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In two dibenzodiazepinones, viz. the tricyclic core structure, 5H-dibenzo[b,e]diazepin-11(10H)-one, C13H10N2O, and an acyl­ated derivative, 1-(11-hydroxy-5H-dibenzo[b,e]diazepin-5-yl)-2-{4-[3-(1H-imidazol-1-yl)propyl]piperidin-1-yl}ethanone ethanol monosolvate, C26H29N5O2·C2H5OH, dimeric association via hydrogen-bond bridging between the cyclic amide entities is evident, but there are considerable differences between the parent compound and the amidated derivative. Highly consistent with reported structures of related tricyclic lactams, two mol­ecules of the nonsubstituted compound are bridged through two N-H...O hydrogen bonds across a crystallographic centre of symmetry and the bond lengths of the cyclic amide entity correspond to the amino-oxo (lactam) tautomeric form. In contrast, the structure of the derivative shows two similar, but crystallographically unique, mol­ecules hydrogen bonded into a dimeric unit exhibiting an approximate (noncrystallographic) C2 axis. The bond lengths of the two derivative cyclic amide groups support their potential presence in the hy­droxy­imine (lactim) tautomeric forms, with the resulting possibility of inter­molecular tautomerism. Likely driving forces for the two extreme configurations are discussed.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112019622/wq3014sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270112019622/wq3014Isup2.hkl
Contains datablock I

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Structure factor file (CIF format) https://doi.org/10.1107/S0108270112019622/wq3014IIsup3.hkl
Contains datablock II

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Portable Document Format (PDF) file https://doi.org/10.1107/S0108270112019622/wq3014sup4.pdf
Supplementary material

CCDC references: 889386; 889387

Comment top

Crystal structures of molecules that contain the dibenzodiazepinone nucleus have not been reported to date, even though the synthesis and crystallization of the parent dibenzodiazepinone, 5H-dibenzo[b,e]diazepin-11(10H)-one, (I) (Fig. 1), has been known for decades (Clemo et al., 1924; Giani et al., 1985). Substitution at the 5-position (positional numbering based on systematic IUPAC nomenclature and used throughout the text, but different from crystallographic positional numbering) of (I) with acyl residues containing one or two aminergic basic entities was reported to be a promising strategy for the development of highly potent ligands for muscarinic receptors (Cohen et al., 1993; Kassiou et al., 1997). Aiming at the preparation of muscarinic receptor ligands with improved selectivity, as well as potential radioligands for muscarinic receptors, we synthesized dibenzodiazepinone derivatives with basic heterocycles at the terminal 5-position of the side chain of (I). This approach prompted us to synthesize the dibenzodiazepinone derivative 5-(2-{4-[3-(1H-imidazol-1-yl)propyl]piperidin-1-yl}ethanoyl)-5H-benzo[b,e]diazepin-11(10H)-one ethanol monosolvate, (II) (Fig. 2), which crystallizes from ethanol–diethyl ether as translucent needles. The previously described parent compound (I), a crucial intermediate for the preparation of (II), was crystallized from ethanol–ethyl acetate as a mixture of hexagonal and rhombic plates with a yellow–green appearance.

X-ray crystallographic analyses of the parent compound, (I) (hexagonal plates), and of its amide derivative, (II), reveal consistencies and differences in the molecular and intermolecular structures of the two dibenzodiazepinones. A major and obvious common feature is the hydrogen-bond bridging of two monomers through the dibenzodiazepinone lactam group (Figs. 3a and 3b). In a second point of similarity, the seven-membered diazepinone rings adopt a puckered conformation (Figs. 1, 2, 3c and 3d), such that the two aromatic rings are parallel, adopting a butterfly conformation; the puckering is more pronounced in lactam (II) [angles between the benzene rings: (I) 139.3°, and (II) 120.0 (molecule A) and 126.6 ° (molecule B).

Closer examination reveals the first point of difference. In the case of (I), the hydrogen-bonded pair exhibits a centre of symmetry, which implies a relative association between the curved dibenzodiazepinone ring systems as two cupped hands held side-by-side, with one cup upright and the other inverted (Fig. 3c). A completely different situation is found in the crystal structure of (II). Here, the association between the two butterfly-shaped tricyclic systems is such that the aromatic rings of both molecules are oriented in the same direction. It is noted that in this structure the N5-bound side chains are folded back over the convex surface of the two molecules (Fig. 3d). This latter type of dimeric structure normally assumes a C2 symmetry, with the axis extended perpendicular to the mean planes of the two tricyclic entities of the pair. In practice there is only an approximate twofold symmetry, as there are minor conformational differences between the two molecules in the dimeric unit of (II).

It should be noted at the outset that the crystallographic data for (II) were relatively weak and there is a level of disorder brought about in part by the presence of disordered solvent in the crystal. However, with this in mind, and within the limits of the data, an overlay of the two individual molecules A and B (Fig. 4) reveals that most differences occur in the orientation of the remote sections of the N5 amide side chain (see Supplementary materials). Compounding these differences is the observation of a degree of apparent disorder in the position of the N—C—O atoms within each of the H-bound partner lactam/lactim moieties. Modelling of this disorder leads to the conclusion that there is the equivalent of an approximately 0.75:0.25 ratio of contributors in which the H—N and C—O atom pairs are interchanged. This amounts to there being present an identical ratio of diastereoisomeric pairs of H-bound molecules in the unit cell. These diastereoisomeric molecules would equate to the E and Z rotameric molecules that are evident by 1H and 13C NMR spectroscopy in solution (see below), but within the crystallographic constraints in which the side chains remain fixed.

In order to determine the propensity of the symmetry involved in the overall dimeric association of similar tricyclic structures, a search of the Cambridge Structural Database (CSD, Version ????; Allen, 2002) for seven-membered lactams fused with two six-membered aromatic rings was carried out. The search gave seven hits, namely dimeric units of dibenzazepinone, (III), dibenzoxazepinone, (IV), dibenzothiazepinone, (V), and dipyridodiazepinones, (VIa)–(VId), all of which show the former crystallographic behaviour of (I), i.e. a centrosymmetric association of hydrogen-bonded molecules. The type of association found for structure (II) has not been reported so far. Geometric parameters for dimeric units of the related lactams (I)–(IV) and (VIa)–(VId) are given in Table 1.

In the wider crystal structure of the parent compound, (I), the N5 H atom serves as a hydrogen-bond donor and forms an additional hydrogen-bond contact to the lactam carbonyl O atom, over and above the contact of the O atom with the N10 H atom of its partner lactam (Fig. 5a). This can not take place in the derivative, (II), but leads, in (I), to both lone pairs of the carbonyl O atom being involved in hydrogen bonding. As a consequence, there is a hydrogen bond cross-coupling between hydrogen-bonded dimeric pairs of molecules in (I) that creates a second dimension parallel to (100). This second dimension is reinforced through an additional interaction (2.61 Å) between H10A and N2iii [symmetry code: (iii) x, -y+1/2, z+1/2] (Fig. 5a). Furthermore, ππ interactions [3.372 (3) Å] between aromatic atom C6 of one molecule and at atom C8 of its symmetry-related partner molecule at (-x+1, -y+1, -z+1) and atom C8 of the original molecule and atom C6 of the same partner, and H···π interactions (2.86 and 2.80 Å) between aromatic atom H7 from one molecule and C1/C13 of its symmetry-related partner at (-x+1, -y, -z+1) are identified in the crystal structure of (I) (cf. Fig. 5a).

In contrast with the situation in (I), the unit cell of (II) comprises two chemically equivalent but crystallographically non-identical hydrogen-bonded partner molecules. These partner pairs are in turn held together in part by H···π interactions through atom H10A from one molecule and C14A/C1A/C2A/C3A from a benzenoid aromatic ring of its equivalent molecule in an adjacent partner pair (Fig. 5b). Cocrystallized solvent ethanol is evident both in the 1H NMR spectrum and the X-ray crystal structure. Present in a 1:1 ratio, the ethanol molecule is in a hydrogen-bond donor contact with the unsubstituted N atoms [N5A and N5B, respectively) in each of the imidazole heterocycles in the pendant side chains (contacts H1Eiii···N5A and H1Fii···N5B in Figs. 3d and 5b; symmetry codes: (ii) x-1, y, z; (iii) x+1, y+1, z]. The ethanol molecule bonded to atom N5B is also in a hydrogen-bond acceptor contact with one of the aromatic H atoms (H2A) from the partner molecule of an adjacent molecular pair [O1F···H2Aiv; symmetry code: (iv) -x, -y+1, -z+1]. These contacts reinforce the H···π contact in holding the partner pairs together (Fig. 5b). In contrast, the second ethanol solvent molecule is slightly disordered, possibly due to a partial escape of the solvent. It is also associated as a hydrogen-bond donor with an imidazole N atom (H1E—N5A), but not as an acceptor.

In addition to the main hydrogen bond between the cyclic amide groups, there is a hydrogen-bond contact between the exocyclic amide carbonyl atom O2A of one molecule and atom H24D of the methylene group adjacent to the imidazole ring of its partner molecule, as well as H···π interactions between the π bond between atoms C7A and C12A of the original molecule and the same partner methylene H atom (H24C), and between atom C10A of the original molecule and imidazole atom H27B of its partner molecule, all evident within the asymmetric dimeric unit of (II) (Figs. 3d and 5b). As a further example of the non-equivalence of the two sub-units, atom H24A of the methylene group next to the imidazole ring of the original molecule interacts with exocyclic amide atom O2B of the second molecule, while imidazole atom H27A from the original molecule participates in an H···π interaction with atoms C9B and C10B of the adjacent molecule. Both sets of interactions occur across the non-identical molecules of the asymmetric pair and most likely stabilize the complementary back-folding of the N5-bound side chains (Fig. 3d).

In the two crystal structures, within the limits imposed by the quality of the data for (II), the cyclic amide (lactam) entities, which form the interface of the dibenzodiazepinone dimeric structure, show significant features in their C—N and CO bond lengths. The parent compound, (I), contains a relatively short C—N bond [1.330 (3) Å; shorter than for the comparable compounds (III)–(V) and (VIa)–(VId), but equal to (VIb)] and a relatively long carbonyl bond [1.265 (3) Å; longer than for (III)–(V) and (VIa)–(VId)]. These observations indicate the presence of some hydroxyimine character in the molecule but a preference for the amide (keto) tautomer (cf. Fig. 6). However, the two monomeric species in the structure of (II) has considerably shorter C—N bonds [1.298 (6) and 1.309 (7) Å] and longer lactam carbonyl bonds [1.311 (6) and 1.309 (6) Å], even than for (I). This provides strong support for primarily hydroxyimine character. Interestingly, the two C—N and CO bond lengths for the two partner molecules in (II) are the same, within experimental error. This is despite the fact that the two component molecules were refined freely, and similarity restraints (SADI in SHELXL97; Sheldrick, 2008) were applied only for the amide moieties of the major (3/4) and minor (1/4) diastereomers, where they occupy the same crystallographic coordinates.

A search of the CSD for bond lengths of doubly hydrogen-bonded amides revealed that of those amides (2091 hits), 89% had CO bonds in the range 1.22–1.26 Å (Fig. 7a), and 95% had C—N bonds in the range 1.32–1.40 Å. Amongst the outliers, only two cases (highlighted with shading in Fig. 7b) had C—N and CO bond lengths (<1.31 Å and >1.30 Å, respectively) that come close to those observed for lactam (II) (Antoniadis et al., 2005; Romero & Woerpel, 2006).

A referee has rightly questioned the wisdom of placing too much emphasis on these differences, given the poor data quality for (II). However, the untypical values indicated for the bond lengths of the cyclic amide entity in (II) suggest its occurrence as the hydroxyimine (enol) tautomer (cf. Fig. 6), and consequently infer an example of intermolecular tautomerism in the crystal structure. This possibility should be investigated further. Such an intermolecular exchange of H atoms in the crystal structure was recently described in the study of 1H,2H-indazolin-3-one dimers, where O was hydrogen-bonded to O and N to N (enol form to keto form) (Perez-Torralba et al., 2010). The source of such a preference for the hydroxyimine structure of this heterocyclic portion of the N5-acyl derivative, (II), remains unknown but it might be brought about by the unique additional intermolecular interactions observed between the acyl side-chain elements in the crystal structure. Resolution of this matter requires further structural studies on similar molecules but this fell outside the bounds of the current investigation.

Related literature top

For related literature, see: Allen (2002); Antoniadis et al. (2005); Clemo et al. (1924); Cohen et al. (1993); Giani et al. (1985); Kassiou et al. (1997); Perez-Torralba, Lopez, Perez-Medina, Claramunt, Pinilla, Torres, Alkorta & Elguero (2010); Romero & Woerpel (2006); Sheldrick (2008); Wei & Weigele (1984).

Experimental top

Compound (I) was prepared as described previously (Clemo et al., 1924; Giani et al., 1985). It was recrystallized from EtOH–EtOAc [Solvent ratio?] to yield yellow–green rhombic and hexagonal plates [m.p. 532–534 K; literature m.p. 529–530 K (Giani et al., 1985)].

For the preparation of (II), 5-(2-chloroacetyl)-5H-dibenzo[b,e][1,4]diazepin- 11(10H)-one (254 mg, 0.886 mmol) and 4-[3-(1H-imidazol-1-yl)propyl]piperidine (180 mg, 0.93 mmol) were dissolved together in anhydrous MeCN (2 ml). [5-(2-Chloroacetyl)-5H-dibenzo[b,e][1,4]diazepin-11(10H)-one was synthesized from (I) and 2-chloroacetyl chloride as described by Cohen et al. (1993). The preparation of 4-[3-(1H-imidazol-1-yl)propyl]piperidine was reported by Wei & Weigele (1984), but a different synthetic route was used. A description of the synthetic route for (II), general experimental conditions, experimental protocols and analytical data for all intermediates for the preparation of (II), as well as 1H and 13C NMR spectra of (II) and all intermediates, are provided as Supplementary materials. [Please supply]

Finely ground potassium carbonate (122 mg, 0.886 mmol) was added to the above mixture and the whole kept under stirring in a microwave reactor (Biotage Initiator 8) at 373 K (microwave power?, pressure ca 2 bar; 1 bar = 100 000 Pa) for 100 min. Solid material was removed by filtration, the filtrate evaporated to dryness and the residue subjected to column chromatography using mixtures of CH2Cl2, Et2O and MeOH as solvent. The major fraction (CH2Cl2–Et2O–MeOH 20:4:1 to 10:2:1) was evaporated to dryness under reduced pressure, then taken up in CH2Cl2 (0.5 ml) and pentane (0.8 ml). Removal of the solvent in vacuo afforded the product, 5-(2-{4-[3-(1H-imidazol-1-yl)propyl]piperidin-1-yl}ethanoyl)-5H-benzo[b,e]diazepin-11(10H)-one, as a pale-tan glass (yield 187 mg, 48%; m.p. 368–370 K). RF = 0.4 (CH2Cl2–MeOH 5:1). IR (Nujol): 1660, 1600 cm-1.

A portion (150 mg) of this material was dissolved in EtOH (0.8 ml), Et2O (1 ml) was added, and the solution was kept at 253 K to afford white rosettes (ca 100 mg), which were kept in vacuo at 353 K for 7 h. Separation of the mother liquor and storage at 253 K afforded the ethanol solvate of the same substance, (II), as translucent needles (10 mg; m.p. 371–373 K) that were suitable for X-ray crystallographic analysis (contained one equivalent of cocrystallized EtOH, as evident from NMR spectroscopic and X-ray crystallographic analyses). Analysis, calculated for C26H29N5O2.C2H6O: C 68.83, H 7.01, N 14.33%; found: C 68.78, H 7.13, N 14.18%.

Due to a slow rotation about the exocyclic amide group on the NMR time scale, two isomers (ratio 1:1) were evident in the NMR spectra of (II). 1H NMR (700 MHz, [D4]MeOH, δ, p.p.m.): 1.00–1.11 (m, 1H), 1.12–1.30 (m, 6.5H), 1.49 (d, 0.5H, J = 11.8 Hz), 1.56 (m, 1H), 1.64 (d, 0.5H, J = 12.2 Hz), 1.79 (m, 2H), 1.90–2.04 (m, 2H), 2.50 (d, 0.5H, J = 9.5 Hz), 2.65 (d, 0.5H, J = 10.1 Hz), 2.82 (d, 1H, J = 10.2 Hz), 2.85 (d, 1H, J = 10.2 Hz), 3.06 (m, 0.5H), 3.16 (m, 0.5H), 3.20–3.25 (m, 1H), 3.64 (q, 1.3H, J = 7.1 Hz), 4.01 (t, 2H, J = 7.0 Hz), 6.97 (t, 1H, J = ca 0.9 Hz), 7.13 (t, 1H, J = ca 1.1 Hz), 7.23–7.31 (m, 2H), 7.36 (t, 0.5H, J = 7.2 Hz), 7.42 (t, 0.5H, J = 7.4 Hz), 7.46–7.52 (m, 1.5H), 7.54 (t, 0.5H, J = 7.4 Hz), 7.58 (t, 1H, J = 7.7 Hz), 7.65 (s, 1H), 7.68 (m, 1H), 7.89 (d, 0.5H, J = 7.5 Hz), 7.92 (d, 0.5H, J = 7.4 Hz). 1H NMR [600 MHz, [D6]DMSO–D2O 15:1 (v/v), rosettes, δ, p.p.m.]: 0.64–0.79 (m, 1H), 0.92–1.10 (m, 4H), 1.24–1.48 (m, 2H), 1.62 (m, 2H), 1.73–1.86 (m, 2H), 2.11 (d, 0.5H, J = 10.0 Hz), 2.66 (d, 0.5H, J = 10.1 Hz), 2.57 (m, 1H), 2.86 (d, 0.5H, J = 14.3 Hz), 2.93 (d, 0.5H, J = 14.5 Hz), 3.11 (d, 0.5H, J = 14.5 Hz), 3.29 (d, 0.5H, J = 14.3 Hz), 3.88 (br s, 2H), 6.86 (s, 1H), 7.13 (s, 1H), 7.14–7.23 (m, 2H), 7.25–7.32 (m, 1H), 7.37–7.46 (m, 2H), 7.54–7.63 (m, 3H), 7.73–7.79 (m, 1H). 13C NMR [150 MHz, [D6]DMSO–D2O 15:1 (v/v), rosettes, δ, p.p.m.; provided that adjacent signals in the 13C NMR spectra could be unambiguously clarified (using 1H COSY and HSQC spectra) to arise from one carbon nucleus, these signals are depicted as a set of signals (e.g. 123.7/123.9 p.p.m.)]: 28.1, 31.3/31.67/31.74/31.9, 32.9, 34.4/34.5, 46.5, 52.8/53.0/53.36/53.41, 60.3/60.8, 119.6, 121.7/121.8, 124.9/125.2, 126.4, 127.5, 128.17, 128.24, 128.30, 128.37, 128.5/128.9, 129.2, 130.2, 130.7, 130.8, 132.9/133.2, 134.6, 134.9, 135.0, 135.8, 137.4, 142.6/142.9, 166.8, 169.0/169.4. MS (ESI, MeOH) m/z (%) 887 (8) [2M + H]+, 444 (100) [M + H]+. HRMS (ESI, MeOH) m/z, calculated for [C26H30N5O2]+: 444.2394; found: 444.2390. C26H29N5O2 (443.5).

Refinement top

For (I), the H atom on N1 [and that on N2?] was [were?] allowed to refine freely without using the stereochemical constraints available in the riding-model option in SHELX97 (Sheldrick, 2008). For (II), the O-bound H atom was located in a difference map and treated as riding, with O—H = 0.82 Å and with Uiso(H) = 1.5Ueq(O). For both compounds, C-bound H atoms were positioned geometrically and treated as riding, with C—H = 0.93–0.97 Å and Uiso(H) = 1.2Ueq(C). [Please check added text]

Crystals of (II), in the form of thin plates, diffracted weakly (37% of the reflections were observed), as reflected in the higher values of Rint (0.148), final weighted R factor (0.294) and R factor (0.098). The final difference Fourier contained two strong peaks (1.4 e Å-3) between hydrogen-bonded N/O pairs N1A···O1B and N1B···O1A, which as H atoms were not stable in the least-squares refinement. Therefore, H atoms with half-occupancy each were fixed on atoms O1A and O1B (as the C13—O lengths were > 1.30 A). The final difference Fourier still contained two strong peaks (1.4 Å-3) near the centres of the N···O pairs. These were interpreted as traces of O atoms arising from the diastereomeric disorder. This disorder implied that a pair of hydrogen-bonded diasteromers occupied the same location, keeping the positions of all atoms unchanged, and only affecting the positions of atoms N1A/C13A/O1A and N1B/C13B/O1B. The structure was refined with this disorder model, in which alternative positions of N1A/C13A and N1B/C13B overlap with C13A'/N1A' and C13B'/N1B', respectively. At the same time, new positions were generated for atoms O1A' and O1B', accounting for the electron density observed in the difference Fourier map. The full-matrix least-squares refinement thus modelled did not contain any significant residual electron density and the ratio of the two diastereomers converged to 0.75:0.25.

In (II), the crystal lattice contained two ethanol solvent molecules, of which one was found to be orientationally disordered over two positions, viz. C1E/C2E/O1E and C1E'/C2E'/O1E'. In this model, atoms C2E and C2E' and the H atoms of O1E and O1E'(H1E) shared common positions, respectively. SADI restraints were applied to keep the bond lengths in the two positions similar (s.u. = 0.01 Å). Restraints DELU (0.008) and SIMU (0.008) were applied to keep the atomic displacement parameters of atoms in both the positions similar and within reasonable limits.

Computing details top

For both compounds, data collection: APEX2 (Bruker, 2007); cell refinement: APEX2 (Bruker, 2007); data reduction: APEX2 (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of dibenzodiazepinone (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 40% probability level.
[Figure 2] Fig. 2. The molecular structure of dibenzodiazepinone (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 40% probability level.
[Figure 3] Fig. 3. (a) Perpendicular and (c) parallel views of the dimeric unit in (I) [symmetry code: (i) -x+1, -y, -z+1], and (b) perpendicular and (b) parallel views of the dimeric unit in (II) [symmetry codes: (ii) x-1, y, z; (iii) x+1, y+1, z]. Only the major contributing diastereomeric pair is shown for (II). Displacement ellipsoids are drawn at the 40% probability level and dotted lines indicate hydrogen bonds.
[Figure 4] Fig. 4. Overlay of the near identical components of the diastereomeric pair A (light; pale green in the electronic version of the paper) and B (dark; dark green) for (II), in accordance with Figs. 4(b), 4(d) and 7(b).
[Figure 5] Fig. 5. The crystal packing of molecules in the unit cells of (a) (I) [symmetry codes: (i) -x+1, -y, -z+1; (ii) -x+1, y+1/2, -z+1/2; (iii) x, -y+1/2, z+1/2; (iv) -x+1, -y+1, -z+1] and (b) (II) [symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x-1, y, z; (iii) x+1, y+1, z]. Significant intermolecular interactions are indicated (dotted lines).
[Figure 6] Fig. 6. Possible mesomeric and tautomeric structures of the dibenzodiazepinone amide group.
[Figure 7] Fig. 7. Cambridge Structural Database search for doubly bridged N—H···O-bonded amide dimers (1924 hits). Medial carbonyl bond length (a, a') = 1.235 Å.
(I) 5H-dibenzo[b,e]diazepin-11(10H)-one top
Crystal data top
C13H10N2OF(000) = 440
Mr = 210.23Dx = 1.393 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 872 reflections
a = 7.4767 (16) Åθ = 2.8–24.2°
b = 10.861 (2) ŵ = 0.09 mm1
c = 12.475 (2) ÅT = 147 K
β = 98.277 (6)°Hexagonal plate, green
V = 1002.5 (3) Å30.28 × 0.25 × 0.07 mm
Z = 4
Data collection top
Bruker APEXII CCD area-detector
diffractometer
1698 independent reflections
Radiation source: fine-focus sealed tube1161 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.055
ϕ scans, and ω scans with κ offsetsθmax = 25.0°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Bruker, 2007)
h = 88
Tmin = 0.975, Tmax = 0.994k = 1212
6162 measured reflectionsl = 814
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)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.120H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0518P)2 + 0.3703P]
where P = (Fo2 + 2Fc2)/3
1698 reflections(Δ/σ)max < 0.001
153 parametersΔρmax = 0.26 e Å3
0 restraintsΔρmin = 0.23 e Å3
Crystal data top
C13H10N2OV = 1002.5 (3) Å3
Mr = 210.23Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.4767 (16) ŵ = 0.09 mm1
b = 10.861 (2) ÅT = 147 K
c = 12.475 (2) Å0.28 × 0.25 × 0.07 mm
β = 98.277 (6)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer
1698 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2007)
1161 reflections with I > 2σ(I)
Tmin = 0.975, Tmax = 0.994Rint = 0.055
6162 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0480 restraints
wR(F2) = 0.120H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.26 e Å3
1698 reflectionsΔρmin = 0.23 e Å3
153 parameters
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.6631 (2)0.01813 (15)0.41768 (14)0.0357 (5)
N10.4645 (3)0.16498 (17)0.44435 (17)0.0286 (5)
H1N0.392 (3)0.106 (2)0.502 (2)0.040 (7)*
N20.4677 (3)0.35066 (19)0.27848 (17)0.0279 (5)
C10.9002 (3)0.1774 (2)0.3407 (2)0.0314 (6)
H10.95210.11280.38630.038*
C21.0033 (4)0.2348 (3)0.2735 (2)0.0365 (7)
H21.12580.21160.27350.044*
C30.9266 (4)0.3272 (2)0.2056 (2)0.0391 (7)
H30.99520.36520.15630.047*
C40.7517 (4)0.3644 (2)0.2090 (2)0.0339 (7)
H40.70180.42870.16250.041*
C50.6455 (3)0.3097 (2)0.27932 (19)0.0268 (6)
C60.3950 (3)0.3754 (2)0.37451 (19)0.0240 (6)
C70.3124 (3)0.4885 (2)0.3868 (2)0.0276 (6)
H70.31380.55010.33290.033*
C80.2288 (3)0.5122 (2)0.4760 (2)0.0309 (6)
H80.17150.58920.48300.037*
C90.2285 (3)0.4226 (2)0.5558 (2)0.0316 (6)
H90.17150.43850.61770.038*
C100.3109 (3)0.3113 (2)0.5446 (2)0.0299 (6)
H100.31080.25030.59920.036*
C110.3939 (3)0.2869 (2)0.45485 (19)0.0245 (6)
C120.6121 (3)0.1287 (2)0.4049 (2)0.0274 (6)
C130.7191 (3)0.2114 (2)0.34418 (19)0.0262 (6)
H2N0.439 (3)0.406 (3)0.226 (2)0.041 (8)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0494 (12)0.0189 (10)0.0408 (11)0.0023 (8)0.0130 (9)0.0015 (8)
N10.0380 (13)0.0173 (11)0.0308 (13)0.0033 (9)0.0056 (10)0.0025 (9)
N20.0374 (13)0.0250 (12)0.0209 (12)0.0011 (10)0.0032 (10)0.0051 (9)
C10.0401 (16)0.0215 (14)0.0312 (15)0.0002 (11)0.0001 (12)0.0082 (11)
C20.0318 (15)0.0372 (17)0.0407 (17)0.0062 (12)0.0061 (13)0.0107 (13)
C30.0474 (18)0.0337 (17)0.0388 (17)0.0109 (14)0.0146 (14)0.0040 (13)
C40.0444 (17)0.0248 (15)0.0339 (16)0.0036 (12)0.0108 (13)0.0001 (11)
C50.0338 (14)0.0222 (14)0.0236 (14)0.0037 (11)0.0014 (11)0.0063 (11)
C60.0278 (13)0.0214 (13)0.0218 (14)0.0055 (10)0.0003 (10)0.0003 (10)
C70.0304 (14)0.0207 (13)0.0300 (14)0.0039 (11)0.0006 (11)0.0038 (11)
C80.0284 (14)0.0249 (14)0.0385 (17)0.0003 (11)0.0020 (12)0.0031 (12)
C90.0310 (15)0.0369 (16)0.0277 (15)0.0041 (12)0.0064 (12)0.0030 (12)
C100.0340 (15)0.0262 (14)0.0296 (15)0.0055 (11)0.0051 (12)0.0046 (11)
C110.0277 (13)0.0193 (13)0.0262 (14)0.0059 (10)0.0023 (11)0.0010 (10)
C120.0356 (15)0.0208 (14)0.0244 (14)0.0038 (11)0.0002 (11)0.0034 (10)
C130.0357 (15)0.0175 (13)0.0248 (14)0.0040 (10)0.0024 (11)0.0052 (10)
Geometric parameters (Å, º) top
O1—C121.263 (3)C4—C51.397 (3)
N1—C121.331 (3)C4—H40.9500
N1—C111.439 (3)C5—C131.404 (3)
N1—H1N1.15 (3)C6—C111.389 (3)
N2—C51.400 (3)C6—C71.393 (3)
N2—C61.411 (3)C7—C81.377 (3)
N2—H2N0.89 (3)C7—H70.9500
C1—C21.368 (4)C8—C91.392 (4)
C1—C131.410 (3)C8—H80.9500
C1—H10.9500C9—C101.374 (3)
C2—C31.383 (4)C9—H90.9500
C2—H20.9500C10—C111.382 (3)
C3—C41.375 (4)C10—H100.9500
C3—H30.9500C12—C131.482 (3)
C12—N1—C11129.9 (2)C7—C6—N2119.5 (2)
C12—N1—H1N123.6 (13)C8—C7—C6120.9 (2)
C11—N1—H1N104.1 (13)C8—C7—H7119.6
C5—N2—C6122.4 (2)C6—C7—H7119.6
C5—N2—H2N110.4 (17)C7—C8—C9119.7 (2)
C6—N2—H2N114.5 (18)C7—C8—H8120.1
C2—C1—C13121.9 (2)C9—C8—H8120.1
C2—C1—H1119.1C10—C9—C8119.7 (2)
C13—C1—H1119.1C10—C9—H9120.2
C1—C2—C3119.1 (3)C8—C9—H9120.2
C1—C2—H2120.5C9—C10—C11120.7 (2)
C3—C2—H2120.5C9—C10—H10119.6
C4—C3—C2120.4 (3)C11—C10—H10119.6
C4—C3—H3119.8C10—C11—C6120.2 (2)
C2—C3—H3119.8C10—C11—N1117.6 (2)
C3—C4—C5121.6 (3)C6—C11—N1122.0 (2)
C3—C4—H4119.2O1—C12—N1119.1 (2)
C5—C4—H4119.2O1—C12—C13117.7 (2)
C4—C5—N2119.0 (2)N1—C12—C13123.1 (2)
C4—C5—C13118.3 (2)C5—C13—C1118.6 (2)
N2—C5—C13122.6 (2)C5—C13—C12124.1 (2)
C11—C6—C7118.8 (2)C1—C13—C12116.7 (2)
C11—C6—N2121.6 (2)
C13—C1—C2—C31.3 (4)N2—C6—C11—C10175.7 (2)
C1—C2—C3—C42.8 (4)C7—C6—C11—N1175.4 (2)
C2—C3—C4—C50.9 (4)N2—C6—C11—N10.7 (3)
C3—C4—C5—N2179.4 (2)C12—N1—C11—C10144.3 (3)
C3—C4—C5—C132.6 (4)C12—N1—C11—C640.7 (4)
C6—N2—C5—C4134.3 (2)C11—N1—C12—O1169.8 (2)
C6—N2—C5—C1349.0 (3)C11—N1—C12—C1311.5 (4)
C5—N2—C6—C1156.1 (3)C4—C5—C13—C14.1 (3)
C5—N2—C6—C7127.8 (2)N2—C5—C13—C1179.3 (2)
C11—C6—C7—C80.9 (3)C4—C5—C13—C12166.9 (2)
N2—C6—C7—C8175.3 (2)N2—C5—C13—C129.8 (4)
C6—C7—C8—C90.8 (3)C2—C1—C13—C52.2 (4)
C7—C8—C9—C100.3 (4)C2—C1—C13—C12169.4 (2)
C8—C9—C10—C110.1 (4)O1—C12—C13—C5148.0 (2)
C9—C10—C11—C60.1 (4)N1—C12—C13—C530.7 (4)
C9—C10—C11—N1175.1 (2)O1—C12—C13—C123.1 (3)
C7—C6—C11—C100.4 (3)N1—C12—C13—C1158.1 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O1i1.15 (3)1.77 (3)2.881 (3)161 (2)
C10—H10···N2ii0.952.613.463 (3)149
N2—H2N···O1iii0.89 (3)2.21 (3)3.093 (3)170 (2)
C7—H7···C1iii0.952.863.673 (3)145
Symmetry codes: (i) x+1, y, z+1; (ii) x, y+1/2, z+1/2; (iii) x+1, y+1/2, z+1/2.
(II) 1-(11-hydroxy-5H-dibenzo[b,e]diazepin-5-yl)-2- {4-[3-(1H-imidazol-1-yl)propyl]piperidin-1-yl}ethanone ethanol monosolvate top
Crystal data top
C26H29N5O2·C2H6OZ = 4
Mr = 489.61F(000) = 1048
Triclinic, P1Dx = 1.215 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.7319 (8) ÅCell parameters from 1679 reflections
b = 16.0343 (16) Åθ = 2.5–17.8°
c = 19.2802 (18) ŵ = 0.08 mm1
α = 93.029 (5)°T = 293 K
β = 95.427 (5)°Plate, colourless
γ = 93.662 (5)°0.22 × 0.13 × 0.08 mm
V = 2677.1 (4) Å3
Data collection top
Bruker APEXII CCD area-detector
diffractometer
9341 independent reflections
Radiation source: fine-focus sealed tube3471 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.143
ϕ scans, and ω scans with κ offsetsθmax = 25.0°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Bruker, 2007)
h = 910
Tmin = 0.983, Tmax = 0.994k = 1919
35426 measured reflectionsl = 2222
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)] = 0.086Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.270H-atom parameters constrained
S = 0.99 w = 1/[σ2(Fo2) + (0.1212P)2]
where P = (Fo2 + 2Fc2)/3
9341 reflections(Δ/σ)max < 0.001
690 parametersΔρmax = 0.50 e Å3
88 restraintsΔρmin = 0.67 e Å3
Crystal data top
C26H29N5O2·C2H6Oγ = 93.662 (5)°
Mr = 489.61V = 2677.1 (4) Å3
Triclinic, P1Z = 4
a = 8.7319 (8) ÅMo Kα radiation
b = 16.0343 (16) ŵ = 0.08 mm1
c = 19.2802 (18) ÅT = 293 K
α = 93.029 (5)°0.22 × 0.13 × 0.08 mm
β = 95.427 (5)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer
9341 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2007)
3471 reflections with I > 2σ(I)
Tmin = 0.983, Tmax = 0.994Rint = 0.143
35426 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.08688 restraints
wR(F2) = 0.270H-atom parameters constrained
S = 0.99Δρmax = 0.50 e Å3
9341 reflectionsΔρmin = 0.67 e Å3
690 parameters
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Crystals of 2, in the form of thin plates, diffracted weakly (37% of the reflections were observed) as reflected in higher values of Rint (0.143), final weighted R factor (0.270) and R factor (0.086). The final difference Fourier contained two strong peaks ( 1.4 eA-3) between hydrogen bonded nitrogen and oxygen pairs N1A ···O1B and N1B···O1A, which as H-atoms were not stable in the least-squares refinement. Therefore, H-atoms with half occupancy each were fixed on the oxygens O1A, O1B (as C13-O lengths were > 1.30?A). The final difference Fourier still contained two strong peaks ( 1.4 eA-3) near the centres of the N···O pairs.These have been interpreted as the traces of oxygen atoms that arise from the diastereomeric disorder. This disorder implied that a pair of hydrogen bonded diasteromers occupied the same location, keeping positions of all atoms unchanged, and only affecting positions of N1A, C13A, O1A and N1B, C13B, O1B. The structure was refined with this disorder model, in which alternative positions of N1A, C13A and N1B, C13B overlap with C13A', N1A' and C13B' and N1B', respectively. At the same time, new positions were generated for oxygen atoms O1A' and O1B', accounting for the electron density observed in the difference Fourier. The full-matrix least-squares refinement thus modelled did not contain any significant residual electron density and the ratio of two diastereomers converged to 75: 25.

Crystal lattice contained two solvent (ethanol) molecules, ofwhich one was found to be orientationally disordered over two positions C1E, C2E and O1E and C1E', C2E' and O1E'. In this model, atoms C2E and C2E' and the H-atoms of the O1E and O1E'(H1E) shared common positions respectively. SADI restraints were applied to keep the bond lengths in the two positions similar (with s.u. 0.01).Restraints DELU (0.008) and SIMU (0.008) were applied to keep the atomic displacement parameters of atoms in both the positions similar and within reasonable limits.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
C1A0.2827 (7)0.2274 (3)0.4720 (4)0.0470 (16)
H1A0.19260.22330.44190.056*
C2A0.2816 (8)0.1983 (4)0.5376 (4)0.0569 (19)
H2A0.19020.17480.55160.068*
C3A0.4143 (8)0.2035 (3)0.5834 (3)0.0480 (17)
H3A0.41260.18370.62780.058*
C4A0.5506 (7)0.2390 (3)0.5618 (3)0.0404 (15)
H4A0.64090.24310.59180.048*
C5A0.5508 (6)0.2678 (3)0.4958 (3)0.0323 (14)
N2A0.6895 (5)0.3058 (3)0.4734 (2)0.0298 (11)
C7A0.6866 (6)0.3931 (3)0.4629 (3)0.0292 (13)
C8A0.7850 (6)0.4510 (3)0.5034 (3)0.0327 (14)
H8A0.85410.43290.53820.039*
C9A0.7821 (7)0.5360 (4)0.4930 (3)0.0404 (15)
H9A0.85020.57450.51990.048*
C10A0.6774 (6)0.5623 (4)0.4425 (3)0.0385 (15)
H10A0.67290.61920.43600.046*
C11A0.5792 (7)0.5055 (4)0.4014 (3)0.0430 (16)
H11A0.50910.52440.36740.052*
C12A0.5836 (6)0.4201 (3)0.4103 (3)0.0308 (13)
C13A0.4814 (6)0.3605 (4)0.3624 (3)0.0407 (15)0.751 (4)
N1A0.4141 (5)0.2918 (3)0.3809 (2)0.0353 (12)0.751 (4)
O1A0.4552 (5)0.3875 (3)0.2997 (2)0.0345 (14)0.751 (4)
H1A10.39860.35280.27510.052*0.751 (4)
C13'0.4141 (5)0.2918 (3)0.3809 (2)0.0353 (12)0.249 (4)
N1A'0.4814 (6)0.3605 (4)0.3624 (3)0.0407 (15)0.249 (4)
O1A'0.3156 (13)0.2353 (7)0.3470 (6)0.036 (2)0.249 (4)
H1A'0.30430.24550.30570.054*0.249 (4)
O2A0.9346 (4)0.2999 (2)0.4447 (2)0.0434 (11)
N3A0.6746 (5)0.1347 (3)0.4094 (2)0.0319 (11)
N4A0.2242 (7)0.1338 (3)0.1328 (2)0.0457 (13)
N5A0.0200 (7)0.2170 (4)0.1512 (3)0.0642 (16)
C14A0.4168 (6)0.2627 (3)0.4507 (3)0.0360 (14)
C15A0.8181 (7)0.2631 (3)0.4600 (3)0.0349 (14)
C16A0.7981 (6)0.1685 (3)0.4613 (3)0.0374 (15)
H16A0.89360.14440.45180.045*
H16B0.77420.15330.50730.045*
C17A0.7257 (6)0.1367 (3)0.3394 (3)0.0394 (15)
H17A0.81090.10120.33620.047*
H17B0.76220.19340.33120.047*
C18A0.5965 (6)0.1071 (3)0.2841 (3)0.0395 (15)
H18A0.63460.10780.23850.047*
H18B0.51450.14510.28510.047*
C19A0.5322 (7)0.0185 (3)0.2958 (3)0.0422 (16)
H19A0.61560.01920.29300.051*
C20A0.4845 (7)0.0199 (3)0.3700 (3)0.0432 (16)
H20A0.44810.03620.38010.052*
H20B0.39990.05580.37330.052*
C21A0.6175 (7)0.0513 (3)0.4241 (3)0.0412 (15)
H21A0.58240.05230.47040.049*
H21B0.70000.01370.42310.049*
C22A0.3998 (7)0.0134 (4)0.2420 (3)0.0469 (16)
H22A0.32370.02800.23930.056*
H22B0.35100.06410.25780.056*
C23A0.4478 (7)0.0322 (4)0.1691 (3)0.0526 (17)
H23A0.50130.01750.15400.063*
H23B0.51920.07610.17100.063*
C24A0.3126 (8)0.0592 (4)0.1163 (3)0.0537 (18)
H24A0.24460.01380.11250.064*
H24B0.35050.06910.07110.064*
C25A0.2757 (10)0.2108 (4)0.1446 (3)0.060 (2)
H25A0.37660.22610.14470.072*
C26A0.1514 (10)0.2602 (4)0.1561 (3)0.062 (2)
H26A0.15390.31630.16610.074*
C27A0.0702 (9)0.1425 (4)0.1378 (3)0.0523 (18)
H27A0.00620.09860.13210.063*
C1B0.2282 (7)0.4230 (4)0.1298 (4)0.0559 (18)
H1B0.25720.45260.17230.067*
C2B0.1871 (8)0.4660 (4)0.0727 (4)0.066 (2)
H2B0.19030.52420.07620.079*
C3B0.1396 (8)0.4222 (4)0.0082 (4)0.062 (2)
H3B0.10730.45100.03060.074*
C4B0.1416 (7)0.3362 (4)0.0030 (3)0.0493 (17)
H4B0.11070.30640.03920.059*
C5B0.1902 (6)0.2948 (3)0.0616 (3)0.0376 (14)
C7B0.0948 (7)0.1576 (3)0.0918 (3)0.0376 (15)
C8B0.0136 (7)0.1020 (4)0.0548 (3)0.0465 (16)
H8B0.01800.09720.00640.056*
C9B0.1156 (8)0.0535 (4)0.0884 (4)0.063 (2)
H9B0.18810.01670.06220.076*
C10B0.1123 (9)0.0585 (4)0.1580 (5)0.068 (2)
H10B0.18130.02470.17980.082*
C11B0.0072 (9)0.1133 (5)0.1970 (4)0.061 (2)
H11B0.00490.11640.24540.073*
C12B0.0990 (7)0.1659 (4)0.1640 (3)0.0411 (15)
C13B0.2127 (8)0.2237 (4)0.2071 (3)0.0574 (18)0.751 (4)
N1B0.2738 (6)0.2948 (4)0.1884 (3)0.0442 (13)0.751 (4)
O1B0.2383 (5)0.1971 (3)0.2699 (2)0.0383 (14)0.751 (4)
H1B10.30160.22980.29330.057*0.751 (4)
C13"0.2738 (6)0.2948 (4)0.1884 (3)0.0442 (13)0.249 (4)
N1B'0.2127 (8)0.2237 (4)0.2071 (3)0.0574 (18)0.249 (4)
O1B'0.3615 (15)0.3594 (8)0.2192 (7)0.046 (2)0.249 (4)
H1B'0.39970.34670.25730.070*0.249 (4)
O2B0.3131 (5)0.0925 (2)0.0165 (2)0.0523 (12)
N3B0.5202 (5)0.2769 (3)0.0553 (2)0.0375 (12)
N4B1.0497 (6)0.5129 (3)0.3226 (2)0.0412 (12)
N5B1.0864 (7)0.6516 (3)0.3218 (3)0.0528 (14)
C14B0.2278 (7)0.3372 (4)0.1263 (3)0.0433 (16)
C15B0.3129 (7)0.1683 (4)0.0220 (3)0.0383 (15)
C16B0.4387 (7)0.2250 (4)0.0027 (3)0.0442 (16)
H16C0.51120.19140.02470.053*
H16D0.39400.26060.03720.053*
C17B0.6262 (7)0.2280 (4)0.0972 (3)0.0507 (17)
H17C0.70880.21210.07000.061*
H17D0.57160.17720.10970.061*
N2B0.2007 (5)0.2057 (3)0.0559 (2)0.0364 (12)
C18B0.6931 (7)0.2783 (3)0.1624 (3)0.0444 (16)
H18C0.76790.24620.18780.053*
H18D0.61130.28800.19200.053*
C19B0.7707 (6)0.3621 (3)0.1476 (3)0.0413 (15)
H19B0.86230.35100.12380.050*
C20B0.6622 (7)0.4058 (4)0.0982 (3)0.0528 (18)
H20C0.57690.42330.12290.063*
H20D0.71640.45570.08390.063*
C21B0.5992 (8)0.3527 (4)0.0343 (3)0.0580 (19)
H21C0.52780.38350.00560.070*
H21D0.68260.33830.00700.070*
C22B0.8233 (7)0.4160 (4)0.2141 (3)0.0445 (16)
H22C0.86900.46890.20110.053*
H22D0.73300.42800.23760.053*
C23B0.9374 (7)0.3789 (4)0.2654 (3)0.0484 (17)
H23C1.03080.37060.24320.058*
H23D0.89480.32440.27640.058*
C24B0.9792 (8)0.4314 (4)0.3327 (3)0.0601 (19)
H24C0.88670.43810.35600.072*
H24D1.04960.40190.36300.072*
C25B1.1952 (7)0.5309 (4)0.3047 (3)0.0469 (16)
H25B1.26660.49250.29470.056*
C26B1.2157 (8)0.6147 (4)0.3043 (3)0.0517 (17)
H26B1.30530.64370.29360.062*
C27B0.9903 (7)0.5877 (4)0.3321 (3)0.0499 (17)
H27B0.89110.59370.34460.060*
C1E0.5884 (19)0.6271 (9)0.2102 (9)0.096 (4)0.50
H1E10.55910.61780.16100.145*0.50
H1E20.49770.62520.23480.145*0.50
H1E30.65350.58440.22580.145*0.50
C2E0.6696 (13)0.7068 (8)0.2237 (6)0.138 (3)0.50
H2E10.76020.70060.25580.166*0.50
H2E20.60440.74370.24710.166*0.50
O1E0.718 (4)0.7464 (16)0.1638 (13)0.118 (5)0.50
H1E0.76180.79230.17600.177*
C1E'0.693 (3)0.6339 (11)0.1834 (10)0.127 (5)0.50
H1E40.75450.64810.14660.190*0.50
H1E50.59480.60830.16370.190*0.50
H1E60.74450.59550.21250.190*0.50
C2E'0.6696 (13)0.7068 (8)0.2237 (6)0.138 (3)0.50
H2E30.74450.71570.26440.166*0.50
H2E40.56620.70620.23820.166*0.50
O1E'0.694 (4)0.7673 (18)0.1731 (14)0.114 (5)0.50
O1F0.0465 (6)0.8115 (3)0.3772 (2)0.0778 (15)
H1F0.04940.76630.35550.117*
C1F0.0436 (12)0.9543 (6)0.3619 (6)0.145 (5)
H1F10.06420.99430.32810.218*
H1F20.11220.96710.40360.218*
H1F30.06110.95650.37280.218*
C2F0.0664 (13)0.8736 (5)0.3344 (4)0.117 (4)
H2F10.00400.86160.29260.140*
H2F20.17040.87360.32070.140*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C1A0.025 (4)0.042 (4)0.073 (5)0.000 (3)0.009 (3)0.007 (3)
C2A0.034 (4)0.042 (4)0.099 (6)0.001 (3)0.030 (4)0.000 (4)
C3A0.047 (5)0.045 (4)0.055 (4)0.007 (3)0.023 (4)0.000 (3)
C4A0.036 (4)0.044 (4)0.042 (4)0.002 (3)0.012 (3)0.005 (3)
C5A0.022 (3)0.042 (3)0.033 (4)0.002 (3)0.007 (3)0.003 (3)
N2A0.017 (3)0.036 (3)0.037 (3)0.003 (2)0.004 (2)0.001 (2)
C7A0.018 (3)0.043 (4)0.027 (3)0.005 (3)0.005 (3)0.001 (3)
C8A0.023 (3)0.043 (4)0.032 (3)0.004 (3)0.002 (3)0.001 (3)
C9A0.037 (4)0.047 (4)0.037 (4)0.002 (3)0.009 (3)0.003 (3)
C10A0.027 (4)0.043 (4)0.047 (4)0.007 (3)0.010 (3)0.002 (3)
C11A0.033 (4)0.057 (4)0.043 (4)0.022 (3)0.006 (3)0.013 (3)
C12A0.022 (3)0.044 (4)0.026 (3)0.008 (3)0.002 (3)0.004 (3)
C13A0.022 (3)0.059 (4)0.040 (4)0.009 (3)0.002 (3)0.013 (3)
N1A0.032 (3)0.045 (3)0.028 (3)0.005 (2)0.001 (2)0.008 (2)
O1A0.033 (3)0.034 (3)0.032 (3)0.002 (2)0.009 (2)0.002 (2)
C13'0.032 (3)0.045 (3)0.028 (3)0.005 (2)0.001 (2)0.008 (2)
N1A'0.022 (3)0.059 (4)0.040 (4)0.009 (3)0.002 (3)0.013 (3)
O1A'0.034 (5)0.051 (5)0.022 (4)0.007 (4)0.004 (4)0.009 (4)
O2A0.019 (2)0.049 (3)0.066 (3)0.0053 (19)0.014 (2)0.012 (2)
N3A0.026 (3)0.035 (3)0.037 (3)0.002 (2)0.011 (2)0.005 (2)
N4A0.061 (4)0.044 (3)0.032 (3)0.007 (3)0.000 (3)0.004 (2)
N5A0.087 (5)0.053 (4)0.048 (4)0.011 (4)0.004 (3)0.000 (3)
C14A0.020 (3)0.039 (3)0.048 (4)0.008 (3)0.005 (3)0.012 (3)
C15A0.027 (4)0.044 (4)0.034 (4)0.012 (3)0.002 (3)0.006 (3)
C16A0.035 (4)0.037 (4)0.042 (4)0.009 (3)0.010 (3)0.005 (3)
C17A0.038 (4)0.038 (3)0.045 (4)0.004 (3)0.011 (3)0.009 (3)
C18A0.036 (4)0.044 (4)0.039 (4)0.004 (3)0.007 (3)0.002 (3)
C19A0.053 (4)0.033 (3)0.045 (4)0.008 (3)0.020 (3)0.005 (3)
C20A0.045 (4)0.042 (4)0.044 (4)0.006 (3)0.018 (3)0.006 (3)
C21A0.039 (4)0.041 (4)0.047 (4)0.007 (3)0.013 (3)0.007 (3)
C22A0.045 (4)0.047 (4)0.049 (4)0.000 (3)0.012 (3)0.002 (3)
C23A0.058 (5)0.049 (4)0.050 (4)0.002 (3)0.009 (4)0.003 (3)
C24A0.078 (5)0.035 (4)0.049 (4)0.003 (3)0.012 (4)0.005 (3)
C25A0.098 (6)0.041 (4)0.044 (4)0.020 (4)0.009 (4)0.003 (3)
C26A0.099 (7)0.040 (4)0.047 (5)0.002 (5)0.006 (4)0.008 (3)
C27A0.062 (5)0.051 (5)0.041 (4)0.011 (4)0.006 (4)0.006 (3)
C1B0.048 (5)0.055 (5)0.062 (5)0.004 (4)0.005 (4)0.013 (4)
C2B0.063 (5)0.042 (4)0.093 (6)0.002 (4)0.025 (5)0.015 (4)
C3B0.063 (5)0.038 (4)0.087 (6)0.007 (3)0.011 (4)0.013 (4)
C4B0.045 (4)0.054 (4)0.049 (4)0.010 (3)0.002 (3)0.008 (3)
C5B0.035 (4)0.036 (3)0.042 (4)0.006 (3)0.001 (3)0.005 (3)
C7B0.039 (4)0.038 (3)0.036 (4)0.012 (3)0.004 (3)0.002 (3)
C8B0.039 (4)0.050 (4)0.051 (4)0.007 (3)0.003 (3)0.008 (3)
C9B0.043 (5)0.061 (5)0.089 (6)0.018 (4)0.012 (4)0.007 (4)
C10B0.054 (5)0.055 (5)0.100 (7)0.014 (4)0.026 (5)0.010 (5)
C11B0.070 (5)0.077 (5)0.050 (4)0.050 (4)0.037 (4)0.025 (4)
C12B0.041 (4)0.050 (4)0.034 (4)0.021 (3)0.002 (3)0.001 (3)
C13B0.057 (5)0.073 (5)0.044 (4)0.041 (4)0.003 (4)0.008 (4)
N1B0.027 (3)0.073 (4)0.032 (3)0.013 (3)0.002 (2)0.012 (3)
O1B0.040 (3)0.038 (3)0.032 (3)0.010 (2)0.009 (3)0.003 (2)
C13"0.027 (3)0.073 (4)0.032 (3)0.013 (3)0.002 (2)0.012 (3)
N1B'0.057 (5)0.073 (5)0.044 (4)0.041 (4)0.003 (4)0.008 (4)
O1B'0.031 (5)0.078 (5)0.030 (5)0.017 (4)0.006 (4)0.005 (4)
O2B0.055 (3)0.039 (3)0.067 (3)0.010 (2)0.022 (2)0.001 (2)
N3B0.035 (3)0.039 (3)0.039 (3)0.005 (2)0.002 (2)0.003 (2)
N4B0.032 (3)0.053 (3)0.039 (3)0.003 (3)0.004 (2)0.005 (2)
N5B0.055 (4)0.058 (4)0.047 (3)0.017 (3)0.007 (3)0.004 (3)
C14B0.036 (4)0.047 (4)0.046 (4)0.005 (3)0.003 (3)0.016 (3)
C15B0.037 (4)0.042 (4)0.036 (4)0.012 (3)0.001 (3)0.002 (3)
C16B0.043 (4)0.050 (4)0.042 (4)0.006 (3)0.017 (3)0.006 (3)
C17B0.036 (4)0.044 (4)0.073 (5)0.013 (3)0.005 (3)0.003 (3)
N2B0.038 (3)0.041 (3)0.030 (3)0.000 (2)0.006 (2)0.002 (2)
C18B0.035 (4)0.037 (4)0.060 (4)0.003 (3)0.007 (3)0.009 (3)
C19B0.029 (4)0.043 (4)0.054 (4)0.000 (3)0.010 (3)0.015 (3)
C20B0.058 (5)0.040 (4)0.059 (4)0.009 (3)0.002 (4)0.013 (3)
C21B0.063 (5)0.050 (4)0.060 (5)0.017 (4)0.002 (4)0.014 (3)
C22B0.036 (4)0.049 (4)0.050 (4)0.003 (3)0.007 (3)0.008 (3)
C23B0.034 (4)0.053 (4)0.058 (4)0.004 (3)0.002 (3)0.012 (3)
C24B0.050 (5)0.071 (5)0.058 (5)0.008 (4)0.004 (4)0.020 (4)
C25B0.027 (4)0.064 (5)0.049 (4)0.009 (3)0.003 (3)0.007 (3)
C26B0.044 (4)0.061 (5)0.049 (4)0.006 (4)0.016 (3)0.009 (3)
C27B0.035 (4)0.074 (5)0.041 (4)0.010 (4)0.003 (3)0.008 (4)
C1E0.090 (9)0.107 (8)0.104 (9)0.040 (7)0.031 (7)0.035 (7)
C2E0.124 (5)0.175 (6)0.114 (5)0.004 (5)0.008 (4)0.042 (5)
O1E0.101 (10)0.164 (10)0.085 (7)0.013 (9)0.017 (6)0.049 (8)
C1E'0.127 (10)0.142 (8)0.113 (10)0.026 (9)0.017 (8)0.043 (7)
C2E'0.124 (5)0.175 (6)0.114 (5)0.004 (5)0.008 (4)0.042 (5)
O1E'0.088 (9)0.155 (8)0.098 (8)0.002 (8)0.014 (7)0.049 (7)
O1F0.090 (4)0.066 (3)0.078 (4)0.001 (3)0.028 (3)0.014 (3)
C1F0.137 (9)0.098 (8)0.232 (13)0.060 (7)0.105 (9)0.081 (8)
C2F0.227 (12)0.068 (6)0.061 (6)0.015 (7)0.061 (7)0.015 (5)
Geometric parameters (Å, º) top
C1A—C2A1.372 (8)C5B—N2B1.436 (6)
C1A—C14A1.375 (7)C7B—C8B1.377 (8)
C1A—H1A0.9300C7B—C12B1.388 (7)
C2A—C3A1.383 (8)C7B—N2B1.420 (7)
C2A—H2A0.9300C8B—C9B1.374 (8)
C3A—C4A1.395 (8)C8B—H8B0.9300
C3A—H3A0.9300C9B—C10B1.337 (9)
C4A—C5A1.375 (7)C9B—H9B0.9300
C4A—H4A0.9300C10B—C11B1.371 (9)
C5A—C14A1.385 (7)C10B—H10B0.9300
C5A—N2A1.435 (6)C11B—C12B1.430 (8)
N2A—C15A1.389 (6)C11B—H11B0.9300
N2A—C7A1.427 (6)C12B—C13B1.476 (8)
C7A—C8A1.380 (7)C13B—N1B1.310 (8)
C7A—C12A1.396 (7)C13B—O1B1.310 (6)
C8A—C9A1.388 (7)N1B—C14B1.445 (8)
C8A—H8A0.9300O1B—H1B10.8200
C9A—C10A1.374 (7)O1B'—H1B'0.8200
C9A—H9A0.9300O2B—C15B1.215 (6)
C10A—C11A1.374 (8)N3B—C21B1.453 (6)
C10A—H10A0.9300N3B—C16B1.458 (7)
C11A—C12A1.393 (7)N3B—C17B1.464 (7)
C11A—H11A0.9300N4B—C27B1.348 (7)
C12A—C13A1.484 (7)N4B—C25B1.365 (7)
C13A—N1A1.299 (7)N4B—C24B1.439 (7)
C13A—O1A1.309 (6)N5B—C27B1.318 (7)
N1A—C14A1.446 (7)N5B—C26B1.369 (7)
O1A—H1A10.8200C15B—N2B1.380 (7)
O1A'—H1A'0.8200C15B—C16B1.510 (8)
O2A—C15A1.212 (6)C16B—H16C0.9700
N3A—C21A1.449 (6)C16B—H16D0.9700
N3A—C16A1.455 (6)C17B—C18B1.506 (8)
N3A—C17A1.462 (6)C17B—H17C0.9700
N4A—C27A1.356 (8)C17B—H17D0.9700
N4A—C25A1.363 (7)C18B—C19B1.518 (7)
N4A—C24A1.449 (7)C18B—H18C0.9700
N5A—C27A1.294 (7)C18B—H18D0.9700
N5A—C26A1.375 (8)C19B—C20B1.509 (8)
C15A—C16A1.518 (7)C19B—C22B1.525 (7)
C16A—H16A0.9700C19B—H19B0.9800
C16A—H16B0.9700C20B—C21B1.499 (8)
C17A—C18A1.511 (7)C20B—H20C0.9700
C17A—H17A0.9700C20B—H20D0.9700
C17A—H17B0.9700C21B—H21C0.9700
C18A—C19A1.529 (7)C21B—H21D0.9700
C18A—H18A0.9700C22B—C23B1.508 (7)
C18A—H18B0.9700C22B—H22C0.9700
C19A—C22A1.522 (8)C22B—H22D0.9700
C19A—C20A1.526 (7)C23B—C24B1.510 (8)
C19A—H19A0.9800C23B—H23C0.9700
C20A—C21A1.528 (7)C23B—H23D0.9700
C20A—H20A0.9700C24B—H24C0.9700
C20A—H20B0.9700C24B—H24D0.9700
C21A—H21A0.9700C25B—C26B1.345 (8)
C21A—H21B0.9700C25B—H25B0.9300
C22A—C23A1.523 (7)C26B—H26B0.9300
C22A—H22A0.9700C27B—H27B0.9300
C22A—H22B0.9700C1E—C2E1.421 (14)
C23A—C24A1.510 (8)C1E—H1E10.9600
C23A—H23A0.9700C1E—H1E20.9600
C23A—H23B0.9700C1E—H1E30.9600
C24A—H24A0.9700C2E—O1E1.432 (12)
C24A—H24B0.9700C2E—H2E10.9700
C25A—C26A1.345 (9)C2E—H2E20.9700
C25A—H25A0.9300O1E—H1E0.8200
C26A—H26A0.9300C1E'—H1E40.9600
C27A—H27A0.9300C1E'—H1E50.9600
C1B—C2B1.362 (9)C1E'—H1E60.9600
C1B—C14B1.374 (8)O1F—C2F1.339 (7)
C1B—H1B0.9300O1F—H1F0.8200
C2B—C3B1.409 (9)C1F—C2F1.405 (10)
C2B—H2B0.9300C1F—H1F10.9600
C3B—C4B1.378 (8)C1F—H1F20.9600
C3B—H3B0.9300C1F—H1F30.9600
C4B—C5B1.387 (7)C2F—H2F10.9700
C4B—H4B0.9300C2F—H2F20.9700
C5B—C14B1.389 (7)
C2A—C1A—C14A120.2 (6)C5B—C4B—H4B120.4
C2A—C1A—H1A119.9C4B—C5B—C14B121.6 (6)
C14A—C1A—H1A119.9C4B—C5B—N2B119.5 (5)
C1A—C2A—C3A121.0 (6)C14B—C5B—N2B118.8 (5)
C1A—C2A—H2A119.5C8B—C7B—C12B119.5 (6)
C3A—C2A—H2A119.5C8B—C7B—N2B119.8 (5)
C2A—C3A—C4A118.9 (6)C12B—C7B—N2B120.7 (5)
C2A—C3A—H3A120.6C9B—C8B—C7B121.0 (6)
C4A—C3A—H3A120.6C9B—C8B—H8B119.5
C5A—C4A—C3A119.7 (6)C7B—C8B—H8B119.5
C5A—C4A—H4A120.2C10B—C9B—C8B121.1 (7)
C3A—C4A—H4A120.2C10B—C9B—H9B119.4
C4A—C5A—C14A120.8 (5)C8B—C9B—H9B119.4
C4A—C5A—N2A120.2 (5)C9B—C10B—C11B120.0 (7)
C14A—C5A—N2A118.9 (5)C9B—C10B—H10B120.0
C15A—N2A—C7A120.4 (4)C11B—C10B—H10B120.0
C15A—N2A—C5A124.6 (4)C10B—C11B—C12B120.6 (7)
C7A—N2A—C5A114.9 (4)C10B—C11B—H11B119.7
C8A—C7A—C12A119.6 (5)C12B—C11B—H11B119.7
C8A—C7A—N2A121.1 (5)C7B—C12B—C11B117.8 (6)
C12A—C7A—N2A119.3 (5)C7B—C12B—C13B122.4 (6)
C7A—C8A—C9A121.0 (5)C11B—C12B—C13B119.8 (6)
C7A—C8A—H8A119.5N1B—C13B—O1B123.2 (6)
C9A—C8A—H8A119.5N1B—C13B—C12B126.3 (6)
C10A—C9A—C8A119.1 (6)O1B—C13B—C12B110.4 (6)
C10A—C9A—H9A120.4C13B—N1B—C14B126.6 (5)
C8A—C9A—H9A120.4C13B—O1B—H1B1109.5
C11A—C10A—C9A120.7 (6)C21B—N3B—C16B113.9 (4)
C11A—C10A—H10A119.6C21B—N3B—C17B111.1 (5)
C9A—C10A—H10A119.6C16B—N3B—C17B110.6 (5)
C10A—C11A—C12A120.6 (5)C27B—N4B—C25B105.2 (5)
C10A—C11A—H11A119.7C27B—N4B—C24B127.8 (6)
C12A—C11A—H11A119.7C25B—N4B—C24B126.9 (5)
C11A—C12A—C7A118.9 (5)C27B—N5B—C26B103.7 (5)
C11A—C12A—C13A118.9 (5)C1B—C14B—C5B118.0 (6)
C7A—C12A—C13A122.2 (5)C1B—C14B—N1B119.4 (6)
N1A—C13A—O1A122.5 (5)C5B—C14B—N1B122.5 (5)
N1A—C13A—C12A124.4 (5)O2B—C15B—N2B120.2 (5)
O1A—C13A—C12A112.9 (5)O2B—C15B—C16B122.4 (5)
C13A—N1A—C14A126.9 (5)N2B—C15B—C16B117.3 (5)
C13A—O1A—H1A1109.5N3B—C16B—C15B111.1 (4)
C21A—N3A—C16A111.9 (4)N3B—C16B—H16C109.4
C21A—N3A—C17A111.6 (4)C15B—C16B—H16C109.4
C16A—N3A—C17A110.3 (4)N3B—C16B—H16D109.4
C27A—N4A—C25A105.1 (6)C15B—C16B—H16D109.4
C27A—N4A—C24A126.9 (5)H16C—C16B—H16D108.0
C25A—N4A—C24A128.0 (6)N3B—C17B—C18B110.3 (5)
C27A—N5A—C26A103.3 (6)N3B—C17B—H17C109.6
C1A—C14A—C5A119.4 (6)C18B—C17B—H17C109.6
C1A—C14A—N1A118.7 (5)N3B—C17B—H17D109.6
C5A—C14A—N1A121.9 (5)C18B—C17B—H17D109.6
O2A—C15A—N2A121.1 (5)H17C—C17B—H17D108.1
O2A—C15A—C16A123.2 (5)C15B—N2B—C7B120.9 (5)
N2A—C15A—C16A115.6 (5)C15B—N2B—C5B122.9 (5)
N3A—C16A—C15A110.7 (4)C7B—N2B—C5B116.0 (4)
N3A—C16A—H16A109.5C17B—C18B—C19B112.9 (5)
C15A—C16A—H16A109.5C17B—C18B—H18C109.0
N3A—C16A—H16B109.5C19B—C18B—H18C109.0
C15A—C16A—H16B109.5C17B—C18B—H18D109.0
H16A—C16A—H16B108.1C19B—C18B—H18D109.0
N3A—C17A—C18A111.4 (5)H18C—C18B—H18D107.8
N3A—C17A—H17A109.3C20B—C19B—C18B108.7 (5)
C18A—C17A—H17A109.3C20B—C19B—C22B112.1 (5)
N3A—C17A—H17B109.3C18B—C19B—C22B112.3 (5)
C18A—C17A—H17B109.3C20B—C19B—H19B107.8
H17A—C17A—H17B108.0C18B—C19B—H19B107.8
C17A—C18A—C19A111.3 (5)C22B—C19B—H19B107.8
C17A—C18A—H18A109.4C21B—C20B—C19B113.8 (5)
C19A—C18A—H18A109.4C21B—C20B—H20C108.8
C17A—C18A—H18B109.4C19B—C20B—H20C108.8
C19A—C18A—H18B109.4C21B—C20B—H20D108.8
H18A—C18A—H18B108.0C19B—C20B—H20D108.8
C22A—C19A—C20A112.0 (5)H20C—C20B—H20D107.7
C22A—C19A—C18A113.2 (5)N3B—C21B—C20B109.2 (5)
C20A—C19A—C18A106.9 (4)N3B—C21B—H21C109.8
C22A—C19A—H19A108.2C20B—C21B—H21C109.9
C20A—C19A—H19A108.2N3B—C21B—H21D109.8
C18A—C19A—H19A108.2C20B—C21B—H21D109.8
C19A—C20A—C21A112.1 (5)H21C—C21B—H21D108.3
C19A—C20A—H20A109.2C23B—C22B—C19B116.0 (5)
C21A—C20A—H20A109.2C23B—C22B—H22C108.3
C19A—C20A—H20B109.2C19B—C22B—H22C108.3
C21A—C20A—H20B109.2C23B—C22B—H22D108.3
H20A—C20A—H20B107.9C19B—C22B—H22D108.3
N3A—C21A—C20A110.1 (4)H22C—C22B—H22D107.4
N3A—C21A—H21A109.6C22B—C23B—C24B114.6 (5)
C20A—C21A—H21A109.6C22B—C23B—H23C108.6
N3A—C21A—H21B109.6C24B—C23B—H23C108.6
C20A—C21A—H21B109.6C22B—C23B—H23D108.6
H21A—C21A—H21B108.2C24B—C23B—H23D108.6
C19A—C22A—C23A114.3 (5)H23C—C23B—H23D107.6
C19A—C22A—H22A108.7N4B—C24B—C23B113.3 (5)
C23A—C22A—H22A108.7N4B—C24B—H24C108.9
C19A—C22A—H22B108.7C23B—C24B—H24C108.9
C23A—C22A—H22B108.7N4B—C24B—H24D108.9
H22A—C22A—H22B107.6C23B—C24B—H24D108.9
C24A—C23A—C22A112.8 (5)H24C—C24B—H24D107.7
C24A—C23A—H23A109.0C26B—C25B—N4B107.0 (5)
C22A—C23A—H23A109.0C26B—C25B—H25B126.5
C24A—C23A—H23B109.0N4B—C25B—H25B126.5
C22A—C23A—H23B109.0C25B—C26B—N5B110.7 (6)
H23A—C23A—H23B107.8C25B—C26B—H26B124.7
N4A—C24A—C23A114.2 (5)N5B—C26B—H26B124.7
N4A—C24A—H24A108.7N5B—C27B—N4B113.4 (6)
C23A—C24A—H24A108.7N5B—C27B—H27B123.3
N4A—C24A—H24B108.7N4B—C27B—H27B123.3
C23A—C24A—H24B108.7C1E—C2E—O1E115.7 (18)
H24A—C24A—H24B107.6C1E—C2E—H2E1108.4
C26A—C25A—N4A106.4 (7)O1E—C2E—H2E1108.4
C26A—C25A—H25A126.8C1E—C2E—H2E2108.4
N4A—C25A—H25A126.8O1E—C2E—H2E2108.4
C25A—C26A—N5A111.1 (6)H2E1—C2E—H2E2107.4
C25A—C26A—H26A124.4H1E4—C1E'—H1E5109.5
N5A—C26A—H26A124.4H1E4—C1E'—H1E6109.5
N5A—C27A—N4A114.1 (6)H1E5—C1E'—H1E6109.5
N5A—C27A—H27A122.9C2F—O1F—H1F109.5
N4A—C27A—H27A122.9C2F—C1F—H1F1109.5
C2B—C1B—C14B121.7 (6)C2F—C1F—H1F2109.5
C2B—C1B—H1B119.1H1F1—C1F—H1F2109.5
C14B—C1B—H1B119.1C2F—C1F—H1F3109.5
C1B—C2B—C3B119.9 (6)H1F1—C1F—H1F3109.5
C1B—C2B—H2B120.1H1F2—C1F—H1F3109.5
C3B—C2B—H2B120.1O1F—C2F—C1F115.8 (7)
C4B—C3B—C2B119.4 (7)O1F—C2F—H2F1108.3
C4B—C3B—H3B120.3C1F—C2F—H2F1108.3
C2B—C3B—H3B120.3O1F—C2F—H2F2108.3
C3B—C4B—C5B119.1 (6)C1F—C2F—H2F2108.3
C3B—C4B—H4B120.4H2F1—C2F—H2F2107.4
C14A—C1A—C2A—C3A0.2 (9)C14B—C1B—C2B—C3B1.3 (10)
C1A—C2A—C3A—C4A0.0 (9)C1B—C2B—C3B—C4B2.7 (10)
C2A—C3A—C4A—C5A0.1 (8)C2B—C3B—C4B—C5B0.0 (9)
C3A—C4A—C5A—C14A0.6 (8)C3B—C4B—C5B—C14B4.1 (9)
C3A—C4A—C5A—N2A178.8 (5)C3B—C4B—C5B—N2B176.6 (5)
C4A—C5A—N2A—C15A69.8 (7)C12B—C7B—C8B—C9B1.4 (9)
C14A—C5A—N2A—C15A111.9 (6)N2B—C7B—C8B—C9B178.8 (5)
C4A—C5A—N2A—C7A112.3 (5)C7B—C8B—C9B—C10B0.3 (9)
C14A—C5A—N2A—C7A66.0 (6)C8B—C9B—C10B—C11B0.8 (10)
C15A—N2A—C7A—C8A66.0 (6)C9B—C10B—C11B—C12B0.3 (10)
C5A—N2A—C7A—C8A116.0 (5)C8B—C7B—C12B—C11B2.4 (8)
C15A—N2A—C7A—C12A113.4 (5)N2B—C7B—C12B—C11B177.8 (5)
C5A—N2A—C7A—C12A64.7 (6)C8B—C7B—C12B—C13B179.5 (5)
C12A—C7A—C8A—C9A0.6 (8)N2B—C7B—C12B—C13B0.6 (8)
N2A—C7A—C8A—C9A179.9 (4)C10B—C11B—C12B—C7B1.9 (9)
C7A—C8A—C9A—C10A1.3 (8)C10B—C11B—C12B—C13B179.1 (6)
C8A—C9A—C10A—C11A1.7 (8)C7B—C12B—C13B—N1B31.0 (9)
C9A—C10A—C11A—C12A0.1 (8)C11B—C12B—C13B—N1B151.9 (6)
C10A—C11A—C12A—C7A1.8 (8)C7B—C12B—C13B—O1B153.4 (5)
C10A—C11A—C12A—C13A176.8 (5)C11B—C12B—C13B—O1B23.7 (7)
C8A—C7A—C12A—C11A2.1 (7)O1B—C13B—N1B—C14B165.9 (5)
N2A—C7A—C12A—C11A178.6 (4)C12B—C13B—N1B—C14B9.3 (9)
C8A—C7A—C12A—C13A176.4 (5)C2B—C1B—C14B—C5B2.6 (9)
N2A—C7A—C12A—C13A2.9 (7)C2B—C1B—C14B—N1B179.4 (6)
C11A—C12A—C13A—N1A143.5 (5)C4B—C5B—C14B—C1B5.4 (8)
C7A—C12A—C13A—N1A38.1 (8)N2B—C5B—C14B—C1B175.3 (5)
C11A—C12A—C13A—O1A31.4 (7)C4B—C5B—C14B—N1B177.9 (5)
C7A—C12A—C13A—O1A147.1 (5)N2B—C5B—C14B—N1B1.4 (8)
O1A—C13A—N1A—C14A170.3 (5)C13B—N1B—C14B—C1B141.9 (6)
C12A—C13A—N1A—C14A4.1 (8)C13B—N1B—C14B—C5B41.4 (9)
C2A—C1A—C14A—C5A0.7 (8)C21B—N3B—C16B—C15B157.8 (5)
C2A—C1A—C14A—N1A179.3 (5)C17B—N3B—C16B—C15B76.2 (6)
C4A—C5A—C14A—C1A0.8 (8)O2B—C15B—C16B—N3B117.8 (6)
N2A—C5A—C14A—C1A179.1 (5)N2B—C15B—C16B—N3B57.9 (7)
C4A—C5A—C14A—N1A179.5 (5)C21B—N3B—C17B—C18B60.5 (6)
N2A—C5A—C14A—N1A2.3 (7)C16B—N3B—C17B—C18B172.0 (5)
C13A—N1A—C14A—C1A138.5 (6)O2B—C15B—N2B—C7B7.3 (8)
C13A—N1A—C14A—C5A42.9 (8)C16B—C15B—N2B—C7B168.4 (5)
C7A—N2A—C15A—O2A6.0 (8)O2B—C15B—N2B—C5B177.3 (5)
C5A—N2A—C15A—O2A176.2 (5)C16B—C15B—N2B—C5B6.9 (7)
C7A—N2A—C15A—C16A170.1 (4)C8B—C7B—N2B—C15B67.8 (7)
C5A—N2A—C15A—C16A7.7 (7)C12B—C7B—N2B—C15B112.4 (6)
C21A—N3A—C16A—C15A160.6 (4)C8B—C7B—N2B—C5B116.5 (6)
C17A—N3A—C16A—C15A74.5 (5)C12B—C7B—N2B—C5B63.3 (7)
O2A—C15A—C16A—N3A116.4 (6)C4B—C5B—N2B—C15B71.5 (7)
N2A—C15A—C16A—N3A59.7 (6)C14B—C5B—N2B—C15B109.2 (6)
C21A—N3A—C17A—C18A58.5 (6)C4B—C5B—N2B—C7B112.9 (6)
C16A—N3A—C17A—C18A176.4 (4)C14B—C5B—N2B—C7B66.4 (7)
N3A—C17A—C18A—C19A57.7 (6)N3B—C17B—C18B—C19B55.0 (6)
C17A—C18A—C19A—C22A179.0 (5)C17B—C18B—C19B—C20B49.5 (7)
C17A—C18A—C19A—C20A55.2 (6)C17B—C18B—C19B—C22B174.2 (5)
C22A—C19A—C20A—C21A179.6 (5)C18B—C19B—C20B—C21B51.2 (7)
C18A—C19A—C20A—C21A55.8 (6)C22B—C19B—C20B—C21B176.0 (5)
C16A—N3A—C21A—C20A177.9 (4)C16B—N3B—C21B—C20B173.2 (5)
C17A—N3A—C21A—C20A58.0 (6)C17B—N3B—C21B—C20B61.0 (7)
C19A—C20A—C21A—N3A58.3 (6)C19B—C20B—C21B—N3B57.5 (7)
C20A—C19A—C22A—C23A168.7 (5)C20B—C19B—C22B—C23B177.5 (5)
C18A—C19A—C22A—C23A70.2 (6)C18B—C19B—C22B—C23B59.6 (7)
C19A—C22A—C23A—C24A176.8 (5)C19B—C22B—C23B—C24B176.2 (5)
C27A—N4A—C24A—C23A125.8 (6)C27B—N4B—C24B—C23B111.0 (7)
C25A—N4A—C24A—C23A56.4 (8)C25B—N4B—C24B—C23B72.6 (8)
C22A—C23A—C24A—N4A59.5 (7)C22B—C23B—C24B—N4B60.8 (7)
C27A—N4A—C25A—C26A0.3 (6)C27B—N4B—C25B—C26B0.0 (6)
C24A—N4A—C25A—C26A178.5 (5)C24B—N4B—C25B—C26B177.0 (5)
N4A—C25A—C26A—N5A0.7 (7)N4B—C25B—C26B—N5B0.2 (7)
C27A—N5A—C26A—C25A0.9 (7)C27B—N5B—C26B—C25B0.3 (7)
C26A—N5A—C27A—N4A0.7 (7)C26B—N5B—C27B—N4B0.3 (7)
C25A—N4A—C27A—N5A0.3 (7)C25B—N4B—C27B—N5B0.2 (7)
C24A—N4A—C27A—N5A177.9 (5)C24B—N4B—C27B—N5B176.8 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1A—H1A1···N1B0.822.052.835 (7)160
O1B—H1B1···N1A0.822.052.824 (6)158
O1A—H1A···N1B0.822.002.755 (13)154
O1B—H1B···N1A0.822.082.857 (14)159
C10A—H10A···C1Ai0.932.943.655 (8)135
O1F—H1F···N5Bii0.821.972.779 (7)167
O1E—H1E···N5Aiii0.822.362.70 (3)106
C2A—H2A···O1Fiv0.932.603.433 (8)149
Symmetry codes: (i) x+1, y+1, z+1; (ii) x1, y, z; (iii) x+1, y+1, z; (iv) x, y+1, z+1.

Experimental details

(I)(II)
Crystal data
Chemical formulaC13H10N2OC26H29N5O2·C2H6O
Mr210.23489.61
Crystal system, space groupMonoclinic, P21/cTriclinic, P1
Temperature (K)147293
a, b, c (Å)7.4767 (16), 10.861 (2), 12.475 (2)8.7319 (8), 16.0343 (16), 19.2802 (18)
α, β, γ (°)90, 98.277 (6), 9093.029 (5), 95.427 (5), 93.662 (5)
V3)1002.5 (3)2677.1 (4)
Z44
Radiation typeMo KαMo Kα
µ (mm1)0.090.08
Crystal size (mm)0.28 × 0.25 × 0.070.22 × 0.13 × 0.08
Data collection
DiffractometerBruker APEXII CCD area-detector
diffractometer
Bruker APEXII CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2007)
Multi-scan
(SADABS; Bruker, 2007)
Tmin, Tmax0.975, 0.9940.983, 0.994
No. of measured, independent and
observed [I > 2σ(I)] reflections
6162, 1698, 1161 35426, 9341, 3471
Rint0.0550.143
(sin θ/λ)max1)0.5950.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.120, 1.04 0.086, 0.270, 0.99
No. of reflections16989341
No. of parameters153690
No. of restraints088
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.26, 0.230.50, 0.67

Computer programs: APEX2 (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL-Plus (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O1i1.15 (3)1.77 (3)2.881 (3)161 (2)
C10—H10···N2ii0.952.613.463 (3)149.3
N2—H2N···O1iii0.89 (3)2.21 (3)3.093 (3)170 (2)
C7—H7···C1iii0.952.863.673 (3)144.6
Symmetry codes: (i) x+1, y, z+1; (ii) x, y+1/2, z+1/2; (iii) x+1, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O1A—H1A1···N1B0.822.052.835 (7)160.1
O1B—H1B1···N1A0.822.052.824 (6)157.9
O1A'—H1A'···N1B'0.822.002.755 (13)153.7
O1B'—H1B'···N1A'0.822.082.857 (14)158.6
C10A—H10A···C1Ai0.932.943.655 (8)135.0
O1F—H1F···N5Bii0.821.972.779 (7)167.2
O1E—H1E···N5Aiii0.822.362.70 (3)105.7
C2A—H2A···O1Fiv0.932.603.433 (8)149.2
Symmetry codes: (i) x+1, y+1, z+1; (ii) x1, y, z; (iii) x+1, y+1, z; (iv) x, y+1, z+1.
Selected bond lengths and intermolecular N···O distances (Å) in the hydrogen-bond bridged dimeric single-crystal X-ray structures of dibenzodiazepinones (I) and (II), and structurally related lactams (III)–(V) and (VIa)–(VId). Where bond lengths a and a', b and b' and distances d1 and d2 are equal due to a centre of symmetry in the dimeric unit (A = B), the value is given only once. The numbering of atoms is derived from dibenzodiazepinone (I), where X = NH, Y = CH and R1 = R2 = R3 = H. top
CompoundXYR1R2R3CO bond length a/a'CN bond length b/b'N···O'/N'···O distance d1/d2Reference
(I)NHCHHHH1.265 (3)1.330 (3)2.879 (2)
(II)NR4CHHHH1.311 (6)/1.309 (6)1.298 (6)/1.309 (7)2.836 (6)/2.824 (6)
(III)CH2CHHHH1.239 (2)1.345 (2)2.868 (2)(a)
(IV)OCHNO2N3H1.237 (2)1.346 (2)2.829 (2)(b)
(V)SCHHHH1.238 (3)1.348 (3)2.845 (3)(c)
(VIa)NR5NHHMe1.231 (2)1.356 (2)2.934 (2)(d)
(VIb)NR5NHHMe1.247 (3)1.330 (4)2.938 (4)(e)
(VIc)NR5NHHMe1.240 (2)1.345 (2)2.914 (1)(f)
(VId)NR5NHHMe1.241 (2)1.350 (2)2.838 (1)(f)
(VIe)NR5NHHMe1.239 (2)1.350 (2)2.898 (1)(f)
References: (a) Li et al. (2006); (b) Samet et al. (2007); (c) De Souza et al. (2006); (d) Harrison et al. (2007); (e) Mui et al. (1992); (f) Caira et al. (2008).
 

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