Alaninyl­tryptophan hydrate, glycyl­tryptophan dihydrate and tryptophyl­glycine hydrate

The crystal structures of the title tryptophan-containing dipeptides, C₁₄H₁₇N₃O₃·H₂O, (I), C₁₃H₁₅N₃O₃·2H₂O, (II), and C₁₃H₁₅N₃O₃·H₂O, (III), respectively, contain at least one water mol­ecule of solvation. As a result, the crystal packing of these compounds is composed of regions of water-mediated hydrogen bonding and tryptophan ring-to-ring stacking separated by the length of the mol­ecule. The tryptophan rings stack in a continuous layer that, when viewed edge-on from the outermost part of the tryptophan ring, exhibits a herring-bone motif. However, owing to the lack of direct overlap of adjacent rings, no degree of [pi] contact or long-range delocalization of ring systems is possible here. The overall molecular conformations of (I) and (III) contain a folding of one peptide over the other, such that a minimum in molecular volume occurs without any intramolecular hydrogen bonding. In these two dipeptides, extensive hydrogen bonding is observed to and from the single water mol­ecule of solvation. In the crystal structure of (II), however, an extended mol­ecule conformation complements a more extensive hydrogen-bonding scheme involving two water mol­ecules of solvation per dipeptide.

S1. Comment

We have determined the crystal structures of three dipeptides containing tryptophan, namely alaninyltryptophan hydrate [Ala-Trp, (I)], glycyltryptophan dihydrate [Gly-Trp, (II)] and tryptophylglycine hydrate [Trp-Gly, (III)]. It is expected that the sequence and certain features of the solid-state peptide geometry will play a key role in the binding affinity and conformation of the peptide. Another important factor is the presence of significant hydrogen bonding due to the presence of water molecules in the immediate vicinity of the dipeptide. Noteworthy di- (or higher) peptides containing Trp include Trp-Gly-Gly dihydrate (Subramanian et al., 1989), Gly-Trp dihydrate (Pasternak 1956) and Trp-Glu 7-methylguanosine-5'-phosphate trihydrate (Ishida et al., 1991). The second of these, Gly-Trp, (II), needed to be redetermined [e.g. dated 1956 with R(F) = 0.165 and included no H-atom coordinates].

The role of hydrogen bonding of the dipeptide appears to be a generally important one for crystallization of the dipeptide hydrates (Allen et al., 1983). In fact, the size and quality of the crystals formed after solvent evaporation generally follows the apparent strength and number of hydrogen bonds, namely (I) > (II) > (III). There are three short hydrogen-bond contacts in (I), and all are from the one water molecule of solvation to the dipeptide (e.g. no short water–water hydrogen-bond contacts).

The overall conformation of (I) is that of a hairpin that segregates the hydrogen-bond donors and acceptors on one side and the methyl and tryptophan groups on the other. The maximum atom–atom distance within the molecule is therefore short, at 9.0 Å. Analogous maxima for (II) and (III) are 11.6 and 8.6 Å, respectively. The hairpin or `u' shape of (I) is also observed in (III), which contrasts the fully extended conformation of (II). The hairpin motif is also found in Trp-Gly-Gly (Subramanian et al., 1989). These comformations are further described by the selected torsion angles about the respective dipeptide bonds (see Tables 1, 3 and 5). The unique hydrogen-bond contacts are comprised of the acceptor carboxylate, carbonyl and water O atoms and the donor protons from the water molecule and the primary and quaternary amines of the dipeptide bonds and the N termini. The two-dimensional networks of these sheets of hydrogen bonds extend throughout the crystallographic ab, ab and ac planes, respectively, for (I), (II) and (III). Connecting these layers of hydrogen-bond interactions, are layers of adjacent and parallel tryptophan rings. The tryptophan rings in these sheets, when viewed edge-on, compose a herring-bone motif rather than a direct ring-over-ring overlap. As a result, the interplanar separations are close (e.g. 3.3, 3.0 and 3.9 Å for (I), (II) and (III), respectively), but not overlapping. The non-overlapping herring-bone motif of tryptophan rings and adjacent sheets of hydrogen-bond interactions are obtained for (II) and (III) also. This situation may be expected, although the tryptophan rings have been known to overlap directly with similar ring systems, such as that in tryptophanylglutamic acid 7-methylguanosine-5'-phosphate trihydrate (Ishida et al., 1991). The unit-cell packing motif may thus be described as having alternating hydrogen-bond-containing (e.g. hydrophilic) regions and tryptophan ring (e.g. hydrophobic) regions. For (III), which has tetragonal symmetry, the hydrogen-bonding regions appear in both the ac and bc planes, the intersection of which contains rather large channels of hydrogen-bonding water molecules along the c axis.

S2. Experimental

Crystallization of the dipeptides occurred upon solvent evaporation: 50 mg of dipeptide, 1 ml me thanol and 1 ml water were combined in a 1-dram vial, placed with a loose-fitting cap on the shelf. The dipeptides were obtained from BAChem, the methanol was reagent grade (Fisher), and the water was distilled and deionized. Large colourless rods of (I) formed overnight after evaporation of either aqueous or 1:1 water–methanol solutions. The crystals of (II) also formed overnight from aqueous or 1:1 water–methanol solutions producing large colourless plates. The crystals of (III) formed only after very slow evaporation from the 1:1 water–methanol solution and produced only very thin irregularly shaped plates. Attempts to crystallize (I), (II) or (III) from non-aqueous solutions were not successful.

S3. Refinement

All H atoms were observed on difference Fourier maps. The positional and isotropic displacement parameters (U_iso) of the H atoms were refined, with C—H, N—H and O—H bond lengths in the ranges 0.92–1.02, 0.84–0.97 and 0.88–0.95 Å, respectively, for (I); 0.95–1.04, 0.89—0.93 and 0.87–0.94 Å, respectively, for (II); 0.91–1.01, 0.85–0.97 and 0.95–0.97 Å, respectively, for (III); except for H2WB of (II), which had x, y, and z fixed to the values observed on the map (O—H of 1.07 Å), and U_iso fixed to 0.35 Ų. For the refinement of (III), the bond distances of the H atoms were restrained to the refined values from (I) with estimated standard deviations of 0.04 Å. Extinction corrections were significant in all of the structure determinations, and the following reflections were omitted from the refinement of (III): 1 1 0, 2 2 0, 1 2 0. No other reflections were omitted in the refinements. For each of the structures here, the stereochemistry of each peptide was known (natural, l- or S-conformation). The absolute structure determinations were not necessary, although (III) showed an ambiguous Flack parameter of 0.6 (7). For (III), the calculated ranges of indicies h, k and l are ±19, ±19 and ±6, respectively, for θ < 70°. Some reflections with ABS(h) > ABS(k) were not measured, since their -khl equivalents were collected. The presence of many weak reflections, the asymmetrical shape of the sample (very thin and long plate) and the likelihood of anisotropic extinction (e.g., the isotropic value in SHELXL97 was high) led to an R_int value (0.106) that is slightly poorer than usually acceptable (<0.100).

Computing details

For all compounds, 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: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).

(I)

Crystal data

C14H17N3O3·H2O	Dx = 1.363 Mg m^−3
Mr = 293.32	Cu Kα radiation, λ = 1.54180 Å
Orthorhombic, P212121	Cell parameters from 25 reflections
a = 4.9475 (5) Å	θ = 26.1–28.8°
b = 8.2059 (12) Å	µ = 0.84 mm^−1
c = 35.213 (5) Å	T = 295 K
V = 1429.6 (3) Å^3	Rod, colourless
Z = 4	0.35 × 0.17 × 0.15 mm
F(000) = 624

Data collection

Nonius CAD-4 diffractometer	2538 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.012
Graphite monochromator	θmax = 70.0°, θmin = 2.5°
ω–θ scans	h = 0→6
Absorption correction: ψ scan (North et al., 1968)	k = 0→10
Tmin = 0.768, Tmax = 0.881	l = −42→42
3190 measured reflections	3 standard reflections every 60 min
2688 independent reflections	intensity decay: 1%

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	All H-atom parameters refined
R[F^2 > 2σ(F^2)] = 0.026	w = 1/[σ^2(Fo^2) + (0.025P)^2 + 0.315P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.063	(Δ/σ)max < 0.001'
S = 1.00	Δρmax = 0.14 e Å^−3
2688 reflections	Δρmin = −0.10 e Å^−3
267 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0259 (7)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1067 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.02 (18)

Special details

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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 3.2656(0.0019) x + 2.5895(0.0029) y − 24.0053(0.0117) z = 3.8154(0.0017) * −0.0090 (0.0013) N3 * 0.0457 (0.0011) C6 * −0.0133 (0.0012) C7 * −0.0113 (0.0013) C8 * −0.0303 (0.0014) C9 * −0.0115 (0.0015) C10 * 0.0213 (0.0016) C11 * 0.0266 (0.0015) C12 * −0.0005 (0.0014) C13 * −0.0178 (0.0014) C14 − 0.0165 (0.0244) H3N −0.5252 (0.0169) H6A −0.2842 (0.0156) H6B −0.0345 (0.0199) H9 0.0603 (0.0238) H10 0.0882 (0.0230) H11 0.0106 (0.0243) H12 − 0.0556 (0.0192) H14 Rms deviation of fitted atoms = 0.0224

3.2656(0.0019) x + 2.5895(0.0029) y − 24.0053(0.0117) z = 7.0810(0.0034) A ngle to previous plane (with approximate e.s.d.) = 0.00 (0.07) * −0.0090 (0.0013) N3 1_655 * 0.0457 (0.0011) C6 1_655 * −0.0133 (0.0012) C7 1_655 * −0.0113 (0.0013) C8 1_655 * −0.0303 (0.0014) C9 1_655 * −0.0115 (0.0015) C10 1_655 * 0.0213 (0.0016) C11 1_655 * 0.0266 (0.0015) C12 1_655 * −0.0005 (0.0014) C13 1_655 * −0.0178 (0.0014) C14 1_655 − 3.2551 (0.0243) H12 Rms deviation of fitted atoms = 0.0224

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.46933 (19)	−0.08683 (12)	−0.17340 (3)	0.0391 (3)
O2	0.5989 (3)	−0.38871 (12)	−0.22298 (3)	0.0450 (3)
O3	0.4148 (2)	−0.55802 (12)	−0.18147 (3)	0.0436 (3)
N1	0.7162 (3)	0.16433 (14)	−0.21145 (3)	0.0317 (3)
N2	0.8676 (2)	−0.22006 (13)	−0.16684 (3)	0.0273 (2)
N3	1.1100 (3)	−0.3232 (2)	−0.04242 (4)	0.0611 (4)
C1	0.8795 (3)	0.06174 (15)	−0.18529 (4)	0.0289 (3)
C2	0.7178 (3)	−0.08945 (15)	−0.17477 (4)	0.0279 (3)
C3	0.9554 (4)	0.16083 (19)	−0.15034 (4)	0.0397 (4)
C4	0.7538 (3)	−0.37928 (15)	−0.15802 (4)	0.0285 (3)
C5	0.5713 (3)	−0.44347 (15)	−0.19035 (4)	0.0301 (3)
C6	0.6120 (3)	−0.38588 (18)	−0.11921 (4)	0.0363 (3)
C7	0.7871 (3)	−0.33073 (19)	−0.08698 (4)	0.0381 (3)
C8	0.7888 (3)	−0.1720 (2)	−0.06972 (4)	0.0396 (3)
C9	0.6351 (4)	−0.0313 (2)	−0.07466 (5)	0.0482 (4)
C10	0.6911 (5)	0.1046 (3)	−0.05317 (5)	0.0615 (5)
C11	0.8996 (5)	0.1029 (3)	−0.02634 (5)	0.0677 (6)
C12	1.0527 (5)	−0.0330 (3)	−0.02040 (5)	0.0666 (6)
C13	0.9951 (3)	−0.1716 (2)	−0.04206 (4)	0.0492 (4)
C14	0.9844 (4)	−0.4183 (3)	−0.06940 (4)	0.0508 (4)
H1NA	0.834 (4)	0.242 (2)	−0.2241 (5)	0.056 (5)*
H1NB	0.632 (4)	0.104 (2)	−0.2299 (5)	0.050 (5)*
H1NC	0.586 (4)	0.228 (2)	−0.1976 (5)	0.052 (5)*
H2N	1.036 (4)	−0.2143 (19)	−0.1701 (5)	0.041 (5)*
H3N	1.239 (5)	−0.352 (3)	−0.0277 (7)	0.088 (8)*
H1	1.040 (3)	0.0265 (17)	−0.1986 (4)	0.029 (4)*
H3A	1.072 (4)	0.260 (2)	−0.1571 (5)	0.050 (5)*
H3B	0.792 (4)	0.201 (2)	−0.1363 (5)	0.055 (5)*
H3C	1.044 (4)	0.095 (2)	−0.1324 (5)	0.049 (5)*
H4	0.903 (3)	−0.4547 (18)	−0.1582 (4)	0.031 (4)*
H6A	0.558 (4)	−0.5017 (19)	−0.1152 (4)	0.041 (4)*
H6B	0.451 (3)	−0.3183 (18)	−0.1201 (4)	0.037 (4)*
H9	0.499 (4)	−0.029 (2)	−0.0928 (6)	0.061 (6)*
H10	0.592 (5)	0.211 (3)	−0.0582 (6)	0.082 (7)*
H11	0.938 (5)	0.208 (3)	−0.0127 (6)	0.077 (7)*
H12	1.186 (5)	−0.040 (3)	−0.0024 (7)	0.087 (8)*
H14	1.034 (4)	−0.532 (2)	−0.0733 (5)	0.058 (6)*
O1W	0.1118 (2)	−0.64928 (13)	−0.24289 (3)	0.0403 (3)
H1WA	0.203 (5)	−0.724 (3)	−0.2554 (6)	0.069 (7)*
H1WB	0.213 (5)	−0.606 (3)	−0.2222 (7)	0.078 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0231 (5)	0.0355 (5)	0.0587 (6)	0.0008 (4)	0.0004 (4)	0.0048 (5)
O2	0.0576 (7)	0.0439 (6)	0.0334 (5)	−0.0135 (6)	−0.0102 (5)	0.0034 (4)
O3	0.0476 (6)	0.0401 (5)	0.0431 (5)	−0.0153 (5)	0.0004 (5)	−0.0042 (4)
N1	0.0346 (6)	0.0281 (5)	0.0325 (6)	0.0002 (5)	−0.0029 (5)	0.0008 (5)
N2	0.0227 (6)	0.0258 (5)	0.0334 (6)	−0.0005 (4)	−0.0017 (5)	0.0002 (4)
N3	0.0454 (8)	0.0982 (13)	0.0398 (7)	0.0030 (10)	−0.0121 (7)	0.0054 (8)
C1	0.0274 (6)	0.0251 (6)	0.0342 (6)	−0.0002 (6)	−0.0018 (6)	0.0006 (5)
C2	0.0272 (6)	0.0272 (6)	0.0293 (6)	−0.0007 (5)	−0.0010 (5)	−0.0028 (5)
C3	0.0464 (9)	0.0347 (7)	0.0379 (7)	−0.0081 (7)	−0.0095 (7)	−0.0006 (6)
C4	0.0297 (7)	0.0246 (6)	0.0313 (6)	0.0012 (5)	−0.0013 (5)	0.0005 (5)
C5	0.0320 (7)	0.0231 (6)	0.0352 (7)	0.0020 (6)	−0.0014 (5)	−0.0031 (5)
C6	0.0368 (7)	0.0397 (8)	0.0324 (7)	−0.0069 (7)	0.0010 (6)	0.0017 (6)
C7	0.0369 (8)	0.0495 (8)	0.0278 (6)	−0.0036 (7)	0.0016 (6)	0.0045 (6)
C8	0.0354 (8)	0.0574 (9)	0.0261 (6)	−0.0094 (7)	0.0046 (5)	−0.0007 (6)
C9	0.0498 (10)	0.0571 (10)	0.0378 (8)	−0.0043 (8)	0.0040 (8)	−0.0049 (7)
C10	0.0693 (13)	0.0633 (12)	0.0519 (10)	−0.0097 (11)	0.0158 (9)	−0.0130 (9)
C11	0.0696 (13)	0.0822 (14)	0.0513 (10)	−0.0306 (13)	0.0149 (10)	−0.0241 (10)
C12	0.0515 (12)	0.1110 (18)	0.0372 (9)	−0.0309 (13)	0.0023 (8)	−0.0172 (10)
C13	0.0375 (8)	0.0783 (12)	0.0319 (7)	−0.0124 (9)	0.0014 (6)	−0.0016 (8)
C14	0.0492 (9)	0.0667 (12)	0.0365 (8)	0.0047 (9)	−0.0022 (7)	0.0079 (8)
O1W	0.0436 (6)	0.0401 (6)	0.0371 (5)	−0.0013 (5)	−0.0005 (5)	0.0002 (4)

Geometric parameters (Å, º)

O1—C2	1.2307 (16)	C4—C5	1.5458 (18)
O2—C5	1.2412 (16)	C4—H4	0.963 (16)
O3—C5	1.2573 (17)	C6—C7	1.498 (2)
N1—C1	1.4867 (17)	C6—H6A	0.996 (16)
N1—H1NA	0.97 (2)	C6—H6B	0.973 (17)
N1—H1NB	0.92 (2)	C7—C14	1.361 (2)
N1—H1NC	0.963 (19)	C7—C8	1.437 (2)
N2—C2	1.3324 (17)	C8—C9	1.394 (2)
N2—C4	1.4562 (17)	C8—C13	1.411 (2)
N2—H2N	0.842 (19)	C9—C10	1.376 (3)
N3—C13	1.368 (3)	C9—H9	0.93 (2)
N3—C14	1.378 (2)	C10—C11	1.399 (3)
N3—H3N	0.86 (3)	C10—H10	1.02 (2)
C1—C2	1.5219 (18)	C11—C12	1.364 (3)
C1—C3	1.5222 (19)	C11—H11	1.00 (2)
C1—H1	0.967 (15)	C12—C13	1.399 (3)
C3—H3A	1.025 (19)	C12—H12	0.92 (3)
C3—H3B	1.00 (2)	C14—H14	0.972 (19)
C3—H3C	0.940 (19)	O1W—H1WA	0.88 (2)
C4—C6	1.5369 (18)	O1W—H1WB	0.95 (2)
C1—N1—H1NA	109.2 (11)	O2—C5—C4	119.61 (12)
C1—N1—H1NB	112.3 (11)	O3—C5—C4	115.55 (11)
H1NA—N1—H1NB	107.7 (16)	C7—C6—C4	113.52 (12)
C1—N1—H1NC	110.9 (10)	C7—C6—H6A	109.5 (9)
H1NA—N1—H1NC	106.2 (15)	C4—C6—H6A	106.3 (9)
H1NB—N1—H1NC	110.3 (16)	C7—C6—H6B	109.2 (9)
C2—N2—C4	123.47 (11)	C4—C6—H6B	108.9 (9)
C2—N2—H2N	118.5 (11)	H6A—C6—H6B	109.3 (14)
C4—N2—H2N	117.5 (11)	C14—C7—C8	106.36 (14)
C13—N3—C14	109.51 (15)	C14—C7—C6	126.88 (15)
C13—N3—H3N	124.1 (17)	C8—C7—C6	126.70 (14)
C14—N3—H3N	126.4 (17)	C9—C8—C13	118.62 (16)
N1—C1—C2	109.07 (11)	C9—C8—C7	134.01 (14)
N1—C1—C3	109.43 (11)	C13—C8—C7	107.36 (15)
C2—C1—C3	111.61 (11)	C10—C9—C8	119.52 (18)
N1—C1—H1	108.3 (8)	C10—C9—H9	120.6 (12)
C2—C1—H1	107.8 (9)	C8—C9—H9	119.8 (12)
C3—C1—H1	110.5 (9)	C9—C10—C11	120.8 (2)
O1—C2—N2	124.15 (13)	C9—C10—H10	120.1 (13)
O1—C2—C1	121.35 (12)	C11—C10—H10	118.9 (14)
N2—C2—C1	114.49 (11)	C12—C11—C10	121.40 (18)
C1—C3—H3A	112.1 (10)	C12—C11—H11	121.5 (14)
C1—C3—H3B	112.1 (11)	C10—C11—H11	117.0 (14)
H3A—C3—H3B	107.8 (14)	C11—C12—C13	117.89 (19)
C1—C3—H3C	110.5 (10)	C11—C12—H12	123.8 (16)
H3A—C3—H3C	110.4 (15)	C13—C12—H12	118.3 (16)
H3B—C3—H3C	103.7 (15)	N3—C13—C12	131.28 (17)
N2—C4—C6	113.44 (11)	N3—C13—C8	106.99 (15)
N2—C4—C5	111.99 (11)	C12—C13—C8	121.73 (19)
C6—C4—C5	112.10 (11)	C7—C14—N3	109.78 (17)
N2—C4—H4	106.2 (9)	C7—C14—H14	128.3 (12)
C6—C4—H4	109.4 (9)	N3—C14—H14	121.8 (12)
C5—C4—H4	103.0 (9)	H1WA—O1W—H1WB	112.0 (19)
O2—C5—O3	124.67 (13)
H1NA—N1—C1—C2	−163 (1)	C14—C7—C8—C13	0.60 (17)
N1—C1—C2—N2	151.0 (1)	C6—C7—C8—C13	−176.69 (13)
C1—C2—N2—C4	−176.8 (1)	C13—C8—C9—C10	1.3 (2)
C2—N2—C4—C5	57.9 (2)	C7—C8—C9—C10	−179.53 (16)
N2—C4—C5—O2	21.5 (2)	C8—C9—C10—C11	−0.2 (3)
C4—N2—C2—O1	4.3 (2)	C9—C10—C11—C12	−0.4 (3)
N1—C1—C2—O1	−30.04 (18)	C10—C11—C12—C13	0.1 (3)
C3—C1—C2—O1	90.99 (17)	C14—N3—C13—C12	−179.10 (17)
C3—C1—C2—N2	−88.00 (15)	C14—N3—C13—C8	0.30 (18)
C2—N2—C4—C6	−70.25 (16)	C11—C12—C13—N3	−179.66 (18)
C6—C4—C5—O2	150.35 (13)	C11—C12—C13—C8	1.0 (3)
N2—C4—C5—O3	−163.09 (12)	C9—C8—C13—N3	178.84 (14)
C6—C4—C5—O3	−34.26 (16)	C7—C8—C13—N3	−0.56 (17)
N2—C4—C6—C7	−54.24 (17)	C9—C8—C13—C12	−1.7 (2)
C5—C4—C6—C7	177.70 (12)	C7—C8—C13—C12	178.91 (15)
C4—C6—C7—C14	−78.70 (19)	C8—C7—C14—N3	−0.43 (18)
C4—C6—C7—C8	98.05 (17)	C6—C7—C14—N3	176.86 (14)
C14—C7—C8—C9	−178.66 (17)	C13—N3—C14—C7	0.1 (2)
C6—C7—C8—C9	4.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1NA···O1W^i	0.97 (2)	1.77 (2)	2.720 (2)	166 (1)
O1W—H1WB···O3	0.95 (2)	1.79 (2)	2.737 (2)	171 (1)
O1W—H1WA···O2^ii	0.88 (2)	1.83 (2)	2.712 (2)	175 (1)
N1—H1NB···O2^iii	0.92 (2)	2.02 (2)	2.820 (2)	146 (1)
N1—H1NC···O3^iv	0.96 (2)	2.03 (2)	2.920 (2)	153 (1)
N2—H2N···O1^v	0.84 (2)	2.39 (2)	3.180 (2)	157 (1)

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

(II)

Crystal data

C13H15N3O3·2H2O	F(000) = 316
Mr = 297.31	Dx = 1.391 Mg m^−3
Monoclinic, P21	Cu Kα radiation, λ = 1.54180 Å
a = 5.8404 (6) Å	Cell parameters from 25 reflections
b = 8.2429 (8) Å	θ = 35.4–42.8°
c = 14.8299 (10) Å	µ = 0.91 mm^−1
β = 96.178 (8)°	T = 295 K
V = 709.79 (11) Å^3	Plate, colourless
Z = 2	0.60 × 0.32 × 0.02 mm

Data collection

Nonius CAD-4 diffractometer	1404 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.015
Graphite monochromator	θmax = 69.9°, θmin = 3.0°
ω–θ scans	h = 0→7
Absorption correction: ψ scan (North et al., 1968)	k = 0→10
Tmin = 0.811, Tmax = 0.982	l = −18→17
1583 measured reflections	3 standard reflections every 3600 min
1440 independent reflections	intensity decay: 1%

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms: see text
R[F^2 > 2σ(F^2)] = 0.034	w = 1/[σ^2(Fo^2) + (0.033P)^2 + 0.295P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.080	(Δ/σ)max = 0.001
S = 1.00	Δρmax = 0.17 e Å^−3
1440 reflections	Δρmin = −0.17 e Å^−3
263 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.0227 (17)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), no Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.0 (3)

Special details

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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) −3.0006(0.0047) x + 6.9611(0.0043) y − 1.4095(0.0099) z = 1.0443(0.0013) * −0.0083 (0.0029) N3 * 0.0079 (0.0021) C5 * −0.0044 (0.0026) C6 * −0.0023 (0.0024) C7 * −0.0039 (0.0027) C8 * −0.0036 (0.0028) C9 * 0.0025 (0.0028) C10 * 0.0086 (0.0029) C11 * 0.0012 (0.0029) C12 * 0.0024 (0.0031) C13 − 0.0962 (0.0689) H3N 0.0019 (0.0358) H5B −0.0406 (0.0318) H8 − 0.0695 (0.0434) H9 0.0553 (0.0357) H10 − 0.0520 (0.0407) H11 0.0174 (0.0505) H13 Rms deviation of fitted atoms = 0.0052

3.0006(0.0047) x − 6.9611(0.0043) y + 1.4095(0.0099) z = 1.9563(0.0040) A ngle to previous plane (with approximate e.s.d.) = 0.00 (0.12) * 0.0083 (0.0029) N3 1_655 * −0.0079 (0.0021) C5 1_655 * 0.0044 (0.0026) C6 1_655 * 0.0023 (0.0024) C7 1_655 * 0.0039 (0.0027) C8 1_655 * 0.0036 (0.0028) C9 1_655 * −0.0025 (0.0028) C10 1_655 * −0.0086 (0.0029) C11 1_655 * −0.0012 (0.0029) C12 1_655 * −0.0024 (0.0031) C13 1_655 − 2.9600 (0.0320) H8 Rms deviation of fitted atoms = 0.0052

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	−0.0226 (3)	−0.2538 (3)	0.36209 (14)	0.0520 (6)
O2	0.0773 (3)	0.1764 (3)	0.38823 (13)	0.0550 (6)
O3	0.3526 (3)	0.1228 (3)	0.30149 (13)	0.0464 (5)
N1	−0.3879 (4)	−0.3496 (3)	0.44959 (16)	0.0429 (6)
N2	−0.2160 (3)	−0.0433 (3)	0.29312 (14)	0.0347 (5)
N3	−0.5126 (5)	−0.0712 (4)	0.0048 (2)	0.0592 (8)
C1	−0.4259 (5)	−0.2261 (4)	0.3785 (2)	0.0437 (7)
C2	−0.2004 (4)	−0.1748 (3)	0.34440 (16)	0.0352 (6)
C3	−0.0202 (4)	0.0227 (3)	0.25173 (16)	0.0319 (5)
C4	0.1498 (4)	0.1133 (3)	0.32004 (15)	0.0338 (5)
C5	−0.1070 (5)	0.1405 (4)	0.17519 (17)	0.0402 (6)
C6	−0.2446 (4)	0.0631 (4)	0.09479 (17)	0.0384 (6)
C7	−0.1874 (4)	0.0696 (3)	0.00347 (17)	0.0363 (6)
C8	−0.0060 (5)	0.1392 (4)	−0.03820 (19)	0.0455 (6)
C9	−0.0042 (6)	0.1212 (5)	−0.1306 (2)	0.0562 (8)
C10	−0.1759 (6)	0.0374 (5)	−0.1832 (2)	0.0568 (8)
C11	−0.3573 (6)	−0.0321 (5)	−0.1450 (2)	0.0543 (8)
C12	−0.3596 (4)	−0.0153 (4)	−0.05183 (19)	0.0428 (6)
C13	−0.4445 (5)	−0.0227 (5)	0.0917 (2)	0.0556 (8)
H1NA	−0.524 (8)	−0.363 (6)	0.470 (3)	0.087 (13)*
H1NB	−0.286 (6)	−0.324 (5)	0.500 (3)	0.065 (11)*
H1NC	−0.335 (7)	−0.440 (6)	0.420 (3)	0.087 (14)*
H2N	−0.350 (6)	0.013 (5)	0.284 (2)	0.055 (9)*
H3N	−0.636 (10)	−0.139 (9)	−0.004 (4)	0.15 (2)*
H1A	−0.511 (7)	−0.135 (5)	0.399 (3)	0.070 (11)*
H1B	−0.539 (6)	−0.268 (5)	0.324 (2)	0.057 (9)*
H3	0.062 (4)	−0.071 (4)	0.2285 (17)	0.028 (6)*
H5A	−0.195 (6)	0.228 (5)	0.203 (2)	0.061 (10)*
H5B	0.032 (6)	0.195 (5)	0.153 (2)	0.058 (10)*
H8	0.117 (5)	0.195 (4)	0.002 (2)	0.044 (8)*
H9	0.124 (6)	0.161 (6)	−0.162 (2)	0.071 (11)*
H10	−0.178 (5)	0.031 (5)	−0.249 (2)	0.053 (9)*
H11	−0.472 (7)	−0.097 (5)	−0.179 (2)	0.071 (12)*
H13	−0.538 (7)	−0.051 (7)	0.141 (3)	0.083 (13)*
O1W	0.6617 (5)	0.3387 (4)	0.3906 (3)	0.0977 (13)
H1WA	0.543 (8)	0.277 (7)	0.361 (3)	0.092 (14)*
H1WB	0.788 (12)	0.315 (11)	0.367 (4)	0.16 (3)*
O2W	0.1908 (4)	−0.4914 (4)	0.4744 (2)	0.0837 (9)
H2WA	0.126 (11)	−0.446 (10)	0.419 (4)	0.16 (3)*
H2WB	0.0960	−0.4338	0.5232	0.350*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0398 (10)	0.0575 (13)	0.0609 (12)	0.0160 (10)	0.0161 (8)	0.0205 (11)
O2	0.0340 (9)	0.0864 (17)	0.0450 (10)	−0.0016 (10)	0.0062 (8)	−0.0202 (11)
O3	0.0234 (8)	0.0554 (12)	0.0609 (11)	−0.0007 (9)	0.0072 (7)	−0.0066 (11)
N1	0.0378 (12)	0.0494 (15)	0.0426 (12)	−0.0033 (11)	0.0089 (10)	0.0050 (12)
N2	0.0246 (10)	0.0398 (12)	0.0404 (11)	0.0019 (9)	0.0062 (8)	0.0041 (10)
N3	0.0438 (12)	0.083 (2)	0.0485 (13)	−0.0217 (15)	−0.0050 (10)	0.0017 (14)
C1	0.0320 (13)	0.0516 (18)	0.0479 (15)	−0.0024 (13)	0.0068 (11)	0.0103 (14)
C2	0.0323 (12)	0.0389 (14)	0.0346 (11)	0.0021 (11)	0.0050 (9)	0.0019 (11)
C3	0.0255 (10)	0.0358 (13)	0.0350 (12)	0.0006 (10)	0.0066 (9)	0.0018 (10)
C4	0.0259 (10)	0.0396 (14)	0.0359 (11)	0.0039 (11)	0.0031 (9)	0.0028 (11)
C5	0.0406 (13)	0.0424 (15)	0.0363 (12)	−0.0049 (13)	−0.0018 (10)	0.0043 (13)
C6	0.0333 (11)	0.0430 (14)	0.0375 (12)	−0.0034 (11)	−0.0024 (10)	0.0043 (12)
C7	0.0348 (12)	0.0332 (13)	0.0395 (13)	0.0035 (11)	−0.0029 (10)	0.0049 (11)
C8	0.0453 (14)	0.0427 (15)	0.0483 (14)	−0.0047 (13)	0.0040 (11)	0.0089 (13)
C9	0.0606 (17)	0.057 (2)	0.0533 (16)	0.0027 (17)	0.0166 (14)	0.0121 (16)
C10	0.071 (2)	0.058 (2)	0.0415 (16)	0.0099 (17)	0.0063 (14)	0.0025 (15)
C11	0.0580 (18)	0.057 (2)	0.0449 (15)	0.0022 (16)	−0.0081 (14)	−0.0041 (15)
C12	0.0370 (13)	0.0439 (16)	0.0454 (14)	−0.0010 (12)	−0.0048 (11)	0.0026 (13)
C13	0.0407 (14)	0.080 (2)	0.0456 (15)	−0.0153 (16)	0.0010 (12)	0.0052 (17)
O1W	0.0459 (15)	0.079 (2)	0.165 (3)	0.0081 (14)	−0.0053 (18)	−0.061 (2)
O2W	0.0462 (13)	0.084 (2)	0.120 (2)	−0.0063 (13)	0.0053 (14)	0.0323 (19)

Geometric parameters (Å, º)

O1—C2	1.230 (3)	C5—H5A	1.00 (4)
O2—C4	1.251 (3)	C5—H5B	1.01 (4)
O3—C4	1.247 (3)	C6—C13	1.362 (4)
N1—C1	1.465 (4)	C6—C7	1.430 (4)
N1—H1NA	0.89 (5)	C7—C8	1.405 (4)
N1—H1NB	0.93 (4)	C7—C12	1.413 (4)
N1—H1NC	0.93 (5)	C8—C9	1.379 (4)
N2—C2	1.322 (4)	C8—H8	1.00 (3)
N2—C3	1.460 (3)	C9—C10	1.387 (5)
N2—H2N	0.90 (4)	C9—H9	0.98 (4)
N3—C13	1.366 (4)	C10—C11	1.379 (5)
N3—C12	1.370 (4)	C10—H10	0.97 (3)
N3—H3N	0.91 (6)	C11—C12	1.390 (4)
C1—C2	1.521 (3)	C11—H11	0.95 (4)
C1—H1A	0.97 (4)	C13—H13	0.99 (4)
C1—H1B	1.05 (3)	O1W—H1WA	0.93 (5)
C3—C4	1.534 (3)	O1W—H1WB	0.87 (7)
C3—C5	1.538 (3)	O2W—H2WA	0.94 (7)
C3—H3	0.99 (3)	O2W—H2WB	1.068 (3)
C5—C6	1.506 (3)
C1—N1—H1NA	105 (3)	C6—C5—H5A	112.4 (19)
C1—N1—H1NB	117 (3)	C3—C5—H5A	107 (2)
H1NA—N1—H1NB	106 (3)	C6—C5—H5B	108.0 (18)
C1—N1—H1NC	105 (3)	C3—C5—H5B	107.9 (18)
H1NA—N1—H1NC	114 (4)	H5A—C5—H5B	106 (3)
H1NB—N1—H1NC	110 (4)	C13—C6—C7	105.9 (2)
C2—N2—C3	122.6 (2)	C13—C6—C5	129.0 (3)
C2—N2—H2N	121 (2)	C7—C6—C5	125.1 (2)
C3—N2—H2N	117 (2)	C8—C7—C12	118.1 (2)
C13—N3—C12	109.7 (3)	C8—C7—C6	134.1 (2)
C13—N3—H3N	117 (4)	C12—C7—C6	107.9 (2)
C12—N3—H3N	133 (4)	C9—C8—C7	118.7 (3)
N1—C1—C2	111.3 (2)	C9—C8—H8	124.5 (17)
N1—C1—H1A	111 (2)	C7—C8—H8	116.7 (17)
C2—C1—H1A	113 (2)	C8—C9—C10	122.0 (3)
N1—C1—H1B	111 (2)	C8—C9—H9	122 (2)
C2—C1—H1B	109.5 (18)	C10—C9—H9	116 (2)
H1A—C1—H1B	101 (3)	C11—C10—C9	121.1 (3)
O1—C2—N2	124.2 (2)	C11—C10—H10	117 (2)
O1—C2—C1	121.6 (2)	C9—C10—H10	122 (2)
N2—C2—C1	114.2 (2)	C10—C11—C12	117.2 (3)
N2—C3—C4	112.60 (19)	C10—C11—H11	123 (2)
N2—C3—C5	109.54 (19)	C12—C11—H11	120 (2)
C4—C3—C5	108.6 (2)	N3—C12—C11	130.8 (3)
N2—C3—H3	106.6 (16)	N3—C12—C7	106.3 (2)
C4—C3—H3	108.0 (15)	C11—C12—C7	122.9 (3)
C5—C3—H3	111.6 (15)	C6—C13—N3	110.2 (3)
O3—C4—O2	124.4 (2)	C6—C13—H13	129 (3)
O3—C4—C3	116.6 (2)	N3—C13—H13	120 (3)
O2—C4—C3	119.04 (19)	H1WA—O1W—H1WB	108 (6)
C6—C5—C3	115.0 (2)	H2WA—O2W—H2WB	103 (4)
H1NA—N1—C1—C2	173 (2)	C5—C6—C7—C12	−179.2 (3)
N1—C1—C2—N2	−167.8 (3)	C12—C7—C8—C9	−0.1 (4)
C1—C2—N2—C3	−178.2 (2)	C6—C7—C8—C9	179.9 (3)
C2—N2—C3—C4	−76.1 (3)	C7—C8—C9—C10	0.2 (5)
N2—C3—C4—O2	−26.9 (3)	C8—C9—C10—C11	0.0 (5)
C3—N2—C2—O1	−0.1 (4)	C9—C10—C11—C12	−0.3 (5)
N1—C1—C2—O1	14.0 (4)	C13—N3—C12—C11	−179.3 (4)
C2—N2—C3—C5	163.0 (2)	C13—N3—C12—C7	0.9 (4)
N2—C3—C4—O3	155.2 (2)	C10—C11—C12—N3	−179.3 (4)
C5—C3—C4—O3	−83.3 (3)	C10—C11—C12—C7	0.5 (5)
C5—C3—C4—O2	94.6 (3)	C8—C7—C12—N3	179.5 (3)
N2—C3—C5—C6	−66.4 (3)	C6—C7—C12—N3	−0.4 (3)
C4—C3—C5—C6	170.3 (2)	C8—C7—C12—C11	−0.3 (4)
C3—C5—C6—C13	59.7 (4)	C6—C7—C12—C11	179.8 (3)
C3—C5—C6—C7	−121.5 (3)	C7—C6—C13—N3	0.8 (4)
C13—C6—C7—C8	179.8 (3)	C5—C6—C13—N3	179.8 (3)
C5—C6—C7—C8	0.8 (5)	C12—N3—C13—C6	−1.1 (4)
C13—C6—C7—C12	−0.2 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O3	0.93 (5)	1.85 (4)	2.767 (3)	169 (3)
N1—H1NC···O1W^i	0.93 (5)	1.88 (6)	2.740 (4)	153 (4)
N1—H1NB···O2^ii	0.93 (4)	1.95 (4)	2.860 (3)	166 (3)
O2W—H2WA···O1	0.94 (7)	1.95 (6)	2.778 (4)	145 (4)
O2W—H2WB···O2^ii	1.07	1.97	3.034 (5)	179
N1—H1NA···O2W^iii	0.89 (5)	1.98 (6)	2.784 (4)	150 (4)
N2—H2N···O3^iii	0.90 (4)	2.00 (4)	2.884 (3)	164 (3)
O1W—H1WB···O2^iv	0.87 (7)	2.04 (6)	2.775 (4)	142 (4)

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

(III)

Crystal data

C13H15N3O3·H2O	Dx = 1.373 Mg m^−3
Mr = 279.30	Cu Kα radiation, λ = 1.54180 Å
Tetragonal, P41	Cell parameters from 25 reflections
Hall symbol: P 41	θ = 24.3–24.9°
a = 16.128 (2) Å	µ = 0.86 mm^−1
c = 5.195 (1) Å	T = 295 K
V = 1351.3 (4) Å^3	Thin elongated plates, colourless
Z = 4	0.44 × 0.12 × 0.02 mm
F(000) = 592

Data collection

Nonius CAD-4 diffractometer	871 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.107
Graphite monochromator	θmax = 70.0°, θmin = 2.7°
ω–θ scans	h = −13→13
Absorption correction: ψ scan (North et al., 1968)	k = −10→19
Tmin = 0.719, Tmax = 0.996	l = 0→6
3174 measured reflections	3 standard reflections every 3600 min
1438 independent reflections	intensity decay: 1%

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms: see text
R[F^2 > 2σ(F^2)] = 0.061	w = 1/[σ^2(Fo^2) + (0.04P)^2 + 1.0P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.147	(Δ/σ)max < 0.001
S = 1.01	Δρmax = 0.30 e Å^−3
1434 reflections	Δρmin = −0.23 e Å^−3
250 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
27 restraints	Extinction coefficient: 0.0101 (13)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), no Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.6 (7)

Special details

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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 7.5085(0.0228) x + 7.4397(0.0181) y − 3.9238(0.0042) z = 4.5624(0.0068) * −0.6122 (0.0039) N3 * 0.4562 (0.0054) C3 * 0.1230 (0.0053) C4 * 0.1356 (0.0055) C5 * 0.4457 (0.0059) C6 * 0.3293 (0.0056) C7 * −0.0586 (0.0056) C8 * −0.3613 (0.0057) C9 * −0.2349 (0.0050) C10 * −0.2229 (0.0051) C11 1.1316 (0.0464) H3A 0.4788 (0.0555) H3B 0.6194 (0.0542) H6 0.6518 (0.0763) H7 0.0084 (0.0643) H8 − 0.6113 (0.0715) H9 − 0.4804 (0.0644) H11 Rms deviation of fitted atoms = 0.3409

7.5085(0.0228) x + 7.4397(0.0181) y − 3.9238(0.0042) z = 0.6386(0.0106) A ngle to previous plane (with approximate e.s.d.) = 0.00 (0.21) * −0.6122 (0.0039) N3 1_556 * 0.4562 (0.0054) C3 1_556 * 0.1230 (0.0053) C4 1_556 * 0.1356 (0.0055) C5 1_556 * 0.4457 (0.0059) C6 1_556 * 0.3293 (0.0056) C7 1_556 * −0.0586 (0.0056) C8 1_556 * −0.3613 (0.0057) C9 1_556 * −0.2349 (0.0050) C10 1_556 * −0.2229 (0.0051) C11 1_556 Rms deviation of fitted atoms = 0.3409

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.1942 (3)	0.2068 (3)	0.1682 (7)	0.0550 (12)
O2	0.2508 (3)	0.0199 (3)	0.1125 (9)	0.0586 (12)
O3	0.3419 (3)	0.0621 (3)	0.4073 (8)	0.0552 (12)
N1	0.0632 (4)	0.2361 (4)	−0.1287 (11)	0.0523 (14)
N2	0.1340 (4)	0.4892 (4)	0.1427 (11)	0.0573 (15)
N3	0.2758 (4)	0.1674 (4)	−0.1616 (9)	0.0509 (14)
C1	0.2076 (4)	0.2019 (3)	−0.0678 (11)	0.0452 (15)
C2	0.1455 (4)	0.2368 (4)	−0.2544 (11)	0.0436 (15)
C3	0.1664 (4)	0.3249 (4)	−0.3446 (12)	0.0454 (15)
C4	0.1698 (4)	0.3887 (4)	−0.1322 (12)	0.0437 (14)
C5	0.2388 (4)	0.4055 (3)	0.0285 (11)	0.0389 (13)
C6	0.3186 (4)	0.3756 (4)	0.0454 (12)	0.0498 (16)
C7	0.3718 (5)	0.4052 (4)	0.2331 (14)	0.0589 (18)
C8	0.3459 (5)	0.4677 (4)	0.4008 (13)	0.0559 (17)
C9	0.2671 (5)	0.4994 (4)	0.3874 (14)	0.0563 (17)
C10	0.2143 (4)	0.4693 (4)	0.1969 (11)	0.0442 (14)
C11	0.1082 (4)	0.4402 (4)	−0.0644 (14)	0.0518 (16)
C12	0.3381 (4)	0.1353 (4)	0.0114 (14)	0.0513 (16)
C13	0.3060 (4)	0.0668 (4)	0.1831 (12)	0.0469 (15)
H1NA	0.025 (3)	0.268 (3)	−0.217 (14)	0.08 (2)*
H1NB	0.071 (6)	0.266 (4)	0.032 (11)	0.15 (4)*
H1NC	0.040 (3)	0.185 (3)	−0.088 (12)	0.07 (2)*
H2N	0.105 (3)	0.533 (3)	0.177 (13)	0.040 (16)*
H3N	0.283 (4)	0.160 (4)	−0.321 (8)	0.06 (2)*
H2	0.136 (4)	0.195 (3)	−0.368 (11)	0.055 (19)*
H3A	0.222 (2)	0.324 (3)	−0.412 (11)	0.034 (14)*
H3B	0.113 (2)	0.338 (3)	−0.428 (11)	0.040 (15)*
H6	0.337 (3)	0.331 (3)	−0.048 (10)	0.036 (15)*
H7	0.432 (3)	0.392 (4)	0.241 (17)	0.07 (2)*
H8	0.390 (3)	0.486 (4)	0.502 (12)	0.056 (19)*
H9	0.239 (4)	0.543 (3)	0.479 (14)	0.07 (2)*
H11	0.050 (2)	0.446 (4)	−0.099 (14)	0.055 (17)*
H12A	0.360 (3)	0.185 (3)	0.106 (13)	0.057 (19)*
H12B	0.387 (2)	0.119 (3)	−0.088 (10)	0.030 (13)*
O1W	0.0890 (4)	0.0528 (4)	−0.011 (2)	0.119 (3)
H1WA	0.087 (4)	0.003 (3)	−0.116 (12)	0.07 (2)*
H1WB	0.141 (4)	0.048 (5)	0.075 (19)	0.14 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.074 (3)	0.075 (3)	0.015 (2)	0.012 (2)	0.003 (2)	−0.005 (2)
O2	0.073 (3)	0.061 (3)	0.043 (3)	−0.014 (2)	−0.006 (2)	−0.001 (2)
O3	0.070 (3)	0.075 (3)	0.021 (2)	−0.004 (2)	−0.003 (2)	0.008 (2)
N1	0.064 (4)	0.065 (4)	0.028 (3)	−0.005 (3)	−0.002 (3)	0.007 (3)
N2	0.069 (4)	0.060 (3)	0.043 (3)	0.013 (3)	0.007 (3)	−0.015 (3)
N3	0.070 (4)	0.065 (3)	0.017 (2)	0.005 (3)	0.009 (3)	0.002 (2)
C1	0.071 (4)	0.045 (3)	0.020 (3)	−0.007 (3)	0.004 (3)	0.002 (3)
C2	0.058 (4)	0.054 (4)	0.019 (3)	0.003 (3)	−0.002 (3)	−0.005 (3)
C3	0.056 (4)	0.058 (4)	0.022 (3)	−0.001 (3)	−0.006 (3)	−0.001 (3)
C4	0.052 (3)	0.051 (3)	0.028 (3)	0.005 (3)	0.004 (3)	0.009 (3)
C5	0.053 (3)	0.043 (3)	0.021 (3)	0.003 (3)	0.005 (3)	0.001 (2)
C6	0.069 (4)	0.052 (4)	0.028 (3)	0.008 (3)	0.003 (3)	−0.003 (3)
C7	0.067 (5)	0.068 (4)	0.042 (4)	−0.001 (4)	−0.005 (4)	0.012 (3)
C8	0.072 (5)	0.067 (4)	0.028 (3)	−0.019 (4)	−0.007 (4)	−0.002 (3)
C9	0.080 (5)	0.062 (4)	0.027 (3)	−0.011 (4)	0.002 (3)	−0.004 (3)
C10	0.060 (4)	0.048 (3)	0.025 (3)	−0.006 (3)	0.008 (3)	−0.003 (3)
C11	0.055 (4)	0.059 (4)	0.042 (4)	−0.005 (3)	−0.002 (3)	0.006 (3)
C12	0.057 (4)	0.057 (4)	0.039 (3)	0.005 (3)	0.007 (3)	0.007 (3)
C13	0.051 (3)	0.056 (4)	0.034 (3)	0.000 (3)	0.011 (3)	0.002 (3)
O1W	0.093 (5)	0.115 (6)	0.148 (8)	−0.016 (4)	−0.006 (5)	−0.027 (5)

Geometric parameters (Å, º)

O1—C1	1.247 (7)	C3—H3B	0.98 (3)
O2—C13	1.224 (7)	C4—C11	1.341 (9)
O2—H1WB	1.84 (6)	C4—C5	1.417 (8)
O3—C13	1.303 (8)	C5—C6	1.377 (8)
O3—H1NA^i	1.95 (4)	C5—C10	1.407 (8)
O3—H2N^ii	2.14 (4)	C6—C7	1.384 (9)
N1—C2	1.480 (8)	C6—H6	0.92 (3)
N1—H1NA	0.93 (4)	C7—C8	1.396 (10)
N1—H1NB	0.97 (4)	C7—H7	1.00 (4)
N1—H1NC	0.93 (4)	C8—C9	1.371 (10)
N2—C10	1.364 (8)	C8—H8	0.93 (4)
N2—C11	1.399 (9)	C9—C10	1.394 (9)
N2—H2N	0.86 (3)	C9—H9	0.96 (4)
N3—C1	1.326 (8)	C11—H11	0.95 (4)
N3—C12	1.444 (8)	C12—C13	1.512 (9)
N3—H3N	0.85 (4)	C12—H12A	1.01 (4)
C1—C2	1.503 (9)	C12—H12B	0.97 (3)
C2—C3	1.533 (8)	O1W—H1WA^iii	1.75 (4)
C2—H2	0.91 (4)	O1W—H1NC	2.30 (5)
C3—C4	1.510 (8)	O1W—H1WA	0.97 (4)
C3—H3A	0.97 (3)	O1W—H1WB	0.95 (4)
C13—O2—H1WB	125 (2)	C6—C5—C4	134.8 (6)
C13—O3—H1NA^i	94 (2)	C10—C5—C4	106.5 (5)
C13—O3—H2N^ii	116.4 (18)	C5—C6—C7	120.3 (7)
H1NA^i—O3—H2N^ii	143 (2)	C5—C6—H6	123 (3)
C2—N1—H1NA	112 (5)	C7—C6—H6	116 (3)
C2—N1—H1NB	105 (6)	C6—C7—C8	120.2 (7)
H1NA—N1—H1NB	104 (5)	C6—C7—H7	124 (5)
C2—N1—H1NC	117 (4)	C8—C7—H7	115 (5)
H1NA—N1—H1NC	110 (4)	C9—C8—C7	121.0 (7)
H1NB—N1—H1NC	107 (5)	C9—C8—H8	128 (4)
C10—N2—C11	107.9 (5)	C7—C8—H8	111 (4)
C10—N2—H2N	131 (4)	C8—C9—C10	118.2 (7)
C11—N2—H2N	118 (4)	C8—C9—H9	133 (4)
C1—N3—C12	120.0 (5)	C10—C9—H9	108 (4)
C1—N3—H3N	122 (5)	N2—C10—C9	130.2 (6)
C12—N3—H3N	118 (5)	N2—C10—C5	108.1 (5)
O1—C1—N3	122.1 (6)	C9—C10—C5	121.6 (6)
O1—C1—C2	119.6 (6)	C4—C11—N2	109.3 (6)
N3—C1—C2	118.2 (5)	C4—C11—H11	137 (4)
N1—C2—C1	108.1 (5)	N2—C11—H11	112 (4)
N1—C2—C3	109.8 (5)	N3—C12—C13	112.9 (6)
C1—C2—C3	113.5 (5)	N3—C12—H12A	105 (4)
N1—C2—H2	98 (4)	C13—C12—H12A	114 (4)
C1—C2—H2	105 (4)	N3—C12—H12B	109 (3)
C3—C2—H2	122 (4)	C13—C12—H12B	113 (3)
C4—C3—C2	114.6 (5)	H12A—C12—H12B	101 (4)
C4—C3—H3A	104 (3)	O2—C13—O3	123.7 (6)
C2—C3—H3A	107 (3)	O2—C13—C12	121.6 (6)
C4—C3—H3B	102 (3)	O3—C13—C12	114.7 (6)
C2—C3—H3B	98 (3)	H1WA^iii—O1W—H1NC	60 (3)
H3A—C3—H3B	131 (5)	H1WA^iii—O1W—H1WA	118 (5)
C11—C4—C5	108.0 (6)	H1NC—O1W—H1WA	131 (5)
C11—C4—C3	125.9 (6)	H1WA^iii—O1W—H1WB	124 (7)
C5—C4—C3	126.1 (5)	H1NC—O1W—H1WB	117 (5)
C6—C5—C10	118.6 (6)	H1WA—O1W—H1WB	104 (5)
H1NA—N1—C2—C1	167 (3)	C6—C7—C8—C9	1.6 (10)
N1—C2—C1—N3	154.7 (6)	C7—C8—C9—C10	−1.8 (10)
C2—C1—N3—C12	178.1 (6)	C11—N2—C10—C9	−178.8 (6)
C1—N3—C12—C13	60.7 (8)	C11—N2—C10—C5	−1.7 (7)
N3—C12—C13—O2	30.5 (9)	C8—C9—C10—N2	179.4 (7)
C12—N3—C1—O1	−1.1 (10)	C8—C9—C10—C5	2.7 (9)
O1—C1—C2—N1	−26.1 (8)	C6—C5—C10—N2	179.2 (6)
O1—C1—C2—C3	95.9 (7)	C4—C5—C10—N2	0.8 (7)
N3—C1—C2—C3	−83.3 (7)	C6—C5—C10—C9	−3.4 (9)
N1—C2—C3—C4	60.1 (7)	C4—C5—C10—C9	178.1 (5)
C1—C2—C3—C4	−60.9 (7)	C5—C4—C11—N2	−1.6 (7)
C2—C3—C4—C11	−96.7 (7)	C3—C4—C11—N2	179.1 (5)
C2—C3—C4—C5	84.1 (8)	C10—N2—C11—C4	2.1 (7)
C11—C4—C5—C6	−177.6 (7)	H1WB—O2—C13—O3	109 (4)
C3—C4—C5—C6	1.8 (11)	H1WB—O2—C13—C12	−72 (4)
C11—C4—C5—C10	0.5 (7)	H1NA^i—O3—C13—O2	−6 (2)
C3—C4—C5—C10	179.9 (5)	H2N^ii—O3—C13—O2	151.7 (16)
C10—C5—C6—C7	3.1 (9)	H1NA^i—O3—C13—C12	174.6 (19)
C4—C5—C6—C7	−178.9 (7)	H2N^ii—O3—C13—C12	−27.9 (17)
C5—C6—C7—C8	−2.2 (10)	N3—C12—C13—O3	−149.9 (5)

Symmetry codes: (i) y, −x, z+3/4; (ii) −y+1, x, z+1/4; (iii) −y, x, z+1/4.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O1W^iv	0.97 (4)	1.75 (4)	2.695 (8)	163 (3)
O1W—H1WB···O2	0.95 (4)	1.84 (5)	2.738 (7)	156 (3)
N1—H1NA···O3^v	0.93 (4)	1.95 (4)	2.868 (6)	170 (4)
N2—H2N···O3^vi	0.86 (3)	2.14 (4)	2.961 (6)	160 (3)
N1—H1NB···O2^iii	0.97 (4)	2.27 (4)	2.892 (6)	121 (3)
N1—H1NC···O1W	0.93 (4)	2.30 (4)	3.048 (7)	137 (4)
N1—H1NA···O2^v	0.93 (4)	2.31 (4)	2.973 (8)	128 (4)

Symmetry codes: (iii) −y, x, z+1/4; (iv) y, −x, z−1/4; (v) −y, x, z−3/4; (vi) y, −x+1, z−1/4.