Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113020908/yf3044sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113020908/yf3044Isup2.hkl | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270113020908/yf3044Isup3.cml |
CCDC reference: 964777
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).
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.
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.
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 π–π 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).
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).
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). |
C22H20N2O5·2H2O | F(000) = 903.5 |
Mr = 428.30 | Dx = 1.394 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4663 reflections |
a = 8.3637 (9) Å | θ = 2.7–27.5° |
b = 21.493 (3) Å | µ = 0.11 mm−1 |
c = 13.0968 (14) Å | T = 120 K |
β = 119.941 (13)° | Plate, yellow |
V = 2040.1 (5) Å3 | 0.37 × 0.32 × 0.17 mm |
Z = 4 |
Bruker–Nonius KappaCCD diffractometer | 4660 independent reflections |
Radiation source: Bruker–Nonius FR591 rotating anode | 2963 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.066 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.4° |
ϕ & ω scans | h = −10→10 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −27→27 |
Tmin = 0.962, Tmax = 0.982 | l = −16→16 |
29665 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.120 | H-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 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C22H20N2O5·2H2O | V = 2040.1 (5) Å3 |
Mr = 428.30 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.3637 (9) Å | µ = 0.11 mm−1 |
b = 21.493 (3) Å | T = 120 K |
c = 13.0968 (14) Å | 0.37 × 0.32 × 0.17 mm |
β = 119.941 (13)° |
Bruker–Nonius KappaCCD diffractometer | 4660 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2963 reflections with I > 2σ(I) |
Tmin = 0.962, Tmax = 0.982 | Rint = 0.066 |
29665 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.27 e Å−3 |
4660 reflections | Δρmin = −0.26 e Å−3 |
284 parameters |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 0.3417 (2) | 0.45841 (9) | 0.26258 (17) | 0.0185 (4) | |
H1 | 0.4792 | 0.4624 | 0.3075 | 0.022* | |
C2 | 0.2650 (2) | 0.51897 (9) | 0.28000 (16) | 0.0181 (4) | |
O2 | 0.15423 (18) | 0.52092 (6) | 0.31400 (12) | 0.0236 (3) | |
C3 | 0.3354 (3) | 0.57617 (9) | 0.24640 (17) | 0.0191 (4) | |
H3 | 0.4731 | 0.5751 | 0.2952 | 0.023* | |
C4 | 0.2870 (3) | 0.57006 (10) | 0.11620 (18) | 0.0239 (5) | |
H4A | 0.1515 | 0.5725 | 0.0645 | 0.029* | |
H4B | 0.3427 | 0.6052 | 0.0961 | 0.029* | |
C5 | 0.3563 (3) | 0.50893 (10) | 0.09325 (19) | 0.0261 (5) | |
H5A | 0.3149 | 0.5055 | 0.0082 | 0.031* | |
H5B | 0.4929 | 0.5086 | 0.1373 | 0.031* | |
C6 | 0.2848 (3) | 0.45333 (10) | 0.13093 (17) | 0.0229 (4) | |
H6A | 0.3353 | 0.4145 | 0.1177 | 0.028* | |
H6B | 0.1486 | 0.4516 | 0.0824 | 0.028* | |
N11 | 0.2799 (2) | 0.30064 (8) | 0.23199 (14) | 0.0206 (4) | |
H11 | 0.3221 | 0.2663 | 0.2168 | 0.025* | |
C12 | 0.3998 (3) | 0.34498 (9) | 0.29759 (17) | 0.0191 (4) | |
O12 | 0.56900 (17) | 0.34327 (6) | 0.33965 (12) | 0.0246 (3) | |
C13 | 0.2936 (3) | 0.40039 (9) | 0.31158 (17) | 0.0189 (4) | |
O13 | 0.36617 (18) | 0.40609 (7) | 0.43517 (11) | 0.0230 (3) | |
H13 | 0.2979 | 0.4227 | 0.4599 | 0.035* | |
C13A | 0.0962 (3) | 0.37645 (9) | 0.24388 (17) | 0.0199 (4) | |
C14 | −0.0693 (3) | 0.40100 (10) | 0.22609 (18) | 0.0236 (5) | |
H14 | −0.0730 | 0.4406 | 0.2569 | 0.028* | |
C15 | −0.2304 (3) | 0.36618 (11) | 0.16187 (18) | 0.0271 (5) | |
H15 | −0.3449 | 0.3826 | 0.1483 | 0.033* | |
C16 | −0.2255 (3) | 0.30803 (10) | 0.11763 (18) | 0.0263 (5) | |
H16 | −0.3368 | 0.2852 | 0.0741 | 0.032* | |
C17 | −0.0602 (3) | 0.28250 (10) | 0.13594 (17) | 0.0240 (5) | |
H17 | −0.0560 | 0.2426 | 0.1062 | 0.029* | |
C17A | 0.0973 (3) | 0.31780 (9) | 0.19931 (17) | 0.0205 (4) | |
N31 | 0.2610 (2) | 0.73167 (8) | 0.17168 (14) | 0.0210 (4) | |
H31 | 0.3010 | 0.7667 | 0.1575 | 0.025* | |
C32 | 0.3821 (3) | 0.69078 (9) | 0.25050 (17) | 0.0193 (4) | |
O32 | 0.55185 (18) | 0.69348 (7) | 0.30025 (12) | 0.0251 (3) | |
C33 | 0.2737 (2) | 0.63865 (9) | 0.27184 (16) | 0.0185 (4) | |
O33 | 0.31219 (17) | 0.64421 (6) | 0.39055 (11) | 0.0214 (3) | |
H33 | 0.4232 | 0.6318 | 0.4373 | 0.032* | |
C33A | 0.0756 (2) | 0.65958 (9) | 0.19125 (16) | 0.0190 (4) | |
C34 | −0.0908 (3) | 0.63601 (10) | 0.17301 (18) | 0.0245 (5) | |
H34 | −0.0950 | 0.5981 | 0.2090 | 0.029* | |
C35 | −0.2522 (3) | 0.66909 (10) | 0.10063 (18) | 0.0264 (5) | |
H35 | −0.3674 | 0.6535 | 0.0872 | 0.032* | |
C36 | −0.2465 (3) | 0.72436 (10) | 0.04818 (18) | 0.0261 (5) | |
H36 | −0.3581 | 0.7462 | −0.0005 | 0.031* | |
C37 | −0.0807 (3) | 0.74850 (10) | 0.06538 (17) | 0.0239 (5) | |
H37 | −0.0766 | 0.7863 | 0.0291 | 0.029* | |
C37A | 0.0780 (2) | 0.71529 (9) | 0.13738 (17) | 0.0196 (4) | |
O1W | 0.2134 (2) | 0.45984 (8) | 0.54722 (13) | 0.0290 (4) | 0.933 (3) |
H1A | 0.0962 | 0.4403 | 0.5260 | 0.043* | 0.933 (3) |
H1B | 0.1845 | 0.5037 | 0.5305 | 0.043* | 0.933 (3) |
O1WA | 0.095 (3) | 0.4778 (11) | 0.5793 (19) | 0.0290 (4) | 0.067 (3) |
O2W | 0.1265 (2) | 0.58793 (8) | 0.49903 (14) | 0.0388 (4) | |
H2A | 0.2103 | 0.6154 | 0.5600 | 0.058* | |
H2B | 0.1572 | 0.5947 | 0.4410 | 0.058* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0149 (9) | 0.0174 (10) | 0.0235 (10) | −0.0004 (8) | 0.0096 (8) | −0.0011 (8) |
C2 | 0.0144 (9) | 0.0203 (11) | 0.0141 (9) | −0.0004 (8) | 0.0029 (7) | 0.0003 (8) |
O2 | 0.0246 (8) | 0.0210 (8) | 0.0299 (8) | 0.0007 (6) | 0.0170 (6) | 0.0004 (6) |
C3 | 0.0158 (9) | 0.0186 (11) | 0.0227 (10) | −0.0001 (8) | 0.0094 (8) | 0.0000 (8) |
C4 | 0.0260 (11) | 0.0224 (11) | 0.0253 (11) | −0.0015 (9) | 0.0142 (9) | 0.0000 (9) |
C5 | 0.0332 (12) | 0.0247 (12) | 0.0261 (11) | 0.0002 (9) | 0.0190 (9) | −0.0008 (9) |
C6 | 0.0250 (11) | 0.0215 (11) | 0.0247 (11) | −0.0012 (8) | 0.0141 (9) | −0.0030 (9) |
N11 | 0.0183 (8) | 0.0181 (9) | 0.0250 (9) | 0.0015 (7) | 0.0107 (7) | −0.0016 (7) |
C12 | 0.0205 (11) | 0.0174 (11) | 0.0207 (10) | 0.0009 (8) | 0.0112 (8) | 0.0013 (8) |
O12 | 0.0177 (7) | 0.0225 (8) | 0.0319 (8) | 0.0013 (6) | 0.0112 (6) | −0.0044 (6) |
C13 | 0.0193 (10) | 0.0186 (11) | 0.0192 (10) | 0.0026 (8) | 0.0098 (8) | −0.0015 (8) |
O13 | 0.0234 (7) | 0.0250 (8) | 0.0213 (7) | 0.0052 (6) | 0.0115 (6) | 0.0004 (6) |
C13A | 0.0183 (10) | 0.0208 (11) | 0.0213 (10) | 0.0000 (8) | 0.0105 (8) | 0.0034 (8) |
C14 | 0.0221 (11) | 0.0216 (12) | 0.0286 (11) | 0.0018 (8) | 0.0138 (9) | 0.0026 (9) |
C15 | 0.0186 (10) | 0.0332 (13) | 0.0310 (12) | 0.0017 (9) | 0.0135 (9) | 0.0079 (10) |
C16 | 0.0188 (10) | 0.0308 (13) | 0.0259 (11) | −0.0063 (9) | 0.0085 (9) | 0.0029 (9) |
C17 | 0.0259 (11) | 0.0229 (12) | 0.0223 (10) | −0.0040 (9) | 0.0114 (9) | 0.0001 (9) |
C17A | 0.0194 (10) | 0.0213 (11) | 0.0211 (10) | 0.0003 (8) | 0.0103 (8) | 0.0021 (8) |
N31 | 0.0200 (9) | 0.0181 (9) | 0.0236 (9) | −0.0004 (7) | 0.0098 (7) | 0.0036 (7) |
C32 | 0.0209 (11) | 0.0174 (11) | 0.0193 (10) | −0.0025 (8) | 0.0098 (8) | −0.0036 (8) |
O32 | 0.0178 (8) | 0.0223 (8) | 0.0309 (8) | −0.0034 (6) | 0.0090 (6) | 0.0009 (6) |
C33 | 0.0171 (10) | 0.0180 (10) | 0.0184 (10) | 0.0000 (8) | 0.0071 (8) | 0.0009 (8) |
O33 | 0.0212 (7) | 0.0219 (8) | 0.0190 (7) | 0.0019 (6) | 0.0084 (6) | 0.0001 (6) |
C33A | 0.0183 (10) | 0.0188 (11) | 0.0188 (10) | 0.0008 (8) | 0.0085 (8) | −0.0011 (8) |
C34 | 0.0230 (11) | 0.0229 (12) | 0.0272 (11) | −0.0005 (8) | 0.0121 (9) | 0.0012 (9) |
C35 | 0.0186 (11) | 0.0304 (13) | 0.0299 (11) | −0.0002 (9) | 0.0118 (9) | −0.0004 (10) |
C36 | 0.0185 (10) | 0.0320 (13) | 0.0235 (11) | 0.0061 (9) | 0.0072 (9) | 0.0016 (9) |
C37 | 0.0255 (11) | 0.0205 (11) | 0.0241 (11) | 0.0037 (8) | 0.0112 (9) | 0.0031 (9) |
C37A | 0.0184 (10) | 0.0206 (11) | 0.0195 (10) | −0.0005 (8) | 0.0092 (8) | −0.0035 (8) |
O1W | 0.0221 (8) | 0.0355 (10) | 0.0310 (9) | 0.0019 (7) | 0.0146 (7) | −0.0007 (7) |
O1WA | 0.0221 (8) | 0.0355 (10) | 0.0310 (9) | 0.0019 (7) | 0.0146 (7) | −0.0007 (7) |
O2W | 0.0396 (9) | 0.0456 (11) | 0.0382 (9) | −0.0153 (8) | 0.0246 (8) | −0.0126 (8) |
C1—C2 | 1.518 (3) | C15—C16 | 1.387 (3) |
C1—C13 | 1.545 (3) | C15—H15 | 0.9500 |
C1—C6 | 1.547 (3) | C16—C17 | 1.392 (3) |
C1—H1 | 1.0000 | C16—H16 | 0.9500 |
C2—O2 | 1.212 (2) | C17—C17A | 1.382 (3) |
C2—C3 | 1.520 (3) | C17—H17 | 0.9500 |
C3—C33 | 1.534 (3) | N31—C32 | 1.349 (3) |
C3—C4 | 1.549 (3) | N31—C37A | 1.408 (2) |
C3—H3 | 1.0000 | N31—H31 | 0.8801 |
C4—C5 | 1.525 (3) | C32—O32 | 1.233 (2) |
C4—H4A | 0.9900 | C32—C33 | 1.552 (3) |
C4—H4B | 0.9900 | C33—O33 | 1.427 (2) |
C5—C6 | 1.525 (3) | C33—C33A | 1.521 (3) |
C5—H5A | 0.9900 | O33—H33 | 0.8607 |
C5—H5B | 0.9900 | C33A—C34 | 1.386 (3) |
C6—H6A | 0.9900 | C33A—C37A | 1.395 (3) |
C6—H6B | 0.9900 | C34—C35 | 1.396 (3) |
N11—C12 | 1.339 (2) | C34—H34 | 0.9500 |
N11—C17A | 1.413 (2) | C35—C36 | 1.385 (3) |
N11—H11 | 0.8828 | C35—H35 | 0.9500 |
C12—O12 | 1.236 (2) | C36—C37 | 1.390 (3) |
C12—C13 | 1.550 (3) | C36—H36 | 0.9500 |
C13—O13 | 1.422 (2) | C37—C37A | 1.382 (3) |
C13—C13A | 1.522 (3) | C37—H37 | 0.9500 |
O13—H13 | 0.8620 | O1W—H1A | 0.9710 |
C13A—C14 | 1.388 (3) | O1W—H1B | 0.9696 |
C13A—C17A | 1.391 (3) | O2W—H2A | 0.9594 |
C14—C15 | 1.397 (3) | O2W—H2B | 0.9265 |
C14—H14 | 0.9500 | ||
C2—C1—C13 | 114.36 (15) | C13A—C14—C15 | 118.6 (2) |
C2—C1—C6 | 108.06 (16) | C13A—C14—H14 | 120.7 |
C13—C1—C6 | 114.01 (16) | C15—C14—H14 | 120.7 |
C2—C1—H1 | 106.6 | C16—C15—C14 | 120.92 (19) |
C13—C1—H1 | 106.6 | C16—C15—H15 | 119.5 |
C6—C1—H1 | 106.6 | C14—C15—H15 | 119.5 |
O2—C2—C1 | 122.87 (17) | C15—C16—C17 | 121.13 (19) |
O2—C2—C3 | 123.78 (18) | C15—C16—H16 | 119.4 |
C1—C2—C3 | 113.32 (16) | C17—C16—H16 | 119.4 |
C2—C3—C33 | 115.08 (16) | C17A—C17—C16 | 117.0 (2) |
C2—C3—C4 | 108.90 (16) | C17A—C17—H17 | 121.5 |
C33—C3—C4 | 112.46 (16) | C16—C17—H17 | 121.5 |
C2—C3—H3 | 106.6 | C17—C17A—C13A | 123.05 (18) |
C33—C3—H3 | 106.6 | C17—C17A—N11 | 126.93 (19) |
C4—C3—H3 | 106.6 | C13A—C17A—N11 | 109.99 (17) |
C5—C4—C3 | 111.94 (17) | C32—N31—C37A | 111.29 (16) |
C5—C4—H4A | 109.2 | C32—N31—H31 | 119.9 |
C3—C4—H4A | 109.2 | C37A—N31—H31 | 127.9 |
C5—C4—H4B | 109.2 | O32—C32—N31 | 126.93 (18) |
C3—C4—H4B | 109.2 | O32—C32—C33 | 124.12 (17) |
H4A—C4—H4B | 107.9 | N31—C32—C33 | 108.94 (15) |
C6—C5—C4 | 111.23 (17) | O33—C33—C33A | 107.86 (15) |
C6—C5—H5A | 109.4 | O33—C33—C3 | 113.12 (15) |
C4—C5—H5A | 109.4 | C33A—C33—C3 | 118.44 (16) |
C6—C5—H5B | 109.4 | O33—C33—C32 | 107.54 (15) |
C4—C5—H5B | 109.4 | C33A—C33—C32 | 101.15 (15) |
H5A—C5—H5B | 108.0 | C3—C33—C32 | 107.60 (15) |
C5—C6—C1 | 110.69 (16) | C33—O33—H33 | 109.1 |
C5—C6—H6A | 109.5 | C34—C33A—C37A | 119.55 (18) |
C1—C6—H6A | 109.5 | C34—C33A—C33 | 131.59 (18) |
C5—C6—H6B | 109.5 | C37A—C33A—C33 | 108.63 (16) |
C1—C6—H6B | 109.5 | C33A—C34—C35 | 118.6 (2) |
H6A—C6—H6B | 108.1 | C33A—C34—H34 | 120.7 |
C12—N11—C17A | 111.04 (16) | C35—C34—H34 | 120.7 |
C12—N11—H11 | 118.9 | C36—C35—C34 | 120.87 (19) |
C17A—N11—H11 | 130.1 | C36—C35—H35 | 119.6 |
O12—C12—N11 | 126.11 (18) | C34—C35—H35 | 119.6 |
O12—C12—C13 | 124.47 (17) | C35—C36—C37 | 121.21 (19) |
N11—C12—C13 | 109.41 (16) | C35—C36—H36 | 119.4 |
O13—C13—C13A | 114.50 (15) | C37—C36—H36 | 119.4 |
O13—C13—C1 | 110.59 (15) | C37A—C37—C36 | 117.30 (19) |
C13A—C13—C1 | 117.56 (16) | C37A—C37—H37 | 121.3 |
O13—C13—C12 | 104.86 (15) | C36—C37—H37 | 121.3 |
C13A—C13—C12 | 100.98 (15) | C37—C37A—C33A | 122.48 (18) |
C1—C13—C12 | 106.71 (15) | C37—C37A—N31 | 127.55 (19) |
C13—O13—H13 | 118.5 | C33A—C37A—N31 | 109.92 (16) |
C14—C13A—C17A | 119.27 (18) | H1A—O1W—H1B | 104.7 |
C14—C13A—C13 | 132.10 (19) | H2A—O2W—H2B | 101.5 |
C17A—C13A—C13 | 108.56 (16) | ||
O2—C2—C1—C13 | −10.0 (3) | C14—C13A—C17A—C17 | 0.9 (3) |
C2—C1—C13—C12 | −174.19 (15) | C13—C13A—C17A—C17 | 178.22 (18) |
C2—C1—C13—C13A | 73.4 (2) | C14—C13A—C17A—N11 | −177.23 (17) |
C2—C1—C13—O13 | −60.7 (2) | C13—C13A—C17A—N11 | 0.1 (2) |
C6—C1—C2—O2 | 118.2 (2) | C12—N11—C17A—C17 | −177.20 (19) |
C13—C1—C2—C3 | 172.14 (15) | C12—N11—C17A—C13A | 0.9 (2) |
C6—C1—C2—C3 | −59.73 (19) | C37A—N31—C32—O32 | −177.21 (19) |
C1—C2—C3—C33 | −175.33 (16) | C37A—N31—C32—C33 | 1.9 (2) |
O2—C2—C3—C4 | −120.5 (2) | C4—C3—C33—O33 | 178.17 (15) |
C1—C2—C3—C4 | 57.4 (2) | C4—C3—C33—C33A | 50.5 (2) |
C2—C3—C4—C5 | −53.6 (2) | O2—C2—C3—C33 | 6.8 (3) |
C33—C3—C4—C5 | 177.59 (16) | C2—C3—C33—C32 | 171.33 (15) |
C3—C4—C5—C6 | 55.0 (2) | C2—C3—C33—C33A | −74.9 (2) |
C4—C5—C6—C1 | −57.2 (2) | C2—C3—C33—O33 | 52.7 (2) |
C2—C1—C6—C5 | 58.2 (2) | C4—C3—C33—C32 | −63.19 (19) |
C13—C1—C6—C5 | −173.51 (16) | O32—C32—C33—O33 | 65.8 (2) |
C17A—N11—C12—O12 | 179.65 (18) | N31—C32—C33—O33 | −113.27 (17) |
C17A—N11—C12—C13 | −1.4 (2) | O32—C32—C33—C33A | 178.79 (18) |
C6—C1—C13—O13 | 174.28 (14) | N31—C32—C33—C33A | −0.3 (2) |
C6—C1—C13—C13A | −51.6 (2) | O32—C32—C33—C3 | −56.3 (2) |
C6—C1—C13—C12 | 60.77 (19) | N31—C32—C33—C3 | 124.57 (17) |
O12—C12—C13—O13 | −60.4 (2) | O33—C33—C33A—C34 | −62.9 (3) |
N11—C12—C13—O13 | 120.58 (17) | C3—C33—C33A—C34 | 67.2 (3) |
O12—C12—C13—C13A | −179.70 (18) | C32—C33—C33A—C34 | −175.6 (2) |
N11—C12—C13—C13A | 1.3 (2) | O33—C33—C33A—C37A | 111.39 (17) |
O12—C12—C13—C1 | 56.9 (2) | C3—C33—C33A—C37A | −118.54 (19) |
N11—C12—C13—C1 | −122.06 (17) | C32—C33—C33A—C37A | −1.3 (2) |
O13—C13—C13A—C14 | 63.9 (3) | C37A—C33A—C34—C35 | 0.0 (3) |
C1—C13—C13A—C14 | −68.4 (3) | C33—C33A—C34—C35 | 173.81 (19) |
C12—C13—C13A—C14 | 176.0 (2) | C33A—C34—C35—C36 | −0.1 (3) |
O13—C13—C13A—C17A | −112.86 (18) | C34—C35—C36—C37 | 0.3 (3) |
C1—C13—C13A—C17A | 114.78 (18) | C35—C36—C37—C37A | −0.4 (3) |
C12—C13—C13A—C17A | −0.8 (2) | C36—C37—C37A—C33A | 0.3 (3) |
C17A—C13A—C14—C15 | −1.1 (3) | C36—C37—C37A—N31 | −177.02 (19) |
C13—C13A—C14—C15 | −177.66 (19) | C34—C33A—C37A—C37 | −0.1 (3) |
C13A—C14—C15—C16 | 0.6 (3) | C33—C33A—C37A—C37 | −175.20 (18) |
C14—C15—C16—C17 | 0.1 (3) | C34—C33A—C37A—N31 | 177.61 (17) |
C15—C16—C17—C17A | −0.3 (3) | C33—C33A—C37A—N31 | 2.5 (2) |
C16—C17—C17A—C13A | −0.2 (3) | C32—N31—C37A—C37 | 174.76 (19) |
C16—C17—C17A—N11 | 177.65 (19) | C32—N31—C37A—C33A | −2.8 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11···O32i | 0.88 | 1.96 | 2.838 (2) | 172 |
N31—H31···O12ii | 0.88 | 1.96 | 2.830 (2) | 168 |
O13—H13···O1W | 0.86 | 1.80 | 2.644 (2) | 165 |
O33—H33···O13iii | 0.86 | 1.90 | 2.736 (2) | 163 |
O1W—H1A···O2Wiv | 0.97 | 1.83 | 2.790 (3) | 171 |
O1W—H1B···O2W | 0.97 | 1.87 | 2.837 (2) | 179 |
O2W—H2A···O12iii | 0.96 | 1.87 | 2.787 (2) | 159 |
O2W—H2B···O2 | 0.93 | 2.29 | 2.926 (2) | 125 |
O2W—H2B···O33 | 0.93 | 2.03 | 2.845 (2) | 147 |
Symmetry codes: (i) −x+1, y−1/2, −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 formula | C22H20N2O5·2H2O |
Mr | 428.30 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 120 |
a, b, c (Å) | 8.3637 (9), 21.493 (3), 13.0968 (14) |
β (°) | 119.941 (13) |
V (Å3) | 2040.1 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.37 × 0.32 × 0.17 |
Data collection | |
Diffractometer | Bruker–Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.962, 0.982 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 29665, 4660, 2963 |
Rint | 0.066 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.120, 1.03 |
No. of reflections | 4660 |
No. of parameters | 284 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 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).
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11···O32i | 0.88 | 1.96 | 2.838 (2) | 172 |
N31—H31···O12ii | 0.88 | 1.96 | 2.830 (2) | 168 |
O13—H13···O1W | 0.86 | 1.80 | 2.644 (2) | 165 |
O33—H33···O13iii | 0.86 | 1.90 | 2.736 (2) | 163 |
O1W—H1A···O2Wiv | 0.97 | 1.83 | 2.790 (3) | 171 |
O1W—H1B···O2W | 0.97 | 1.87 | 2.837 (2) | 179 |
O2W—H2A···O12iii | 0.96 | 1.87 | 2.787 (2) | 159 |
O2W—H2B···O2 | 0.93 | 2.29 | 2.926 (2) | 125 |
O2W—H2B···O33 | 0.93 | 2.03 | 2.845 (2) | 147 |
Symmetry codes: (i) −x+1, y−1/2, −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. |
O2—C2—C1—C13 | −10.0 (3) | O2—C2—C3—C33 | 6.8 (3) |
C2—C1—C13—C12 | −174.19 (15) | C2—C3—C33—C32 | 171.33 (15) |
C2—C1—C13—C13A | 73.4 (2) | C2—C3—C33—C33A | −74.9 (2) |
C2—C1—C13—O13 | −60.7 (2) | C2—C3—C33—O33 | 52.7 (2) |