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Acta Cryst. (2006). C62, o22-o25
https://doi.org/10.1107/S0108270105038928
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L-Isoleucyl-L-serine 0.33-hydrate, L-phenyl­alanyl-L-serine and L-methionyl-L-serine 0.34-hydrate

C. H. Görbitz, M. Bruvoll, S. Dizdarevic, N. Fimland, J. Hafizovic, H. T. Kalfjøs, A. Krivokapic and K. Vestli
The structures of the title dipeptides, C9H18N2O4·0.33H2O, C12H16N2O4 and C8H16N2O4S·0.34H2O, complete a series of investigations focused on L-Xaa-L-serine peptides, where Xaa is a hydro­phobic residue. All three structures are divided into hydro­philic and hydro­phobic layers. The hydro­philic layers are thin for L-phenyl­alanyl-L-serine, rendered possible by an unusual peptide conformation, and thick for L-isoleucyl-L-serine and L-methionyl-L-serine, which include cocrystallized water mol­ecules on the twofold axes.
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Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105038928/fg1882sup1.cif
Contains datablocks IS, FS, MS, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105038928/fg1882ISsup2.hkl
Contains datablock IS

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105038928/fg1882FSsup3.hkl
Contains datablock FS

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105038928/fg1882MSsup4.hkl
Contains datablock MS

CCDC references: 296339; 296340; 296341

Comment top

In a series of papers, we have focused on the crystal structures of dipeptides with two hydrophobic residues (Görbitz, 2003, and references therein). Recently, this investigation was extended to include compounds with one hydrophobic and one hydrophilic residue (Netland et al., 2004). The most interesting structure of such a mixed dipeptide is L-leucyl-L-serine (LS), which was found to form a completely new type of nanoporous structure (Görbitz et al., 2005). Glycyl-L-serine (Görbitz, 1999) and L-alanyl-L-serine (Jones et al., 1978) are not isostructural with LS. Furthermore, we have previously shown that L-valyl-L-serine crystallizes as a layered trihydrate (VS-3w) from aqueous solutions (Johansen et al., 2005), but that a nanoporous structure related, not to LS, but to the L-valyl-L-alanine family of isostructural dipeptides (Görbitz, 2003), is obtained when trifluoroethanol is used as the solvent (Görbitz, 2005). It is nevertheless conceivable that L-isoleucyl-L-serine (IS), L-phenylalanyl-L-serine (FS) or L-methionyl-L-serine (MS) could form crystals with LS-type packing arrangements. We present here the structures of these three dipeptides.

The crystal structures of IS, FS and MS are shown in Fig. 1, while torsion angles and hydrogen-bonding data are listed in Tables 1–6. There is an intramolecular hydrogen bond for FS; equivalent interactions occur for L-alanyl-L-threonine (Netland et al., 2004) and LS (Görbitz et al., 2005). The unit cells and the crystal-packing arrangements are shown in Figs. 2–4. A l l structures are non-porous and are divided into hydrophobic and hydrophilic layers. Each hydrophilic layer can in turn be divided into two hydrogen-bonded sheets, but the construction of individual sheets and the way they are connected differ.

An FS sheet includes intermolecular amino···carboxylate, amino..carbonyl and amide···hydroxyl interactions (Fig. 5 and Table 4). Two sheets are joined tightly together by N1—H3···O4 hydrogen bonds into a compact hydrophilic double-layer. This is a rare motif in the structures of enantiopure L–L dipeptides, since it requires that the main chains adopt unusual conformations, with both side chains on the same side of the peptide plane. In FS, this is achieved primarily by the 146° φ2 torsion angle (C9—N2—C10—C12; Table 3), which may be compared with the values of around -163° for IS and MS (Tables 1 and 5) that are typical for dipeptides in extended conformations.

The sheets of IS and MS (Fig. 5) are rather similar to the sheets of VS-3w (Johansen et al., 2005) and L-glutamyl-L-aspartic acid (Eggleston & Hodgson, 1985). Short >N2—H4···O1═C< contacts are, however, missing for IS and MS, while interactions involving the serine side chains have been added. In contrast with FS, adjacent sheets are not in direct contact through amino···carboxylate interactions. The presence of such hydrogen bonds is only compatible with a small inter-sheet separation, which in each case is effectively prevented by peptide main-chain conformations that put side chains on opposing sides of the peptide plane (Figs. 2 and 4). The sheets are instead connected by two types of bridges, one involving the co-crystallized water molecules and one involving the serine side chain.

There is a small difference between the independent hydrophobic layers in the MS structure. Layers formed by the peptide B molecules are largely identical to the IS layers, while in layers formed by A molecules, the hydroxyl H atoms of the serine side chains are donated to the water molecules embedded in the layer rather than to the main-chain carboxylate groups. Water molecule 1, in the A layer, is thus fixed by a total of four hydrogen bonds, and the refined occupancy is 1.00. Water molecule 2 and the water molecule of IS are not hydrogen-bond acceptors and thus are not fixed to the same extent. The refined occupancies are 0.354 (18) and 0.668 (9), respectively.

The methionine side chains in the two molecules of MS have different conformations: N1—C1—C2—C3 is gauche and trans in molecules A and B, respectively, while both molecules have C1—C2—C3—S trans and C2—C3—S—C4 gauche (Table 5). The hydrophobic layers, with contributions from both A and B molecules, contain C—H···S interactions that may be described as weak hydrogen bonds. The associated H···S distances range from 2.90 Å for C3B—H32B···S1A(x, y + 1, z) and up.

Experimental top

The title compounds were obtained from Bachem. Crystals were grown by diffusion of acetonitrile into 40 µl of an aqueous solution containing about 1 mg of the respective peptide.

Refinement top

Positional parameters were refined for IS and FS amino and amide H atoms, for IS and MS water molecules and for hydroxyl groups in all structures. Other H atoms were positioned with idealized geometry and with fixed X—H distances (X = C or N) in the range 0.88–1.00 Å. Uiso(H) values were 1.2Ueq of the carrier atom, or 1.5Ueq for hydroxyl, amino and methyl groups and for water molecules. The geometries of the two independent molecules in the MS structure were constrained by mild SHELX SAME 0.008 0.012 constraints, while DFIX constraints were used for the geometries of the water molecules. Due to the low crystal quality, the final R factor is rather high for MS, and the presence of S atoms was not enough to give a reliable determination of the absolute structure; without merging of Friedel pairs, the Flack parameter (Flack, 1983) was -0.1 (2). Accordingly, 476 Friedel pairs were merged in the final refinements, as were, in the absence of significant anomalous scattering effects, 700 and 339 Friedel pairs for IS and FS, respectively. The absolute configuration was known for the purchased materials.

Structure description top

In a series of papers, we have focused on the crystal structures of dipeptides with two hydrophobic residues (Görbitz, 2003, and references therein). Recently, this investigation was extended to include compounds with one hydrophobic and one hydrophilic residue (Netland et al., 2004). The most interesting structure of such a mixed dipeptide is L-leucyl-L-serine (LS), which was found to form a completely new type of nanoporous structure (Görbitz et al., 2005). Glycyl-L-serine (Görbitz, 1999) and L-alanyl-L-serine (Jones et al., 1978) are not isostructural with LS. Furthermore, we have previously shown that L-valyl-L-serine crystallizes as a layered trihydrate (VS-3w) from aqueous solutions (Johansen et al., 2005), but that a nanoporous structure related, not to LS, but to the L-valyl-L-alanine family of isostructural dipeptides (Görbitz, 2003), is obtained when trifluoroethanol is used as the solvent (Görbitz, 2005). It is nevertheless conceivable that L-isoleucyl-L-serine (IS), L-phenylalanyl-L-serine (FS) or L-methionyl-L-serine (MS) could form crystals with LS-type packing arrangements. We present here the structures of these three dipeptides.

The crystal structures of IS, FS and MS are shown in Fig. 1, while torsion angles and hydrogen-bonding data are listed in Tables 1–6. There is an intramolecular hydrogen bond for FS; equivalent interactions occur for L-alanyl-L-threonine (Netland et al., 2004) and LS (Görbitz et al., 2005). The unit cells and the crystal-packing arrangements are shown in Figs. 2–4. A l l structures are non-porous and are divided into hydrophobic and hydrophilic layers. Each hydrophilic layer can in turn be divided into two hydrogen-bonded sheets, but the construction of individual sheets and the way they are connected differ.

An FS sheet includes intermolecular amino···carboxylate, amino..carbonyl and amide···hydroxyl interactions (Fig. 5 and Table 4). Two sheets are joined tightly together by N1—H3···O4 hydrogen bonds into a compact hydrophilic double-layer. This is a rare motif in the structures of enantiopure L–L dipeptides, since it requires that the main chains adopt unusual conformations, with both side chains on the same side of the peptide plane. In FS, this is achieved primarily by the 146° φ2 torsion angle (C9—N2—C10—C12; Table 3), which may be compared with the values of around -163° for IS and MS (Tables 1 and 5) that are typical for dipeptides in extended conformations.

The sheets of IS and MS (Fig. 5) are rather similar to the sheets of VS-3w (Johansen et al., 2005) and L-glutamyl-L-aspartic acid (Eggleston & Hodgson, 1985). Short >N2—H4···O1═C< contacts are, however, missing for IS and MS, while interactions involving the serine side chains have been added. In contrast with FS, adjacent sheets are not in direct contact through amino···carboxylate interactions. The presence of such hydrogen bonds is only compatible with a small inter-sheet separation, which in each case is effectively prevented by peptide main-chain conformations that put side chains on opposing sides of the peptide plane (Figs. 2 and 4). The sheets are instead connected by two types of bridges, one involving the co-crystallized water molecules and one involving the serine side chain.

There is a small difference between the independent hydrophobic layers in the MS structure. Layers formed by the peptide B molecules are largely identical to the IS layers, while in layers formed by A molecules, the hydroxyl H atoms of the serine side chains are donated to the water molecules embedded in the layer rather than to the main-chain carboxylate groups. Water molecule 1, in the A layer, is thus fixed by a total of four hydrogen bonds, and the refined occupancy is 1.00. Water molecule 2 and the water molecule of IS are not hydrogen-bond acceptors and thus are not fixed to the same extent. The refined occupancies are 0.354 (18) and 0.668 (9), respectively.

The methionine side chains in the two molecules of MS have different conformations: N1—C1—C2—C3 is gauche and trans in molecules A and B, respectively, while both molecules have C1—C2—C3—S trans and C2—C3—S—C4 gauche (Table 5). The hydrophobic layers, with contributions from both A and B molecules, contain C—H···S interactions that may be described as weak hydrogen bonds. The associated H···S distances range from 2.90 Å for C3B—H32B···S1A(x, y + 1, z) and up.

Computing details top

For all compounds, data collection: SMART (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The structures of IS, FS and MS, with the atomic numbering schemes. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary size. Hydrogen bonds are indicated by dashed lines.
[Figure 2] Fig. 2. The unit cell and crystal packing of IS, viewed along the b axis.
[Figure 3] Fig. 3. The unit cell and crystal packing of FS. viewed along the b axis.
[Figure 4] Fig. 4. The unit cell and crystal packing of MS. viewed along the b axis. The letter A identifies a hydrophilic layer generated by peptide A molecules, while B identifies a corresponding layer generated by peptide B molecules, shown in a darker tone.
[Figure 5] Fig. 5. Hydrogen-bonded sheets in the structures of IS (left) and FS (right). The hydrophobic side chains and the methylene H atoms of the serine side chains have been omitted for clarity. [For IS, symmetry codes: (i) x - 1/2, 1/2 + y, z; (ii) x - 1/2, y - 1/2, z; (iii) x, y - 1, z; (iv) x, 1 + y, z. For FS, symmetry codes: (i) 1 + x, 1 + y, z; (ii) x, 1 + y, z; (iii) 1 + x, y, z.]
(IS) L-isoleucyl-L-serin 0.33-hydrate top
Crystal data top
C9H18N2O4·0.33H2OF(000) = 485.4
Mr = 224.27Dx = 1.357 Mg m−3
Monoclinic, C2Mo Kα radiation, λ = 0.71073 Å
a = 16.9692 (11) ÅCell parameters from 3409 reflections
b = 5.2167 (3) Åθ = 2.4–28.3°
c = 12.4065 (8) ŵ = 0.11 mm−1
β = 90.942 (1)°T = 105 K
V = 1098.11 (12) Å3Needle, colourless
Z = 40.40 × 0.25 × 0.10 mm
Data collection top
Siemens SMART CCD area-detector
diffractometer		1454 independent reflections
Radiation source: fine-focus sealed tube1373 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.023
Detector resolution: 8.3 pixels mm-1θmax = 28.3°, θmin = 1.6°
Sets of exposures each taken over 0.3° ω rotation scansh = −19→22
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		k = −5→6
Tmin = 0.858, Tmax = 0.989l = −16→16
4482 measured reflections
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)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.091H atoms treated by a mixture of independent and constrained refinement
S = 1.10 w = 1/[σ2(Fo2) + (0.0524P)2 + 0.4828P]
where P = (Fo2 + 2Fc2)/3
1454 reflections(Δ/σ)max = 0.003
162 parametersΔρmax = 0.32 e Å−3
1 restraintΔρmin = −0.21 e Å−3
Crystal data top
C9H18N2O4·0.33H2OV = 1098.11 (12) Å3
Mr = 224.27Z = 4
Monoclinic, C2Mo Kα radiation
a = 16.9692 (11) ŵ = 0.11 mm−1
b = 5.2167 (3) ÅT = 105 K
c = 12.4065 (8) Å0.40 × 0.25 × 0.10 mm
β = 90.942 (1)°
Data collection top
Siemens SMART CCD area-detector
diffractometer		1454 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1373 reflections with I > 2σ(I)
Tmin = 0.858, Tmax = 0.989Rint = 0.023
4482 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0341 restraint
wR(F2) = 0.091H atoms treated by a mixture of independent and constrained refinement
S = 1.10Δρmax = 0.32 e Å−3
1454 reflectionsΔρmin = −0.21 e Å−3
162 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
O10.17779 (8)0.4492 (3)0.69462 (12)0.0240 (3)
O20.38873 (8)0.3939 (3)0.53174 (11)0.0245 (3)
H50.3846 (16)0.282 (7)0.582 (2)0.037*
O30.38543 (8)1.0734 (3)0.70512 (12)0.0232 (3)
O40.46639 (7)0.7373 (3)0.70364 (12)0.0269 (3)
N10.04799 (8)0.7822 (4)0.67305 (12)0.0189 (3)
H10.0597 (14)0.785 (6)0.601 (2)0.028*
H20.0076 (15)0.897 (6)0.684 (2)0.028*
H30.0287 (15)0.631 (6)0.692 (2)0.028*
N20.25631 (8)0.8009 (3)0.69495 (12)0.0160 (3)
H40.2567 (13)0.954 (7)0.7021 (18)0.019*
C10.11885 (9)0.8560 (4)0.73958 (13)0.0156 (3)
H110.13311.03720.72220.019*
C20.09915 (10)0.8396 (4)0.86059 (14)0.0210 (4)
H210.05370.95690.87340.025*
C40.14529 (18)0.9799 (9)1.04789 (19)0.0612 (11)
H410.18871.06691.08600.092*
H420.13470.81541.08290.092*
H430.09791.08731.04990.092*
C30.16802 (12)0.9332 (8)0.93015 (17)0.0443 (7)
H310.18851.09470.89940.053*
H320.21080.80440.92830.053*
C50.0745 (3)0.5726 (7)0.8944 (2)0.0649 (10)
H510.06430.57110.97190.097*
H520.11670.45090.87850.097*
H530.02650.52330.85460.097*
C60.18702 (10)0.6814 (4)0.70727 (13)0.0161 (4)
C70.32891 (9)0.6616 (4)0.67230 (14)0.0152 (3)
H710.33230.50590.71920.018*
C80.32924 (10)0.5795 (4)0.55242 (14)0.0187 (4)
H810.27710.50730.53240.022*
H820.33810.73230.50690.022*
C90.39909 (10)0.8379 (4)0.69732 (14)0.0179 (4)
O1W0.50000.9217 (7)0.50000.0284 (10)0.668 (9)
H1W0.493 (3)0.807 (11)0.551 (4)0.043*0.668 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0168 (6)0.0153 (7)0.0400 (8)−0.0015 (5)0.0031 (5)−0.0019 (6)
O20.0260 (7)0.0244 (8)0.0234 (6)0.0098 (6)0.0063 (5)−0.0015 (6)
O30.0150 (6)0.0184 (7)0.0363 (7)−0.0018 (5)0.0011 (5)−0.0033 (6)
O40.0105 (6)0.0301 (9)0.0401 (8)0.0042 (6)−0.0030 (5)−0.0070 (7)
N10.0106 (7)0.0244 (9)0.0218 (7)−0.0009 (6)0.0003 (5)−0.0024 (7)
N20.0108 (6)0.0133 (8)0.0240 (7)−0.0001 (6)0.0019 (5)−0.0026 (6)
C10.0091 (7)0.0174 (8)0.0205 (7)−0.0005 (6)0.0006 (5)0.0003 (7)
C20.0166 (8)0.0263 (10)0.0203 (7)−0.0007 (7)0.0038 (6)−0.0039 (8)
C40.0554 (15)0.102 (3)0.0262 (10)−0.0338 (19)0.0023 (10)−0.0174 (16)
C30.0227 (10)0.085 (2)0.0258 (9)−0.0138 (13)0.0000 (7)−0.0103 (13)
C50.122 (3)0.0432 (16)0.0306 (12)−0.0327 (19)0.0270 (15)−0.0002 (12)
C60.0114 (7)0.0185 (9)0.0185 (7)0.0000 (7)0.0002 (6)0.0001 (7)
C70.0098 (7)0.0159 (8)0.0200 (7)0.0006 (6)0.0003 (5)−0.0002 (7)
C80.0144 (7)0.0216 (9)0.0200 (7)0.0034 (7)−0.0006 (6)−0.0017 (7)
C90.0118 (7)0.0201 (9)0.0217 (7)−0.0006 (7)0.0000 (6)−0.0009 (7)
O1W0.0344 (18)0.0227 (18)0.0285 (16)0.0000.0112 (12)0.000
Geometric parameters (Å, º) top
O1—C61.231 (2)C2—H211.0000
O2—C81.425 (2)C4—C31.536 (3)
O2—H50.86 (3)C4—H410.9800
O3—C91.254 (3)C4—H420.9800
O4—C91.258 (2)C4—H430.9800
N1—C11.498 (2)C3—H310.9900
N1—H10.92 (3)C3—H320.9900
N1—H20.92 (3)C5—H510.9800
N1—H30.89 (3)C5—H520.9800
N2—C61.342 (2)C5—H530.9800
N2—C71.462 (2)C7—C91.532 (2)
N2—H40.81 (4)C7—C81.548 (2)
C1—C61.531 (2)C7—H711.0000
C1—C21.546 (2)C8—H810.9900
C1—H111.0000C8—H820.9900
C2—C51.515 (4)O1W—H1W0.88 (5)
C2—C31.522 (3)
C8—O2—H5105.2 (19)C2—C3—H31109.0
C1—N1—H1110.4 (15)C4—C3—H31109.0
C1—N1—H2110.3 (17)C2—C3—H32109.0
H1—N1—H2107 (2)C4—C3—H32109.0
C1—N1—H3112.2 (16)H31—C3—H32107.8
H1—N1—H3111 (2)C2—C5—H51109.5
H2—N1—H3105 (2)C2—C5—H52109.5
C6—N2—C7122.26 (16)H51—C5—H52109.5
C6—N2—H4117.1 (16)C2—C5—H53109.5
C7—N2—H4120.7 (16)H51—C5—H53109.5
N1—C1—C6107.81 (14)H52—C5—H53109.5
N1—C1—C2109.67 (13)O1—C6—N2123.54 (18)
C6—C1—C2113.43 (14)O1—C6—C1121.58 (16)
N1—C1—H11108.6N2—C6—C1114.87 (16)
C6—C1—H11108.6N2—C7—C9108.49 (15)
C2—C1—H11108.6N2—C7—C8109.79 (13)
C5—C2—C3110.5 (2)C9—C7—C8110.21 (14)
C5—C2—C1112.64 (17)N2—C7—H71109.4
C3—C2—C1110.90 (15)C9—C7—H71109.4
C5—C2—H21107.5C8—C7—H71109.4
C3—C2—H21107.5O2—C8—C7112.00 (14)
C1—C2—H21107.5O2—C8—H81109.2
C3—C4—H41109.5C7—C8—H81109.2
C3—C4—H42109.5O2—C8—H82109.2
H41—C4—H42109.5C7—C8—H82109.2
C3—C4—H43109.5H81—C8—H82107.9
H41—C4—H43109.5O3—C9—O4124.93 (18)
H42—C4—H43109.5O3—C9—C7117.36 (16)
C2—C3—C4112.81 (18)O4—C9—C7117.63 (17)
N1—C1—C6—N2136.37 (16)C5—C2—C3—C4−67.7 (4)
C1—C6—N2—C7175.27 (14)C7—N2—C6—O1−4.3 (3)
C6—N2—C7—C9−162.77 (16)N1—C1—C6—O1−44.1 (2)
N2—C7—C9—O3−17.1 (2)C2—C1—C6—O177.6 (2)
N1—C1—C2—C3−175.7 (2)C2—C1—C6—N2−102.00 (18)
N1—C1—C2—C559.9 (3)C6—N2—C7—C876.7 (2)
C1—C2—C3—C4166.7 (3)C9—C7—C8—O274.30 (19)
N2—C7—C8—O2−166.25 (15)C8—C7—C9—O3103.17 (19)
C7—C8—O2—H545.9 (17)N2—C7—C9—O4166.06 (15)
C6—C1—C2—C5−60.7 (3)C8—C7—C9—O4−73.7 (2)
C6—C1—C2—C363.8 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O2i0.92 (3)1.95 (2)2.8353 (17)158 (2)
N1—H2···O4ii0.92 (3)1.95 (3)2.777 (2)153 (2)
N1—H3···O4iii0.89 (3)2.31 (3)3.187 (2)167.0 (18)
N1—H3···O3iii0.89 (3)2.46 (2)2.9983 (17)119.7 (17)
N2—H4···O30.81 (4)2.26 (2)2.6132 (18)106.0 (16)
O2—H5···O3iv0.86 (3)1.88 (3)2.7258 (18)172 (2)
C1—H11···O1v1.002.313.302 (2)174
C7—H71···O3iv1.002.443.240 (2)137
O1W—H1W···O40.88 (5)1.99 (4)2.771 (17)149 (4)
Symmetry codes: (i) −x+1/2, y+1/2, −z+1; (ii) x−1/2, y+1/2, z; (iii) x−1/2, y−1/2, z; (iv) x, y−1, z; (v) x, y+1, z.
(FS) L-phenylalanyl-L-serine top
Crystal data top
C12H16N2O4F(000) = 268
Mr = 252.27Dx = 1.419 Mg m−3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
a = 7.6434 (7) ÅCell parameters from 3332 reflections
b = 5.7609 (5) Åθ = 1.5–37.0°
c = 13.4396 (12) ŵ = 0.11 mm−1
β = 93.754 (4)°T = 105 K
V = 590.51 (9) Å3Needle, colourless
Z = 20.70 × 0.15 × 0.15 mm
Data collection top
Siemens SMART CCD area-detector
diffractometer		2392 independent reflections
Radiation source: fine-focus sealed tube2268 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.019
Detector resolution: 8.3 pixels mm-1θmax = 37.0°, θmin = 1.5°
Sets of exposures each taken over 0.3° ω rotation scansh = −12→11
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		k = −9→4
Tmin = 0.820, Tmax = 0.984l = −17→18
5381 measured reflections
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)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.0562P)2 + 0.0336P]
where P = (Fo2 + 2Fc2)/3
2392 reflections(Δ/σ)max = 0.002
178 parametersΔρmax = 0.35 e Å−3
1 restraintΔρmin = −0.21 e Å−3
Crystal data top
C12H16N2O4V = 590.51 (9) Å3
Mr = 252.27Z = 2
Monoclinic, P21Mo Kα radiation
a = 7.6434 (7) ŵ = 0.11 mm−1
b = 5.7609 (5) ÅT = 105 K
c = 13.4396 (12) Å0.70 × 0.15 × 0.15 mm
β = 93.754 (4)°
Data collection top
Siemens SMART CCD area-detector
diffractometer		2392 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2268 reflections with I > 2σ(I)
Tmin = 0.820, Tmax = 0.984Rint = 0.019
5381 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0311 restraint
wR(F2) = 0.084H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.35 e Å−3
2392 reflectionsΔρmin = −0.21 e Å−3
178 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.86909 (11)0.39194 (14)0.87700 (7)0.01600 (17)
O20.41423 (11)−0.02221 (14)0.78603 (8)0.01862 (19)
H50.351 (3)−0.011 (4)0.8356 (17)0.028*
O30.28647 (11)0.60015 (14)0.92519 (8)0.01730 (19)
O40.24140 (10)0.21585 (15)0.92656 (8)0.01771 (19)
N10.97767 (11)0.85932 (15)0.92233 (8)0.01302 (18)
H11.018 (2)1.002 (4)0.9144 (16)0.020*
H21.071 (2)0.760 (4)0.9210 (14)0.020*
H30.917 (2)0.848 (4)0.9748 (14)0.020*
N20.60028 (11)0.55660 (16)0.84561 (8)0.01343 (19)
H40.544 (2)0.680 (3)0.8295 (14)0.016*
C10.85775 (13)0.79648 (18)0.83458 (9)0.0132 (2)
H110.76400.91670.82410.016*
C20.96727 (15)0.7849 (2)0.74285 (10)0.0193 (2)
H210.99660.94510.72320.023*
H221.07870.70390.76180.023*
C30.87900 (14)0.66349 (19)0.65394 (10)0.0158 (2)
C40.93755 (17)0.4446 (2)0.62669 (11)0.0207 (2)
H411.02640.36900.66750.025*
C50.86780 (18)0.3355 (2)0.54077 (13)0.0268 (3)
H510.90980.18700.52280.032*
C60.73728 (19)0.4431 (3)0.48154 (13)0.0298 (3)
H610.69140.37060.42190.036*
C70.67342 (18)0.6574 (3)0.50940 (12)0.0281 (3)
H710.58170.73000.46970.034*
C80.74345 (16)0.7662 (2)0.59534 (11)0.0208 (2)
H810.69830.91220.61430.025*
C90.77557 (13)0.56133 (18)0.85539 (9)0.01184 (19)
C100.50565 (13)0.34512 (17)0.86448 (9)0.0126 (2)
H1010.57890.24870.91300.015*
C110.47358 (15)0.20685 (19)0.76770 (10)0.0163 (2)
H1110.38500.28820.72340.020*
H1120.58380.19900.73300.020*
C120.33007 (13)0.39552 (18)0.90922 (9)0.0127 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0128 (3)0.0140 (3)0.0211 (5)0.0005 (2)0.0011 (3)0.0030 (3)
O20.0195 (4)0.0118 (3)0.0250 (5)−0.0024 (3)0.0046 (4)−0.0028 (3)
O30.0124 (3)0.0151 (3)0.0247 (5)0.0011 (2)0.0031 (3)−0.0045 (3)
O40.0125 (3)0.0160 (3)0.0252 (5)−0.0025 (3)0.0058 (3)0.0023 (3)
N10.0116 (3)0.0132 (3)0.0144 (5)−0.0021 (3)0.0023 (3)−0.0013 (3)
N20.0097 (3)0.0114 (3)0.0193 (6)−0.0011 (3)0.0024 (3)0.0003 (3)
C10.0115 (4)0.0132 (4)0.0150 (6)−0.0025 (3)0.0000 (4)0.0008 (4)
C20.0176 (4)0.0260 (5)0.0145 (6)−0.0091 (4)0.0032 (4)−0.0001 (5)
C30.0166 (4)0.0160 (4)0.0151 (6)−0.0028 (3)0.0039 (4)0.0006 (4)
C40.0224 (5)0.0165 (4)0.0240 (7)0.0009 (4)0.0070 (5)0.0032 (4)
C50.0307 (6)0.0195 (5)0.0317 (8)−0.0062 (4)0.0149 (6)−0.0078 (5)
C60.0249 (6)0.0416 (8)0.0235 (8)−0.0111 (6)0.0062 (6)−0.0143 (7)
C70.0195 (5)0.0457 (8)0.0189 (7)0.0038 (5)−0.0013 (5)−0.0048 (6)
C80.0204 (5)0.0235 (5)0.0187 (7)0.0038 (4)0.0027 (5)−0.0015 (5)
C90.0104 (3)0.0133 (4)0.0119 (6)−0.0019 (3)0.0016 (3)0.0000 (3)
C100.0105 (3)0.0113 (3)0.0163 (6)−0.0007 (3)0.0028 (4)0.0006 (3)
C110.0175 (4)0.0127 (4)0.0190 (6)−0.0005 (3)0.0038 (4)−0.0007 (4)
C120.0096 (4)0.0148 (4)0.0136 (6)−0.0007 (3)0.0016 (4)−0.0011 (4)
Geometric parameters (Å, º) top
O1—C91.2331 (13)C2—H220.9900
O2—C111.4221 (14)C3—C81.3918 (18)
O2—H50.85 (2)C3—C41.3949 (16)
O3—C121.2475 (13)C4—C51.390 (2)
O4—C121.2672 (13)C4—H410.9500
N1—C11.4901 (16)C5—C61.382 (3)
N1—H10.89 (2)C5—H510.9500
N1—H20.917 (19)C6—C71.388 (2)
N1—H30.869 (19)C6—H610.9500
N2—C91.3379 (13)C7—C81.390 (2)
N2—C101.4477 (13)C7—H710.9500
N2—H40.85 (2)C8—H810.9500
C1—C91.5267 (14)C10—C111.5312 (18)
C1—C21.5363 (16)C10—C121.5337 (13)
C1—H111.0000C10—H1011.0000
C2—C31.5055 (18)C11—H1110.9900
C2—H210.9900C11—H1120.9900
C11—O2—H5105.6 (16)C6—C5—H51120.0
C1—N1—H1109.2 (14)C4—C5—H51120.0
C1—N1—H2105.9 (12)C5—C6—C7119.81 (15)
H1—N1—H2107.5 (18)C5—C6—H61120.1
C1—N1—H3107.0 (12)C7—C6—H61120.1
H1—N1—H3111.8 (19)C6—C7—C8120.13 (15)
H2—N1—H3115.2 (17)C6—C7—H71119.9
C9—N2—C10120.56 (9)C8—C7—H71119.9
C9—N2—H4119.3 (12)C7—C8—C3120.71 (12)
C10—N2—H4120.1 (12)C7—C8—H81119.6
N1—C1—C9108.04 (9)C3—C8—H81119.6
N1—C1—C2107.84 (8)O1—C9—N2124.64 (9)
C9—C1—C2111.15 (9)O1—C9—C1120.41 (9)
N1—C1—H11109.9N2—C9—C1114.93 (9)
C9—C1—H11109.9N2—C10—C11110.06 (9)
C2—C1—H11109.9N2—C10—C12111.68 (8)
C3—C2—C1114.68 (9)C11—C10—C12109.63 (9)
C3—C2—H21108.6N2—C10—H101108.5
C1—C2—H21108.6C11—C10—H101108.5
C3—C2—H22108.6C12—C10—H101108.5
C1—C2—H22108.6O2—C11—C10111.76 (10)
H21—C2—H22107.6O2—C11—H111109.3
C8—C3—C4118.38 (13)C10—C11—H111109.3
C8—C3—C2122.00 (11)O2—C11—H112109.3
C4—C3—C2119.58 (12)C10—C11—H112109.3
C5—C4—C3120.99 (13)H111—C11—H112107.9
C5—C4—H41119.5O3—C12—O4126.02 (9)
C3—C4—H41119.5O3—C12—C10119.79 (9)
C6—C5—C4119.91 (13)O4—C12—C10114.19 (9)
N1—C1—C9—N2126.45 (11)C5—C6—C7—C81.6 (2)
C1—C9—N2—C10−179.18 (10)C6—C7—C8—C30.6 (2)
C9—N2—C10—C12146.35 (11)C4—C3—C8—C7−2.72 (18)
N2—C10—C12—O3−0.41 (17)C2—C3—C8—C7175.09 (12)
N1—C1—C2—C3164.51 (10)C10—N2—C9—O12.55 (19)
C1—C2—C3—C4−108.05 (13)N1—C1—C9—O1−55.20 (14)
C1—C2—C3—C874.17 (15)C2—C1—C9—O162.94 (15)
N2—C10—C11—O2167.83 (9)C2—C1—C9—N2−115.41 (12)
C10—C11—O2—H534.7 (14)C9—N2—C10—C11−91.65 (13)
C9—C1—C2—C346.25 (14)C12—C10—C11—O2−68.97 (11)
C8—C3—C4—C52.74 (17)C11—C10—C12—O3−122.66 (12)
C2—C3—C4—C5−175.12 (11)N2—C10—C12—O4179.55 (10)
C3—C4—C5—C6−0.63 (19)C11—C10—C12—O457.31 (14)
C4—C5—C6—C7−1.5 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O4i0.89 (2)2.106 (19)2.8758 (12)144.9 (17)
N1—H1···O1ii0.89 (2)2.55 (2)3.2262 (13)133.5 (16)
N1—H2···O3iii0.917 (19)1.883 (18)2.7910 (12)170.2 (18)
N1—H3···O4iv0.869 (19)2.006 (19)2.8384 (13)160.0 (19)
N2—H4···O2ii0.85 (2)2.05 (2)2.8986 (13)178.0 (18)
O2—H5···O40.85 (2)2.01 (2)2.7422 (13)144 (2)
Symmetry codes: (i) x+1, y+1, z; (ii) x, y+1, z; (iii) x+1, y, z; (iv) −x+1, y+1/2, −z+2.
(MS) L-Methionyl-L-Serine 0.34-hydrate top
Crystal data top
C8H16N2O4S·0.34H2OF(000) = 1035.2
Mr = 242.41Dx = 1.435 Mg m−3
Monoclinic, C2Mo Kα radiation, λ = 0.71073 Å
a = 16.791 (4) ÅCell parameters from 3955 reflections
b = 5.0711 (11) Åθ = 4.6–56.4°
c = 26.851 (6) ŵ = 0.29 mm−1
β = 100.926 (4)°T = 105 K
V = 2244.8 (8) Å3Plate, colourless
Z = 80.45 × 0.22 × 0.03 mm
Data collection top
Siemens SMART CCD area-detector
diffractometer		2849 independent reflections
Radiation source: fine-focus sealed tube2445 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.066
Detector resolution: 8.3 pixels mm-1θmax = 28.2°, θmin = 1.5°
Sets of exposures each taken over 0.3° ω rotation scansh = −22→20
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		k = −3→6
Tmin = 0.744, Tmax = 0.991l = 0→34
3325 measured reflections
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)] = 0.073Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.201H atoms treated by a mixture of independent and constrained refinement
S = 1.54 w = 1/[σ2(Fo2) + (0.0748P)2 + 3.98P]
where P = (Fo2 + 2Fc2)/3
2849 reflections(Δ/σ)max = 0.001
298 parametersΔρmax = 0.58 e Å−3
57 restraintsΔρmin = −0.49 e Å−3
Crystal data top
C8H16N2O4S·0.34H2OV = 2244.8 (8) Å3
Mr = 242.41Z = 8
Monoclinic, C2Mo Kα radiation
a = 16.791 (4) ŵ = 0.29 mm−1
b = 5.0711 (11) ÅT = 105 K
c = 26.851 (6) Å0.45 × 0.22 × 0.03 mm
β = 100.926 (4)°
Data collection top
Siemens SMART CCD area-detector
diffractometer		2849 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2445 reflections with I > 2σ(I)
Tmin = 0.744, Tmax = 0.991Rint = 0.066
3325 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.07357 restraints
wR(F2) = 0.201H atoms treated by a mixture of independent and constrained refinement
S = 1.54Δρmax = 0.58 e Å−3
2849 reflectionsΔρmin = −0.49 e Å−3
298 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
S1A0.24104 (12)0.1459 (4)0.22534 (6)0.0377 (5)
O1A0.4448 (3)0.4913 (8)0.41707 (17)0.0252 (10)
O2A0.6421 (3)0.0642 (9)0.49175 (16)0.0230 (10)
H5A0.599 (3)−0.017 (14)0.491 (3)0.035*
O3A0.6330 (3)−0.1281 (8)0.36837 (17)0.0226 (10)
O4A0.7305 (2)0.1755 (8)0.38936 (16)0.0203 (9)
N1A0.3084 (3)0.1692 (10)0.40402 (16)0.0162 (10)
H1A0.26790.05580.39450.024*
H2A0.28990.33320.39850.024*
H3A0.32850.14800.43690.024*
N2A0.5199 (2)0.1497 (10)0.39587 (18)0.0194 (10)
H4A0.5173−0.01260.38640.023*
C1A0.3728 (3)0.1206 (11)0.37446 (18)0.0171 (12)
H11A0.3844−0.06880.37430.020*
C2A0.3436 (3)0.2167 (13)0.31965 (18)0.0222 (13)
H21A0.32940.40190.32020.027*
H22A0.38780.20050.30120.027*
C3A0.2707 (4)0.0630 (13)0.2917 (2)0.0312 (16)
H31A0.22510.09480.30830.037*
H32A0.2832−0.12380.29460.037*
C4A0.1885 (6)0.4492 (15)0.2306 (3)0.059 (3)
H41A0.16670.51550.19740.088*
H42A0.22560.57590.24870.088*
H43A0.14520.41870.24860.088*
C5A0.4498 (3)0.2695 (10)0.3986 (2)0.0163 (12)
C6A0.6006 (3)0.2690 (9)0.40745 (19)0.0150 (12)
H61A0.59870.44130.39070.018*
C7A0.6303 (4)0.3068 (11)0.4643 (2)0.0202 (13)
H71A0.68110.40320.46970.024*
H72A0.59110.41280.47770.024*
C8A0.6582 (3)0.0913 (10)0.3859 (2)0.0190 (13)
S1B0.47168 (13)0.7180 (4)0.27065 (7)0.0362 (5)
O1B0.3519 (2)1.1794 (8)0.09606 (19)0.0262 (10)
O2B0.1172 (3)1.2299 (9)0.01705 (16)0.0247 (10)
H5B0.131 (5)1.350 (12)0.038 (2)0.037*
O3B0.1468 (3)0.5314 (7)0.10009 (18)0.0220 (10)
O4B0.0628 (2)0.8742 (9)0.09727 (18)0.0254 (10)
N1B0.4775 (3)0.8443 (10)0.07909 (18)0.0184 (11)
H1B0.45090.84490.04710.028*
H2B0.51850.73040.08230.028*
H3B0.49671.00510.08750.028*
N2B0.2748 (2)0.8095 (9)0.09422 (18)0.0166 (10)
H4B0.27450.64040.09660.020*
C1B0.4219 (3)0.7658 (10)0.11283 (18)0.0153 (12)
H11B0.40670.58050.10660.018*
C2B0.4653 (4)0.7985 (13)0.16800 (19)0.0234 (13)
H21B0.51660.70520.17280.028*
H22B0.47690.98390.17460.028*
C3B0.4161 (4)0.6958 (15)0.2061 (2)0.0289 (15)
H31B0.40150.51320.19830.035*
H32B0.36630.79690.20300.035*
C4B0.5428 (4)0.4551 (14)0.2712 (3)0.0317 (16)
H41B0.58220.46120.30220.048*
H42B0.56970.47370.24290.048*
H43B0.51480.28940.26890.048*
C5B0.3461 (3)0.9373 (10)0.1004 (2)0.0196 (13)
C6B0.1972 (3)0.9519 (10)0.0835 (2)0.0154 (11)
H61B0.20091.10890.10510.018*
C7B0.1796 (4)1.0369 (12)0.0275 (2)0.0217 (13)
H71B0.22881.10770.01870.026*
H72B0.16380.88340.00640.026*
C8B0.1309 (3)0.7736 (10)0.0951 (2)0.0171 (13)
O1W0.50000.8124 (12)0.50000.0187 (13)
H1W0.470 (3)0.710 (9)0.4793 (15)0.028*
O2W0.00000.718 (3)0.00000.018 (5)0.355 (18)
H2W0.017 (8)0.822 (11)0.0253 (13)0.028*0.355 (18)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S1A0.0396 (11)0.0502 (11)0.0212 (7)0.0045 (10)0.0000 (7)−0.0035 (8)
O1A0.027 (2)0.0173 (19)0.031 (2)0.0044 (18)0.0070 (18)−0.0097 (18)
O2A0.018 (2)0.026 (2)0.025 (2)−0.0040 (19)0.0020 (19)0.0038 (19)
O3A0.019 (2)0.016 (2)0.034 (2)0.0021 (18)0.0055 (19)−0.0041 (18)
O4A0.012 (2)0.015 (2)0.035 (2)0.0002 (17)0.0076 (17)−0.0005 (19)
N1A0.011 (2)0.017 (2)0.020 (2)0.001 (2)0.0032 (18)−0.001 (2)
N2A0.018 (2)0.014 (2)0.026 (2)0.000 (2)0.003 (2)−0.003 (2)
C1A0.018 (3)0.013 (2)0.022 (3)0.002 (2)0.007 (2)−0.002 (2)
C2A0.020 (3)0.025 (3)0.022 (3)0.000 (3)0.007 (2)0.005 (3)
C3A0.041 (4)0.024 (3)0.025 (3)−0.015 (3)−0.005 (3)−0.004 (3)
C4A0.088 (8)0.029 (4)0.044 (5)0.006 (5)−0.027 (5)0.006 (4)
C5A0.014 (3)0.014 (3)0.021 (3)−0.001 (2)0.003 (2)0.004 (2)
C6A0.011 (3)0.011 (3)0.024 (3)0.003 (2)0.006 (2)0.001 (2)
C7A0.015 (3)0.019 (3)0.027 (3)−0.001 (2)0.001 (2)−0.002 (2)
C8A0.025 (3)0.013 (3)0.019 (3)0.007 (2)0.003 (2)0.000 (2)
S1B0.0547 (12)0.0291 (9)0.0269 (8)0.0042 (9)0.0127 (8)0.0011 (7)
O1B0.015 (2)0.015 (2)0.050 (3)−0.0010 (19)0.010 (2)0.001 (2)
O2B0.025 (2)0.023 (2)0.025 (2)0.011 (2)0.0012 (19)0.001 (2)
O3B0.014 (2)0.015 (2)0.038 (3)−0.0006 (17)0.0062 (19)0.0007 (19)
O4B0.012 (2)0.025 (2)0.042 (2)0.0062 (18)0.0127 (18)0.0060 (19)
N1B0.015 (3)0.018 (2)0.024 (2)−0.004 (2)0.008 (2)0.000 (2)
N2B0.009 (2)0.011 (2)0.029 (3)0.0012 (19)0.001 (2)0.002 (2)
C1B0.009 (2)0.014 (2)0.022 (2)0.000 (2)0.002 (2)0.001 (2)
C2B0.021 (3)0.026 (3)0.024 (3)−0.005 (3)0.006 (3)0.000 (3)
C3B0.021 (3)0.033 (4)0.033 (3)0.008 (3)0.008 (3)0.002 (3)
C4B0.032 (4)0.037 (4)0.027 (3)−0.002 (3)0.005 (3)0.006 (3)
C5B0.020 (3)0.014 (3)0.025 (3)−0.002 (2)0.005 (3)0.001 (2)
C6B0.008 (3)0.014 (3)0.024 (3)0.003 (2)0.005 (2)0.003 (2)
C7B0.023 (3)0.019 (3)0.025 (3)0.001 (3)0.007 (3)0.003 (3)
C8B0.009 (3)0.021 (3)0.021 (3)0.004 (2)0.002 (2)0.002 (2)
O1W0.015 (3)0.015 (3)0.025 (3)0.0000.002 (2)0.000
O2W0.018 (9)0.018 (8)0.017 (8)0.0000.001 (6)0.000
Geometric parameters (Å, º) top
S1A—C4A1.792 (7)S1B—C3B1.810 (6)
S1A—C3A1.807 (6)O1B—C5B1.239 (6)
O1A—C5A1.239 (6)O2B—C7B1.423 (6)
O2A—C7A1.429 (6)O2B—H5B0.83 (3)
O2A—H5A0.84 (3)O3B—C8B1.258 (6)
O3A—C8A1.250 (6)O4B—C8B1.263 (6)
O4A—C8A1.273 (6)N1B—C1B1.474 (6)
N1A—C1A1.479 (6)N1B—H1B0.8900
N1A—H1A0.8900N1B—H2B0.8900
N1A—H2A0.8900N1B—H3B0.8900
N1A—H3A0.8900N2B—C5B1.344 (6)
N2A—C5A1.340 (6)N2B—C6B1.469 (6)
N2A—C6A1.462 (6)N2B—H4B0.8600
N2A—H4A0.8600C1B—C5B1.525 (6)
C1A—C5A1.531 (6)C1B—C2B1.531 (6)
C1A—C2A1.539 (6)C1B—H11B0.9800
C1A—H11A0.9800C2B—C3B1.523 (7)
C2A—C3A1.523 (7)C2B—H21B0.9700
C2A—H21A0.9700C2B—H22B0.9700
C2A—H22A0.9700C3B—H31B0.9700
C3A—H31A0.9700C3B—H32B0.9700
C3A—H32A0.9700C4B—H41B0.9600
C4A—H41A0.9600C4B—H42B0.9600
C4A—H42A0.9600C4B—H43B0.9600
C4A—H43A0.9600C6B—C8B1.512 (6)
C6A—C8A1.515 (6)C6B—C7B1.538 (7)
C6A—C7A1.526 (7)C6B—H61B0.9800
C6A—H61A0.9800C7B—H71B0.9700
C7A—H71A0.9700C7B—H72B0.9700
C7A—H72A0.9700O1W—H1W0.85 (3)
S1B—C4B1.788 (7)O2W—H2W0.87 (3)
C4A—S1A—C3A99.7 (4)C4B—S1B—C3B100.6 (3)
C7A—O2A—H5A113 (5)C7B—O2B—H5B106 (6)
C1A—N1A—H1A109.5C1B—N1B—H1B109.5
C1A—N1A—H2A109.5C1B—N1B—H2B109.5
H1A—N1A—H2A109.5H1B—N1B—H2B109.5
C1A—N1A—H3A109.5C1B—N1B—H3B109.5
H1A—N1A—H3A109.5H1B—N1B—H3B109.5
H2A—N1A—H3A109.5H2B—N1B—H3B109.5
C5A—N2A—C6A126.1 (4)C5B—N2B—C6B121.6 (4)
C5A—N2A—H4A116.9C5B—N2B—H4B119.2
C6A—N2A—H4A116.9C6B—N2B—H4B119.2
N1A—C1A—C5A109.6 (4)N1B—C1B—C5B108.1 (4)
N1A—C1A—C2A109.1 (4)N1B—C1B—C2B109.0 (4)
C5A—C1A—C2A109.8 (4)C5B—C1B—C2B111.9 (4)
N1A—C1A—H11A109.4N1B—C1B—H11B109.2
C5A—C1A—H11A109.4C5B—C1B—H11B109.2
C2A—C1A—H11A109.4C2B—C1B—H11B109.2
C1A—C2A—C3A112.9 (4)C3B—C2B—C1B113.2 (4)
C1A—C2A—H21A109.0C3B—C2B—H21B108.9
C3A—C2A—H21A109.0C1B—C2B—H21B108.9
C1A—C2A—H22A109.0C3B—C2B—H22B108.9
C3A—C2A—H22A109.0C1B—C2B—H22B108.9
H21A—C2A—H22A107.8H21B—C2B—H22B107.7
C2A—C3A—S1A114.3 (4)C2B—C3B—S1B112.0 (4)
C2A—C3A—H31A108.7C2B—C3B—H31B109.2
S1A—C3A—H31A108.7S1B—C3B—H31B109.2
C2A—C3A—H32A108.7C2B—C3B—H32B109.2
S1A—C3A—H32A108.7S1B—C3B—H32B109.2
H31A—C3A—H32A107.6H31B—C3B—H32B107.9
S1A—C4A—H41A109.5S1B—C4B—H41B109.5
S1A—C4A—H42A109.5S1B—C4B—H42B109.5
H41A—C4A—H42A109.5H41B—C4B—H42B109.5
S1A—C4A—H43A109.5S1B—C4B—H43B109.5
H41A—C4A—H43A109.5H41B—C4B—H43B109.5
H42A—C4A—H43A109.5H42B—C4B—H43B109.5
O1A—C5A—N2A124.1 (5)O1B—C5B—N2B123.3 (5)
O1A—C5A—C1A120.1 (5)O1B—C5B—C1B120.6 (5)
N2A—C5A—C1A115.7 (4)N2B—C5B—C1B116.1 (4)
N2A—C6A—C8A107.8 (4)N2B—C6B—C8B109.0 (4)
N2A—C6A—C7A112.2 (4)N2B—C6B—C7B109.2 (4)
C8A—C6A—C7A110.2 (4)C8B—C6B—C7B110.9 (4)
N2A—C6A—H61A108.8N2B—C6B—H61B109.2
C8A—C6A—H61A108.8C8B—C6B—H61B109.2
C7A—C6A—H61A108.8C7B—C6B—H61B109.2
O2A—C7A—C6A113.3 (4)O2B—C7B—C6B112.5 (4)
O2A—C7A—H71A108.9O2B—C7B—H71B109.1
C6A—C7A—H71A108.9C6B—C7B—H71B109.1
O2A—C7A—H72A108.9O2B—C7B—H72B109.1
C6A—C7A—H72A108.9C6B—C7B—H72B109.1
H71A—C7A—H72A107.7H71B—C7B—H72B107.8
O3A—C8A—O4A125.2 (5)O4B—C8B—O3B124.3 (5)
O3A—C8A—C6A118.6 (5)O4B—C8B—C6B118.4 (4)
O4A—C8A—C6A116.2 (4)O3B—C8B—C6B117.2 (5)
N1A—C1A—C5A—N2A145.6 (5)N1B—C1B—C5B—N2B131.9 (5)
C1A—C5A—N2A—C6A168.1 (5)C1B—C5B—N2B—C6B178.4 (5)
C5A—N2A—C6A—C8A−164.8 (5)C5B—N2B—C6B—C8B−161.9 (5)
N2A—C6A—C8A—O3A−8.0 (7)N2B—C6B—C8B—O3B−15.5 (7)
N1A—C1A—C2A—C3A−64.2 (7)N1B—C1B—C2B—C3B−174.1 (5)
C1A—C2A—C3A—S1A−173.9 (4)C1B—C2B—C3B—S1B176.3 (4)
C2A—C3A—S1A—C4A−78.0 (6)C2B—C3B—S1B—C4B−73.8 (6)
N2A—C6A—C7A—O2A64.7 (6)N2B—C6B—C7B—O2B−165.2 (5)
C6A—C7A—O2A—H5A−66 (6)C6B—C7B—O2B—H5B52 (6)
C5A—C1A—C2A—C3A175.7 (5)C5B—C1B—C2B—C3B66.4 (7)
C6A—N2A—C5A—O1A−8.7 (9)C6B—N2B—C5B—O1B−2.4 (9)
N1A—C1A—C5A—O1A−37.5 (7)N1B—C1B—C5B—O1B−47.3 (7)
C2A—C1A—C5A—O1A82.3 (6)C2B—C1B—C5B—O1B72.7 (7)
C2A—C1A—C5A—N2A−94.6 (6)C2B—C1B—C5B—N2B−108.0 (6)
C5A—N2A—C6A—C7A73.6 (6)C5B—N2B—C6B—C7B76.8 (6)
C8A—C6A—C7A—O2A−55.5 (6)C8B—C6B—C7B—O2B74.6 (6)
C7A—C6A—C8A—O3A114.8 (5)N2B—C6B—C8B—O4B167.2 (5)
N2A—C6A—C8A—O4A175.1 (5)C7B—C6B—C8B—O4B−72.5 (6)
C7A—C6A—C8A—O4A−62.1 (6)C7B—C6B—C8B—O3B104.8 (6)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H1A···O4Ai0.892.032.818 (7)148
N1A—H2A···O4Aii0.891.992.874 (7)170
N1A—H3A···O2Aiii0.891.932.815 (6)171
N2A—H4A···O3A0.862.172.582 (6)109
O2A—H5A···O1Wiv0.84 (3)1.92 (3)2.752 (5)172 (8)
C6A—H61A···O3Av0.982.373.311 (6)162
N1B—H1B···O2Bvi0.891.972.824 (6)161
N1B—H2B···O4Bvii0.891.972.777 (7)151
N1B—H3B···O4Bviii0.892.173.041 (7)167
N2B—H4B···O3B0.862.232.600 (6)106
O2B—H5B···O3Bv0.84 (4)1.87 (4)2.671 (7)160 (8)
C1B—H11B···O1Biv0.982.233.198 (7)170
C3B—H32B···S1Av0.972.903.833 (7)162
C6B—H61B···O3Bv0.982.323.114 (6)137
O1W—H1W···O1A0.86 (3)1.98 (4)2.773 (5)153 (6)
O2W—H2W···O4B0.87 (3)1.96 (4)2.742 (7)150 (5)
Symmetry codes: (i) x−1/2, y−1/2, z; (ii) x−1/2, y+1/2, z; (iii) −x+1, y, −z+1; (iv) x, y−1, z; (v) x, y+1, z; (vi) −x+1/2, y−1/2, −z; (vii) x+1/2, y−1/2, z; (viii) x+1/2, y+1/2, z.

Experimental details

(IS)(FS)(MS)
Crystal data
Chemical formulaC9H18N2O4·0.33H2OC12H16N2O4C8H16N2O4S·0.34H2O
Mr224.27252.27242.41
Crystal system, space groupMonoclinic, C2Monoclinic, P21Monoclinic, C2
Temperature (K)105105105
a, b, c (Å)16.9692 (11), 5.2167 (3), 12.4065 (8)7.6434 (7), 5.7609 (5), 13.4396 (12)16.791 (4), 5.0711 (11), 26.851 (6)
β (°) 90.942 (1) 93.754 (4) 100.926 (4)
V (Å3)1098.11 (12)590.51 (9)2244.8 (8)
Z428
Radiation typeMo KαMo KαMo Kα
µ (mm−1)0.110.110.29
Crystal size (mm)0.40 × 0.25 × 0.100.70 × 0.15 × 0.150.45 × 0.22 × 0.03
Data collection
DiffractometerSiemens SMART CCD area-detectorSiemens SMART CCD area-detectorSiemens SMART CCD area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)		Multi-scan
(SADABS; Sheldrick, 1996)		Multi-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.858, 0.9890.820, 0.9840.744, 0.991
No. of measured, independent and
observed [I > 2σ(I)] reflections		4482, 1454, 1373 5381, 2392, 2268 3325, 2849, 2445
Rint0.0230.0190.066
(sin θ/λ)max (Å−1)0.6680.8470.665
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.091, 1.10 0.031, 0.084, 1.06 0.073, 0.201, 1.54
No. of reflections145423922849
No. of parameters162178298
No. of restraints1157
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)0.32, −0.210.35, −0.210.58, −0.49

Computer programs: SMART (Bruker, 1998), SAINT-Plus (Bruker, 2001), SAINT-Plus, SHELXTL (Bruker, 2000), SHELXTL.

Selected torsion angles (º) for (IS) top
N1—C1—C6—N2136.37 (16)N1—C1—C2—C559.9 (3)
C1—C6—N2—C7175.27 (14)C1—C2—C3—C4166.7 (3)
C6—N2—C7—C9−162.77 (16)N2—C7—C8—O2−166.25 (15)
N2—C7—C9—O3−17.1 (2)C7—C8—O2—H545.9 (17)
N1—C1—C2—C3−175.7 (2)
Hydrogen-bond geometry (Å, º) for (IS) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O2i0.92 (3)1.95 (2)2.8353 (17)158 (2)
N1—H2···O4ii0.92 (3)1.95 (3)2.777 (2)153 (2)
N1—H3···O4iii0.89 (3)2.31 (3)3.187 (2)167.0 (18)
N1—H3···O3iii0.89 (3)2.46 (2)2.9983 (17)119.7 (17)
N2—H4···O30.81 (4)2.26 (2)2.6132 (18)106.0 (16)
O2—H5···O3iv0.86 (3)1.88 (3)2.7258 (18)172 (2)
C1—H11···O1v1.002.313.302 (2)174
C7—H71···O3iv1.002.443.240 (2)137
O1W—H1W···O40.88 (5)1.99 (4)2.771 (17)149 (4)
Symmetry codes: (i) −x+1/2, y+1/2, −z+1; (ii) x−1/2, y+1/2, z; (iii) x−1/2, y−1/2, z; (iv) x, y−1, z; (v) x, y+1, z.
Selected torsion angles (º) for (FS) top
N1—C1—C9—N2126.45 (11)C1—C2—C3—C4−108.05 (13)
C1—C9—N2—C10−179.18 (10)C1—C2—C3—C874.17 (15)
C9—N2—C10—C12146.35 (11)N2—C10—C11—O2167.83 (9)
N2—C10—C12—O3−0.41 (17)C10—C11—O2—H534.7 (14)
N1—C1—C2—C3164.51 (10)
Hydrogen-bond geometry (Å, º) for (FS) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O4i0.89 (2)2.106 (19)2.8758 (12)144.9 (17)
N1—H1···O1ii0.89 (2)2.55 (2)3.2262 (13)133.5 (16)
N1—H2···O3iii0.917 (19)1.883 (18)2.7910 (12)170.2 (18)
N1—H3···O4iv0.869 (19)2.006 (19)2.8384 (13)160.0 (19)
N2—H4···O2ii0.85 (2)2.05 (2)2.8986 (13)178.0 (18)
O2—H5···O40.85 (2)2.01 (2)2.7422 (13)144 (2)
Symmetry codes: (i) x+1, y+1, z; (ii) x, y+1, z; (iii) x+1, y, z; (iv) −x+1, y+1/2, −z+2.
Selected torsion angles (º) for (MS) top
N1A—C1A—C5A—N2A145.6 (5)N1B—C1B—C5B—N2B131.9 (5)
C1A—C5A—N2A—C6A168.1 (5)C1B—C5B—N2B—C6B178.4 (5)
C5A—N2A—C6A—C8A−164.8 (5)C5B—N2B—C6B—C8B−161.9 (5)
N2A—C6A—C8A—O3A−8.0 (7)N2B—C6B—C8B—O3B−15.5 (7)
N1A—C1A—C2A—C3A−64.2 (7)N1B—C1B—C2B—C3B−174.1 (5)
C1A—C2A—C3A—S1A−173.9 (4)C1B—C2B—C3B—S1B176.3 (4)
C2A—C3A—S1A—C4A−78.0 (6)C2B—C3B—S1B—C4B−73.8 (6)
N2A—C6A—C7A—O2A64.7 (6)N2B—C6B—C7B—O2B−165.2 (5)
C6A—C7A—O2A—H5A−66 (6)C6B—C7B—O2B—H5B52 (6)
Hydrogen-bond geometry (Å, º) for (MS) top
D—H···AD—HH···AD···AD—H···A
N1A—H1A···O4Ai0.892.032.818 (7)148
N1A—H2A···O4Aii0.891.992.874 (7)170
N1A—H3A···O2Aiii0.891.932.815 (6)171
N2A—H4A···O3A0.862.172.582 (6)109
O2A—H5A···O1Wiv0.84 (3)1.92 (3)2.752 (5)172 (8)
C6A—H61A···O3Av0.982.373.311 (6)162
N1B—H1B···O2Bvi0.891.972.824 (6)161
N1B—H2B···O4Bvii0.891.972.777 (7)151
N1B—H3B···O4Bviii0.892.173.041 (7)167
N2B—H4B···O3B0.862.232.600 (6)106
O2B—H5B···O3Bv0.84 (4)1.87 (4)2.671 (7)160 (8)
C1B—H11B···O1Biv0.982.233.198 (7)170
C3B—H32B···S1Av0.972.903.833 (7)162
C6B—H61B···O3Bv0.982.323.114 (6)137
O1W—H1W···O1A0.86 (3)1.98 (4)2.773 (5)153 (6)
O2W—H2W···O4B0.87 (3)1.96 (4)2.742 (7)150 (5)
Symmetry codes: (i) x−1/2, y−1/2, z; (ii) x−1/2, y+1/2, z; (iii) −x+1, y, −z+1; (iv) x, y−1, z; (v) x, y+1, z; (vi) −x+1/2, y−1/2, −z; (vii) x+1/2, y−1/2, z; (viii) x+1/2, y+1/2, z.
 

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