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The crystal structures of lenalidomide [systematic name: (RS)-3-(4-amino-1-oxoisoindolin-2-yl)piperidine-2,6-dione], C13H13N3O3, (I), an anti­neoplastic drug, and its hemihydrate, C13H13N3O3·0.5H2O, (II), have been determined by single-crystal X-ray diffraction analysis. The overall conformation of the mol­ecule defined by the orientation of the two ring portions, viz. pyridine­dione and isoindolinone, is twisted in both structures. The influence of the self-complementary pyridine­dione ring is seen in the crystal packing of both structures through its involvement in forming hydrogen-bonded dimers, although alternate dione O atoms are utilized. An extensive series of N-H...O hydrogen bonds link the dimers into two-dimensional supra­molecular arrays built up from infinite chains. The water mol­ecule in (II) has a cohesive function, connecting three lenalidomide mol­ecules by hydrogen bonds. The significance of this study lies in the analysis of the inter­actions in these structures and the aggregations occurring via hydrogen bonds in the hydrated and dehydrated crystalline forms of the title compound.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109033642/sf3114sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109033642/sf3114Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109033642/sf3114IIsup3.hkl
Contains datablock II

CCDC references: 755982; 755983

Comment top

Lenalidomide, initially known as CC-5013 and marketed as Revlimid by Celgene Europe Ltd., is one of a number of novel compounds based on the molecular structure of thalidomide that were developed with a view to improving the immunomodulatory effect of the parent compound, whilst also providing a better safety profile (Bartlett et al., 2004; Richardson et al., 2002). It is a synthetic derivative of glutamic acid and is structurally close to thalidomide, in that it has an identical backbone but has been subject to removal of an O atom from the phthalyl ring and addition of an amine group. Although it is chiral and possesses an asymmetric C atom, it has been developed as a racemic mixture since it undergoes racemization under physiological conditions. In a phase III clinical study, Weber et al. (2007) found that treatment with lenalidomide plus dexamethasone in patients with relapsed or refractory multiple myeloma was superior to the old treatment of multiple myeloma consisting of high-dose dexamethasone alone. On June 29 2006, lenalidomide received US Food and Drug Administration (FDA) clearance for use in combination with dexamethasone in patients with multiple myeloma who have received at least one prior therapy.

In the course of our investigations on the structural characterization of pharmaceutical compounds (Ravikumar et al., 2008a,b), the title compound was obtained in two crystal types, as blocks and a small number of fine needles. The data collected suggest the structure of lenalidomide, (I) (triclinic, P1), in the case of the blocks, whereas for the needles, the larger asymmetric unit indicates the presence of two molecules (monoclinic, P21/c, Z = 8) and proved to contain a water molecule as well, considered as lenalidomide hemihydrate, (II). The crystal structures of (I) and (II) are presented here.

Views of the molecules of (I) and (II), showing the atom labelling, are presented in Figs. 1 and 2, respectively. The significant difference between the two molecules of (II) is seen in the central C5—C4—N2—C13 torsion angle, defining the twist between the pyridinedione ring and the aminoisoindolinone portion; this angle is 121.9 (1)° in molecule A and 87.4 (2)° in molecule B. This is the only available point for conformation flexibility in the molecule. The corresponding angle in (I) is 87.6 (1)°. This twist is further illustrated by the non-bonding distance between the carbonyl O atoms of the two rings: O2···O3 = 3.566 (2) Å in (I), 4.317 (2) Å in molecule A of (II) and 3.536 (2) Å in molecule B of (II). An overlay of the molecules of (I) and (II) with thalidomide polymorphs [α form (Allen & Trotter, 1971) and β form (Reepmeyer et al., 1994)], superimposing the planar isoindolinone systems, reveals the conformational flexibility (Fig. 3). The conformation of the pyridinedione ring in both structures has a distorted half-chair conformation in which atoms C3 and C4 lie on opposite sides of the plane defined by atoms C1/C2/N1/C5. The half-chair conformation is distorted towards a C3 envelope.

In both structures (I) and (II), the main interest centres on the crystal packing features, where hydrogen bonds (Tables 1 and 2) play a major part in controlling the supramolecular assembly of the molecules.

In the crystal packing (Fig. 4) of (I), the self-complementary pyridinedione ring forms centrosymmetric dimers (N1—H1N···O2), the hydrogen-bonding motif of which has graph set R22(8) (Etter, 1990; Etter et al., 1990; Bernstein et al., 1995). Amino atom N3 donates one of its H atoms to dione atom O1 at (x, y, z - 1), linking the dimers to generate a cyclic centrosymmetric tetramer of graph set R44(26). These self-complementary tetramers form infinite chains parallel to the c axis, for which the complete graph set can be written as C11(11)[R22(8)R44(26)]. In addition, the molecules are further linked into an additional centrosymmetric dimeric aggregate by N—H···N hydrogen bonds along the a axis, wherein amino atom N3 acts as both donor and acceptor [N3—H2···N2(-x + 1, -y + 2, -z + 1)] to generate a motif of graph set R22(4) propagating along the b axis. Carbonyl atom O3 of the indolinone ring is not involved in any conventional hydrogen bonds, but participates in an acceptable C—H···O interaction (Table 1).

In the hemihydrate, (II), the crystal structure is built up from two lenalidomide molecules, A and B, in the asymmetric unit, with solvent water molecules, via hydrogen-bonding interactions. The self-complementary pyridinedione ring dimer found in (I) forms only between B molecules through N1B—H4N···O1B hydrogen bonds (Fig. 5). Molecule A links to molecule B through pyridine atom N1A to carbonyl atom O3B. It is interesting to note that whilst the dimer formation in (I) is through dione atom O1, it is through atom O2 in (II), thus making use of the alternate presence of dione atoms O1 and O2. The amine atom N3 of both molecules connects neighbouring lenalidomide molecules via N—H···O hydrogen bonds and generates tetramers based on the R44(29) synthon along the c axis.

Two adjacent tetramers thus generate a centrosymmetic hexamer along the a axis, based on the R64(36) synthon, accommodating the N—H···O dimers in its cavity. Symmetry-related N—H···O hydrogen bonds generate an additional centrosymmetic hexamer of R66(42) motif along the b axis, which links the earlier formed R64(36) hexamers, resulting in a continuous linkage of molecules along the c and b axes (Fig. 6).

The cohesive role of water is embodied by its interaction as an acceptor of a hydrogen bond donated by amine atom N3B, and as a donor to the two different carbonyl atoms O1B and O2B of the pyridinedione ring, generating a graph-set motif of R23(8) (Fig. 7). It is interesting to note that the water molecule interacts only with molecule B. Carbonyl atom O2A of the pyridinedione ring is not involved in any conventional hydrogen bonds, but participates in an acceptable C—H···O interaction (Table 2).

To sum up, the crystal structure analysis of (I) and (II) illustrates the arrangements of supramolecular aggregates formed by hydrogen-bonding interactions in the hydrated and dehydrated forms of lenalidomide. The observed crystal packing features, with and without the interposition of water molecules, may provide some insight to understand ways of improving the tablet-formation ability and densification properties of drug substances.

Experimental top

Lenalidomide (Pharmacology Department, IICT, Hyderabad) (80 mg) was dissolved in methanol (5 ml) and water (1 ml). After 3 d, crystals of (I) and (II) were obtained, distinguished by their distinct crystal habits.

Refinement top

All N-bound H atoms of (I) and (II), and the O-bound H atoms of (II), were located in difference Fourier maps and their positions and isotropic displacement parameters refined. All other H atoms were located in a difference density map, positioned geometrically and included as riding atoms, with C—H = 0.93–0.98 Å and with Uiso(H) = 1.2Ueq(C). Distance restraints were applied to O1W—H1W and O1W—H2W of the water molecule of (II), with a set value of 0.89 (1) Å.

Computing details top

For both compounds, data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A view of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. A view of the two lenalidomide molecules (suffixes A and B) and the water molecule in the asymmetric unit of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. Dashed lines indicate hydrogen bonds.
[Figure 3] Fig. 3. A superposition of the molecular conformations of the lenalidomide molecules of (I) and (II) with thalidomide. The overlay was made by making a least-squares fit through the isoindolinone ring system of (I). The labels and r.m.s deviations (Å) are as follows: molecule A of (II) [labelled (II), A] 0.019; molecule B of (II) [labelled (II), B] 0.020; thalidomide α form (labelled 3) 0.028; and thalidomide β form 2 (labelled 4) 0.035.
[Figure 4] Fig. 4. Part of the crystal packing of (I), showing the centrosymmetric tetramolecular R44(26) (in ball and stick representation) and dimeric R22(8) ring motifs, forming infinite chains parallel to the c axis, for which the complete graph-set notation is C11(11)[R22(8) R44(26)]. Also shown are the centrosymmetric dimeric R22(4) ring motifs formed by N—H···N hydrogen bonds. Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity. Selected atoms are labelled, primarily to provide a key for the coding of the atoms. [Symmetry codes: (i) -x + 2, -y + 2, -z + 2; (ii) -x + 1, -y + 2, -z + 1; (iii) x, y, z - 1.]
[Figure 5] Fig. 5. Part of the crystal structure of (II), showing the formation of the centrosymmetric hexamolecular R64(36) and dimeric R22(8) ring motifs, along with the tetramolecular R44(29) ring motif. Hydrogen bonds are shown as dashed lines. Selected atoms of the molecules present in the asymmetric unit are labelled, primarily to provide a key for the coding of the atoms. The hydrogen bonding of the water molecule is not shown. For the sake of clarity, the unit-cell outline has been omitted, along with H atoms not involved in hydrogen bonding. [Symmetry codes: (i) x + 1, -y + 3/2, z + 1/2; (ii) x, -y + 3/2, z + 1/2; (iii) -x - 1, -y + 1, -z + 1; (iv) -x, y - 1/2, -z + 3/2.]
[Figure 6] Fig. 6. A more extensive view of the hydrogen-bonding within a layer of molecules of (II), showing the formation of the centrosymmetric hexamolecular R66(42) ring motif. The representation is the same as in Fig. 5. The water molecules, and H atoms not involved in hydrogen bonding, have been omitted for clarity. Hydrogen bonds are shown as dashed lines. Symmetry codes and atom labelling have been omitted and the outline of the unit cell is shown.
[Figure 7] Fig. 7. A partial packing view of (II), showing the water molecule involved in hydrogen-bonding interactions (dashed lines) with molecule B. H atoms not involved in hydrogen bonding have been omitted for clarity. [Symmetry codes: (v) x, -y + 1/2, z + 1/2; (vi) -x - 1, y - 1/2, -z + 3/2.]
(I) (RS)-3-(4-amino-1-oxoisoindolin-2-yl)piperidine-2,6-dione top
Crystal data top
C13H13N3O3Z = 2
Mr = 259.26F(000) = 272
Triclinic, P1Dx = 1.442 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.9983 (5) ÅCell parameters from 5070 reflections
b = 8.9198 (8) Åθ = 2.4–28.1°
c = 11.5785 (10) ŵ = 0.11 mm1
α = 75.711 (1)°T = 294 K
β = 84.660 (1)°Block, colourless
γ = 86.038 (1)°0.19 × 0.15 × 0.12 mm
V = 597.04 (9) Å3
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
1975 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.016
Graphite monochromatorθmax = 25.0°, θmin = 1.8°
ω scansh = 77
5703 measured reflectionsk = 1010
2092 independent reflectionsl = 1313
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.039H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.104 w = 1/[σ2(Fo2) + (0.0565P)2 + 0.1503P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
2092 reflectionsΔρmax = 0.22 e Å3
185 parametersΔρmin = 0.20 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.069 (8)
Crystal data top
C13H13N3O3γ = 86.038 (1)°
Mr = 259.26V = 597.04 (9) Å3
Triclinic, P1Z = 2
a = 5.9983 (5) ÅMo Kα radiation
b = 8.9198 (8) ŵ = 0.11 mm1
c = 11.5785 (10) ÅT = 294 K
α = 75.711 (1)°0.19 × 0.15 × 0.12 mm
β = 84.660 (1)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
1975 reflections with I > 2σ(I)
5703 measured reflectionsRint = 0.016
2092 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.104H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.22 e Å3
2092 reflectionsΔρmin = 0.20 e Å3
185 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.5579 (2)0.82780 (15)1.11014 (11)0.0377 (3)
C20.4347 (2)0.70981 (16)1.07203 (13)0.0416 (3)
H2A0.27480.72981.08660.050*
H2B0.47350.60781.12060.050*
C30.4871 (2)0.71039 (16)0.94097 (12)0.0382 (3)
H3A0.42710.80590.89120.046*
H3B0.41730.62460.92330.046*
C40.7402 (2)0.69600 (14)0.91373 (11)0.0337 (3)
H40.79520.59980.96670.040*
C50.8484 (2)0.82910 (15)0.94414 (11)0.0339 (3)
C60.7203 (3)0.79641 (17)0.68838 (12)0.0452 (4)
H6A0.72710.90280.69370.054*
H6B0.56700.77620.67900.054*
C70.8771 (2)0.76305 (17)0.58847 (12)0.0429 (3)
C80.8739 (3)0.82670 (19)0.46597 (13)0.0545 (4)
C91.0466 (3)0.7790 (2)0.39317 (14)0.0598 (5)
H91.05190.82120.31110.072*
C101.2101 (3)0.6711 (2)0.43898 (15)0.0667 (5)
H101.32360.64210.38730.080*
C111.2098 (3)0.6045 (2)0.56047 (14)0.0579 (4)
H111.31920.53020.59150.069*
C121.0399 (2)0.65336 (16)0.63332 (12)0.0399 (3)
C130.9968 (2)0.60616 (15)0.76452 (12)0.0363 (3)
N10.75510 (19)0.87523 (14)1.04327 (10)0.0380 (3)
H1N0.825 (3)0.947 (2)1.0643 (15)0.050 (4)*
N20.80718 (18)0.68780 (12)0.79265 (9)0.0363 (3)
N30.7069 (4)0.9356 (3)0.42101 (15)0.0904 (7)
H2N0.575 (7)0.906 (5)0.462 (4)0.110 (18)*
H3N0.705 (5)0.949 (3)0.349 (3)0.114 (9)*
O10.49436 (19)0.88326 (13)1.19327 (9)0.0559 (3)
O21.01178 (15)0.89120 (12)0.88665 (9)0.0459 (3)
O31.10446 (18)0.51219 (12)0.83683 (9)0.0520 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0401 (7)0.0403 (7)0.0303 (7)0.0009 (5)0.0001 (5)0.0056 (5)
C20.0359 (7)0.0428 (7)0.0442 (8)0.0051 (6)0.0045 (6)0.0089 (6)
C30.0341 (7)0.0402 (7)0.0415 (7)0.0035 (5)0.0041 (5)0.0114 (6)
C40.0346 (7)0.0351 (6)0.0306 (6)0.0024 (5)0.0045 (5)0.0068 (5)
C50.0289 (6)0.0406 (7)0.0316 (6)0.0020 (5)0.0045 (5)0.0076 (5)
C60.0490 (8)0.0515 (8)0.0332 (7)0.0167 (6)0.0093 (6)0.0100 (6)
C70.0467 (8)0.0464 (8)0.0346 (7)0.0078 (6)0.0050 (6)0.0099 (6)
C80.0656 (10)0.0596 (9)0.0342 (8)0.0171 (8)0.0058 (7)0.0087 (7)
C90.0720 (11)0.0665 (10)0.0350 (8)0.0065 (8)0.0050 (7)0.0073 (7)
C100.0628 (11)0.0816 (12)0.0478 (9)0.0159 (9)0.0137 (8)0.0130 (8)
C110.0503 (9)0.0673 (10)0.0496 (9)0.0181 (8)0.0030 (7)0.0100 (8)
C120.0391 (7)0.0422 (7)0.0376 (7)0.0033 (6)0.0028 (6)0.0093 (6)
C130.0355 (7)0.0373 (7)0.0367 (7)0.0031 (5)0.0068 (5)0.0098 (5)
N10.0380 (6)0.0440 (6)0.0349 (6)0.0065 (5)0.0001 (5)0.0146 (5)
N20.0382 (6)0.0406 (6)0.0299 (6)0.0076 (5)0.0066 (4)0.0095 (4)
N30.1094 (16)0.1134 (15)0.0343 (8)0.0609 (13)0.0141 (9)0.0062 (9)
O10.0616 (7)0.0674 (7)0.0420 (6)0.0103 (5)0.0124 (5)0.0237 (5)
O20.0358 (5)0.0585 (6)0.0466 (6)0.0107 (4)0.0050 (4)0.0192 (5)
O30.0527 (6)0.0568 (6)0.0415 (6)0.0199 (5)0.0107 (5)0.0062 (5)
Geometric parameters (Å, º) top
C1—O11.2072 (16)C6—H6B0.9700
C1—N11.3835 (17)C7—C121.3758 (19)
C1—C21.4987 (19)C7—C81.393 (2)
C2—C31.5195 (19)C8—C91.385 (2)
C2—H2A0.9700C8—N31.389 (2)
C2—H2B0.9700C9—C101.373 (3)
C3—C41.5248 (18)C9—H90.9300
C3—H3A0.9700C10—C111.385 (2)
C3—H3B0.9700C10—H100.9300
C4—N21.4401 (16)C11—C121.378 (2)
C4—C51.5201 (18)C11—H110.9300
C4—H40.9800C12—C131.4758 (18)
C5—O21.2172 (16)C13—O31.2246 (16)
C5—N11.3718 (17)C13—N21.3653 (16)
C6—N21.4620 (17)N1—H1N0.882 (19)
C6—C71.4965 (19)N3—H2N0.91 (4)
C6—H6A0.9700N3—H3N0.81 (3)
O1—C1—N1119.34 (13)C12—C7—C8120.95 (13)
O1—C1—C2124.14 (12)C12—C7—C6110.07 (12)
N1—C1—C2116.51 (11)C8—C7—C6128.97 (13)
C1—C2—C3113.11 (11)C9—C8—N3122.43 (15)
C1—C2—H2A109.0C9—C8—C7116.84 (14)
C3—C2—H2A109.0N3—C8—C7120.72 (15)
C1—C2—H2B109.0C10—C9—C8121.72 (15)
C3—C2—H2B109.0C10—C9—H9119.1
H2A—C2—H2B107.8C8—C9—H9119.1
C2—C3—C4109.58 (11)C9—C10—C11121.47 (15)
C2—C3—H3A109.8C9—C10—H10119.3
C4—C3—H3A109.8C11—C10—H10119.3
C2—C3—H3B109.8C12—C11—C10116.94 (15)
C4—C3—H3B109.8C12—C11—H11121.5
H3A—C3—H3B108.2C10—C11—H11121.5
N2—C4—C5110.83 (10)C7—C12—C11122.04 (13)
N2—C4—C3113.93 (10)C7—C12—C13108.44 (12)
C5—C4—C3109.36 (10)C11—C12—C13129.52 (13)
N2—C4—H4107.5O3—C13—N2125.03 (12)
C5—C4—H4107.5O3—C13—C12128.45 (12)
C3—C4—H4107.5N2—C13—C12106.52 (11)
O2—C5—N1120.59 (12)C5—N1—C1127.36 (12)
O2—C5—C4123.07 (11)C5—N1—H1N116.2 (11)
N1—C5—C4116.32 (11)C1—N1—H1N116.4 (11)
N2—C6—C7101.99 (10)C13—N2—C4121.88 (10)
N2—C6—H6A111.4C13—N2—C6112.86 (11)
C7—C6—H6A111.4C4—N2—C6123.15 (10)
N2—C6—H6B111.4C8—N3—H2N109 (3)
C7—C6—H6B111.4C8—N3—H3N112 (2)
H6A—C6—H6B109.2H2N—N3—H3N114 (3)
O1—C1—C2—C3154.97 (13)C6—C7—C12—C131.18 (17)
N1—C1—C2—C324.26 (17)C10—C11—C12—C70.1 (3)
C1—C2—C3—C452.80 (15)C10—C11—C12—C13179.14 (16)
C2—C3—C4—N2177.12 (10)C7—C12—C13—O3179.46 (14)
C2—C3—C4—C558.25 (14)C11—C12—C13—O30.2 (3)
N2—C4—C5—O218.13 (17)C7—C12—C13—N21.04 (15)
C3—C4—C5—O2144.55 (12)C11—C12—C13—N2179.68 (16)
N2—C4—C5—N1163.35 (11)O2—C5—N1—C1172.80 (12)
C3—C4—C5—N136.93 (15)C4—C5—N1—C18.63 (19)
N2—C6—C7—C122.75 (16)O1—C1—N1—C5177.66 (12)
N2—C6—C7—C8177.30 (16)C2—C1—N1—C51.6 (2)
C12—C7—C8—C92.6 (2)O3—C13—N2—C413.6 (2)
C6—C7—C8—C9177.36 (16)C12—C13—N2—C4166.90 (11)
C12—C7—C8—N3178.96 (19)O3—C13—N2—C6177.52 (14)
C6—C7—C8—N31.1 (3)C12—C13—N2—C62.96 (15)
N3—C8—C9—C10179.9 (2)C5—C4—N2—C1387.61 (14)
C7—C8—C9—C101.7 (3)C3—C4—N2—C13148.55 (12)
C8—C9—C10—C110.1 (3)C5—C4—N2—C674.66 (15)
C9—C10—C11—C121.0 (3)C3—C4—N2—C649.18 (17)
C8—C7—C12—C111.8 (2)C7—C6—N2—C133.53 (15)
C6—C7—C12—C11178.16 (15)C7—C6—N2—C4167.23 (12)
C8—C7—C12—C13178.86 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O2i0.88 (2)2.02 (2)2.899 (2)179 (2)
N3—H2N···N3ii0.91 (4)2.62 (4)3.260 (4)128 (3)
N3—H3N···O1iii0.81 (3)2.50 (3)3.180 (2)142 (3)
C3—H3A···O2iv0.972.563.213 (2)125
C3—H3B···O3iv0.972.583.461 (2)152
C4—H4···O3v0.982.363.205 (2)144
Symmetry codes: (i) x+2, y+2, z+2; (ii) x+1, y+2, z+1; (iii) x, y, z1; (iv) x1, y, z; (v) x+2, y+1, z+2.
(II) (RS)-3-(4-amino-1-oxoisoindolin-2-yl)piperidine-2,6-dione hemihydrate top
Crystal data top
C13H13N3O3·0.5H2OF(000) = 1128
Mr = 268.27Dx = 1.413 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 7073 reflections
a = 8.4425 (7) Åθ = 2.4–27.9°
b = 22.2874 (19) ŵ = 0.11 mm1
c = 13.6627 (12) ÅT = 294 K
β = 101.069 (1)°Needle, colourless
V = 2523.0 (4) Å30.18 × 0.11 × 0.07 mm
Z = 8
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
3972 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.022
Graphite monochromatorθmax = 25.0°, θmin = 1.8°
ω scansh = 1010
23782 measured reflectionsk = 2626
4430 independent reflectionsl = 1616
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)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.105H atoms treated by a mixture of independent and constrained refinement
S = 1.02 w = 1/[σ2(Fo2) + (0.0566P)2 + 0.8341P]
where P = (Fo2 + 2Fc2)/3
4430 reflections(Δ/σ)max = 0.001
383 parametersΔρmax = 0.39 e Å3
2 restraintsΔρmin = 0.18 e Å3
Crystal data top
C13H13N3O3·0.5H2OV = 2523.0 (4) Å3
Mr = 268.27Z = 8
Monoclinic, P21/cMo Kα radiation
a = 8.4425 (7) ŵ = 0.11 mm1
b = 22.2874 (19) ÅT = 294 K
c = 13.6627 (12) Å0.18 × 0.11 × 0.07 mm
β = 101.069 (1)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
3972 reflections with I > 2σ(I)
23782 measured reflectionsRint = 0.022
4430 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0362 restraints
wR(F2) = 0.105H atoms treated by a mixture of independent and constrained refinement
S = 1.02Δρmax = 0.39 e Å3
4430 reflectionsΔρmin = 0.18 e Å3
383 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C1A0.09157 (18)0.63219 (7)0.72003 (11)0.0392 (3)
C2A0.10504 (18)0.69363 (7)0.67547 (12)0.0410 (3)
H2A0.20900.71040.68090.049*
H2B0.10170.69040.60510.049*
C3A0.02640 (17)0.73648 (6)0.72388 (11)0.0361 (3)
H3A0.00880.74810.78940.043*
H3B0.02450.77240.68360.043*
C4A0.18888 (16)0.70521 (6)0.73302 (10)0.0337 (3)
H4A0.19550.69080.66620.040*
C5A0.19246 (17)0.65009 (6)0.79865 (11)0.0354 (3)
C6A0.36338 (17)0.77535 (6)0.85997 (10)0.0352 (3)
H6A0.38700.74740.91530.042*
H6B0.27490.80120.86900.042*
C7A0.50935 (16)0.81104 (6)0.84967 (10)0.0328 (3)
C8A0.60135 (17)0.84984 (6)0.91874 (11)0.0370 (3)
C9A0.73399 (19)0.87669 (7)0.88835 (13)0.0467 (4)
H9A0.79930.90250.93200.056*
C10A0.77113 (19)0.86612 (7)0.79564 (14)0.0493 (4)
H10A0.86030.88500.77870.059*
C11A0.67870 (18)0.82803 (7)0.72735 (12)0.0429 (4)
H11A0.70290.82110.66470.051*
C12A0.54805 (16)0.80081 (6)0.75744 (10)0.0335 (3)
C13A0.42950 (16)0.75842 (6)0.70268 (10)0.0333 (3)
N1A0.05125 (15)0.61700 (6)0.78172 (10)0.0396 (3)
N2A0.32699 (14)0.74385 (5)0.76453 (8)0.0349 (3)
N3A0.55867 (19)0.86233 (7)1.00857 (11)0.0485 (3)
O1A0.20231 (14)0.59650 (5)0.70355 (10)0.0603 (4)
O2A0.30804 (13)0.63410 (5)0.85893 (9)0.0495 (3)
O3A0.41846 (13)0.74021 (5)0.61636 (8)0.0468 (3)
H1N0.054 (2)0.5817 (9)0.8129 (13)0.047 (5)*
H2N0.634 (2)0.8811 (9)1.0539 (15)0.058 (5)*
H3N0.503 (3)0.8340 (10)1.0356 (16)0.073 (7)*
C1B0.52664 (19)0.50584 (7)0.65301 (13)0.0447 (4)
C2B0.5386 (2)0.51510 (8)0.75929 (13)0.0520 (4)
H2C0.65010.50970.76590.062*
H2D0.50850.55610.77780.062*
C3B0.43253 (19)0.47278 (7)0.83158 (12)0.0450 (4)
H3C0.43110.48530.89980.054*
H3D0.47500.43230.82330.054*
C4B0.26297 (18)0.47447 (6)0.80992 (11)0.0378 (3)
H4B0.22670.51630.81600.045*
C5B0.26602 (19)0.45528 (7)0.70313 (11)0.0421 (4)
C6B0.18099 (18)0.37917 (6)0.90983 (11)0.0380 (3)
H6C0.22060.35340.85320.046*
H6D0.25890.37980.95360.046*
C7B0.01835 (17)0.35940 (6)0.96413 (10)0.0335 (3)
C8B0.02691 (17)0.30487 (6)1.01154 (10)0.0352 (3)
C9B0.18859 (19)0.29889 (7)1.05720 (11)0.0431 (4)
H9B0.22310.26331.09010.052*
C10B0.29905 (19)0.34443 (8)1.05485 (13)0.0491 (4)
H10B0.40580.33891.08660.059*
C11B0.25411 (19)0.39800 (7)1.00627 (12)0.0452 (4)
H11B0.32860.42841.00370.054*
C12B0.09341 (17)0.40425 (6)0.96164 (10)0.0361 (3)
C13B0.01063 (18)0.45503 (6)0.90361 (10)0.0374 (3)
N1B0.39466 (16)0.47573 (6)0.63377 (10)0.0445 (3)
N2B0.14721 (15)0.43951 (5)0.87799 (9)0.0379 (3)
N3B0.08375 (18)0.25977 (6)1.01624 (11)0.0446 (3)
O1B0.62886 (15)0.52360 (6)0.58373 (10)0.0632 (4)
O2B0.16241 (16)0.42439 (7)0.67838 (9)0.0653 (4)
O3B0.07036 (14)0.50219 (5)0.88195 (9)0.0522 (3)
H4N0.390 (2)0.4706 (9)0.5704 (17)0.065 (6)*
H5N0.179 (3)0.2621 (9)0.9750 (15)0.059 (6)*
H6N0.044 (2)0.2225 (10)1.0280 (15)0.061 (6)*
O1W0.1268 (2)0.11826 (8)0.98185 (14)0.0869 (5)
H1W0.128 (4)0.1007 (15)1.0473 (13)0.132*
H2W0.125 (4)0.0815 (9)0.943 (2)0.132*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C1A0.0364 (8)0.0391 (8)0.0393 (8)0.0064 (6)0.0004 (6)0.0028 (6)
C2A0.0350 (8)0.0399 (8)0.0447 (8)0.0028 (6)0.0009 (6)0.0072 (6)
C3A0.0369 (8)0.0335 (7)0.0365 (8)0.0014 (6)0.0031 (6)0.0040 (6)
C4A0.0339 (7)0.0340 (7)0.0325 (7)0.0048 (6)0.0045 (6)0.0033 (6)
C5A0.0338 (7)0.0323 (7)0.0386 (7)0.0003 (6)0.0033 (6)0.0037 (6)
C6A0.0350 (7)0.0371 (7)0.0332 (7)0.0041 (6)0.0061 (6)0.0033 (6)
C7A0.0293 (7)0.0297 (7)0.0376 (7)0.0022 (5)0.0018 (5)0.0035 (5)
C8A0.0332 (7)0.0314 (7)0.0426 (8)0.0022 (6)0.0020 (6)0.0001 (6)
C9A0.0358 (8)0.0372 (8)0.0622 (10)0.0055 (6)0.0031 (7)0.0023 (7)
C10A0.0333 (8)0.0449 (9)0.0703 (11)0.0069 (7)0.0116 (8)0.0057 (8)
C11A0.0360 (8)0.0426 (8)0.0521 (9)0.0002 (6)0.0134 (7)0.0058 (7)
C12A0.0297 (7)0.0311 (7)0.0390 (7)0.0031 (5)0.0048 (6)0.0037 (6)
C13A0.0320 (7)0.0332 (7)0.0349 (7)0.0032 (5)0.0068 (6)0.0017 (6)
N1A0.0388 (7)0.0317 (6)0.0446 (7)0.0048 (5)0.0010 (5)0.0076 (5)
N2A0.0342 (6)0.0374 (6)0.0331 (6)0.0069 (5)0.0069 (5)0.0045 (5)
N3A0.0514 (8)0.0494 (8)0.0407 (7)0.0074 (7)0.0010 (6)0.0076 (6)
O1A0.0480 (7)0.0506 (7)0.0720 (8)0.0189 (6)0.0140 (6)0.0178 (6)
O2A0.0381 (6)0.0422 (6)0.0615 (7)0.0016 (5)0.0072 (5)0.0056 (5)
O3A0.0483 (6)0.0565 (7)0.0374 (6)0.0050 (5)0.0130 (5)0.0084 (5)
C1B0.0404 (8)0.0350 (8)0.0541 (9)0.0020 (6)0.0024 (7)0.0054 (7)
C2B0.0454 (9)0.0465 (9)0.0622 (11)0.0122 (7)0.0057 (8)0.0019 (8)
C3B0.0455 (9)0.0429 (9)0.0456 (9)0.0024 (7)0.0062 (7)0.0001 (7)
C4B0.0398 (8)0.0303 (7)0.0399 (8)0.0005 (6)0.0010 (6)0.0024 (6)
C5B0.0403 (8)0.0423 (8)0.0411 (8)0.0054 (7)0.0012 (6)0.0030 (6)
C6B0.0374 (8)0.0347 (7)0.0396 (8)0.0027 (6)0.0018 (6)0.0050 (6)
C7B0.0366 (7)0.0347 (7)0.0283 (7)0.0007 (6)0.0039 (5)0.0016 (5)
C8B0.0410 (8)0.0359 (7)0.0288 (7)0.0027 (6)0.0071 (6)0.0006 (6)
C9B0.0433 (9)0.0424 (8)0.0412 (8)0.0098 (7)0.0022 (7)0.0024 (6)
C10B0.0368 (8)0.0538 (10)0.0519 (10)0.0066 (7)0.0033 (7)0.0046 (8)
C11B0.0373 (8)0.0446 (9)0.0510 (9)0.0057 (7)0.0020 (7)0.0068 (7)
C12B0.0394 (8)0.0345 (7)0.0330 (7)0.0006 (6)0.0036 (6)0.0047 (6)
C13B0.0416 (8)0.0330 (7)0.0355 (7)0.0032 (6)0.0023 (6)0.0022 (6)
N1B0.0441 (8)0.0478 (8)0.0376 (7)0.0047 (6)0.0022 (6)0.0007 (6)
N2B0.0406 (7)0.0325 (6)0.0368 (6)0.0017 (5)0.0020 (5)0.0047 (5)
N3B0.0481 (8)0.0393 (8)0.0454 (8)0.0020 (6)0.0063 (6)0.0098 (6)
O1B0.0511 (7)0.0688 (8)0.0628 (8)0.0157 (6)0.0062 (6)0.0155 (6)
O2B0.0588 (8)0.0871 (10)0.0480 (7)0.0303 (7)0.0053 (6)0.0034 (6)
O3B0.0517 (7)0.0356 (6)0.0653 (8)0.0096 (5)0.0011 (6)0.0077 (5)
O1W0.0873 (11)0.0819 (11)0.0844 (12)0.0316 (9)0.0013 (9)0.0246 (9)
Geometric parameters (Å, º) top
C1A—O1A1.2152 (18)C1B—N1B1.369 (2)
C1A—N1A1.3743 (19)C1B—C2B1.489 (2)
C1A—C2A1.494 (2)C2B—C3B1.526 (2)
C2A—C3A1.516 (2)C2B—H2C0.9700
C2A—H2A0.9700C2B—H2D0.9700
C2A—H2B0.9700C3B—C4B1.517 (2)
C3A—C4A1.522 (2)C3B—H3C0.9700
C3A—H3A0.9700C3B—H3D0.9700
C3A—H3B0.9700C4B—N2B1.4416 (18)
C4A—N2A1.4470 (17)C4B—C5B1.516 (2)
C4A—C5A1.518 (2)C4B—H4B0.9800
C4A—H4A0.9800C5B—O2B1.2112 (19)
C5A—O2A1.2036 (18)C5B—N1B1.3748 (19)
C5A—N1A1.3830 (19)C6B—N2B1.4582 (18)
C6A—N2A1.4606 (18)C6B—C7B1.496 (2)
C6A—C7A1.4960 (19)C6B—H6C0.9700
C6A—H6A0.9700C6B—H6D0.9700
C6A—H6B0.9700C7B—C12B1.379 (2)
C7A—C12A1.380 (2)C7B—C8B1.396 (2)
C7A—C8A1.400 (2)C8B—N3B1.382 (2)
C8A—N3A1.372 (2)C8B—C9B1.394 (2)
C8A—C9A1.401 (2)C9B—C10B1.383 (2)
C9A—C10A1.382 (3)C9B—H9B0.9300
C9A—H9A0.9300C10B—C11B1.383 (2)
C10A—C11A1.386 (2)C10B—H10B0.9300
C10A—H10A0.9300C11B—C12B1.384 (2)
C11A—C12A1.389 (2)C11B—H11B0.9300
C11A—H11A0.9300C12B—C13B1.478 (2)
C12A—C13A1.472 (2)C13B—O3B1.2263 (18)
C13A—O3A1.2337 (17)C13B—N2B1.3560 (19)
C13A—N2A1.3599 (18)N1B—H4N0.88 (2)
N1A—H1N0.893 (19)N3B—H5N0.89 (2)
N3A—H2N0.90 (2)N3B—H6N0.90 (2)
N3A—H3N0.91 (2)O1W—H1W0.978 (10)
C1B—O1B1.2181 (19)O1W—H2W0.977 (10)
O1A—C1A—N1A120.37 (14)O1B—C1B—C2B122.83 (16)
O1A—C1A—C2A121.93 (14)N1B—C1B—C2B117.74 (13)
N1A—C1A—C2A117.70 (13)C1B—C2B—C3B113.84 (13)
C1A—C2A—C3A114.04 (12)C1B—C2B—H2C108.8
C1A—C2A—H2A108.7C3B—C2B—H2C108.8
C3A—C2A—H2A108.7C1B—C2B—H2D108.8
C1A—C2A—H2B108.7C3B—C2B—H2D108.8
C3A—C2A—H2B108.7H2C—C2B—H2D107.7
H2A—C2A—H2B107.6C4B—C3B—C2B108.49 (13)
C2A—C3A—C4A108.67 (12)C4B—C3B—H3C110.0
C2A—C3A—H3A110.0C2B—C3B—H3C110.0
C4A—C3A—H3A110.0C4B—C3B—H3D110.0
C2A—C3A—H3B110.0C2B—C3B—H3D110.0
C4A—C3A—H3B110.0H3C—C3B—H3D108.4
H3A—C3A—H3B108.3N2B—C4B—C5B110.64 (12)
N2A—C4A—C5A112.48 (11)N2B—C4B—C3B114.15 (13)
N2A—C4A—C3A114.46 (12)C5B—C4B—C3B109.78 (12)
C5A—C4A—C3A109.54 (11)N2B—C4B—H4B107.3
N2A—C4A—H4A106.6C5B—C4B—H4B107.3
C5A—C4A—H4A106.6C3B—C4B—H4B107.3
C3A—C4A—H4A106.6O2B—C5B—N1B120.88 (15)
O2A—C5A—N1A121.07 (14)O2B—C5B—C4B123.33 (14)
O2A—C5A—C4A124.43 (13)N1B—C5B—C4B115.79 (13)
N1A—C5A—C4A114.45 (12)N2B—C6B—C7B101.89 (11)
N2A—C6A—C7A101.97 (11)N2B—C6B—H6C111.4
N2A—C6A—H6A111.4C7B—C6B—H6C111.4
C7A—C6A—H6A111.4N2B—C6B—H6D111.4
N2A—C6A—H6B111.4C7B—C6B—H6D111.4
C7A—C6A—H6B111.4H6C—C6B—H6D109.3
H6A—C6A—H6B109.2C12B—C7B—C8B120.99 (13)
C12A—C7A—C8A121.30 (13)C12B—C7B—C6B109.96 (12)
C12A—C7A—C6A109.98 (12)C8B—C7B—C6B129.05 (13)
C8A—C7A—C6A128.72 (13)N3B—C8B—C9B121.48 (14)
N3A—C8A—C7A121.41 (14)N3B—C8B—C7B121.85 (14)
N3A—C8A—C9A122.71 (14)C9B—C8B—C7B116.63 (14)
C7A—C8A—C9A115.83 (14)C10B—C9B—C8B121.76 (14)
C10A—C9A—C8A122.24 (14)C10B—C9B—H9B119.1
C10A—C9A—H9A118.9C8B—C9B—H9B119.1
C8A—C9A—H9A118.9C9B—C10B—C11B121.37 (15)
C9A—C10A—C11A121.60 (15)C9B—C10B—H10B119.3
C9A—C10A—H10A119.2C11B—C10B—H10B119.3
C11A—C10A—H10A119.2C10B—C11B—C12B116.99 (15)
C10A—C11A—C12A116.42 (15)C10B—C11B—H11B121.5
C10A—C11A—H11A121.8C12B—C11B—H11B121.5
C12A—C11A—H11A121.8C7B—C12B—C11B122.25 (14)
C7A—C12A—C11A122.61 (14)C7B—C12B—C13B108.22 (12)
C7A—C12A—C13A108.25 (12)C11B—C12B—C13B129.51 (14)
C11A—C12A—C13A129.14 (14)O3B—C13B—N2B125.85 (14)
O3A—C13A—N2A125.12 (13)O3B—C13B—C12B127.71 (14)
O3A—C13A—C12A128.04 (13)N2B—C13B—C12B106.44 (12)
N2A—C13A—C12A106.80 (12)C1B—N1B—C5B126.48 (15)
C1A—N1A—C5A126.72 (13)C1B—N1B—H4N116.2 (13)
C1A—N1A—H1N116.6 (11)C5B—N1B—H4N117.3 (14)
C5A—N1A—H1N116.6 (11)C13B—N2B—C4B122.64 (12)
C13A—N2A—C4A121.99 (12)C13B—N2B—C6B113.40 (12)
C13A—N2A—C6A112.96 (11)C4B—N2B—C6B122.94 (12)
C4A—N2A—C6A124.82 (11)C8B—N3B—H5N117.7 (13)
C8A—N3A—H2N115.9 (13)C8B—N3B—H6N116.5 (13)
C8A—N3A—H3N118.0 (14)H5N—N3B—H6N115.5 (19)
H2N—N3A—H3N113.3 (18)H1W—O1W—H2W99 (3)
O1B—C1B—N1B119.44 (16)
O1A—C1A—C2A—C3A165.46 (15)O1B—C1B—C2B—C3B160.63 (16)
N1A—C1A—C2A—C3A14.1 (2)N1B—C1B—C2B—C3B19.0 (2)
C1A—C2A—C3A—C4A47.88 (17)C1B—C2B—C3B—C4B49.94 (19)
C2A—C3A—C4A—N2A171.35 (11)C2B—C3B—C4B—N2B175.80 (12)
C2A—C3A—C4A—C5A61.27 (15)C2B—C3B—C4B—C5B59.32 (16)
N2A—C4A—C5A—O2A12.3 (2)N2B—C4B—C5B—O2B14.4 (2)
C3A—C4A—C5A—O2A140.76 (15)C3B—C4B—C5B—O2B141.31 (17)
N2A—C4A—C5A—N1A169.99 (12)N2B—C4B—C5B—N1B166.26 (13)
C3A—C4A—C5A—N1A41.51 (16)C3B—C4B—C5B—N1B39.39 (18)
N2A—C6A—C7A—C12A0.70 (15)N2B—C6B—C7B—C12B0.39 (15)
N2A—C6A—C7A—C8A179.01 (14)N2B—C6B—C7B—C8B179.66 (14)
C12A—C7A—C8A—N3A176.82 (14)C12B—C7B—C8B—N3B178.93 (13)
C6A—C7A—C8A—N3A3.5 (2)C6B—C7B—C8B—N3B1.9 (2)
C12A—C7A—C8A—C9A0.5 (2)C12B—C7B—C8B—C9B1.2 (2)
C6A—C7A—C8A—C9A179.19 (14)C6B—C7B—C8B—C9B179.61 (14)
N3A—C8A—C9A—C10A176.64 (15)N3B—C8B—C9B—C10B178.38 (15)
C7A—C8A—C9A—C10A0.6 (2)C7B—C8B—C9B—C10B0.6 (2)
C8A—C9A—C10A—C11A0.1 (3)C8B—C9B—C10B—C11B0.5 (3)
C9A—C10A—C11A—C12A0.5 (2)C9B—C10B—C11B—C12B1.0 (2)
C8A—C7A—C12A—C11A0.2 (2)C8B—C7B—C12B—C11B0.7 (2)
C6A—C7A—C12A—C11A179.89 (13)C6B—C7B—C12B—C11B179.98 (14)
C8A—C7A—C12A—C13A179.92 (12)C8B—C7B—C12B—C13B178.01 (12)
C6A—C7A—C12A—C13A0.34 (15)C6B—C7B—C12B—C13B1.33 (16)
C10A—C11A—C12A—C7A0.7 (2)C10B—C11B—C12B—C7B0.4 (2)
C10A—C11A—C12A—C13A179.62 (14)C10B—C11B—C12B—C13B178.82 (15)
C7A—C12A—C13A—O3A176.48 (14)C7B—C12B—C13B—O3B177.26 (15)
C11A—C12A—C13A—O3A3.3 (2)C11B—C12B—C13B—O3B1.3 (3)
C7A—C12A—C13A—N2A1.34 (15)C7B—C12B—C13B—N2B2.66 (16)
C11A—C12A—C13A—N2A178.91 (14)C11B—C12B—C13B—N2B178.78 (15)
O1A—C1A—N1A—C5A172.44 (15)O1B—C1B—N1B—C5B176.92 (16)
C2A—C1A—N1A—C5A8.0 (2)C2B—C1B—N1B—C5B3.4 (2)
O2A—C5A—N1A—C1A175.59 (15)O2B—C5B—N1B—C1B173.28 (16)
C4A—C5A—N1A—C1A6.6 (2)C4B—C5B—N1B—C1B7.4 (2)
O3A—C13A—N2A—C4A1.3 (2)O3B—C13B—N2B—C4B8.1 (2)
C12A—C13A—N2A—C4A176.64 (12)C12B—C13B—N2B—C4B171.79 (12)
O3A—C13A—N2A—C6A176.03 (14)O3B—C13B—N2B—C6B176.88 (15)
C12A—C13A—N2A—C6A1.87 (16)C12B—C13B—N2B—C6B3.05 (16)
C5A—C4A—N2A—C13A121.97 (14)C5B—C4B—N2B—C13B87.42 (16)
C3A—C4A—N2A—C13A112.17 (15)C3B—C4B—N2B—C13B148.16 (14)
C5A—C4A—N2A—C6A63.90 (17)C5B—C4B—N2B—C6B80.25 (17)
C3A—C4A—N2A—C6A61.96 (17)C3B—C4B—N2B—C6B44.17 (19)
C7A—C6A—N2A—C13A1.62 (15)C7B—C6B—N2B—C13B2.20 (16)
C7A—C6A—N2A—C4A176.21 (12)C7B—C6B—N2B—C4B170.90 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3A—H2N···O1Ai0.90 (2)2.29 (2)3.1539 (18)160 (2)
N3A—H3N···O3Aii0.91 (2)2.18 (2)3.076 (2)168 (2)
N1A—H1N···O3B0.893 (19)2.00 (2)2.8921 (17)177 (2)
N3B—H5N···O3Aiii0.89 (2)2.22 (2)3.0808 (19)164 (2)
N3B—H6N···O1W0.90 (2)2.47 (2)3.199 (2)138 (2)
N1B—H4N···O1Biv0.88 (2)2.15 (2)3.016 (2)169 (2)
O1W—H1W···O2Bv0.98 (1)1.95 (1)2.918 (2)170 (3)
O1W—H2W···O1Bvi0.98 (1)2.41 (3)2.966 (2)116 (2)
C3A—H3A···N3Bvii0.972.613.491 (2)150
C4A—H4A···O1Wviii0.982.573.471 (2)154
C4B—H4B···O1A0.982.393.171 (2)136
C10B—H10B···O2Aix0.932.463.335 (2)156
Symmetry codes: (i) x+1, y+3/2, z+1/2; (ii) x, y+3/2, z+1/2; (iii) x, y1/2, z+3/2; (iv) x1, y+1, z+1; (v) x, y+1/2, z+1/2; (vi) x1, y1/2, z+3/2; (vii) x, y+1, z+2; (viii) x, y+1/2, z+3/2; (ix) x+1, y+1, z+2.

Experimental details

(I)(II)
Crystal data
Chemical formulaC13H13N3O3C13H13N3O3·0.5H2O
Mr259.26268.27
Crystal system, space groupTriclinic, P1Monoclinic, P21/c
Temperature (K)294294
a, b, c (Å)5.9983 (5), 8.9198 (8), 11.5785 (10)8.4425 (7), 22.2874 (19), 13.6627 (12)
α, β, γ (°)75.711 (1), 84.660 (1), 86.038 (1)90, 101.069 (1), 90
V3)597.04 (9)2523.0 (4)
Z28
Radiation typeMo KαMo Kα
µ (mm1)0.110.11
Crystal size (mm)0.19 × 0.15 × 0.120.18 × 0.11 × 0.07
Data collection
DiffractometerBruker SMART APEX CCD area-detector
diffractometer
Bruker SMART APEX CCD area-detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
5703, 2092, 1975 23782, 4430, 3972
Rint0.0160.022
(sin θ/λ)max1)0.5950.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.104, 1.05 0.036, 0.105, 1.02
No. of reflections20924430
No. of parameters185383
No. of restraints02
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.22, 0.200.39, 0.18

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O2i0.88 (2)2.02 (2)2.899 (2)179 (2)
N3—H2N···N3ii0.91 (4)2.62 (4)3.260 (4)128 (3)
N3—H3N···O1iii0.81 (3)2.50 (3)3.180 (2)142 (3)
C3—H3A···O2iv0.972.563.213 (2)125
C3—H3B···O3iv0.972.583.461 (2)152
C4—H4···O3v0.982.363.205 (2)144
Symmetry codes: (i) x+2, y+2, z+2; (ii) x+1, y+2, z+1; (iii) x, y, z1; (iv) x1, y, z; (v) x+2, y+1, z+2.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N3A—H2N···O1Ai0.90 (2)2.29 (2)3.1539 (18)160 (2)
N3A—H3N···O3Aii0.91 (2)2.18 (2)3.076 (2)168 (2)
N1A—H1N···O3B0.893 (19)2.00 (2)2.8921 (17)177 (2)
N3B—H5N···O3Aiii0.89 (2)2.22 (2)3.0808 (19)164 (2)
N3B—H6N···O1W0.90 (2)2.47 (2)3.199 (2)138 (2)
N1B—H4N···O1Biv0.88 (2)2.15 (2)3.016 (2)169 (2)
O1W—H1W···O2Bv0.978 (10)1.951 (12)2.918 (2)170 (3)
O1W—H2W···O1Bvi0.977 (10)2.41 (3)2.966 (2)116 (2)
C3A—H3A···N3Bvii0.972.613.491 (2)150
C4A—H4A···O1Wviii0.982.573.471 (2)154
C4B—H4B···O1A0.982.393.171 (2)136
C10B—H10B···O2Aix0.932.463.335 (2)156
Symmetry codes: (i) x+1, y+3/2, z+1/2; (ii) x, y+3/2, z+1/2; (iii) x, y1/2, z+3/2; (iv) x1, y+1, z+1; (v) x, y+1/2, z+1/2; (vi) x1, y1/2, z+3/2; (vii) x, y+1, z+2; (viii) x, y+1/2, z+3/2; (ix) x+1, y+1, z+2.
 

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