2-[(2-Ammonio­ethyl)­amino­carbon­yl]benzoate hemihydrate

Chellappa, D.; Chitraleka, S.; Sakthilatha, D.; Athimoolam, S.; Natarajan, S.

doi:10.1107/S1600536807021599

2-[(2-Ammonioethyl)aminocarbonyl]benzoate hemihydrate

D. Chellappa, S. Chitraleka, D. Sakthilatha, S. Athimoolam and S. Natarajan

The title amino acid-like structure, C₁₀H₁₂N₂O₃·0.5H₂O, consists of two zwitterionic residues and one water molecule in the asymmetric unit. The carboxylate group is twisted from the plane of the attached benzene ring by angles of 35.6 (4) and 36.2 (5)° in the two residues. From the benzene ring, the side-chain conformations are observed to be trans/gauche-I/ gauche-II and trans/gauche-II/gauche-II. The crystal structure is stabilized by an intricate three-dimensional hydrogen-bonding network. The amino and carboxylate groups are connected through intra- and intermolecular hydrogen bonds, forming S(10), C(4), C₂¹(4) and C₃³(8) motifs. The chains run along the a axis of the unit cell. Hydrophobic layers across z = ¼ and ¾ are sandwiched between the hydrophilic layers across z = ½ and 1.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807021599/sj2313sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807021599/sj2313Isup2.hkl Contains datablock I

CCDC reference: 651417

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Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.010 Å
R factor = 0.050
wR factor = 0.153
Data-to-parameter ratio = 6.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.99
PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax .LT. 18) .....       6.61
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...         10
PLAT480_ALERT_4_C Long H...A H-Bond Reported H12A   ..  O21     ..       2.61 Ang.
PLAT731_ALERT_1_C Bond    Calc    0.94(11), Rep     0.94(5) ......       2.20 su-Ra
              O1W  -H1W     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc    0.94(11), Rep     0.94(5) ......       2.20 su-Ra
              O1W  -H1W     1.555   1.555

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           24.94
           From the CIF: _reflns_number_total               1905
           Count of symmetry unique reflns         1905
           Completeness (_total/calc)            100.00%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          4

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
  10 ALERT level C = Check and explain
   4 ALERT level G = General alerts; check

   7 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Amino acids are classic compounds and exhibit various interesting biological activities. As enzymes (biopolymers of α-aminoacids), they catalyze various biochemical transformation with high efficiency by adopting appropriate aminoacid sequences (Salemme, 1977; McCord & Fridovich, 1969). The monomer γ-aminobutyric acid (GABA) serves as neurotransmitter while δ-aminoolevulinic acid is involved in the biosynthesis of heme unit (Fujimori et al., 2006; Tahara et al., 2007). β-amino-iso-butyric acid is a metabolite in the catabolism of pyrimidine bases (Van Kuilenburg et al., 2006). In addition, the aminoacids being bifunctional in nature can act as synthons for a variety of organic compounds (March, 1977). The title compound, (I) is an amino acid-like structure containing a protonated ammonium (NH₃⁺) and a deprotonated carboxylate (COO^-) groups with the amide group in the middle.

The aymmetric part of the unit cell contains two zwitterionic residues (A & B) of 2-[(2-Ammonium-ethylamino)-carbonyl]-benzoate and one lattice water molecule (Fig 1). In both the residues of A and B, the carboxylate group is twisted from the plane of the attached benzene ring with the angles of 35.6 (4) and 36.2 (5)°, respectively. As the title compound has amino acid-like structure it is more appropriate to detail the conformation in the same nomenclature followed in amino acid complexes (Allen, 2002). Thus, from the phenyl ring, the side chain conformations are observed to be trans/gauche I/ gauche II and trans/gauche II/gauche II for residues A and B, respectively (Table 1). The C–O bond distances in the carboxylate groups are nearly equal and lie midway between the usual single and double C–O bond distances as found in many zwitterionic amino acid complexes (Anitha et al., 2005).

In both the residues, the side chain is folded back to form intramolecular ring motif of S(10). This amino-carboxylate interaction is very similar to the head-to-tail sequence observed in amino acid complexes. The crystal structure is stabilized by an intricate three-dimensional hydrogen bonding network (Fig 2). N11—H11···O17 and N21—H21···O27 H-bond interactions in residues A & B respectively, lead to C(4) chain motifs running along the a axis of the unit cell. In residue A, intramolecular N12—H12B···O11 hydrogen bond and an intermolecular N12—H12C···O11 hydrogen bond lead to a distinct C₂¹(4) chain motif running along the a axis of the unit cell. In residue B, the amino and carboxylate groups interact through the water molecule forming a C₃³(8) chain motif. Apart from these, the residues A and B are connected through other N—H···O hydrogen bonds bringing amino and carboxylate groups to close proximity in the unit cell thereby forming hydrophilic layers across z = 1/2 and 1 with hydrophobic layers across z = 1/4 and 3/4. These alternate hydrophobic and hydrophilic layers are often observed in amino acid complexes (e.g., Anitha et al., 2005).

Related literature top

For related literature on hydrogen-bond motifs, see: Etter et al. (1990). For related literature on values of bond lengths and angles, see: Allen (2002). For information on the importance of this type of compounds in chemical syntheses and reactions, see: Salemme (1977); McCord & Fridovich, (1969); Fujimori et al. (2006); Tahara et al. (2007); Van Kuilenburg et al. (2006) and March (1977). For a related structure, see: Anitha et al. (2005).

Experimental top

Diethylphthalate was added to stoichiometric excess of ethylenediamine in ether. The mixture was refluxed for 3 h and then evaporated on a water bath yielding a jelly like mass which was dissolved in water and evaporated once again after washing with chloroform. The resulting mass when treated with ethanol to form a precipitate which was filtered, washed with ether and dried in a vacuum desiccator. The dried precipitate was dissolved in water and, on slow evaporation of this aqueous solution, the title compound was obtained as colourless blocks (yield: 70%; melting point: 160°).

Structure description top

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXTL/PC (Bruker, 2000); program(s) used to refine structure: SHELXTL/PC; molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL/PC.

Figures top

	Fig. 1. The molecular structure of the title compound (I) with the atom numbering scheme and 50% probability displacement ellipsoids. H-bonds are shown as dashed lines.
	Fig. 2. Packing diagram of the molecules viewed down the b-axis. H atoms not involved in the H-bonds (dashed lines) are omitted for clarity.

2-(2-Ammonioethylaminocarbonyl)benzoate hemihydrate top

Crystal data top

C₁₀H₁₂N₂O₃·0.5H₂O	D_x = 1.359 Mg m⁻³
M_r = 217.23	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pca2₁	Cell parameters from 25 reflections
a = 9.0609 (9) Å	θ = 10.3–12.8°
b = 8.6714 (12) Å	µ = 0.10 mm⁻¹
c = 27.0214 (19) Å	T = 293 K
V = 2123.1 (4) Å³	Block, colourless
Z = 8	0.23 × 0.19 × 0.15 mm
F(000) = 920

Data collection top

Nonius MACH3 sealed tube diffractometer	1430 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.015
Graphite monochromator	θ_max = 24.9°, θ_min = 2.4°
ω–2θ scans	h = −10→0
Absorption correction: ψ scan (North et al., 1968)	k = −10→0
T_min = 0.983, T_max = 0.998	l = −1→32
1986 measured reflections	3 standard reflections every 60 min
1905 independent reflections	intensity decay: none

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.153	H atoms treated by a mixture of independent and constrained refinement
S = 1.15	w = 1/[σ²(F_o²) + (0.064P)² + 1.9315P] where P = (F_o² + 2F_c²)/3
1905 reflections	(Δ/σ)_max < 0.001
288 parameters	Δρ_max = 0.28 e Å⁻³
4 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₀H₁₂N₂O₃·0.5H₂O	V = 2123.1 (4) Å³
M_r = 217.23	Z = 8
Orthorhombic, Pca2₁	Mo Kα radiation
a = 9.0609 (9) Å	µ = 0.10 mm⁻¹
b = 8.6714 (12) Å	T = 293 K
c = 27.0214 (19) Å	0.23 × 0.19 × 0.15 mm

Data collection top

Nonius MACH3 sealed tube diffractometer	1430 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.015
T_min = 0.983, T_max = 0.998	3 standard reflections every 60 min
1986 measured reflections	intensity decay: none
1905 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	4 restraints
wR(F²) = 0.153	H atoms treated by a mixture of independent and constrained refinement
S = 1.15	Δρ_max = 0.28 e Å⁻³
1905 reflections	Δρ_min = −0.22 e Å⁻³
288 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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
C11	0.0958 (7)	0.8470 (7)	0.4129 (3)	0.0314 (16)
C111	0.1390 (7)	0.8364 (8)	0.4668 (3)	0.0369 (16)
O11	0.1460 (6)	0.7046 (6)	0.48551 (18)	0.0524 (13)
O12	0.1588 (8)	0.9593 (6)	0.4879 (2)	0.074 (2)
C12	0.0061 (8)	0.9674 (7)	0.3967 (3)	0.0384 (16)
H12	−0.0214	1.0451	0.4185	0.046*
C13	−0.0423 (9)	0.9717 (9)	0.3481 (3)	0.0472 (19)
H13	−0.1049	1.0504	0.3378	0.057*
C14	0.0006 (8)	0.8629 (9)	0.3157 (3)	0.0472 (19)
H14	−0.0314	0.8677	0.2831	0.057*
C15	0.0909 (8)	0.7453 (8)	0.3305 (3)	0.0394 (17)
H15	0.1204	0.6716	0.3075	0.047*
C16	0.1391 (7)	0.7337 (7)	0.3788 (2)	0.0285 (14)
C17	0.2387 (8)	0.6051 (7)	0.3933 (3)	0.0327 (15)
O17	0.3729 (5)	0.6252 (5)	0.3991 (2)	0.0405 (12)
N11	0.1742 (6)	0.4662 (6)	0.3996 (2)	0.0338 (13)
H11	0.0817	0.4580	0.3930	0.041*
C18	0.2517 (8)	0.3301 (7)	0.4167 (3)	0.0396 (17)
H18A	0.3518	0.3322	0.4040	0.048*
H18B	0.2034	0.2393	0.4034	0.048*
C19	0.2568 (9)	0.3176 (8)	0.4715 (3)	0.0502 (19)
H19A	0.1567	0.3202	0.4842	0.060*
H19B	0.2990	0.2186	0.4803	0.060*
N12	0.3421 (7)	0.4391 (7)	0.4955 (2)	0.0555 (16)
H12A	0.3406	0.4250	0.5282	0.083*
H12B	0.3028	0.5305	0.4883	0.083*
H12C	0.4349	0.4360	0.4848	0.083*
C21	0.9036 (7)	0.6445 (7)	0.6746 (3)	0.0307 (15)
C211	0.8532 (7)	0.6411 (8)	0.6216 (3)	0.0374 (17)
O22	0.8559 (7)	0.5169 (6)	0.5986 (2)	0.0663 (17)
O21	0.8076 (6)	0.7632 (5)	0.60255 (17)	0.0516 (14)
C22	0.9971 (7)	0.5287 (7)	0.6914 (3)	0.0384 (16)
H22	1.0258	0.4504	0.6700	0.046*
C23	1.0483 (8)	0.5286 (8)	0.7402 (3)	0.0457 (19)
H23	1.1119	0.4512	0.7509	0.055*
C24	1.0048 (8)	0.6429 (9)	0.7725 (3)	0.049 (2)
H24	1.0389	0.6422	0.8049	0.059*
C25	0.9078 (8)	0.7622 (8)	0.7564 (2)	0.0372 (17)
H25	0.8767	0.8385	0.7782	0.045*
C26	0.8603 (7)	0.7620 (7)	0.7069 (2)	0.0289 (15)
C27	0.7617 (7)	0.8920 (6)	0.6915 (2)	0.0266 (13)
O27	0.6264 (5)	0.8757 (5)	0.6901 (2)	0.0443 (12)
C28	0.7510 (8)	1.1631 (7)	0.6643 (3)	0.0399 (17)
H28A	0.8188	1.2496	0.6643	0.048*
H28B	0.6719	1.1865	0.6873	0.048*
N21	0.8299 (5)	1.0244 (6)	0.68173 (19)	0.0309 (13)
H21	0.9239	1.0294	0.6858	0.037*
C29	0.6868 (8)	1.1457 (9)	0.6131 (3)	0.053 (2)
H29A	0.5994	1.0814	0.6150	0.064*
H29B	0.6567	1.2463	0.6012	0.064*
N22	0.7921 (6)	1.0761 (6)	0.5768 (2)	0.0480 (14)
H22A	0.8650	1.1423	0.5708	0.072*
H22B	0.7447	1.0552	0.5488	0.072*
H22C	0.8292	0.9894	0.5893	0.072*
O1W	0.5242 (6)	0.7194 (6)	0.5655 (2)	0.0600 (14)
H1W	0.600 (11)	0.751 (12)	0.587 (4)	0.15 (5)*
H2W	0.485 (9)	0.625 (7)	0.574 (4)	0.10 (3)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C11	0.025 (3)	0.034 (4)	0.035 (4)	−0.003 (3)	0.005 (3)	0.008 (3)
C111	0.041 (4)	0.036 (4)	0.034 (4)	0.005 (3)	−0.009 (3)	−0.001 (3)
O11	0.073 (3)	0.047 (3)	0.037 (3)	0.014 (3)	−0.007 (2)	0.003 (2)
O12	0.117 (6)	0.048 (3)	0.057 (4)	−0.008 (3)	−0.032 (4)	−0.012 (3)
C12	0.041 (4)	0.033 (4)	0.041 (4)	0.001 (3)	−0.004 (4)	0.008 (3)
C13	0.051 (4)	0.038 (4)	0.052 (4)	0.001 (4)	−0.016 (4)	0.018 (4)
C14	0.045 (4)	0.057 (5)	0.039 (5)	−0.002 (4)	−0.016 (4)	0.016 (4)
C15	0.039 (4)	0.038 (4)	0.041 (4)	−0.006 (3)	0.001 (3)	−0.006 (3)
C16	0.025 (3)	0.030 (3)	0.031 (4)	−0.007 (3)	0.003 (3)	0.001 (3)
C17	0.031 (4)	0.035 (3)	0.032 (3)	0.002 (3)	−0.001 (3)	−0.008 (3)
O17	0.020 (2)	0.045 (3)	0.057 (3)	−0.003 (2)	−0.001 (2)	0.007 (3)
N11	0.021 (3)	0.033 (3)	0.048 (3)	−0.002 (2)	0.000 (3)	−0.001 (3)
C18	0.036 (3)	0.029 (3)	0.054 (5)	0.002 (3)	−0.005 (3)	0.003 (3)
C19	0.054 (4)	0.042 (4)	0.055 (5)	0.012 (3)	0.003 (4)	0.012 (3)
N12	0.062 (4)	0.046 (3)	0.058 (4)	0.008 (3)	−0.007 (3)	0.010 (3)
C21	0.030 (3)	0.026 (3)	0.036 (4)	−0.006 (3)	−0.007 (3)	−0.003 (3)
C211	0.030 (3)	0.041 (4)	0.041 (4)	0.004 (3)	−0.001 (3)	−0.001 (3)
O22	0.092 (4)	0.052 (3)	0.056 (3)	0.023 (3)	−0.021 (3)	−0.022 (3)
O21	0.073 (3)	0.044 (3)	0.038 (3)	0.010 (2)	−0.014 (3)	0.002 (2)
C22	0.033 (3)	0.027 (3)	0.056 (5)	0.001 (3)	0.000 (4)	−0.002 (3)
C23	0.040 (4)	0.041 (4)	0.057 (5)	0.011 (3)	0.000 (4)	0.016 (4)
C24	0.057 (5)	0.052 (5)	0.037 (5)	0.000 (4)	−0.007 (4)	0.012 (3)
C25	0.041 (4)	0.042 (4)	0.029 (4)	0.009 (3)	−0.009 (3)	0.006 (3)
C26	0.022 (3)	0.033 (3)	0.032 (4)	−0.002 (3)	−0.001 (3)	0.004 (3)
C27	0.021 (3)	0.033 (3)	0.026 (3)	−0.002 (3)	0.002 (3)	0.004 (3)
O27	0.024 (2)	0.044 (3)	0.065 (3)	−0.001 (2)	0.000 (2)	0.005 (3)
C28	0.033 (3)	0.029 (3)	0.058 (5)	0.004 (3)	0.009 (3)	0.001 (3)
N21	0.024 (3)	0.028 (3)	0.041 (3)	−0.001 (2)	−0.006 (2)	0.003 (2)
C29	0.037 (4)	0.058 (5)	0.065 (5)	0.009 (4)	−0.007 (4)	0.021 (4)
N22	0.050 (3)	0.044 (3)	0.050 (3)	−0.003 (3)	−0.011 (3)	0.011 (3)
O1W	0.046 (3)	0.061 (3)	0.073 (4)	−0.001 (3)	−0.003 (3)	0.014 (3)

Geometric parameters (Å, º) top

C11—C12	1.394 (9)	C21—C26	1.397 (8)
C11—C16	1.403 (9)	C21—C211	1.503 (10)
C11—C111	1.512 (10)	C211—O22	1.245 (8)
C111—O12	1.222 (8)	C211—O21	1.249 (8)
C111—O11	1.252 (8)	C22—C23	1.398 (11)
C12—C13	1.383 (10)	C22—H22	0.9300
C12—H12	0.9300	C23—C24	1.378 (11)
C13—C14	1.344 (11)	C23—H23	0.9300
C13—H13	0.9300	C24—C25	1.425 (10)
C14—C15	1.368 (10)	C24—H24	0.9300
C14—H14	0.9300	C25—C26	1.406 (8)
C15—C16	1.379 (9)	C25—H25	0.9300
C15—H15	0.9300	C26—C27	1.497 (8)
C16—C17	1.487 (9)	C27—O27	1.235 (7)
C17—O17	1.239 (8)	C27—N21	1.330 (7)
C17—N11	1.349 (8)	C28—N21	1.476 (8)
N11—C18	1.449 (8)	C28—C29	1.507 (12)
N11—H11	0.8600	C28—H28A	0.9700
C18—C19	1.486 (10)	C28—H28B	0.9700
C18—H18A	0.9700	N21—H21	0.8600
C18—H18B	0.9700	C29—N22	1.495 (9)
C19—N12	1.459 (9)	C29—H29A	0.9700
C19—H19A	0.9700	C29—H29B	0.9700
C19—H19B	0.9700	N22—H22A	0.8900
N12—H12A	0.8900	N22—H22B	0.8900
N12—H12B	0.8900	N22—H22C	0.8900
N12—H12C	0.8900	O1W—H1W	0.94 (5)
C21—C22	1.390 (9)	O1W—H2W	0.92 (5)

C12—C11—C16	118.7 (6)	C22—C21—C211	118.8 (6)
C12—C11—C111	119.9 (6)	C26—C21—C211	121.6 (6)
C16—C11—C111	121.3 (6)	O22—C211—O21	122.2 (7)
O12—C111—O11	126.9 (7)	O22—C211—C21	119.2 (6)
O12—C111—C11	115.8 (6)	O21—C211—C21	118.5 (6)
O11—C111—C11	117.2 (6)	C21—C22—C23	120.7 (6)
C13—C12—C11	120.2 (7)	C21—C22—H22	119.6
C13—C12—H12	119.9	C23—C22—H22	119.6
C11—C12—H12	119.9	C24—C23—C22	120.1 (6)
C14—C13—C12	120.5 (7)	C24—C23—H23	120.0
C14—C13—H13	119.8	C22—C23—H23	120.0
C12—C13—H13	119.8	C23—C24—C25	120.4 (7)
C13—C14—C15	120.4 (7)	C23—C24—H24	119.8
C13—C14—H14	119.8	C25—C24—H24	119.8
C15—C14—H14	119.8	C26—C25—C24	118.5 (7)
C14—C15—C16	121.3 (7)	C26—C25—H25	120.7
C14—C15—H15	119.3	C24—C25—H25	120.7
C16—C15—H15	119.3	C21—C26—C25	120.6 (6)
C15—C16—C11	118.8 (6)	C21—C26—C27	122.9 (6)
C15—C16—C17	119.7 (6)	C25—C26—C27	116.5 (6)
C11—C16—C17	121.4 (6)	O27—C27—N21	123.6 (6)
O17—C17—N11	122.3 (6)	O27—C27—C26	121.0 (5)
O17—C17—C16	121.6 (6)	N21—C27—C26	115.3 (5)
N11—C17—C16	116.1 (6)	N21—C28—C29	113.5 (6)
C17—N11—C18	123.9 (5)	N21—C28—H28A	108.9
C17—N11—H11	118.0	C29—C28—H28A	108.9
C18—N11—H11	118.0	N21—C28—H28B	108.9
N11—C18—C19	113.2 (6)	C29—C28—H28B	108.9
N11—C18—H18A	108.9	H28A—C28—H28B	107.7
C19—C18—H18A	108.9	C27—N21—C28	122.8 (5)
N11—C18—H18B	108.9	C27—N21—H21	118.6
C19—C18—H18B	108.9	C28—N21—H21	118.6
H18A—C18—H18B	107.8	N22—C29—C28	113.3 (5)
N12—C19—C18	114.0 (7)	N22—C29—H29A	108.9
N12—C19—H19A	108.7	C28—C29—H29A	108.9
C18—C19—H19A	108.7	N22—C29—H29B	108.9
N12—C19—H19B	108.7	C28—C29—H29B	108.9
C18—C19—H19B	108.7	H29A—C29—H29B	107.7
H19A—C19—H19B	107.6	C29—N22—H22A	109.5
C19—N12—H12A	109.5	C29—N22—H22B	109.5
C19—N12—H12B	109.5	H22A—N22—H22B	109.5
H12A—N12—H12B	109.5	C29—N22—H22C	109.5
C19—N12—H12C	109.5	H22A—N22—H22C	109.5
H12A—N12—H12C	109.5	H22B—N22—H22C	109.5
H12B—N12—H12C	109.5	H1W—O1W—H2W	112 (7)
C22—C21—C26	119.6 (6)

C12—C11—C111—O12	−35.1 (9)	C22—C21—C211—O22	22.1 (9)
C16—C11—C111—O12	147.7 (7)	C26—C21—C211—O22	−158.8 (6)
C12—C11—C111—O11	142.7 (7)	C22—C21—C211—O21	−159.2 (6)
C16—C11—C111—O11	−34.6 (9)	C26—C21—C211—O21	19.9 (10)
C16—C11—C12—C13	1.9 (10)	C26—C21—C22—C23	−0.1 (10)
C111—C11—C12—C13	−175.5 (6)	C211—C21—C22—C23	179.1 (6)
C11—C12—C13—C14	−2.2 (11)	C21—C22—C23—C24	0.9 (11)
C12—C13—C14—C15	1.0 (11)	C22—C23—C24—C25	−0.2 (11)
C13—C14—C15—C16	0.7 (11)	C23—C24—C25—C26	−1.2 (11)
C14—C15—C16—C11	−1.0 (10)	C22—C21—C26—C25	−1.4 (9)
C14—C15—C16—C17	−179.3 (6)	C211—C21—C26—C25	179.5 (6)
C12—C11—C16—C15	−0.3 (9)	C22—C21—C26—C27	179.1 (6)
C111—C11—C16—C15	177.0 (6)	C211—C21—C26—C27	0.0 (9)
C12—C11—C16—C17	177.9 (6)	C24—C25—C26—C21	2.0 (10)
C111—C11—C16—C17	−4.8 (9)	C24—C25—C26—C27	−178.4 (6)
C15—C16—C17—O17	102.6 (8)	C21—C26—C27—O27	81.8 (9)
C11—C16—C17—O17	−75.6 (8)	C25—C26—C27—O27	−97.7 (8)
C15—C16—C17—N11	−77.3 (8)	C21—C26—C27—N21	−100.9 (7)
C11—C16—C17—N11	104.5 (7)	C25—C26—C27—N21	79.6 (7)
O17—C17—N11—C18	4.2 (11)	O27—C27—N21—C28	−5.1 (11)
C16—C17—N11—C18	−175.9 (6)	C26—C27—N21—C28	177.7 (6)
C17—N11—C18—C19	86.8 (9)	C29—C28—N21—C27	−67.1 (9)
N11—C18—C19—N12	−65.4 (8)	N21—C28—C29—N22	−46.0 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···O17ⁱ	0.86	2.03	2.843 (7)	157
N12—H12A···O21ⁱ	0.89	2.61	3.397 (8)	148
N12—H12B···O11	0.89	2.07	2.920 (7)	158
N12—H12C···O11ⁱⁱ	0.89	2.27	3.035 (8)	144
N21—H21···O27ⁱⁱⁱ	0.86	2.01	2.831 (7)	159
N22—H22A···O1Wⁱⁱⁱ	0.89	1.88	2.768 (7)	174
N22—H22B···O12ⁱⁱⁱ	0.89	1.82	2.706 (8)	171
N22—H22C···O21	0.89	2.00	2.804 (7)	149
O1W—H1W···O21	0.94 (5)	1.93 (8)	2.782 (7)	149 (12)
O1W—H2W···O22ⁱ	0.92 (5)	1.82 (5)	2.706 (7)	160 (9)

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₂N₂O₃·0.5H₂O
M_r	217.23
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	293
a, b, c (Å)	9.0609 (9), 8.6714 (12), 27.0214 (19)
V (Å³)	2123.1 (4)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.23 × 0.19 × 0.15

Data collection
Diffractometer	Nonius MACH3 sealed tube
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.983, 0.998
No. of measured, independent and observed [I > 2σ(I)] reflections	1986, 1905, 1430
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.593

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.153, 1.15
No. of reflections	1905
No. of parameters	288
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.22

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), CAD-4 EXPRESS, XCAD4 (Harms & Wocadlo, 1995), SHELXTL/PC (Bruker, 2000), SHELXTL/PC, ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003).