0.0302 (5)
C50.6979 (2)0.1602 (4)0.82805 (11)0.0357 (6)
H50.73790.15620.86810.043*
C60.6657 (2)0.1816 (4)0.72436 (11)0.0333 (6)
C70.6742 (2)0.1930 (5)0.66020 (12)0.0445 (7)
H70.74710.20410.64450.053*
C80.5720 (3)0.1874 (5)0.62093 (12)0.0508 (7)
H80.57560.19510.57780.061*
C90.4630 (2)0.1705 (5)0.64405 (13)0.0507 (7)
H90.39510.16770.61600.061*
C100.4529 (2)0.1579 (5)0.70688 (11)0.0417 (6)
H100.37920.14720.72160.050*
C110.5557 (2)0.1615 (4)0.74880 (11)0.0312 (5)
C130.57628 (19)0.6648 (4)0.76415 (10)0.0286 (5)
C140.5377 (2)0.6733 (4)0.69680 (10)0.0365 (6)
H140.45700.66720.68480.044*
C150.6070 (2)0.6888 (5)0.65258 (11)0.0418 (7)
H150.68800.69940.66320.050*
C160.5603 (2)0.6899 (5)0.58582 (11)0.0447 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0245 (11)0.0520 (14)0.0381 (12)0.0037 (12)0.0067 (9)−0.0028 (12)
N20.0274 (12)0.0345 (12)0.0219 (11)−0.0020 (9)0.0072 (9)0.0000 (9)
O10.0374 (11)0.0818 (15)0.0254 (9)−0.0268 (11)0.0019 (7)−0.0006 (10)
O20.0441 (11)0.0834 (16)0.0183 (9)−0.0273 (11)0.0045 (7)−0.0019 (9)
O30.0300 (9)0.0449 (10)0.0260 (8)−0.0024 (9)0.0056 (7)0.0031 (8)
O40.0278 (9)0.0651 (11)0.0216 (8)−0.0034 (10)0.0026 (6)0.0003 (10)
O50.0548 (13)0.133 (2)0.0237 (9)−0.0004 (17)0.0058 (9)−0.0012 (15)
O60.0464 (12)0.1044 (17)0.0265 (9)0.0027 (13)−0.0027 (8)0.0012 (12)
O70.0511 (13)0.0543 (13)0.0578 (13)0.0096 (11)0.0227 (10)0.0010 (11)
C10.0249 (12)0.0323 (13)0.0220 (11)−0.0021 (10)0.0034 (10)−0.0003 (10)
C20.0250 (13)0.0331 (12)0.0149 (11)0.0015 (10)0.0011 (9)0.0015 (9)
C30.0399 (15)0.0318 (13)0.0275 (13)0.0034 (11)0.0073 (12)−0.0007 (10)
C40.0304 (12)0.0315 (12)0.0295 (12)0.0041 (12)0.0074 (9)−0.0047 (11)
C50.0371 (14)0.0387 (13)0.0312 (13)0.0068 (13)0.0029 (10)−0.0028 (12)
C60.0327 (13)0.0365 (13)0.0317 (12)0.0040 (12)0.0076 (10)−0.0033 (12)
C70.0416 (15)0.0558 (17)0.0384 (14)0.0055 (15)0.0158 (12)−0.0013 (14)
C80.0600 (19)0.0640 (19)0.0291 (13)0.0095 (18)0.0084 (13)0.0003 (15)
C90.0446 (16)0.0678 (19)0.0374 (14)0.0066 (17)−0.0071 (12)−0.0061 (16)
C100.0301 (13)0.0578 (16)0.0373 (14)0.0054 (15)0.0033 (11)−0.0047 (15)
C110.0286 (12)0.0331 (12)0.0323 (12)0.0049 (12)0.0056 (9)−0.0043 (12)
C130.0286 (12)0.0313 (12)0.0257 (11)−0.0016 (12)0.0024 (9)0.0003 (11)
C140.0328 (13)0.0500 (15)0.0263 (12)−0.0002 (14)0.0002 (10)−0.0013 (14)
C150.0339 (14)0.0630 (18)0.0278 (13)0.0024 (15)−0.0002 (11)−0.0004 (14)
C160.0429 (16)0.0637 (19)0.0279 (13)0.0031 (16)0.0053 (11)−0.0018 (15)
Geometric parameters (Å, º) top
N1—C51.359 (3)C3—H3A0.9700
N1—C61.370 (3)C3—H3B0.9700
N1—H10.85 (3)C4—C51.355 (3)
N2—C21.482 (3)C4—C111.433 (3)
N2—H2A0.92 (4)C5—H50.9300
N2—H2B0.94 (3)C6—C71.390 (3)
N2—H2C0.96 (3)C6—C111.413 (3)
O1—C11.240 (3)C7—C81.366 (4)
O2—C11.235 (3)C7—H70.9300
O3—C131.219 (3)C8—C91.387 (4)
O4—C131.303 (3)C8—H80.9300
O4—H4O0.8200C9—C101.365 (4)
O5—C161.285 (3)C9—H90.9300
O5—H5O0.8200C10—C111.401 (3)
O6—C161.229 (3)C10—H100.9300
O7—H7A0.88 (2)C13—C141.466 (3)
O7—H7B0.85 (2)C14—C151.297 (3)
C1—C21.521 (3)C14—H140.9300
C2—C31.529 (3)C15—C161.475 (3)
C2—H20.9800C15—H150.9300
C3—C41.491 (3)
C5—N1—C6108.8 (2)N1—C5—H5124.4
C5—N1—H1123.6 (19)N1—C6—C7131.2 (2)
C6—N1—H1127.6 (19)N1—C6—C11107.1 (2)
C2—N2—H2A113 (2)C7—C6—C11121.7 (2)
C2—N2—H2B109.4 (19)C8—C7—C6117.9 (2)
H2A—N2—H2B108 (3)C8—C7—H7121.1
C2—N2—H2C113.4 (17)C6—C7—H7121.1
H2A—N2—H2C105 (2)C7—C8—C9121.4 (2)
H2B—N2—H2C108 (2)C7—C8—H8119.3
C13—O4—H4O109.5C9—C8—H8119.3
C16—O5—H5O109.5C10—C9—C8121.6 (3)
H7A—O7—H7B107 (3)C10—C9—H9119.2
O2—C1—O1123.9 (2)C8—C9—H9119.2
O2—C1—C2119.2 (2)C9—C10—C11118.9 (2)
O1—C1—C2116.79 (19)C9—C10—H10120.6
N2—C2—C1110.35 (18)C11—C10—H10120.6
N2—C2—C3110.2 (2)C10—C11—C6118.6 (2)
C1—C2—C3109.37 (19)C10—C11—C4134.3 (2)
N2—C2—H2109.0C6—C11—C4107.1 (2)
C1—C2—H2109.0O3—C13—O4123.4 (2)
C3—C2—H2109.0O3—C13—C14121.5 (2)
C4—C3—C2115.7 (2)O4—C13—C14115.07 (19)
C4—C3—H3A108.4C15—C14—C13125.3 (2)
C2—C3—H3A108.4C15—C14—H14117.4
C4—C3—H3B108.4C13—C14—H14117.4
C2—C3—H3B108.4C14—C15—C16121.5 (2)
H3A—C3—H3B107.4C14—C15—H15119.3
C5—C4—C11105.8 (2)C16—C15—H15119.3
C5—C4—C3126.6 (2)O6—C16—O5124.5 (2)
C11—C4—C3127.4 (2)O6—C16—C15121.0 (2)
C4—C5—N1111.1 (2)O5—C16—C15114.6 (2)
C4—C5—H5124.4
O2—C1—C2—N2−21.1 (3)C8—C9—C10—C11−0.3 (5)
O1—C1—C2—N2161.6 (2)C9—C10—C11—C61.1 (4)
O2—C1—C2—C3100.3 (3)C9—C10—C11—C4−177.8 (3)
O1—C1—C2—C3−77.0 (3)N1—C6—C11—C10179.9 (3)
N2—C2—C3—C4−64.7 (3)C7—C6—C11—C10−1.5 (4)
C1—C2—C3—C4173.8 (2)N1—C6—C11—C4−0.9 (3)
C2—C3—C4—C5101.2 (3)C7—C6—C11—C4177.6 (3)
C2—C3—C4—C11−84.9 (3)C5—C4—C11—C10180.0 (3)
C11—C4—C5—N1−0.7 (3)C3—C4—C11—C105.1 (5)
C3—C4—C5—N1174.2 (2)C5—C4—C11—C61.0 (3)
C6—N1—C5—C40.1 (3)C3—C4—C11—C6−173.9 (2)
C5—N1—C6—C7−177.9 (3)O3—C13—C14—C15178.9 (3)
C5—N1—C6—C110.5 (3)O4—C13—C14—C15−1.3 (4)
N1—C6—C7—C8179.2 (3)C13—C14—C15—C16178.1 (3)
C11—C6—C7—C81.0 (4)C14—C15—C16—O64.4 (5)
C6—C7—C8—C9−0.1 (5)C14—C15—C16—O5−175.9 (3)
C7—C8—C9—C10−0.3 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O3i0.85 (3)2.11 (3)2.912 (3)158 (3)
N2—H2A···O70.92 (4)1.94 (4)2.845 (3)170 (3)
N2—H2B···O1ii0.94 (3)2.30 (3)3.085 (3)140 (2)
N2—H2B···O30.94 (3)2.28 (3)2.901 (3)123 (2)
N2—H2C···O2iii0.96 (3)1.87 (3)2.832 (3)174 (3)
O4—H4O···O1ii0.821.742.559 (2)178
O5—H5O···O6iv0.821.812.630 (3)174
O7—H7A···O1v0.88 (2)2.60 (3)3.261 (3)133 (3)
O7—H7A···O2v0.88 (2)1.97 (2)2.824 (3)165 (3)
O7—H7B···O2vi0.85 (2)2.53 (3)3.347 (3)162 (3)
C3—H3B···O3vii0.972.663.255 (3)120
C5—H5···O7i0.932.583.491 (3)166
Symmetry codes: (i) x+1/2, y−1/2, z; (ii) x+1/2, y+1/2, z; (iii) −x+1, y, −z+2; (iv) −x+1, y, −z+1; (v) −x+1/2, y+1/2, −z+2; (vi) x, y+1, z; (vii) x, y−1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O3i0.85 (3)2.11 (3)2.912 (3)158 (3)
N2—H2A···O70.92 (4)1.94 (4)2.845 (3)170 (3)
N2—H2B···O1ii0.94 (3)2.30 (3)3.085 (3)140 (2)
N2—H2B···O30.94 (3)2.28 (3)2.901 (3)123 (2)
N2—H2C···O2iii0.96 (3)1.87 (3)2.832 (3)174 (3)
O4—H4O···O1ii0.821.742.559 (2)178
O5—H5O···O6iv0.821.812.630 (3)174
O7—H7A···O1v0.88 (2)2.60 (3)3.261 (3)133 (3)
O7—H7A···O2v0.88 (2)1.97 (2)2.824 (3)165 (3)
O7—H7B···O2vi0.85 (2)2.53 (3)3.347 (3)162 (3)
C3—H3B···O3vii0.972.663.255 (3)120
C5—H5···O7i0.932.583.491 (3)166
Symmetry codes: (i) x+1/2, y−1/2, z; (ii) x+1/2, y+1/2, z; (iii) −x+1, y, −z+2; (iv) −x+1, y, −z+1; (v) −x+1/2, y+1/2, −z+2; (vi) x, y+1, z; (vii) x, y−1, z.
 

Acknowledgements

The scientific support extended by the Sophisticated Analytical Instruments Facility, Indian Institute of Technology IITM, Chennai, in solving the crystal structure is greatly appreciated. The authors personally thank Professor E. M. Subramanian, retired Professor of Chemistry, Pachayappas College, Kanchipuram, Tamilnadu, for valuable suggestions.

References

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ISSN: 2056-9890
Volume 71| Part 9| September 2015| Pages o661-o662
https://doi.org/10.1107/S205698901501484X
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