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The organic component of the title compound, C22H20N2O5·2H2O, exhibits approximate but noncrystallographic mirror symmetry. The mol­ecules of the organic component are linked by a combination of one O-H...O hydrogen bond and two N-H...O hydrogen bonds to form sheets containing R22(8), R22(16) and R66(40) rings. These sheets are linked into a continuous three-dimensional framework structure by cyclic centrosymmetric R42(8) water tetra­mers. Comparisons are made with some simpler analogues.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113020908/yf3044sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113020908/yf3044Isup2.hkl
Contains datablock I

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270113020908/yf3044Isup3.cml
Supplementary material

CCDC reference: 964777

Introduction top

3-Cyclo­alkanone-3-hy­droxy-2-oxindoles are of importance in medicinal chemistry due to their anti­convulsant properties (Raj et al., 2010). For example, some of these 3-cyclo­alkanone derivatives are antagonists for maximal electroshock seizures (anti-MES) and pentyl­ene­tetra­zol-induced convulsions (anti-PTZ) in mice (Popp & Donigan, 1979; Pajouhesh et al., 1983). Continuing with our current programme on the use of bis-aryl­idene derivatives for the synthesis of diverse heterocyclic frameworks with inter­esting biological properties (Insuasty et al., 2008, 2013a,b), 3,3'-(2-oxocyco­hexane-1,3-diyl)bis­(3-hy­droxy­indolin-2-one) dihydrate, (I) (I) (Fig. 1), has been obtained from the reaction of isatin with cyclo­hexanone. We report here the molecular and supra­molecular structure of (I), which we compare briefly with the structures of the simpler analogues (II)–(VII) (Becerra et al., 2010) (see Scheme).

Experimental top

Synthesis and crystallization top

The organic component of compound (I) was prepared following the general procedure reported previously (Kusanur et al., 2004; Becerra et al., 2010) using piperidine as the catalytic base [yield 75%, m.p. 530–532 K (decomposition)]. MS (EI) m/z: 392 (5) [M+], 245 (43), 227 (49), 147 (81), 119 (100), 98 (29), 92 (47), 28 (70). Analysis found: C 67.4, H 5.2, N 7.2%; C22HN2O5 requires: C 67.3, H 5.1, N 7.1%. Yellow crystals of the title dihydrate suitable for single-crystal X-ray diffraction were grown by slow evaporation from a solution in ethanol–di­methyl­formamide (5:1 v/v) at ambient temperature and in air.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. It was apparent from an early stage of the refinement that the occupancy of the O atom of one of the water molecules, O1W, was less than unity. Refinement of this occupancy gave a value of 0.945 (6), with a peak in the difference map of 0.75 e Å-3 at a distance of 1.29 Å from O1W. When this peak was assigned to another partially occupied O atom, denoted O1WA, refinement of the occupancies of O1W and O1WA, subject to the constraint of having the same isotropic displacement parameter, gave values of 0.943 (5) and 0.069 (3), respectively, with a distance 1.32 (2) Å between the two sites. Similar refinement, with the two sites constrained to have the same anisotropic displacement parameters gave values 0.945 (5) and 0.071 (3), respectively, with a distance of 1.31 (2) Å between them. Thereafter these occupancies were constrained to sum to unity, giving final values of 0.933 (3) and 0.067 (3), respectively. An alternative model, in which the difference peak at ca 1.30 Å from O1W is assigned to an H atom, indicative of positional disorder of the H atoms bonded to O1W, could be discounted firstly on the grounds that the refined O—H distance, 1.32 (3) Å, is far too long, and secondly because the difference maps showed no sign of any maximum which could plausibly be assigned to the second disordered H atom required by this model. Three low angle reflections (100, 002 and 031), which appeared to be wholly or partially attenuated by the beam-stop, were omitted from the final refinements. All H atoms, other than those associated with O1WA were located in difference maps and then treated as riding atoms. H atoms bonded to C atoms were permitted to ride in geometrically idealized positions, with C—H = 0.95 (aromatic), 0.99 (CH2) or 1.00 Å (aliphatic) and with Uiso(H) = 1.2Ueq(C). H atoms bonded to N or O atoms were permitted to ride at the positions located in difference maps, with Uiso(H) = 1.2Ueq(N) or 1.5Ueq(O), giving the N—H and O—H distances shown in Table 2.

Results and discussion top

The organic component of (I) contains a large number of potential hydrogen-bond donors and acceptors and crystallization from ethanol–di­methyl­formamide gives the dihydrate. The water component could arise either from the solvent or by absorption from the air; in any event, the water molecules are an integral part of the hydrogen-bonded supra­molecular assembly. There are four stereogenic centres in the organic component of compound (I) at atoms C1, C3, C13 and C33 (Fig. 1). The reference molecule was selected as one having the R configuration at atom C1 and, on this basis, the reference molecule has the R configuration at atom C13 and the S configuration at atoms C3 and C33. The centrosymmetric space group confirms that compound (I) crystallizes as a racemic mixture, but the relatively high yield indicates a high degree of stereospecificity in the synthesis.

Consistent with the relative configurations at atoms C1 and C3, and at atoms C13 and C33, the organic component of compound (I) exhibits approximate but noncrystallographic mirror symmetry across a plane through atoms C2, O2 and C5, as indicated by the key torsion angles (Table 3), corresponding pairs of which have similar magnitudes but opposite signs. However, the different hydrogen-bonding arrangements involving the donor and acceptor behaviour of atoms O13 and O33 (Table 2), as discussed in more detail below, are sufficient to preclude the possibility of any additional crystallographic symmetry.

For the central carbocyclic ring, the puckering angle θ (Cremer & Pople, 1975) has the value 3.7 (2)°, calculated for the atom sequence C1–C2–C3–C4–C5–C6, with a ring-puckering amplitude of 0.586 (2) Å, indicative of an almost perfect chair conformation, for which the idealized value of θ is 0.0° (Boeyens, 1978). The two indolinone units occupy equatorial sites. The bond lengths and angles present no unusual features.

The presence of three independent molecular component provides considerable flexibility in the selection of the asymmetric unit, but it is possible to specify a compact asymmetric unit in which the two water molecular are linked to the organic component and to each other by a series of two- and three-centre hydrogen bonds (Fig. 1 and Table 2). One of the water molecules is disordered, with the O atom distributed over two sites, denoted O1W and O1WA, with refined occupancies of 0.933 (3) and 0.067 (3), respectively. Because of the very low occupancy of the O1WA site, the discussion of the supra­molecular assembly will omit any consideration of this site.

An extensive series of two-centre N—H···O and O—H···O hydrogen bonds, together with an asymmetric but almost planar three-centre O—H···(O2) inter­action (Table 2), links the molecular components into a continuous three-dimensional framework structure, whose formation is readily analysed in terms of simple sub-structures (Ferguson et al., 1998a,b; Gregson et al., 2000), which can be zero-, one- or two-dimensional. Overall, the organic components are linked into sheets and these sheets are linked by the water molecules, providing a layered structure containing alternating regions consisting respectively of organic molecules and water molecules.

Inversion-related pairs of the organic molecules are linked by paired O—H···O hydrogen bonds, in which one of the hy­droxy O atoms acts solely as a hydrogen-bond donor and the other solely as a hydrogen-bond acceptor (Table 2), to form a cyclic centrosymmetric dimer centred at (1/2, 1/2, 1/2) and characterized by an R22(16) (Bernstein et al., 1995) motif (Fig. 2). The different hydrogen-bonding behaviour of atoms O13 and O33 rules out the possibility of any crystallographic mirror symmetry. This dimer can be regarded as a finite zero-dimensional substructure and as a key building block within the sheet structure.

Two independent N—H···O hydrogen bonds (Table 2) link molecules related by the 21 screw axis along (1/2, y, 1/4) to form a C(10)C(10)[R22(8)] chain of ring (Fig. 2), which can be regarded as a one-dimensional substructure whose action is to link the reference dimer centred at (1/2, 1/2, 1/2) directly to the corresponding dimers centred at (1/2, 0, 0), (1/2, 1, 0), (1/2, 0, 1) and (1/2, 1, 1), so generating a two-dimensional substructure in the form of a sheet lying parallel to (100) and containing only molecules of the organic component, and which contains rings of R22(8), R22(16) and R66(40) types (Fig. 2).

Just one sheet of this type passes through each unit cell, and adjacent sheets are linked by a further finite zero-dimensional substructure in the form of cyclic centrosymmetric water tetra­mers (Fig. 3). The two water molecules at (x, y, z) and the two at (-x, -y+1, -z+1), together form a centrosymmetric R42(8) tetra­mer (Fig. 3 and Table 2) centred at (0, 1/2, 1/2), whose effect is to link two molecules of the organic component which lie in different (100) sheets. Hence, a series of R22(16) dimers formed by the organic component and centred at (n+1/2, 1/2, 1/2) alternates with R42(8) water tetra­mers centred at (n, 1/2, 1/2), where n represents an integer in each case, so linking all of the molecular components into a single framework structure containing alternating organic layers and water layers.

It is of inter­est briefly to compare the supra­molecular assembly in compound (I) with that in the simpler analogues, compounds (II)–(VII) (see Scheme), all of which crystallize in solvent-free form (Becerra et al., 2010). The molecules of compound (II) are linked by a combination of N—H···O and O—H···O hydrogen bonds to form a chain of edge-fused alternating R22(10) and R44(12) rings, so that the supra­molecular assembly is one-dimensional. Compounds (III)–(VIII) are isomorphous but not strictly isostructural; in all of them, a combination of N—H···O and O—H···O hydrogen bonds generates a chain of edge-fused R22(8) and R22(10) rings, and in all of them these chains of rings are linked into sheets by aromatic ππ stacking inter­actions, so that here the supra­molecular assembly is two-dimensional. The structures of compounds (II)–(VII) differ, however, in that C—H···O hydrogen bonds are present only in the structures of compounds (V)–(VII), reinforcing the chain formation, while C—H···π(arene) hydrogen bonds are present only in the structures of compounds (IV) and (V), where they reinforce the linking of the chains into sheets. Accordingly, changes in the identity of a single remote substituent, which plays no direct role in the supra­molecular assembly, is sufficient to induce detailed changes in the two-dimensional assembly of compounds (II)–(VII).

Related literature top

For related literature, see: Becerra et al. (2010); Bernstein et al. (1995); Boeyens (1978); Cremer & Pople (1975); Ferguson et al. (1998a, 1998b); Gregson et al. (2000); Insuasty et al. (2008, 2013a, 2013b); Kusanur et al. (2004); Pajouhesh et al. (1983); Popp & Donigan (1979); Raj et al. (2010).

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
Fig. 1. The independent molecular components in compound (I), showing the atom-labelling scheme and the hydrogen bonds within the selected asymmetric unit. Displacement ellipsoids are drawn at the 30% probability level. The atomic sites O1W and O1WA have refined occupancies 0.933 (3) and 0.067 (3), respectively.

Fig. 2. Part of the crystal structure of compound (I), showing a hydrogen-bonded sheet built from the organic component only and containing rings of R22(8), R22(16) and R66(40 types. Hydrogen bonds are indicated by dashed lines and, for the sake of clarity, the water molecules and H atoms bonded to C atoms have been omitted.

Fig. 3. Part of the crystal structure of compound (I), showing the formation of a centrosymmetric water tetramer which links two sheets of organic molecules. Hydrogen bonds are indicated by dashed lines and, for the sake of clarity, the minor component O1WA and H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*) are at the symmetry position (-x, -y+1, -z+1).
3,3'-[(1RS,3SR)-2-Oxocyclohexane-1,3-diyl]bis[(3RS,3'SR)-3-hydroxyindolin-2-one] dihydrate top
Crystal data top
C22H20N2O5·2H2OF(000) = 903.5
Mr = 428.30Dx = 1.394 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4663 reflections
a = 8.3637 (9) Åθ = 2.7–27.5°
b = 21.493 (3) ŵ = 0.11 mm1
c = 13.0968 (14) ÅT = 120 K
β = 119.941 (13)°Plate, yellow
V = 2040.1 (5) Å30.37 × 0.32 × 0.17 mm
Z = 4
Data collection top
Bruker–Nonius KappaCCD
diffractometer
4660 independent reflections
Radiation source: Bruker–Nonius FR591 rotating anode2963 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.066
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.4°
ϕ & ω scansh = 1010
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 2727
Tmin = 0.962, Tmax = 0.982l = 1616
29665 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)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.120H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0465P)2 + 1.0592P]
where P = (Fo2 + 2Fc2)/3
4660 reflections(Δ/σ)max = 0.001
284 parametersΔρmax = 0.27 e Å3
0 restraintsΔρmin = 0.26 e Å3
Crystal data top
C22H20N2O5·2H2OV = 2040.1 (5) Å3
Mr = 428.30Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.3637 (9) ŵ = 0.11 mm1
b = 21.493 (3) ÅT = 120 K
c = 13.0968 (14) Å0.37 × 0.32 × 0.17 mm
β = 119.941 (13)°
Data collection top
Bruker–Nonius KappaCCD
diffractometer
4660 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
2963 reflections with I > 2σ(I)
Tmin = 0.962, Tmax = 0.982Rint = 0.066
29665 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0490 restraints
wR(F2) = 0.120H-atom parameters constrained
S = 1.03Δρmax = 0.27 e Å3
4660 reflectionsΔρmin = 0.26 e Å3
284 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
C10.3417 (2)0.45841 (9)0.26258 (17)0.0185 (4)
H10.47920.46240.30750.022*
C20.2650 (2)0.51897 (9)0.28000 (16)0.0181 (4)
O20.15423 (18)0.52092 (6)0.31400 (12)0.0236 (3)
C30.3354 (3)0.57617 (9)0.24640 (17)0.0191 (4)
H30.47310.57510.29520.023*
C40.2870 (3)0.57006 (10)0.11620 (18)0.0239 (5)
H4A0.15150.57250.06450.029*
H4B0.34270.60520.09610.029*
C50.3563 (3)0.50893 (10)0.09325 (19)0.0261 (5)
H5A0.31490.50550.00820.031*
H5B0.49290.50860.13730.031*
C60.2848 (3)0.45333 (10)0.13093 (17)0.0229 (4)
H6A0.33530.41450.11770.028*
H6B0.14860.45160.08240.028*
N110.2799 (2)0.30064 (8)0.23199 (14)0.0206 (4)
H110.32210.26630.21680.025*
C120.3998 (3)0.34498 (9)0.29759 (17)0.0191 (4)
O120.56900 (17)0.34327 (6)0.33965 (12)0.0246 (3)
C130.2936 (3)0.40039 (9)0.31158 (17)0.0189 (4)
O130.36617 (18)0.40609 (7)0.43517 (11)0.0230 (3)
H130.29790.42270.45990.035*
C13A0.0962 (3)0.37645 (9)0.24388 (17)0.0199 (4)
C140.0693 (3)0.40100 (10)0.22609 (18)0.0236 (5)
H140.07300.44060.25690.028*
C150.2304 (3)0.36618 (11)0.16187 (18)0.0271 (5)
H150.34490.38260.14830.033*
C160.2255 (3)0.30803 (10)0.11763 (18)0.0263 (5)
H160.33680.28520.07410.032*
C170.0602 (3)0.28250 (10)0.13594 (17)0.0240 (5)
H170.05600.24260.10620.029*
C17A0.0973 (3)0.31780 (9)0.19931 (17)0.0205 (4)
N310.2610 (2)0.73167 (8)0.17168 (14)0.0210 (4)
H310.30100.76670.15750.025*
C320.3821 (3)0.69078 (9)0.25050 (17)0.0193 (4)
O320.55185 (18)0.69348 (7)0.30025 (12)0.0251 (3)
C330.2737 (2)0.63865 (9)0.27184 (16)0.0185 (4)
O330.31219 (17)0.64421 (6)0.39055 (11)0.0214 (3)
H330.42320.63180.43730.032*
C33A0.0756 (2)0.65958 (9)0.19125 (16)0.0190 (4)
C340.0908 (3)0.63601 (10)0.17301 (18)0.0245 (5)
H340.09500.59810.20900.029*
C350.2522 (3)0.66909 (10)0.10063 (18)0.0264 (5)
H350.36740.65350.08720.032*
C360.2465 (3)0.72436 (10)0.04818 (18)0.0261 (5)
H360.35810.74620.00050.031*
C370.0807 (3)0.74850 (10)0.06538 (17)0.0239 (5)
H370.07660.78630.02910.029*
C37A0.0780 (2)0.71529 (9)0.13738 (17)0.0196 (4)
O1W0.2134 (2)0.45984 (8)0.54722 (13)0.0290 (4)0.933 (3)
H1A0.09620.44030.52600.043*0.933 (3)
H1B0.18450.50370.53050.043*0.933 (3)
O1WA0.095 (3)0.4778 (11)0.5793 (19)0.0290 (4)0.067 (3)
O2W0.1265 (2)0.58793 (8)0.49903 (14)0.0388 (4)
H2A0.21030.61540.56000.058*
H2B0.15720.59470.44100.058*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0149 (9)0.0174 (10)0.0235 (10)0.0004 (8)0.0096 (8)0.0011 (8)
C20.0144 (9)0.0203 (11)0.0141 (9)0.0004 (8)0.0029 (7)0.0003 (8)
O20.0246 (8)0.0210 (8)0.0299 (8)0.0007 (6)0.0170 (6)0.0004 (6)
C30.0158 (9)0.0186 (11)0.0227 (10)0.0001 (8)0.0094 (8)0.0000 (8)
C40.0260 (11)0.0224 (11)0.0253 (11)0.0015 (9)0.0142 (9)0.0000 (9)
C50.0332 (12)0.0247 (12)0.0261 (11)0.0002 (9)0.0190 (9)0.0008 (9)
C60.0250 (11)0.0215 (11)0.0247 (11)0.0012 (8)0.0141 (9)0.0030 (9)
N110.0183 (8)0.0181 (9)0.0250 (9)0.0015 (7)0.0107 (7)0.0016 (7)
C120.0205 (11)0.0174 (11)0.0207 (10)0.0009 (8)0.0112 (8)0.0013 (8)
O120.0177 (7)0.0225 (8)0.0319 (8)0.0013 (6)0.0112 (6)0.0044 (6)
C130.0193 (10)0.0186 (11)0.0192 (10)0.0026 (8)0.0098 (8)0.0015 (8)
O130.0234 (7)0.0250 (8)0.0213 (7)0.0052 (6)0.0115 (6)0.0004 (6)
C13A0.0183 (10)0.0208 (11)0.0213 (10)0.0000 (8)0.0105 (8)0.0034 (8)
C140.0221 (11)0.0216 (12)0.0286 (11)0.0018 (8)0.0138 (9)0.0026 (9)
C150.0186 (10)0.0332 (13)0.0310 (12)0.0017 (9)0.0135 (9)0.0079 (10)
C160.0188 (10)0.0308 (13)0.0259 (11)0.0063 (9)0.0085 (9)0.0029 (9)
C170.0259 (11)0.0229 (12)0.0223 (10)0.0040 (9)0.0114 (9)0.0001 (9)
C17A0.0194 (10)0.0213 (11)0.0211 (10)0.0003 (8)0.0103 (8)0.0021 (8)
N310.0200 (9)0.0181 (9)0.0236 (9)0.0004 (7)0.0098 (7)0.0036 (7)
C320.0209 (11)0.0174 (11)0.0193 (10)0.0025 (8)0.0098 (8)0.0036 (8)
O320.0178 (8)0.0223 (8)0.0309 (8)0.0034 (6)0.0090 (6)0.0009 (6)
C330.0171 (10)0.0180 (10)0.0184 (10)0.0000 (8)0.0071 (8)0.0009 (8)
O330.0212 (7)0.0219 (8)0.0190 (7)0.0019 (6)0.0084 (6)0.0001 (6)
C33A0.0183 (10)0.0188 (11)0.0188 (10)0.0008 (8)0.0085 (8)0.0011 (8)
C340.0230 (11)0.0229 (12)0.0272 (11)0.0005 (8)0.0121 (9)0.0012 (9)
C350.0186 (11)0.0304 (13)0.0299 (11)0.0002 (9)0.0118 (9)0.0004 (10)
C360.0185 (10)0.0320 (13)0.0235 (11)0.0061 (9)0.0072 (9)0.0016 (9)
C370.0255 (11)0.0205 (11)0.0241 (11)0.0037 (8)0.0112 (9)0.0031 (9)
C37A0.0184 (10)0.0206 (11)0.0195 (10)0.0005 (8)0.0092 (8)0.0035 (8)
O1W0.0221 (8)0.0355 (10)0.0310 (9)0.0019 (7)0.0146 (7)0.0007 (7)
O1WA0.0221 (8)0.0355 (10)0.0310 (9)0.0019 (7)0.0146 (7)0.0007 (7)
O2W0.0396 (9)0.0456 (11)0.0382 (9)0.0153 (8)0.0246 (8)0.0126 (8)
Geometric parameters (Å, º) top
C1—C21.518 (3)C15—C161.387 (3)
C1—C131.545 (3)C15—H150.9500
C1—C61.547 (3)C16—C171.392 (3)
C1—H11.0000C16—H160.9500
C2—O21.212 (2)C17—C17A1.382 (3)
C2—C31.520 (3)C17—H170.9500
C3—C331.534 (3)N31—C321.349 (3)
C3—C41.549 (3)N31—C37A1.408 (2)
C3—H31.0000N31—H310.8801
C4—C51.525 (3)C32—O321.233 (2)
C4—H4A0.9900C32—C331.552 (3)
C4—H4B0.9900C33—O331.427 (2)
C5—C61.525 (3)C33—C33A1.521 (3)
C5—H5A0.9900O33—H330.8607
C5—H5B0.9900C33A—C341.386 (3)
C6—H6A0.9900C33A—C37A1.395 (3)
C6—H6B0.9900C34—C351.396 (3)
N11—C121.339 (2)C34—H340.9500
N11—C17A1.413 (2)C35—C361.385 (3)
N11—H110.8828C35—H350.9500
C12—O121.236 (2)C36—C371.390 (3)
C12—C131.550 (3)C36—H360.9500
C13—O131.422 (2)C37—C37A1.382 (3)
C13—C13A1.522 (3)C37—H370.9500
O13—H130.8620O1W—H1A0.9710
C13A—C141.388 (3)O1W—H1B0.9696
C13A—C17A1.391 (3)O2W—H2A0.9594
C14—C151.397 (3)O2W—H2B0.9265
C14—H140.9500
C2—C1—C13114.36 (15)C13A—C14—C15118.6 (2)
C2—C1—C6108.06 (16)C13A—C14—H14120.7
C13—C1—C6114.01 (16)C15—C14—H14120.7
C2—C1—H1106.6C16—C15—C14120.92 (19)
C13—C1—H1106.6C16—C15—H15119.5
C6—C1—H1106.6C14—C15—H15119.5
O2—C2—C1122.87 (17)C15—C16—C17121.13 (19)
O2—C2—C3123.78 (18)C15—C16—H16119.4
C1—C2—C3113.32 (16)C17—C16—H16119.4
C2—C3—C33115.08 (16)C17A—C17—C16117.0 (2)
C2—C3—C4108.90 (16)C17A—C17—H17121.5
C33—C3—C4112.46 (16)C16—C17—H17121.5
C2—C3—H3106.6C17—C17A—C13A123.05 (18)
C33—C3—H3106.6C17—C17A—N11126.93 (19)
C4—C3—H3106.6C13A—C17A—N11109.99 (17)
C5—C4—C3111.94 (17)C32—N31—C37A111.29 (16)
C5—C4—H4A109.2C32—N31—H31119.9
C3—C4—H4A109.2C37A—N31—H31127.9
C5—C4—H4B109.2O32—C32—N31126.93 (18)
C3—C4—H4B109.2O32—C32—C33124.12 (17)
H4A—C4—H4B107.9N31—C32—C33108.94 (15)
C6—C5—C4111.23 (17)O33—C33—C33A107.86 (15)
C6—C5—H5A109.4O33—C33—C3113.12 (15)
C4—C5—H5A109.4C33A—C33—C3118.44 (16)
C6—C5—H5B109.4O33—C33—C32107.54 (15)
C4—C5—H5B109.4C33A—C33—C32101.15 (15)
H5A—C5—H5B108.0C3—C33—C32107.60 (15)
C5—C6—C1110.69 (16)C33—O33—H33109.1
C5—C6—H6A109.5C34—C33A—C37A119.55 (18)
C1—C6—H6A109.5C34—C33A—C33131.59 (18)
C5—C6—H6B109.5C37A—C33A—C33108.63 (16)
C1—C6—H6B109.5C33A—C34—C35118.6 (2)
H6A—C6—H6B108.1C33A—C34—H34120.7
C12—N11—C17A111.04 (16)C35—C34—H34120.7
C12—N11—H11118.9C36—C35—C34120.87 (19)
C17A—N11—H11130.1C36—C35—H35119.6
O12—C12—N11126.11 (18)C34—C35—H35119.6
O12—C12—C13124.47 (17)C35—C36—C37121.21 (19)
N11—C12—C13109.41 (16)C35—C36—H36119.4
O13—C13—C13A114.50 (15)C37—C36—H36119.4
O13—C13—C1110.59 (15)C37A—C37—C36117.30 (19)
C13A—C13—C1117.56 (16)C37A—C37—H37121.3
O13—C13—C12104.86 (15)C36—C37—H37121.3
C13A—C13—C12100.98 (15)C37—C37A—C33A122.48 (18)
C1—C13—C12106.71 (15)C37—C37A—N31127.55 (19)
C13—O13—H13118.5C33A—C37A—N31109.92 (16)
C14—C13A—C17A119.27 (18)H1A—O1W—H1B104.7
C14—C13A—C13132.10 (19)H2A—O2W—H2B101.5
C17A—C13A—C13108.56 (16)
O2—C2—C1—C1310.0 (3)C14—C13A—C17A—C170.9 (3)
C2—C1—C13—C12174.19 (15)C13—C13A—C17A—C17178.22 (18)
C2—C1—C13—C13A73.4 (2)C14—C13A—C17A—N11177.23 (17)
C2—C1—C13—O1360.7 (2)C13—C13A—C17A—N110.1 (2)
C6—C1—C2—O2118.2 (2)C12—N11—C17A—C17177.20 (19)
C13—C1—C2—C3172.14 (15)C12—N11—C17A—C13A0.9 (2)
C6—C1—C2—C359.73 (19)C37A—N31—C32—O32177.21 (19)
C1—C2—C3—C33175.33 (16)C37A—N31—C32—C331.9 (2)
O2—C2—C3—C4120.5 (2)C4—C3—C33—O33178.17 (15)
C1—C2—C3—C457.4 (2)C4—C3—C33—C33A50.5 (2)
C2—C3—C4—C553.6 (2)O2—C2—C3—C336.8 (3)
C33—C3—C4—C5177.59 (16)C2—C3—C33—C32171.33 (15)
C3—C4—C5—C655.0 (2)C2—C3—C33—C33A74.9 (2)
C4—C5—C6—C157.2 (2)C2—C3—C33—O3352.7 (2)
C2—C1—C6—C558.2 (2)C4—C3—C33—C3263.19 (19)
C13—C1—C6—C5173.51 (16)O32—C32—C33—O3365.8 (2)
C17A—N11—C12—O12179.65 (18)N31—C32—C33—O33113.27 (17)
C17A—N11—C12—C131.4 (2)O32—C32—C33—C33A178.79 (18)
C6—C1—C13—O13174.28 (14)N31—C32—C33—C33A0.3 (2)
C6—C1—C13—C13A51.6 (2)O32—C32—C33—C356.3 (2)
C6—C1—C13—C1260.77 (19)N31—C32—C33—C3124.57 (17)
O12—C12—C13—O1360.4 (2)O33—C33—C33A—C3462.9 (3)
N11—C12—C13—O13120.58 (17)C3—C33—C33A—C3467.2 (3)
O12—C12—C13—C13A179.70 (18)C32—C33—C33A—C34175.6 (2)
N11—C12—C13—C13A1.3 (2)O33—C33—C33A—C37A111.39 (17)
O12—C12—C13—C156.9 (2)C3—C33—C33A—C37A118.54 (19)
N11—C12—C13—C1122.06 (17)C32—C33—C33A—C37A1.3 (2)
O13—C13—C13A—C1463.9 (3)C37A—C33A—C34—C350.0 (3)
C1—C13—C13A—C1468.4 (3)C33—C33A—C34—C35173.81 (19)
C12—C13—C13A—C14176.0 (2)C33A—C34—C35—C360.1 (3)
O13—C13—C13A—C17A112.86 (18)C34—C35—C36—C370.3 (3)
C1—C13—C13A—C17A114.78 (18)C35—C36—C37—C37A0.4 (3)
C12—C13—C13A—C17A0.8 (2)C36—C37—C37A—C33A0.3 (3)
C17A—C13A—C14—C151.1 (3)C36—C37—C37A—N31177.02 (19)
C13—C13A—C14—C15177.66 (19)C34—C33A—C37A—C370.1 (3)
C13A—C14—C15—C160.6 (3)C33—C33A—C37A—C37175.20 (18)
C14—C15—C16—C170.1 (3)C34—C33A—C37A—N31177.61 (17)
C15—C16—C17—C17A0.3 (3)C33—C33A—C37A—N312.5 (2)
C16—C17—C17A—C13A0.2 (3)C32—N31—C37A—C37174.76 (19)
C16—C17—C17A—N11177.65 (19)C32—N31—C37A—C33A2.8 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N11—H11···O32i0.881.962.838 (2)172
N31—H31···O12ii0.881.962.830 (2)168
O13—H13···O1W0.861.802.644 (2)165
O33—H33···O13iii0.861.902.736 (2)163
O1W—H1A···O2Wiv0.971.832.790 (3)171
O1W—H1B···O2W0.971.872.837 (2)179
O2W—H2A···O12iii0.961.872.787 (2)159
O2W—H2B···O20.932.292.926 (2)125
O2W—H2B···O330.932.032.845 (2)147
Symmetry codes: (i) x+1, y1/2, z+1/2; (ii) x+1, y+1/2, z+1/2; (iii) x+1, y+1, z+1; (iv) x, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC22H20N2O5·2H2O
Mr428.30
Crystal system, space groupMonoclinic, P21/c
Temperature (K)120
a, b, c (Å)8.3637 (9), 21.493 (3), 13.0968 (14)
β (°) 119.941 (13)
V3)2040.1 (5)
Z4
Radiation typeMo Kα
µ (mm1)0.11
Crystal size (mm)0.37 × 0.32 × 0.17
Data collection
DiffractometerBruker–Nonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.962, 0.982
No. of measured, independent and
observed [I > 2σ(I)] reflections
29665, 4660, 2963
Rint0.066
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.049, 0.120, 1.03
No. of reflections4660
No. of parameters284
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.27, 0.26

Computer programs: COLLECT (Hooft, 1998), DIRAX/LSQ (Duisenberg et al., 2000), EVALCCD (Duisenberg et al., 2003), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N11—H11···O32i0.881.962.838 (2)172
N31—H31···O12ii0.881.962.830 (2)168
O13—H13···O1W0.861.802.644 (2)165
O33—H33···O13iii0.861.902.736 (2)163
O1W—H1A···O2Wiv0.971.832.790 (3)171
O1W—H1B···O2W0.971.872.837 (2)179
O2W—H2A···O12iii0.961.872.787 (2)159
O2W—H2B···O20.932.292.926 (2)125
O2W—H2B···O330.932.032.845 (2)147
Symmetry codes: (i) x+1, y1/2, z+1/2; (ii) x+1, y+1/2, z+1/2; (iii) x+1, y+1, z+1; (iv) x, y+1, z+1.
Selected torsion angles (º) top
O2—C2—C1—C1310.0 (3)O2—C2—C3—C336.8 (3)
C2—C1—C13—C12174.19 (15)C2—C3—C33—C32171.33 (15)
C2—C1—C13—C13A73.4 (2)C2—C3—C33—C33A74.9 (2)
C2—C1—C13—O1360.7 (2)C2—C3—C33—O3352.7 (2)
 

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