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In the title racemic hemihydrated solvatomorph of carvedilol (carv), C24H26N2O4·0.5H2O, the asymmetric unit contains two independent organic moieties and one water mol­ecule. Within this 2(carv)·H2O unit, the mol­ecular components are strongly linked by hydrogen bonds and the unit acts as the basic building block for the crystal structure. Inter­actions parallel to (10\overline{1}) generate hydrogen-bonded layers which are further linked by much weaker C—H...N/O inter­actions. The con­for­mations of the organic molecules, as well as the hydrogen-bonding inter­actions connecting them, are compared with other related structures in the literature.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270111019688/gd3393sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270111019688/gd3393Isup2.hkl
Contains datablock I

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270111019688/gd3393Isup3.cml
Supplementary material

CCDC reference: 838150

Comment top

Carvedilol is a drug indicated for use in the treatment of mild-to-moderate congestive heart failure, acting both as a β1/β2-blocker and as an α1-blocker. It counteracts the (sometimes undesirable) effect of natural norepinephrine, a drug/hormone produced in the human body which by binding to the β1- and β2-adrenergic receptors (Stafylas & Sarafidis, 2008) stimulates the nerves controlling the muscles of the heart, and by binding to the α1-adrenergic receptors on blood vessels causes them to constrict and thus raise blood pressure (Othman et al., 2007). Through a blocking action towards these receptors, carvedilol lowers blood pressure and reduces heart failure.

There are at present five reported structures containing some form of carvedilol (carv): two of them are different polymorphs of the carvedilol free base [(II) (Chen et al., 1998) and (III) (Yathirajan et al., 2007)], two others are phosphate salts of the protonated carvH+ cation [carvH+·H2PO4-·0.5H2O, (IV) (Chernyshev et al., 2009), and carvH+·H2PO4-·C3H8O, (V) (Chernyshev et al., 20105)], and the fifth structure is a copper complex with carvedilol acting as a mono-deprotonated ligand {[Cu(carv)Cl(MeOH)]2·4MeOH, (VI); Zoroddu et al., 2003}. We report here a hemihydrated form of the drug, namely 1-(9H-carbazol-4-yloxy)-3-{[2-(2-methoxyphenoxy)ethyl]amino}propan-2-ol hemihydrate, (I), where two independent carvedilol molecules (labelled as A and B) share a single water molecule, itself a key component in the crystal structure organization, as discussed below.

The compound crystallizes as a racemate in the centrosymmetric space group P21/n (Fig. 1). The two independent carvedilol molecules have internal distances and angles quite similar to each other and to those of the previously reported examples. Similarities include the presence in both molecules of an O atom (O1) disordered over two sites on the host C atom (C21), with one configuration clearly dominant (see Refinement section for details).

In spite of their metric similarities, the conformations of molecules A and B in (I) are quite different, even though both central chains are essentially planar and the lateral aromatic side groups are structurally similar. The differences arise at the ends of the central chain, where the carbazole system and the MeOC6H4– groups are attached; it is here that the torsion angles defining the three-dimensional molecular structure show significant differences (Table 2, entries 1–2). Fig. 2(a) presents a combined view of both molecules after a least-squares fit of their `skeletal spine' (atoms C11–C23); the way in which the side wings depart from each other is apparent.

But this behaviour is not exclusive to molecules A and B in (I); a very similar behaviour can be observed in the remaining noncoordinated carvedilol molecules/ions [(II)–(V)] mentioned above: all of them present a rather planar aliphatic central chain, as shown by the torsion angles involving the constituent atoms (Table 1, entries 3–5), differing by just a few degrees from a perfect antiperiplanar local conformation [with the sole exception of C11—C21—C31—N1 for compound (V)]. This can be seen in Fig 2b, where a similar fit as in Fig. 2a is shown, but performed on all six molecular units. Fig. 2a clearly shows the variety of conformations attainable through the combination of the rather low energy barrier to rotation in the aliphatic chain and the highly interactive character of both aromatic ends (the carbazole group, via its donor N92—H92 group, and the MeOC6H4– unit through its O1 acceptor). In the case of (I), this latter tendency is enhanced by the presence of a highly active water molecule, which is determinant for the final packing of the structure.

Table 2 presents numerical values for the most significant hydrogen bonds in the structure and Fig. 1 displays all those in which O1W takes part. The molecule acts as a double donor–double acceptor (Table 2, entries 1–2 and 3–4, respectively). The water molecule is attached to carvedilol molecule A through hydrogen bonds 1 and 2, giving rise to an R22(10) ring (Bernstein et al., 1995). The third hydrogen bond links independent carvedilol molecules A and B into a strongly bound 2(carv)·H2O unit. Finally, the remaining hydrogen bond accepted by O1W (Table 2, entry 4, and Fig. 1) links these three-component units into broad ribbons parallel to [101] (Fig. 3).

There are two further conventional hydrogen bonds in the structure of (I) (Table 2, entries 5–6), which link ribbons together along [010] and define broad planes paralell to (101). Strikingly, neither of the N1A—H1AN nor N92B—H92BN groups are involved in hydrogen-bonding interactions: interplanar linkage is achieved through much weaker C—H···N/O contacts and no significant ππ interactions could be detected in the structure. The resulting packing scheme is schematicaly depicted in Fig. 3, where some of these planes (in different shading) are seen down b, with their projected image running along [101].

As a final remark about which are the leading sites for hydrogen bonding in carvedilol, in unsolvated polymorphs (II) and (III) there are two direct contacts joining adjacent molecules with each other and giving rise to characteristic two-dimensional structures. These interactions, of the hydroxy–amine O—H···N and carbazole–methoxy N—H···O types, are quite similar in both unsolvated structures, in spite of circumstancial differences in the unit cell, the atomic conformation and the packing disposition, as shown in Yathirajan et al. (2007).

In the present hemihydrated form (I), there are instead four hydrogen bonds connecting adjacent A and B molecules, but this is a deceiving difference: a closer look shows that, in fact, the single hydration water molecule can be considered as only an intermediate step in a more complex set-up of the same type of interactions. The scheme below shows the way in which this is achieved, and how the same bonding scheme can be envisioned by just thinking of the interactions involving O1W—H1WA/B as `transparent'. Thus, the water molecule would not play any genuine interacting role but `propagating' instead the leading interactions, generated by the same participants as in (II) and (III). This is only one of the many roles that hydration water molecules can play in crystal structures; a very detailed analysis (for the particular case of inorganic/geological compounds, but readily extendable to any general case) can be found in Hawthorne (1992).

Related literature top

For related literature, see: Bernstein et al. (1995); Chen et al. (1998); Chernyshev et al. (2009, 2010); Hawthorne (1992); Othman et al. (2007); Stafylas & Sarafidis (2008); Yathirajan et al. (2007); Zoroddu et al. (2003).

Experimental top

The original material, kindly provided by Laboratorios Quesada Farmacéutica, was dissolved in chloroform and the solution was left to slowly concentrate at ambient temperature in air. After one week, well developed single crystals in the form of rhomboidal plates, suitable for X-ray diffraction, were obtained. Since no particular effort was made to have a water-free solvent nor to inhibit air/moisture from getting into the solution, the reasons for the presence of a solvation water molecule may be multiple. A thermogravimetric experiment in the temperature range 300–600 K showed a diffuse mass loss in the range 340–370 K (mass loss found = 2.26%; expected mass loss for 0.5H2O = 2.17%).

Refinement top

In both independent molecules, atom O1 attached to C21 appears split over two sites, but with different occupancies, viz. 0.873 (3):0.127 (3) in molecule A and 0.821 (3):0.179 (3) in molecule B. This disorder is thus configurational, with both moieties in the selected asymmetric unit having the S configuration for the major fraction. The split O atoms were restrained to have the same C—O distance and the same anisotropic displacement parameters (SADI and EADP instructions in SHELXL). All the H atoms (except those attached to O1A' and O1B', which consequently were not included in the model) were found in a difference Fourier map. Those attached to C atoms were placed at calculated positions (C—H = 0.93 Å and methyl C—H = 0.96 Å) and were allowed to ride. Those attached to O and N atoms were refined for a further few cycles with restrained O—H = N—H = 0.90 (1) Å distances, and left to ride afterwards. In all cases, displacement parameters were taken as Uiso(H) = kUeq(carrier), where k = 1.5 for the methyl groups and 1.2 for all other H atoms.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-labelling scheme and with ellipsoids drawn at the 30% probability level. Only the major component of disordered atom O1A/B is shown. Hydrogen bonds are shown as dashed lines. [Symmetry code: (i) -x + 1/2, y - 1/2, -z + 1/2.]
[Figure 2] Fig. 2. (a) The overlap of the two independent molecules (A and B) in (I), after a least-squares fit of their `scheletal spine' C11—C21(O1)—C31—N2—C13—C23. (b) The same as for (a) but performed with the remaining carvedilol structures in the literature. [See Comment for definitions of structures (II), (III), (IV) and (V)].
[Figure 3] Fig. 3. A packing diagram for (I), viewed down [010], showing in projection the broad (101) planes (seen as [101] ribbons, drawn in alternating dark and light shading).
1-(9H-Carbazol-4-yloxy)-3-{[2-(2-methoxyphenoxy)ethyl]amino}propan-2-ol hemihydrate top
Crystal data top
C24H26N2O4·0.5H2OF(000) = 1760
Mr = 415.48Dx = 1.268 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 7816 reflections
a = 13.550 (3) Åθ = 4.2–25.5°
b = 16.780 (3) ŵ = 0.09 mm1
c = 19.150 (4) ÅT = 291 K
β = 94.36 (3)°Plate, colourless
V = 4341.5 (15) Å30.28 × 0.18 × 0.08 mm
Z = 8
Data collection top
Oxford Diffraction Gemini CCD S Ultra
diffractometer
8928 independent reflections
Radiation source: fine-focus sealed tube5209 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.035
Thick–slice ω scansθmax = 26.5°, θmin = 3.6°
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
h = 1616
Tmin = 0.98, Tmax = 0.99k = 2120
34926 measured reflectionsl = 2421
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)] = 0.054Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.147H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0606P)2 + 1.0836P]
where P = (Fo2 + 2Fc2)/3
8928 reflections(Δ/σ)max < 0.001
558 parametersΔρmax = 0.44 e Å3
6 restraintsΔρmin = 0.39 e Å3
Crystal data top
C24H26N2O4·0.5H2OV = 4341.5 (15) Å3
Mr = 415.48Z = 8
Monoclinic, P21/nMo Kα radiation
a = 13.550 (3) ŵ = 0.09 mm1
b = 16.780 (3) ÅT = 291 K
c = 19.150 (4) Å0.28 × 0.18 × 0.08 mm
β = 94.36 (3)°
Data collection top
Oxford Diffraction Gemini CCD S Ultra
diffractometer
8928 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
5209 reflections with I > 2σ(I)
Tmin = 0.98, Tmax = 0.99Rint = 0.035
34926 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0546 restraints
wR(F2) = 0.147H-atom parameters constrained
S = 1.05Δρmax = 0.44 e Å3
8928 reflectionsΔρmin = 0.39 e Å3
558 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*/UeqOcc. (<1)
O1W0.28801 (17)0.28032 (13)0.48425 (10)0.0985 (7)
H1WA0.26440.32170.50780.118*
H1WB0.31140.24820.51930.118*
O1A0.24312 (14)0.54882 (11)0.47036 (10)0.0637 (6)0.870 (3)
H1AO0.30250.55490.45300.076*0.870 (3)
O1A'0.2355 (8)0.4141 (5)0.4078 (6)0.0637 (6)0.130 (3)
O2A0.15989 (13)0.52262 (11)0.31989 (8)0.0676 (5)
O3A0.29530 (11)0.28260 (9)0.64066 (8)0.0519 (4)
O4A0.39372 (12)0.17141 (10)0.58257 (9)0.0639 (5)
N1A0.21370 (13)0.41020 (11)0.55305 (10)0.0495 (5)
H1AN0.25260.45150.56710.059*
N92A0.23618 (15)0.67682 (13)0.13462 (12)0.0625 (6)
H92A0.24260.71590.10310.075*
C11A0.11541 (19)0.50437 (19)0.38320 (13)0.0675 (7)
H11A0.06850.46110.37470.081*
H11B0.07930.55060.39800.081*
C21A0.19187 (17)0.48069 (13)0.44078 (12)0.0528 (6)
H21A0.22100.43530.41870.063*0.870 (3)
H21C0.22620.52700.46090.063*0.130 (3)
C31A0.14132 (17)0.44198 (15)0.50011 (12)0.0536 (6)
H31A0.10020.48100.52140.064*
H31B0.09880.39920.48160.064*
C12A0.1941 (2)0.75231 (17)0.24043 (19)0.0772 (9)
H12A0.20250.80280.22180.093*
C22A0.1652 (2)0.7420 (2)0.3070 (2)0.0856 (10)
H22A0.15280.78690.33330.103*
C32A0.1538 (2)0.6672 (2)0.33682 (15)0.0736 (8)
H32A0.13590.66280.38260.088*
C42A0.16935 (17)0.59970 (15)0.29797 (13)0.0530 (6)
C4XA0.19817 (15)0.60798 (13)0.22990 (11)0.0435 (5)
C5XA0.21653 (14)0.55195 (13)0.17577 (11)0.0428 (5)
C52A0.21471 (15)0.46943 (14)0.17002 (13)0.0517 (6)
H52A0.20150.43800.20820.062*
C62A0.23286 (19)0.43474 (17)0.10684 (16)0.0663 (7)
H62A0.23020.37960.10220.080*
C72A0.2549 (2)0.4810 (2)0.05055 (15)0.0749 (8)
H72A0.26730.45610.00870.090*
C82A0.25906 (18)0.5619 (2)0.05430 (13)0.0676 (8)
H82A0.27460.59240.01610.081*
C8XA0.23923 (16)0.59760 (15)0.11726 (12)0.0519 (6)
C1XA0.21006 (17)0.68425 (15)0.20235 (14)0.0554 (6)
C13A0.16927 (17)0.37854 (14)0.61433 (12)0.0522 (6)
H13A0.12490.33520.59990.063*
H13B0.13030.42000.63440.063*
C23A0.24480 (17)0.34895 (14)0.66882 (12)0.0518 (6)
H23A0.29170.39100.68210.062*
H23B0.21300.33260.71020.062*
C14A0.37027 (16)0.24906 (13)0.68254 (12)0.0459 (5)
C24A0.42360 (17)0.18875 (14)0.65094 (13)0.0510 (6)
C34A0.50127 (19)0.15301 (16)0.68881 (15)0.0650 (7)
H34A0.53660.11290.66830.078*
C44A0.5276 (2)0.17556 (19)0.75651 (16)0.0751 (8)
H44A0.58070.15090.78150.090*
C54A0.4760 (2)0.23415 (18)0.78744 (14)0.0690 (7)
H54A0.49410.24930.83340.083*
C64A0.39714 (18)0.27089 (15)0.75053 (13)0.0559 (6)
H64A0.36200.31060.77180.067*
C74A0.4551 (2)0.11854 (18)0.54626 (16)0.0802 (9)
H74A0.42700.11100.49920.120*
H74B0.45950.06810.57000.120*
H74C0.52020.14110.54530.120*
O1B0.43774 (14)0.41066 (13)0.44197 (12)0.0729 (7)0.818 (3)
H1BO0.39570.37090.45040.087*0.818 (3)
O1B'0.5984 (5)0.4352 (4)0.4410 (6)0.0729 (7)0.182 (3)
O2B0.62003 (11)0.26366 (10)0.40459 (9)0.0598 (5)
O3B0.47403 (11)0.47989 (10)0.69084 (9)0.0578 (4)
O4B0.30484 (12)0.55210 (10)0.67066 (9)0.0595 (4)
N1B0.56603 (18)0.40881 (12)0.57276 (11)0.0701 (6)
H1BN0.52430.45060.56890.084*
N92B0.83405 (15)0.05758 (13)0.37494 (11)0.0592 (5)
H92B0.86300.01260.36120.071*
C11B0.52607 (17)0.30175 (15)0.39877 (14)0.0569 (6)
H11C0.47480.26460.41010.068*
H11D0.51090.32080.35130.068*
C21B0.53121 (15)0.37069 (14)0.44955 (13)0.0561 (6)
H21B0.57680.41430.44340.067*0.818 (3)
H21D0.46780.39780.44440.067*0.182 (3)
C31B0.55511 (19)0.34371 (15)0.52308 (13)0.0602 (7)
H31C0.50290.30860.53650.072*
H31D0.61610.31330.52530.072*
C12B0.66218 (19)0.03827 (16)0.31987 (13)0.0620 (7)
H12B0.67240.01260.30250.074*
C22B0.5727 (2)0.07544 (16)0.30890 (14)0.0654 (7)
H22B0.52170.04930.28290.078*
C32B0.55514 (18)0.15063 (16)0.33505 (14)0.0622 (7)
H32B0.49350.17440.32590.075*
C42B0.62921 (16)0.19049 (14)0.37482 (12)0.0490 (6)
C4XB0.72200 (15)0.15456 (14)0.38649 (11)0.0449 (5)
C5XB0.81393 (16)0.17907 (14)0.42352 (11)0.0457 (5)
C52B0.84559 (17)0.24554 (15)0.46309 (12)0.0514 (6)
H52B0.80150.28630.47170.062*
C62B0.94260 (18)0.24983 (17)0.48910 (13)0.0614 (7)
H62B0.96420.29400.51530.074*
C72B1.00929 (19)0.1892 (2)0.47701 (14)0.0694 (8)
H72B1.07500.19420.49420.083*
C82B0.97977 (19)0.12194 (18)0.44005 (14)0.0657 (7)
H82B1.02410.08090.43310.079*
C8XB0.88259 (17)0.11727 (15)0.41375 (12)0.0512 (6)
C1XB0.73731 (17)0.07931 (14)0.35798 (12)0.0503 (6)
C13B0.57266 (17)0.37980 (14)0.64444 (13)0.0545 (6)
H13C0.63350.34970.65280.065*
H13D0.51800.34360.65000.065*
C23B0.57064 (16)0.44389 (15)0.69836 (13)0.0554 (6)
H23C0.58300.42150.74490.066*
H23D0.62120.48340.69130.066*
C14B0.45288 (16)0.53384 (13)0.74099 (13)0.0490 (6)
C24B0.36116 (17)0.57241 (13)0.72988 (13)0.0500 (6)
C34B0.33437 (19)0.62667 (15)0.77908 (15)0.0628 (7)
H34B0.27410.65300.77220.075*
C44B0.3955 (2)0.64255 (16)0.83839 (16)0.0737 (8)
H44B0.37570.67890.87120.088*
C54B0.4851 (2)0.60496 (17)0.84908 (15)0.0686 (7)
H54B0.52620.61590.88900.082*
C64B0.51438 (17)0.55074 (15)0.80040 (14)0.0567 (6)
H64B0.57540.52550.80750.068*
C74B0.21597 (18)0.59679 (16)0.65450 (15)0.0687 (8)
H74D0.18290.57710.61190.103*
H74E0.23220.65200.64890.103*
H74F0.17320.59130.69200.103*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O1W0.1287 (18)0.1000 (17)0.0654 (13)0.0502 (14)0.0013 (12)0.0267 (11)
O1A0.0613 (12)0.0712 (14)0.0597 (12)0.0187 (10)0.0120 (9)0.0040 (10)
O1A'0.0613 (12)0.0712 (14)0.0597 (12)0.0187 (10)0.0120 (9)0.0040 (10)
O2A0.0837 (13)0.0746 (13)0.0470 (10)0.0113 (10)0.0202 (9)0.0092 (9)
O3A0.0552 (10)0.0488 (9)0.0519 (9)0.0090 (7)0.0044 (8)0.0041 (7)
O4A0.0588 (10)0.0612 (11)0.0708 (12)0.0129 (8)0.0016 (9)0.0198 (9)
N1A0.0497 (11)0.0492 (12)0.0501 (11)0.0006 (9)0.0068 (9)0.0015 (9)
N92A0.0622 (13)0.0602 (15)0.0651 (15)0.0086 (10)0.0048 (11)0.0189 (11)
C11A0.0578 (16)0.096 (2)0.0494 (15)0.0009 (14)0.0106 (12)0.0102 (14)
C21A0.0506 (14)0.0591 (15)0.0491 (14)0.0043 (11)0.0064 (11)0.0006 (11)
C31A0.0480 (14)0.0640 (16)0.0493 (14)0.0016 (11)0.0063 (11)0.0039 (12)
C12A0.0649 (18)0.0526 (18)0.112 (3)0.0026 (13)0.0065 (17)0.0087 (17)
C22A0.074 (2)0.070 (2)0.112 (3)0.0104 (16)0.0001 (19)0.039 (2)
C32A0.0644 (17)0.091 (2)0.0663 (18)0.0081 (15)0.0091 (14)0.0236 (17)
C42A0.0446 (14)0.0637 (17)0.0501 (15)0.0086 (11)0.0005 (11)0.0044 (12)
C4XA0.0334 (11)0.0504 (14)0.0457 (13)0.0031 (9)0.0029 (10)0.0010 (10)
C5XA0.0304 (11)0.0531 (14)0.0444 (13)0.0022 (9)0.0000 (9)0.0020 (10)
C52A0.0411 (13)0.0560 (16)0.0573 (15)0.0014 (10)0.0001 (11)0.0005 (12)
C62A0.0559 (16)0.0676 (18)0.074 (2)0.0062 (13)0.0025 (14)0.0177 (16)
C72A0.0644 (18)0.103 (3)0.0573 (18)0.0095 (16)0.0055 (14)0.0205 (17)
C82A0.0549 (16)0.102 (2)0.0463 (16)0.0027 (15)0.0099 (12)0.0036 (15)
C8XA0.0425 (13)0.0612 (16)0.0516 (15)0.0036 (11)0.0013 (11)0.0060 (12)
C1XA0.0421 (13)0.0508 (15)0.0716 (18)0.0001 (11)0.0061 (12)0.0021 (13)
C13A0.0545 (14)0.0514 (14)0.0525 (14)0.0069 (11)0.0155 (12)0.0040 (11)
C23A0.0596 (15)0.0488 (14)0.0483 (14)0.0073 (11)0.0122 (11)0.0012 (11)
C14A0.0440 (13)0.0408 (13)0.0538 (14)0.0036 (10)0.0106 (11)0.0066 (10)
C24A0.0475 (13)0.0444 (13)0.0619 (16)0.0043 (11)0.0093 (12)0.0012 (11)
C34A0.0553 (16)0.0598 (17)0.080 (2)0.0123 (12)0.0055 (14)0.0025 (14)
C44A0.0655 (18)0.088 (2)0.071 (2)0.0162 (15)0.0021 (15)0.0137 (16)
C54A0.0685 (18)0.087 (2)0.0515 (16)0.0080 (15)0.0030 (14)0.0082 (14)
C64A0.0618 (16)0.0587 (16)0.0485 (15)0.0016 (12)0.0124 (12)0.0022 (12)
C74A0.0761 (19)0.076 (2)0.088 (2)0.0175 (15)0.0012 (16)0.0276 (17)
O1B0.0560 (13)0.0698 (15)0.0941 (17)0.0124 (10)0.0143 (12)0.0021 (12)
O1B'0.0560 (13)0.0698 (15)0.0941 (17)0.0124 (10)0.0143 (12)0.0021 (12)
O2B0.0397 (9)0.0614 (11)0.0775 (12)0.0010 (7)0.0015 (8)0.0153 (9)
O3B0.0431 (9)0.0642 (11)0.0662 (11)0.0120 (7)0.0055 (8)0.0127 (9)
O4B0.0516 (10)0.0573 (11)0.0691 (11)0.0133 (8)0.0018 (8)0.0007 (8)
N1B0.1002 (18)0.0449 (13)0.0648 (14)0.0054 (11)0.0041 (12)0.0052 (11)
N92B0.0547 (13)0.0598 (13)0.0637 (13)0.0068 (10)0.0073 (10)0.0087 (11)
C11B0.0422 (13)0.0625 (16)0.0658 (16)0.0008 (11)0.0022 (12)0.0025 (13)
C21B0.0446 (14)0.0534 (15)0.0707 (17)0.0040 (11)0.0076 (12)0.0011 (13)
C31B0.0672 (16)0.0475 (15)0.0663 (17)0.0080 (12)0.0080 (13)0.0049 (12)
C12B0.0641 (17)0.0581 (16)0.0648 (17)0.0097 (13)0.0106 (13)0.0150 (13)
C22B0.0558 (16)0.0673 (18)0.0725 (18)0.0151 (13)0.0006 (13)0.0179 (14)
C32B0.0423 (14)0.0703 (18)0.0733 (18)0.0052 (12)0.0005 (12)0.0104 (14)
C42B0.0443 (13)0.0519 (14)0.0513 (14)0.0058 (11)0.0065 (11)0.0064 (11)
C4XB0.0413 (13)0.0530 (14)0.0409 (12)0.0068 (10)0.0061 (10)0.0027 (10)
C5XB0.0432 (13)0.0585 (15)0.0359 (12)0.0049 (11)0.0061 (10)0.0052 (10)
C52B0.0496 (14)0.0629 (16)0.0420 (13)0.0062 (11)0.0051 (11)0.0040 (11)
C62B0.0551 (16)0.0810 (19)0.0478 (14)0.0122 (14)0.0006 (12)0.0061 (13)
C72B0.0457 (15)0.104 (2)0.0575 (17)0.0020 (15)0.0038 (12)0.0004 (16)
C82B0.0501 (16)0.084 (2)0.0623 (17)0.0081 (13)0.0024 (13)0.0005 (15)
C8XB0.0494 (14)0.0625 (16)0.0423 (13)0.0015 (12)0.0077 (11)0.0033 (11)
C1XB0.0489 (14)0.0552 (15)0.0477 (14)0.0035 (11)0.0100 (11)0.0025 (11)
C13B0.0468 (13)0.0544 (15)0.0642 (16)0.0026 (11)0.0158 (12)0.0003 (12)
C23B0.0409 (13)0.0619 (16)0.0637 (16)0.0085 (11)0.0074 (11)0.0026 (12)
C14B0.0441 (13)0.0436 (13)0.0605 (15)0.0021 (10)0.0127 (11)0.0006 (11)
C24B0.0470 (13)0.0396 (13)0.0645 (16)0.0025 (10)0.0111 (12)0.0027 (11)
C34B0.0547 (15)0.0490 (15)0.085 (2)0.0086 (12)0.0092 (14)0.0062 (14)
C44B0.076 (2)0.0537 (17)0.092 (2)0.0030 (14)0.0118 (17)0.0221 (15)
C54B0.0625 (17)0.0661 (18)0.0768 (19)0.0103 (14)0.0021 (14)0.0163 (15)
C64B0.0408 (13)0.0542 (15)0.0755 (18)0.0037 (11)0.0078 (12)0.0059 (13)
C74B0.0537 (16)0.0650 (18)0.087 (2)0.0154 (12)0.0017 (14)0.0127 (14)
Geometric parameters (Å, º) top
O1W—H1WA0.9000C74A—H74C0.9600
O1W—H1WB0.8999O1B—C21B1.431 (2)
O1A—C21A1.432 (2)O1B—H1BO0.9001
O1A—H1AO0.9000O1B—H21D0.4606
O1A—H21C0.4619O1B'—C21B1.432 (2)
O1A'—C21A1.432 (2)O1B'—H21B0.4617
O1A'—H21A0.4625O2B—C42B1.363 (3)
O2A—C42A1.369 (3)O2B—C11B1.421 (3)
O2A—C11A1.428 (3)O3B—C14B1.366 (3)
O3A—C14A1.367 (3)O3B—C23B1.439 (3)
O3A—C23A1.433 (3)O4B—C24B1.361 (3)
O4A—C24A1.372 (3)O4B—C74B1.432 (3)
O4A—C74A1.432 (3)N1B—C31B1.449 (3)
N1A—C31A1.457 (3)N1B—C13B1.453 (3)
N1A—C13A1.459 (3)N1B—H1BN0.9000
N1A—H1AN0.8999N92B—C1XB1.375 (3)
N92A—C8XA1.372 (3)N92B—C8XB1.383 (3)
N92A—C1XA1.376 (3)N92B—H92B0.9001
N92A—H92A0.9000C11B—C21B1.510 (3)
C11A—C21A1.508 (3)C11B—H11C0.9700
C11A—H11A0.9700C11B—H11D0.9700
C11A—H11B0.9700C21B—C31B1.491 (3)
C21A—C31A1.517 (3)C21B—H21B0.9700
C21A—H21A0.9700C21B—H21D0.9700
C21A—H21C0.9701C31B—H31C0.9700
C31A—H31A0.9700C31B—H31D0.9700
C31A—H31B0.9700C12B—C22B1.365 (4)
C12A—C22A1.372 (5)C12B—C1XB1.389 (3)
C12A—C1XA1.381 (4)C12B—H12B0.9300
C12A—H12A0.9300C22B—C32B1.385 (4)
C22A—C32A1.392 (4)C22B—H22B0.9300
C22A—H22A0.9300C32B—C42B1.385 (3)
C32A—C42A1.380 (4)C32B—H32B0.9300
C32A—H32A0.9300C42B—C4XB1.397 (3)
C42A—C4XA1.396 (3)C4XB—C1XB1.397 (3)
C4XA—C1XA1.398 (3)C4XB—C5XB1.445 (3)
C4XA—C5XA1.435 (3)C5XB—C52B1.397 (3)
C5XA—C52A1.389 (3)C5XB—C8XB1.415 (3)
C5XA—C8XA1.411 (3)C52B—C62B1.372 (3)
C52A—C62A1.381 (4)C52B—H52B0.9300
C52A—H52A0.9300C62B—C72B1.392 (4)
C62A—C72A1.379 (4)C62B—H62B0.9300
C62A—H62A0.9300C72B—C82B1.375 (4)
C72A—C82A1.361 (4)C72B—H72B0.9300
C72A—H72A0.9300C82B—C8XB1.376 (3)
C82A—C8XA1.390 (4)C82B—H82B0.9300
C82A—H82A0.9300C13B—C23B1.493 (3)
C13A—C23A1.490 (3)C13B—H13C0.9700
C13A—H13A0.9700C13B—H13D0.9700
C13A—H13B0.9700C23B—H23C0.9700
C23A—H23A0.9700C23B—H23D0.9700
C23A—H23B0.9700C14B—C64B1.387 (3)
C14A—C64A1.375 (3)C14B—C24B1.403 (3)
C14A—C24A1.407 (3)C24B—C34B1.378 (3)
C24A—C34A1.370 (3)C34B—C44B1.380 (4)
C34A—C44A1.372 (4)C34B—H34B0.9300
C34A—H34A0.9300C44B—C54B1.370 (4)
C44A—C54A1.367 (4)C44B—H44B0.9300
C44A—H44A0.9300C54B—C64B1.382 (4)
C54A—C64A1.381 (4)C54B—H54B0.9300
C54A—H54A0.9300C64B—H64B0.9300
C64A—H64A0.9300C74B—H74D0.9600
C74A—H74A0.9600C74B—H74E0.9600
C74A—H74B0.9600C74B—H74F0.9600
H1WA—O1W—H1WB102.0C21B—O1B—H1BO101.6
C21A—O1A—H1AO111.4C21B—O1B—H21D0.2
C21A—O1A—H21C0.8H1BO—O1B—H21D101.7
H1AO—O1A—H21C112.2C21B—O1B'—H21B1.0
C21A—O1A'—H21A1.1C42B—O2B—C11B118.80 (17)
C42A—O2A—C11A121.2 (2)C14B—O3B—C23B116.47 (18)
C14A—O3A—C23A116.99 (17)C24B—O4B—C74B117.24 (19)
C24A—O4A—C74A117.03 (19)C31B—N1B—C13B111.3 (2)
C31A—N1A—C13A113.31 (17)C31B—N1B—H1BN120.1
C31A—N1A—H1AN105.9C13B—N1B—H1BN109.4
C13A—N1A—H1AN107.9C1XB—N92B—C8XB109.9 (2)
C8XA—N92A—C1XA109.3 (2)C1XB—N92B—H92B125.6
C8XA—N92A—H92A122.5C8XB—N92B—H92B124.4
C1XA—N92A—H92A127.7O2B—C11B—C21B107.27 (18)
O2A—C11A—C21A111.5 (2)O2B—C11B—H11C110.3
O2A—C11A—H11A109.3C21B—C11B—H11C110.3
C21A—C11A—H11A109.3O2B—C11B—H11D110.3
O2A—C11A—H11B109.3C21B—C11B—H11D110.3
C21A—C11A—H11B109.3H11C—C11B—H11D108.5
H11A—C11A—H11B108.0O1B—C21B—O1B'101.5 (4)
O1A—C21A—O1A'126.3 (5)O1B—C21B—C31B111.4 (2)
O1A—C21A—C11A111.4 (2)O1B'—C21B—C31B104.1 (5)
O1A'—C21A—C11A99.6 (6)O1B—C21B—C11B107.26 (19)
O1A—C21A—C31A106.18 (18)O1B'—C21B—C11B120.3 (5)
O1A'—C21A—C31A102.8 (5)C31B—C21B—C11B111.8 (2)
C11A—C21A—C31A109.66 (19)O1B—C21B—H21B101.6
O1A—C21A—H21A126.7O1B'—C21B—H21B0.5
O1A'—C21A—H21A0.5C31B—C21B—H21B104.5
C11A—C21A—H21A99.7C11B—C21B—H21B119.8
C31A—C21A—H21A102.3O1B—C21B—H21D0.1
O1A—C21A—H21C0.4O1B'—C21B—H21D101.5
O1A'—C21A—H21C126.7C31B—C21B—H21D111.5
C11A—C21A—H21C111.2C11B—C21B—H21D107.2
C31A—C21A—H21C106.0H21B—C21B—H21D101.6
H21A—C21A—H21C127.1N1B—C31B—C21B113.3 (2)
N1A—C31A—C21A111.07 (18)N1B—C31B—H31C108.9
N1A—C31A—H31A109.4C21B—C31B—H31C108.9
C21A—C31A—H31A109.4N1B—C31B—H31D108.9
N1A—C31A—H31B109.4C21B—C31B—H31D108.9
C21A—C31A—H31B109.4H31C—C31B—H31D107.7
H31A—C31A—H31B108.0C22B—C12B—C1XB117.4 (2)
C22A—C12A—C1XA116.9 (3)C22B—C12B—H12B121.3
C22A—C12A—H12A121.5C1XB—C12B—H12B121.3
C1XA—C12A—H12A121.5C12B—C22B—C32B122.4 (2)
C12A—C22A—C32A122.9 (3)C12B—C22B—H22B118.8
C12A—C22A—H22A118.5C32B—C22B—H22B118.8
C32A—C22A—H22A118.5C42B—C32B—C22B120.1 (2)
C42A—C32A—C22A119.5 (3)C42B—C32B—H32B119.9
C42A—C32A—H32A120.3C22B—C32B—H32B119.9
C22A—C32A—H32A120.3O2B—C42B—C32B125.4 (2)
O2A—C42A—C32A126.1 (2)O2B—C42B—C4XB115.56 (19)
O2A—C42A—C4XA114.8 (2)C32B—C42B—C4XB119.0 (2)
C32A—C42A—C4XA119.1 (3)C42B—C4XB—C1XB119.1 (2)
C42A—C4XA—C1XA119.5 (2)C42B—C4XB—C5XB133.4 (2)
C42A—C4XA—C5XA133.3 (2)C1XB—C4XB—C5XB107.51 (19)
C1XA—C4XA—C5XA107.2 (2)C52B—C5XB—C8XB118.6 (2)
C52A—C5XA—C8XA118.8 (2)C52B—C5XB—C4XB135.3 (2)
C52A—C5XA—C4XA135.0 (2)C8XB—C5XB—C4XB106.1 (2)
C8XA—C5XA—C4XA106.2 (2)C62B—C52B—C5XB119.0 (2)
C62A—C52A—C5XA119.1 (2)C62B—C52B—H52B120.5
C62A—C52A—H52A120.5C5XB—C52B—H52B120.5
C5XA—C52A—H52A120.5C52B—C62B—C72B121.2 (2)
C72A—C62A—C52A120.7 (3)C52B—C62B—H62B119.4
C72A—C62A—H62A119.6C72B—C62B—H62B119.4
C52A—C62A—H62A119.6C82B—C72B—C62B121.2 (2)
C82A—C72A—C62A122.1 (3)C82B—C72B—H72B119.4
C82A—C72A—H72A119.0C62B—C72B—H72B119.4
C62A—C72A—H72A119.0C72B—C82B—C8XB117.9 (3)
C72A—C82A—C8XA117.7 (3)C72B—C82B—H82B121.0
C72A—C82A—H82A121.1C8XB—C82B—H82B121.0
C8XA—C82A—H82A121.1C82B—C8XB—N92B129.8 (2)
N92A—C8XA—C82A129.7 (2)C82B—C8XB—C5XB122.0 (2)
N92A—C8XA—C5XA108.7 (2)N92B—C8XB—C5XB108.1 (2)
C82A—C8XA—C5XA121.6 (2)N92B—C1XB—C12B129.8 (2)
N92A—C1XA—C12A129.4 (3)N92B—C1XB—C4XB108.3 (2)
N92A—C1XA—C4XA108.5 (2)C12B—C1XB—C4XB121.9 (2)
C12A—C1XA—C4XA122.0 (3)N1B—C13B—C23B114.1 (2)
N1A—C13A—C23A112.40 (19)N1B—C13B—H13C108.7
N1A—C13A—H13A109.1C23B—C13B—H13C108.7
C23A—C13A—H13A109.1N1B—C13B—H13D108.7
N1A—C13A—H13B109.1C23B—C13B—H13D108.7
C23A—C13A—H13B109.1H13C—C13B—H13D107.6
H13A—C13A—H13B107.9O3B—C23B—C13B107.32 (19)
O3A—C23A—C13A108.51 (18)O3B—C23B—H23C110.3
O3A—C23A—H23A110.0C13B—C23B—H23C110.3
C13A—C23A—H23A110.0O3B—C23B—H23D110.3
O3A—C23A—H23B110.0C13B—C23B—H23D110.3
C13A—C23A—H23B110.0H23C—C23B—H23D108.5
H23A—C23A—H23B108.4O3B—C14B—C64B124.5 (2)
O3A—C14A—C64A125.3 (2)O3B—C14B—C24B115.5 (2)
O3A—C14A—C24A115.3 (2)C64B—C14B—C24B120.0 (2)
C64A—C14A—C24A119.4 (2)O4B—C24B—C34B125.1 (2)
C34A—C24A—O4A124.9 (2)O4B—C24B—C14B116.4 (2)
C34A—C24A—C14A119.1 (2)C34B—C24B—C14B118.5 (2)
O4A—C24A—C14A116.0 (2)C24B—C34B—C44B121.2 (2)
C24A—C34A—C44A120.9 (3)C24B—C34B—H34B119.4
C24A—C34A—H34A119.5C44B—C34B—H34B119.4
C44A—C34A—H34A119.5C54B—C44B—C34B120.2 (3)
C54A—C44A—C34A120.2 (3)C54B—C44B—H44B119.9
C54A—C44A—H44A119.9C34B—C44B—H44B119.9
C34A—C44A—H44A119.9C44B—C54B—C64B119.9 (3)
C44A—C54A—C64A120.0 (3)C44B—C54B—H54B120.0
C44A—C54A—H54A120.0C64B—C54B—H54B120.0
C64A—C54A—H54A120.0C54B—C64B—C14B120.1 (2)
C14A—C64A—C54A120.3 (2)C54B—C64B—H64B119.9
C14A—C64A—H64A119.8C14B—C64B—H64B119.9
C54A—C64A—H64A119.8O4B—C74B—H74D109.5
O4A—C74A—H74A109.5O4B—C74B—H74E109.5
O4A—C74A—H74B109.5H74D—C74B—H74E109.5
H74A—C74A—H74B109.5O4B—C74B—H74F109.5
O4A—C74A—H74C109.5H74D—C74B—H74F109.5
H74A—C74A—H74C109.5H74E—C74B—H74F109.5
H74B—C74A—H74C109.5
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···N1A0.901.882.775 (3)178
O1W—H1WB···O4A0.902.042.920 (3)165
O1B—H1BO···O1W0.902.243.131 (4)173
N92A—H92A···O1Wi0.902.012.862 (3)158
N1B—H1BN···O1Bii0.902.403.043 (3)129
O1A—H1AO···N1Bii0.901.982.863 (3)167
Symmetry codes: (i) x+1/2, y+1/2, z+1/2; (ii) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC24H26N2O4·0.5H2O
Mr415.48
Crystal system, space groupMonoclinic, P21/n
Temperature (K)291
a, b, c (Å)13.550 (3), 16.780 (3), 19.150 (4)
β (°) 94.36 (3)
V3)4341.5 (15)
Z8
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.28 × 0.18 × 0.08
Data collection
DiffractometerOxford Diffraction Gemini CCD S Ultra
diffractometer
Absorption correctionMulti-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
Tmin, Tmax0.98, 0.99
No. of measured, independent and
observed [I > 2σ(I)] reflections
34926, 8928, 5209
Rint0.035
(sin θ/λ)max1)0.628
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.054, 0.147, 1.05
No. of reflections8928
No. of parameters558
No. of restraints6
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.44, 0.39

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···N1A0.901.882.775 (3)177.5
O1W—H1WB···O4A0.902.042.920 (3)165.2
O1B—H1BO···O1W0.902.243.131 (4)172.6
N92A—H92A···O1Wi0.902.012.862 (3)157.9
N1B—H1BN···O1Bii0.902.403.043 (3)128.7
O1A—H1AO···N1Bii0.901.982.863 (3)166.9
Symmetry codes: (i) x+1/2, y+1/2, z+1/2; (ii) x+1, y+1, z+1.
Torsion Angle1A1B2345
O2-C11-C21-C31-165.6 (2)-59.5 (3)
N1-C13-C23-O3-64.4 (2)66.5 (3)
C11-C21-C31-N1173.5 (2)176.8 (2)175.0 (2)178.19 (15)168.5 (2)-143.9 (4)
C21-C31-N1-C13174.9 (2)170.4 (2)167.3 (2)178.21 (13)176.3 (2)-176.5 (9)
C31-N1-C13-C23-178.0 (2)-172.4 (2)177.8 (2)174.43 (17)179.3 (2)-178.4 (6)
 

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