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The asymmetric unit of the DL-lysine complex of adipic acid [bis­(DL-lysinium) adipate], 2C6H15N2O2+·C6H8O42−, contains a zwitterionic singly charged lysinium cation and half a doubly charged adipate anion (the complete anion has inversion symmetry). That of the L-lysine complex (lysinium hydrogen adipate), C6H15N2O2+·C6H9O4, consists of a lysinium cation and a singly charged hydrogen adipate anion. In both structures, the lysinium cations organize into layers inter­connected by adipate or hydrogen adipate anions. However, the arrangement of the mol­ecular ions in the layer is profoundly different in the DL- and L-lysine complexes. The hydrogen adipate anions in the L-lysine complex form linear arrays in which adjacent ions are inter­connected by a symmetric O...H...O hydrogen bond.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106003374/jz1784sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106003374/jz1784Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106003374/jz1784IIsup3.hkl
Contains datablock II

CCDC references: 603201; 603202

Comment top

In a long-term programme, we have been investigating the supramolecular association of amino acids and peptides using an approach involving the preparation and X-ray analysis of crystalline complexes of amino acids and peptides among themselves and with other molecules (Vijayan, 1988; Roy et al., 2005). The patterns of association observed in the course of these investigations were found to be of possible relevance to chemical evolution and the origin of life (Vijayan, 1980, 1988). For more than a decade, the focus of the programme has been on complexes of amino acids and peptides, particularly the basic amino acids arginine, lysine and histidine, with carboxylic acids that are believed to have existed in the prebiotic milieu, and with related compounds. The results obtained from the study of complexes involving dicarboxylic acids have been particularly interesting in relation to common features of association, their variability, and the effect of chirality on ionization state, stoichiometry and aggregation patterns. Many of the complexes reported by us have been those of DL- and L-lysine with monocarboxylic acids (Suresh et al., 1994; Suresh & Vijayan, 1983b, 1995) and dicarboxylic acids (Prasad & Vijayan, 1991; Venkatraman et al., 1997; Pratap et al., 2000; Saraswathi et al., 2001, 2003) with varying length. They also often exhibit common features of supramolecular association, despite differences in crystal their structures. The effect of reversing the chirality of half the amino acid molecules, as happens when comparing the crystal structures involving DL and L forms of the same amino acid, is manifested in two different ways in amino acid–carboxylic acid complexes. In some instances, the pattern of aggregation remains the same; the effect is absorbed by small alterations. In other instances, the effect is profound and leads to an entirely different pattern. The latter is true in the lysine complexes. Among the lysine complexes studied by us so far, one conspicuous absence was that of complexes involving adipic acid. Here, we report the crystal structures of the adipic acid complexes of DL-lysine, (I), and L-lysine, (II).

In both complexes, the amino acid exists as a positively charged zwitterion, with protonated amino groups and a deprotonated carboxyl group. Both the carboxyl groups in the adipic acid molecule are deprotonated in the DL-lysine complex, (I). The stoichiometry between the singly charged lysinium cation and the doubly charged adipate anion is 2:1. The lysinium cation occupies a general position, while the adipate ion is located across an inversion centre. In the L-lysine complex, (II), one carboxyl group in the adipic acid molecule is deprotonated and negatively charged while the other is neutral. The stoichiometry between the components is 1:1. The lysinium cation has the most sterically favourable conformation, with an all-trans extended side chain trans to the α-carboxylate group in both complexes (Prasad & Vijayan, 1991) (Fig. 1, Table 1). The adipate and hydrogen adipate anions have nearly fully extended conformations.

The crystal structures of the complexes are illustrated in Figs. 2 and 3, and the parameters of the hydrogen bonds that stabilize them are listed in Tables 2 and 3. The tables include a full description of the three-centred hydrogen bonds, but these are asymmetric and only the shorter branches are given in the figures. Atom N7 in the DL-lysine complex, and atoms N1 and N7 in the L-lysine complex, are involved in these hydrogen bonds. They are characterized by large deviations of the N—H···O angles from 180°.

In (I), the lysinium cations aggregate into layers parallel to the ab plane, as illustrated in Fig. 4. The molecular ions first form hydrogen-bonded dimers across inversion centres, stabilized by a pair of N1···O2 hydrogen bonds. These dimers then form ribbons parallel to a. Neighbouring dimers, related by translation in the ribbon, are interconnected by a pair of N1···O1 hydrogen bonds. We had earlier demonstrated, particularly in the context of prebiotic polymerization, that amino acids almost invariably aggregate in head-to-tail sequences of the type ···NH3+—CHR—COO···NH3+—CHR—COO···, in which the α-amino and the α-carboxylate groups are brought into periodic hydrogen-bonded proximity in a peptide-like arrangement. The adjacent molecules in this sequence are often related by a translation (an S sequence), a 21 screw (Z) or a glide plane (DL). When the O atom involved in the hydrogen bonds is cis to the amino group (conventionally referred to O1), then `1' is added as a suffix to S, Z or DL in the description of the sequence. If the O atom is trans to the amino group, then `2' is added (Suresh & Vijayan, 1983a). The N1···O1 hydrogen bonds referred to above form part of two S1 head-to-tail sequences. Neighbouring ribbons interact through a hydrogen bond between the side-chain terminal amino N atom (N7) from one and a carboxylate O atom (O1) from the other.

The lysinium layers are interconnected by adipate anions. A carboxylate O atom at one end of the adipate anion directly interacts with atom N1 of a lysinium cation in one layer, while its centrosymmetric equivalent interacts with a centrosymmetrically related atom N1 in the adjacent layer. This O atom also has a weak interaction with a side-chain amino group. The other O atom forms hydrogen bonds with the side-chain amino N atoms of two separate lysinium cations at both ends of the adipate anion. The adipate anions do not interact with each other. They are situated in interstitial spaces between packed lysinium cations.

In the present case, the effect of chirality on molecular aggregation is profound. The crystal structure of the L-lysine complex (Fig. 3) is different from that of the DL-lysine complex, except that in the L-lysine complex the lysinium cations also aggregate in layers. In each layer (Fig. 5), the most prominent feature is linear arrays of lysinium cations stabilized by intermolecular hydrogen bonds between side-chain amino groups and α-carboxylate O atoms. The molecules in the array are related by a translation. Adjacent arrays, related by a 21 screw axis, run in opposite directions. They are again interconnected by hydrogen bonds involving the side-chain amino group and carboxylate O atoms. This structure presents a very rare case in which the α-amino group is not involved in intermolecular interactions with the α-carboxylate group. In most cases, such interactions lead to one or more head-to-tail sequences in which the α-amino and α-carboxylate groups are brought into periodic hydrogen-bonded proximity in a peptide-like arrangement (Suresh & Vijayan, 1983a).

The hydrogen adipate anions are also arranged in linear arrays along a. The arrays form corrugated layers parallel to the ab plane (Fig. 6). In each array, adjacent hydrogen adipate anions are connected by a symmetric O···H···O hydrogen bond, in which the H atom can be described as being shared by the two anions (Fig. 7). Adjacent arrays in each layer are related by a 21 screw parallel to b. The arrays in each layer are interconnected by hydrogen bonds involving α-amino groups.

Experimental top

In both cases, aqueous solutions of amino acid (Sigma) and adipic acid in 1:1 molar ratio were used to grow the crystals of the complexes, employing the liquid diffusion method with acetonitrile as the precipitant.

Refinement top

The structure of the L-lysine complex was determined using DIRDIF99 (Beurskens et al., 1999) employing the ORIENT option, in which the coordinates of the lysinium cation taken from Saraswathi et al. (2001) were used as input. In both cases, H atoms were located in differnece Fourier maps with the aid of geometrical considerations. The amino H atoms were constrained, except for rotation about their respective C—N bonds. All remaining H atoms were treated as riding on their parent atoms. The C—H and N—H distances were constrained at 0.97–0.98 and 0.89 Å, respectively. The lone carboxyl H atom in (II) was refined freely. In the case of (II), Friedel opposite reflections were merged, although the space group is non-centrosymmetric. An absolute configuration consistent with natural L-lysine was assumed.

Computing details top

For both compounds, data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT (Bruker, 2001). Program(s) used to solve structure: SHELXS97 (Sheldrick, 1997) for (I); DIRDIF99 (Beurskens et al., 1999) for (II). For both compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. The molecular structures in (a) the DL-lysine complex, (I), and (b) the L-lysine complex, (II). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. The crystal structure of the DL-lysine complex, (I). In this and subsequent figures, only atoms involved in the hydrogen-bonding scheme are labelled. For clarity, the inversion centre at (0, 1/2, 0) is not indicated.
[Figure 3] Fig. 3. The crystal structure of the L-lysine complex, (II).
[Figure 4] Fig. 4. The lysinium layer at a height of z = 1/2 in the DL-lysine complex, (I). Atoms N7 and O2 of neighbouring ions, which partially overlap, are hydrogen bonded. For clarity, the inversion centre at a = b = c = 1/2 is not indicated.
[Figure 5] Fig. 5. The lysinium layer, at a height of z = 1/2, in the L-lysine complex, (II).
[Figure 6] Fig. 6. The arrangement of hydrogen adipate anions in the L-lysine complex, (II).
[Figure 7] Fig. 7. Difference density map corresponding to the H atom in the symmetric hydrogen bond in the L-lysine complex, (II).
(I) bis(DL-lysinium) adipate top
Crystal data top
2C6H15N2O2+·C6H8O42Z = 1
Mr = 438.52F(000) = 238
Triclinic, P1Dx = 1.366 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.4730 (15) ÅCell parameters from 1582 reflections
b = 7.773 (2) Åθ = 1.0–28.0°
c = 13.011 (4) ŵ = 0.11 mm1
α = 100.112 (4)°T = 298 K
β = 93.292 (4)°Plate, colourless
γ = 100.744 (4)°0.69 × 0.60 × 0.20 mm
V = 533.0 (3) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer
2494 independent reflections
Radiation source: fine-focus sealed tube2269 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.014
ω scansθmax = 28.0°, θmin = 2.7°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 77
Tmin = 0.912, Tmax = 0.983k = 1010
6254 measured reflectionsl = 1617
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.120H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0641P)2 + 0.1692P]
where P = (Fo2 + 2Fc2)/3
2494 reflections(Δ/σ)max < 0.001
138 parametersΔρmax = 0.45 e Å3
0 restraintsΔρmin = 0.27 e Å3
Crystal data top
2C6H15N2O2+·C6H8O42γ = 100.744 (4)°
Mr = 438.52V = 533.0 (3) Å3
Triclinic, P1Z = 1
a = 5.4730 (15) ÅMo Kα radiation
b = 7.773 (2) ŵ = 0.11 mm1
c = 13.011 (4) ÅT = 298 K
α = 100.112 (4)°0.69 × 0.60 × 0.20 mm
β = 93.292 (4)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2494 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2269 reflections with I > 2σ(I)
Tmin = 0.912, Tmax = 0.983Rint = 0.014
6254 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0440 restraints
wR(F2) = 0.120H-atom parameters constrained
S = 1.04Δρmax = 0.45 e Å3
2494 reflectionsΔρmin = 0.27 e Å3
138 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
xyzUiso*/Ueq
O11.12680 (17)0.87726 (14)0.36247 (9)0.0408 (3)
O21.14608 (18)0.78844 (13)0.51564 (8)0.0388 (3)
N10.63059 (17)0.87197 (13)0.36834 (8)0.0244 (2)
H1A0.65500.85190.30060.037*
H1B0.70010.98430.39710.037*
H1C0.46740.85330.37530.037*
C11.0308 (2)0.81182 (15)0.43531 (10)0.0264 (3)
C20.7466 (2)0.74863 (15)0.42207 (9)0.0235 (2)
H20.68460.74900.49130.028*
C30.6865 (2)0.55891 (16)0.35872 (10)0.0288 (3)
H3A0.76320.48360.39720.035*
H3B0.76300.55860.29330.035*
C40.4089 (2)0.47602 (16)0.33339 (10)0.0288 (3)
H4A0.32770.47810.39780.035*
H4B0.33080.54460.29050.035*
C50.3782 (2)0.28451 (16)0.27502 (10)0.0294 (3)
H5A0.47850.28290.21590.035*
H5B0.44170.21470.32140.035*
C60.1110 (2)0.19761 (16)0.23543 (10)0.0295 (3)
H6A0.01610.17550.29410.035*
H6B0.03550.27680.19950.035*
N70.1041 (2)0.02726 (15)0.16255 (9)0.0358 (3)
H7A0.20050.04690.11130.054*
H7B0.05220.01870.13530.054*
H7C0.15990.04880.19720.054*
O110.4879 (2)0.19082 (19)0.15658 (8)0.0565 (4)
O120.29642 (18)0.14007 (14)0.01797 (8)0.0413 (3)
C130.4775 (2)0.21272 (16)0.06041 (10)0.0284 (3)
C140.6995 (2)0.32779 (18)0.01104 (10)0.0308 (3)
H14A0.78280.24990.04480.037*
H14B0.63610.40490.06570.037*
C150.8943 (2)0.44398 (17)0.03955 (10)0.0294 (3)
H15A0.81390.52260.07390.035*
H15B0.96380.36840.09280.035*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0205 (4)0.0493 (6)0.0558 (6)0.0041 (4)0.0058 (4)0.0211 (5)
O20.0334 (5)0.0362 (5)0.0415 (5)0.0064 (4)0.0154 (4)0.0004 (4)
N10.0170 (4)0.0266 (5)0.0275 (5)0.0015 (4)0.0005 (3)0.0033 (4)
C10.0202 (5)0.0194 (5)0.0363 (6)0.0034 (4)0.0035 (4)0.0012 (4)
C20.0203 (5)0.0244 (5)0.0241 (5)0.0017 (4)0.0003 (4)0.0036 (4)
C30.0242 (6)0.0239 (6)0.0346 (6)0.0009 (4)0.0006 (5)0.0010 (5)
C40.0254 (6)0.0250 (6)0.0324 (6)0.0007 (5)0.0015 (5)0.0033 (5)
C50.0257 (6)0.0266 (6)0.0315 (6)0.0007 (5)0.0014 (5)0.0012 (5)
C60.0261 (6)0.0264 (6)0.0324 (6)0.0014 (5)0.0013 (5)0.0041 (5)
N70.0289 (6)0.0309 (6)0.0400 (6)0.0007 (4)0.0093 (5)0.0024 (5)
O110.0443 (6)0.0823 (9)0.0288 (5)0.0105 (6)0.0063 (4)0.0005 (5)
O120.0274 (5)0.0442 (6)0.0453 (6)0.0090 (4)0.0005 (4)0.0087 (5)
C130.0229 (6)0.0273 (6)0.0314 (6)0.0009 (4)0.0031 (4)0.0023 (5)
C140.0259 (6)0.0344 (6)0.0267 (6)0.0057 (5)0.0028 (5)0.0059 (5)
C150.0241 (6)0.0304 (6)0.0294 (6)0.0032 (5)0.0004 (5)0.0044 (5)
Geometric parameters (Å, º) top
O1—C11.2489 (16)C5—H5B0.9700
O2—C11.2479 (16)C6—N71.4800 (16)
N1—C21.4907 (15)C6—H6A0.9700
N1—H1A0.8900C6—H6B0.9700
N1—H1B0.8900N7—H7A0.8900
N1—H1C0.8900N7—H7B0.8900
C1—C21.5313 (16)N7—H7C0.8900
C2—C31.5243 (16)O11—C131.2388 (17)
C2—H20.9800O12—C131.2529 (16)
C3—C41.5277 (16)C13—C141.5212 (16)
C3—H3A0.9700C14—C151.5216 (17)
C3—H3B0.9700C14—H14A0.9700
C4—C51.5218 (17)C14—H14B0.9700
C4—H4A0.9700C15—C15i1.526 (2)
C4—H4B0.9700C15—H15A0.9700
C5—C61.5111 (17)C15—H15B0.9700
C5—H5A0.9700
C2—N1—H1A109.5C6—C5—H5B108.8
C2—N1—H1B109.5C4—C5—H5B108.8
H1A—N1—H1B109.5H5A—C5—H5B107.7
C2—N1—H1C109.5N7—C6—C5109.84 (10)
H1A—N1—H1C109.5N7—C6—H6A109.7
H1B—N1—H1C109.5C5—C6—H6A109.7
O2—C1—O1125.91 (12)N7—C6—H6B109.7
O2—C1—C2117.52 (11)C5—C6—H6B109.7
O1—C1—C2116.53 (10)H6A—C6—H6B108.2
N1—C2—C3111.42 (9)C6—N7—H7A109.5
N1—C2—C1109.36 (9)C6—N7—H7B109.5
C3—C2—C1108.17 (9)H7A—N7—H7B109.5
N1—C2—H2109.3C6—N7—H7C109.5
C3—C2—H2109.3H7A—N7—H7C109.5
C1—C2—H2109.3H7B—N7—H7C109.5
C2—C3—C4115.65 (10)O11—C13—O12123.52 (12)
C2—C3—H3A108.4O11—C13—C14118.83 (11)
C4—C3—H3A108.4O12—C13—C14117.60 (11)
C2—C3—H3B108.4C13—C14—C15117.08 (11)
C4—C3—H3B108.4C13—C14—H14A108.0
H3A—C3—H3B107.4C15—C14—H14A108.0
C5—C4—C3109.65 (10)C13—C14—H14B108.0
C5—C4—H4A109.7C15—C14—H14B108.0
C3—C4—H4A109.7H14A—C14—H14B107.3
C5—C4—H4B109.7C14—C15—C15i112.61 (13)
C3—C4—H4B109.7C14—C15—H15A109.1
H4A—C4—H4B108.2C15i—C15—H15A109.1
C6—C5—C4113.64 (11)C14—C15—H15B109.1
C6—C5—H5A108.8C15i—C15—H15B109.1
C4—C5—H5A108.8H15A—C15—H15B107.8
O2—C1—C2—N1145.95 (11)C3—C4—C5—C6173.34 (10)
O1—C1—C2—N136.27 (14)C4—C5—C6—N7168.81 (10)
O2—C1—C2—C392.53 (13)O11—C13—C14—C1514.11 (19)
O1—C1—C2—C385.25 (13)O12—C13—C14—C15168.24 (12)
N1—C2—C3—C457.19 (14)C13—C14—C15—C15i178.96 (13)
C1—C2—C3—C4177.43 (10)C14—C15—C15i—C14i180.0
C2—C3—C4—C5177.16 (10)
Symmetry code: (i) x+2, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AH···AD···AD—H···A
N1—H1A···O11ii1.942.730 (2)148
N1—H1B···O2iii1.942.815 (2)169
N1—H1C···O1iv1.912.762 (2)160
N7—H7A···O122.002.838 (2)156
N7—H7B···O12v1.952.764 (2)152
N7—H7C···O1vi2.333.037 (2)137
N7—H7C···O11vii2.433.042 (2)126
Symmetry codes: (ii) x+1, y+1, z; (iii) x+2, y+2, z+1; (iv) x1, y, z; (v) x, y, z; (vi) x1, y1, z; (vii) x+1, y, z.
(II) L-lysine hydrogen adipate top
Crystal data top
C6H15N2O2+·C6H9O4F(000) = 316
Mr = 292.33Dx = 1.301 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 2077 reflections
a = 10.532 (3) Åθ = 1.0–26.0°
b = 7.2834 (17) ŵ = 0.10 mm1
c = 10.599 (3) ÅT = 298 K
β = 113.352 (3)°Prism, colourless
V = 746.5 (3) Å30.91 × 0.65 × 0.17 mm
Z = 2
Data collection top
Bruker SMART CCD area-detector
diffractometer
1481 independent reflections
Radiation source: fine-focus sealed tube1329 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.017
ω scansθmax = 25.3°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1212
Tmin = 0.891, Tmax = 0.981k = 88
6202 measured reflectionsl = 1212
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.051Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.135H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0766P)2 + 0.245P]
where P = (Fo2 + 2Fc2)/3
2701 reflections(Δ/σ)max < 0.001
187 parametersΔρmax = 0.27 e Å3
1 restraintΔρmin = 0.21 e Å3
Crystal data top
C6H15N2O2+·C6H9O4V = 746.5 (3) Å3
Mr = 292.33Z = 2
Monoclinic, P21Mo Kα radiation
a = 10.532 (3) ŵ = 0.10 mm1
b = 7.2834 (17) ÅT = 298 K
c = 10.599 (3) Å0.91 × 0.65 × 0.17 mm
β = 113.352 (3)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
1481 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1329 reflections with I > 2σ(I)
Tmin = 0.891, Tmax = 0.981Rint = 0.017
6202 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0511 restraint
wR(F2) = 0.135H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.27 e Å3
2701 reflectionsΔρmin = 0.21 e Å3
187 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
xyzUiso*/Ueq
O10.3280 (3)0.1297 (7)0.3506 (4)0.1199 (19)
O20.3483 (3)0.1277 (5)0.4558 (4)0.0816 (11)
N10.0681 (3)0.0957 (6)0.1887 (3)0.0550 (9)
H1A0.08120.20990.22120.083*
H1B0.11280.07990.13380.083*
H1C0.02180.07620.14150.083*
C10.2794 (3)0.0107 (6)0.3761 (4)0.0470 (8)
C20.1221 (3)0.0369 (5)0.3057 (3)0.0439 (9)
H20.10190.16250.27030.053*
C30.0502 (3)0.0004 (6)0.4032 (3)0.0409 (8)
H3A0.05650.12970.42440.049*
H3B0.09950.06580.48850.049*
C40.1013 (3)0.0571 (6)0.3474 (3)0.0455 (9)
H4A0.10790.18970.33850.055*
H4B0.14930.00440.25670.055*
C50.1702 (3)0.0063 (6)0.4411 (3)0.0460 (8)
H5A0.16810.13940.44460.055*
H5B0.11660.03830.53330.055*
C60.3175 (3)0.0562 (7)0.3987 (4)0.0558 (11)
H6A0.32190.18860.38780.067*
H6B0.37410.00190.31070.067*
N70.3734 (3)0.0035 (5)0.5017 (3)0.0500 (8)
H7A0.36300.11690.51690.075*
H7B0.46280.03200.47020.075*
H7C0.32790.06350.57980.075*
O110.7984 (3)0.0598 (9)1.0006 (3)0.1135 (19)
O120.8095 (2)0.0023 (5)0.8049 (2)0.0649 (9)
C130.7443 (3)0.0196 (6)0.8818 (3)0.0467 (9)
C140.5913 (3)0.0121 (8)0.8157 (3)0.0569 (11)
H14A0.57530.13960.78740.068*
H14B0.55350.06260.73330.068*
C150.5130 (3)0.0296 (6)0.9034 (3)0.0473 (9)
H15A0.55630.03470.99020.057*
H15B0.51930.16010.92290.057*
C160.3625 (3)0.0242 (6)0.8382 (3)0.0470 (9)
H16A0.32100.03110.74770.056*
H16B0.35590.15640.82650.056*
C170.2819 (3)0.0340 (7)0.9217 (3)0.0499 (10)
H17A0.29170.16570.93610.060*
H17B0.32200.02461.01110.060*
C180.1315 (3)0.0120 (6)0.8571 (3)0.0450 (9)
O190.0800 (2)0.0972 (5)0.7517 (3)0.0588 (8)
O200.0609 (2)0.0525 (6)0.9238 (3)0.0720 (11)
H200.062 (5)0.035 (8)0.868 (4)0.086 (15)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0345 (16)0.140 (4)0.158 (4)0.014 (2)0.009 (2)0.072 (3)
O20.0387 (15)0.076 (2)0.108 (3)0.0007 (16)0.0056 (16)0.026 (2)
N10.0344 (15)0.090 (2)0.0390 (14)0.0010 (16)0.0132 (12)0.0016 (16)
C10.0280 (16)0.059 (2)0.0551 (18)0.0007 (18)0.0181 (14)0.0025 (19)
C20.0256 (15)0.059 (2)0.0469 (17)0.0017 (15)0.0139 (13)0.0047 (16)
C30.0287 (15)0.052 (2)0.0418 (15)0.0010 (15)0.0141 (12)0.0015 (16)
C40.0297 (15)0.061 (2)0.0482 (17)0.0045 (15)0.0176 (13)0.0049 (16)
C50.0289 (15)0.059 (2)0.0511 (17)0.0023 (17)0.0171 (13)0.0057 (18)
C60.0324 (17)0.081 (3)0.0568 (19)0.0096 (19)0.0204 (15)0.020 (2)
N70.0265 (12)0.068 (2)0.0588 (16)0.0007 (15)0.0206 (12)0.0054 (16)
O110.0268 (12)0.253 (6)0.0573 (16)0.015 (2)0.0128 (12)0.028 (3)
O120.0277 (11)0.117 (3)0.0565 (13)0.0076 (16)0.0234 (10)0.0098 (17)
C130.0244 (15)0.071 (3)0.0443 (17)0.0000 (17)0.0135 (13)0.0011 (18)
C140.0226 (15)0.105 (3)0.0445 (16)0.006 (2)0.0143 (13)0.012 (2)
C150.0246 (15)0.072 (3)0.0489 (16)0.0026 (16)0.0184 (13)0.0071 (18)
C160.0253 (14)0.072 (3)0.0475 (16)0.0049 (17)0.0182 (13)0.0050 (18)
C170.0256 (15)0.077 (3)0.0492 (17)0.0052 (17)0.0172 (13)0.0115 (19)
C180.0256 (15)0.070 (2)0.0406 (16)0.0027 (18)0.0145 (13)0.0023 (18)
O190.0317 (12)0.093 (2)0.0533 (14)0.0143 (14)0.0181 (11)0.0184 (15)
O200.0287 (12)0.134 (3)0.0601 (14)0.0093 (16)0.0250 (11)0.0311 (19)
Geometric parameters (Å, º) top
O1—C11.221 (6)C4—C51.517 (4)
O2—C11.217 (5)C4—H4A0.9700
O11—C131.195 (4)C4—H4B0.9700
O12—C131.264 (4)C5—C61.505 (4)
O19—C181.203 (4)C5—H5A0.9700
O20—C181.300 (4)C5—H5B0.9700
O20—H201.20 (5)C6—H6A0.9700
N1—C21.495 (5)C6—H6B0.9700
N1—H1A0.8900C13—C141.499 (4)
N1—H1B0.8900C14—C151.498 (4)
N1—H1C0.8900C14—H14A0.9700
N7—C61.482 (4)C14—H14B0.9700
N7—H7A0.8900C15—C161.508 (4)
N7—H7B0.8900C15—H15A0.9700
N7—H7C0.8900C15—H15B0.9700
C1—C21.535 (4)C16—C171.509 (4)
C2—C31.527 (4)C16—H16A0.9700
C2—H20.9800C16—H16B0.9700
C3—C41.523 (4)C17—C181.494 (4)
C3—H3A0.9700C17—H17A0.9700
C3—H3B0.9700C17—H17B0.9700
C2—N1—H1A109.5H5A—C5—H5B107.6
C2—N1—H1B109.5N7—C6—C5111.4 (3)
H1A—N1—H1B109.5N7—C6—H6A109.4
C2—N1—H1C109.5C5—C6—H6A109.4
H1A—N1—H1C109.5N7—C6—H6B109.4
H1B—N1—H1C109.5C5—C6—H6B109.4
C6—N7—H7A109.5H6A—C6—H6B108.0
C6—N7—H7B109.5O11—C13—O12123.4 (3)
H7A—N7—H7B109.5O11—C13—C14120.4 (3)
C6—N7—H7C109.5O12—C13—C14116.2 (3)
H7A—N7—H7C109.5C15—C14—C13115.7 (3)
H7B—N7—H7C109.5C15—C14—H14A108.4
O2—C1—O1123.6 (3)C13—C14—H14A108.4
O2—C1—C2118.8 (4)C15—C14—H14B108.4
O1—C1—C2117.6 (4)C13—C14—H14B108.4
N1—C2—C3108.7 (3)H14A—C14—H14B107.4
N1—C2—C1107.8 (3)C14—C15—C16113.6 (3)
C3—C2—C1112.3 (3)C14—C15—H15A108.9
N1—C2—H2109.3C16—C15—H15A108.9
C3—C2—H2109.3C14—C15—H15B108.9
C1—C2—H2109.3C16—C15—H15B108.9
C4—C3—C2114.5 (3)H15A—C15—H15B107.7
C4—C3—H3A108.6C15—C16—C17113.0 (3)
C2—C3—H3A108.6C15—C16—H16A109.0
C4—C3—H3B108.6C17—C16—H16A109.0
C2—C3—H3B108.6C15—C16—H16B109.0
H3A—C3—H3B107.6C17—C16—H16B109.0
C5—C4—C3111.3 (3)H16A—C16—H16B107.8
C5—C4—H4A109.4C18—C17—C16114.2 (3)
C3—C4—H4A109.4C18—C17—H17A108.7
C5—C4—H4B109.4C16—C17—H17A108.7
C3—C4—H4B109.4C18—C17—H17B108.7
H4A—C4—H4B108.0C16—C17—H17B108.7
C6—C5—C4114.6 (3)H17A—C17—H17B107.6
C6—C5—H5A108.6O19—C18—O20123.2 (3)
C4—C5—H5A108.6O19—C18—C17123.2 (3)
C6—C5—H5B108.6O20—C18—C17113.7 (3)
C4—C5—H5B108.6C18—O20—H20116 (2)
O2—C1—C2—N1165.4 (4)C4—C5—C6—N7174.8 (3)
O1—C1—C2—N116.2 (5)O11—C13—C14—C156.3 (7)
O2—C1—C2—C374.9 (5)O12—C13—C14—C15173.3 (4)
O1—C1—C2—C3103.6 (5)C13—C14—C15—C16173.6 (4)
N1—C2—C3—C471.3 (4)C14—C15—C16—C17174.8 (4)
C1—C2—C3—C4169.5 (3)C15—C16—C17—C18178.1 (4)
C2—C3—C4—C5172.4 (3)C16—C17—C18—O194.0 (6)
C3—C4—C5—C6175.7 (4)C16—C17—C18—O20174.4 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AH···AD···AD—H···A
N1—H1A···O19i2.312.935 (5)128
N1—H1A···O12ii2.493.220 (6)140
N1—H1B···O20iii2.082.796 (4)137
N1—H1C···O11iv1.892.761 (4)164
N7—H7A···O2i1.882.770 (5)178
N7—H7B···O2v2.062.918 (4)163
N7—H7B···O1v2.373.066 (4)135
N7—H7C···O12v2.303.022 (4)139
N7—H7C···O1vi2.353.037 (7)134
O20—H20···O12v1.27 (5)2.467 (3)175 (5)
Symmetry codes: (i) x, y1/2, z+1; (ii) x+1, y1/2, z+1; (iii) x, y, z1; (iv) x1, y, z1; (v) x1, y, z; (vi) x, y+1/2, z+1.

Experimental details

(I)(II)
Crystal data
Chemical formula2C6H15N2O2+·C6H8O42C6H15N2O2+·C6H9O4
Mr438.52292.33
Crystal system, space groupTriclinic, P1Monoclinic, P21
Temperature (K)298298
a, b, c (Å)5.4730 (15), 7.773 (2), 13.011 (4)10.532 (3), 7.2834 (17), 10.599 (3)
α, β, γ (°)100.112 (4), 93.292 (4), 100.744 (4)90, 113.352 (3), 90
V3)533.0 (3)746.5 (3)
Z12
Radiation typeMo KαMo Kα
µ (mm1)0.110.10
Crystal size (mm)0.69 × 0.60 × 0.200.91 × 0.65 × 0.17
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Bruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Multi-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.912, 0.9830.891, 0.981
No. of measured, independent and
observed [I > 2σ(I)] reflections
6254, 2494, 2269 6202, 1481, 1329
Rint0.0140.017
(sin θ/λ)max1)0.6600.602
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.120, 1.04 0.051, 0.135, 1.04
No. of reflections24942701
No. of parameters138187
No. of restraints01
H-atom treatmentH-atom parameters constrainedH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.45, 0.270.27, 0.21

Computer programs: SMART (Bruker, 2001), SMART, SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 1997), DIRDIF99 (Beurskens et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AH···AD···AD—H···A
N1—H1A···O11i1.942.730 (2)148
N1—H1B···O2ii1.942.815 (2)169
N1—H1C···O1iii1.912.762 (2)160
N7—H7A···O122.002.838 (2)156
N7—H7B···O12iv1.952.764 (2)152
N7—H7C···O1v2.333.037 (2)137
N7—H7C···O11vi2.433.042 (2)126
Symmetry codes: (i) x+1, y+1, z; (ii) x+2, y+2, z+1; (iii) x1, y, z; (iv) x, y, z; (v) x1, y1, z; (vi) x+1, y, z.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AH···AD···AD—H···A
N1—H1A···O19i2.312.935 (5)128
N1—H1A···O12ii2.493.220 (6)140
N1—H1B···O20iii2.082.796 (4)137
N1—H1C···O11iv1.892.761 (4)164
N7—H7A···O2i1.882.770 (5)178
N7—H7B···O2v2.062.918 (4)163
N7—H7B···O1v2.373.066 (4)135
N7—H7C···O12v2.303.022 (4)139
N7—H7C···O1vi2.353.037 (7)134
O20—H20···O12v1.27 (5)2.467 (3)175 (5)
Symmetry codes: (i) x, y1/2, z+1; (ii) x+1, y1/2, z+1; (iii) x, y, z1; (iv) x1, y, z1; (v) x1, y, z; (vi) x, y+1/2, z+1.
Torsion angles (°) defining the molecular conformations of (I) and (II) top
Torsion(I)(II)
N1-C2-C1-O1(ψ1)-36.3 (1)-16.2 (5)
N1-C2-C3-C4(χ1)-57.2 (1)-71.3 (4)
C2-C3-C4-C5(χ2)-177.2 (1)172.4 (3)
C3-C4-C5-C6(χ3)-173.3 (1)175.7 (4)
C4-C5-C6-N7(χ4)168.8 (1)-174.8 (3)
O11-C13-C14-C1514.1 (1)-6.3 (7)
C13-C14-C15-C16179.0 (1)173.6 (4)
C14-C15-C16-C17180.0 (1)174.8 (4)
C15-C16-C17-C18-178.1 (4)
C16-C17-C18-O19-4.0 (6)
In (I), atoms C16 and C17 correspond to the centrosymmetric equivalents of atoms C15 and C14, respectively.
 

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