Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614019937/sk3563sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614019937/sk3563Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614019937/sk3563IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614019937/sk3563IIIsup4.hkl |
CCDC references: 1022769; 1022770; 1022771
Chalcones, i.e. 1,3-disubstituted prop-2-en-1-one derivatives of the form R1COCH═CHR2, are versatile intermediates for organic synthesis which are readily prepared via Claisen reactions between acetyl compounds R1COCH3 and aldehydes R2CHO. Their versatility stems from their dual modes of reactivity, involving either Michael-type addition across the C═C double bond or condensation reactions at the carbonyl function. When these two modes are active in tandem, new cyclic structures result which can be either carbocyclic (Tabba et al., 1995; Ravindran et al., 2008; Fischer et al., 2008; Fun, Hemamalini et al., 2010b) or heterocyclic (Fun, Hemamalini et al., 2010a; Jasinski, Guild et al., 2010; Jasinski, Pek et al., 2010; Samshuddin et al., 2010).
We now report the synthesis and structures of three closely related cyclohexanol derivatives, namely (1RS,2SR,3SR,4RS,5RS)-3,5-bis(4-fluorophenyl)-2,4-bis(pyridine-2-carbonyl)1-(pyridin-2-yl)cyclohexanol, (I), (1RS,2SR,3SR,4RS,5RS)-3,5-bis(4-chlorophenyl)-2,4-bis(pyridine-2-carbonyl)-1-(pyridin-2-yl)cyclohexanol acetone 0.951-solvate, (II), and (1RS,2SR,3SR,4RS,5RS)- 3,5-bis(4-bromophenyl)-2,4-bis(pyridine-2-carbonyl)-1-(pyridin-2-yl)cyclohexanol, (III) (see Scheme 1). These cyclohexanols were prepared, in a one-pot procedure exploiting the dual reactivity of chalcones and giving satisfactory yields, by the reaction of 3:2 molar ratios of 2-acetylpyridine with a 4-halogenobenzaldehyde in alkaline aqueous ethanol, without the need for any form of heating. The purposes of this study were the definition of the relative stereochemistry of the five stereogenic centres, the comparison of the molecular conformations, and the exploration of the supramolecular assembly. In addition, we compare the structures of compounds (I)–(III) with that of the recently reported analogue (IV) (Fun et al., 2012) (see Scheme 1).
For the synthesis of the solvent-free forms (I), (IIa) and (III) (see Scheme 1), 2-acetylpyridine (0.03 mol) and the appropriate 4-halogenobenzaldehyde (0.02 mol) were dissolved in ethanol (30 ml). Aqueous potassium hydroxide solution (10 ml of 10% w/v solution) was added and the mixtures were then stirred at 293 K for 4 h, and then permitted to stand overnight at ambient temperature. The resulting colourless products were collected by filtration and dried in air. Compound (I): yield 64%, m.p. 493–495 K; NMR (dimethyl sulfoxide-d6): δ(H) 1.69 (m, 2H, CH2), 3.62 (dd, 1H, H-3), 4.04 (m, 1H, H-5), 4.40 (dd, 1H, H-4), 5.52 (s, 1H, OH), 6.04 (d, 1H, H-2), 6.61–8.44 (m, 20H, aryl and pyridyl); IR (KBr, cm-1): 3430 (OH), 1682 (C═ O); analysis found: C 72.9, H 4.7, N 6.5%; C35H27F2N3O3 requires: C 73.0, H 4.7, N 6.6%. Compound (IIa): yield 66%, m.p. 416–419 K; NMR (dimethyl sulfoxide-d6): δ(H) 1.75 (m, 2H, CH2), 3.70 (dd, 1H, H-3), 4.05 (m, 1H, H-5), 4.45 (dd, 1H, H-4), 5.50 (s, 1H, OH), 6.05 (d, 1H, H-2), 6.84–8.44 (m, 20H, aryl and pyridyl); IR (KBr, cm-1): 3434 (OH), 1689 (C═O); analysis found:C 68.9, H 4.5, N 6.9%; C35H27Cl2N3O3 requires: C 69.3, H 4.5, N 6.9%. Compound (III): yield 72%, m.p. 508–510 K; NMR (chloroform-d3): δ(H) 1.95 (m, 2H, CH2), 3.50 (dd, 1H, H-3), 4.15 (m, 1H, H-5), 4.40 (dd, 1H, H-4), 5.50 (s, 1H, OH), 6.22 (m, 1H, H-2), 6.86–7.49 (m, 20H, aryl and pyridyl); δ(C) 37.9, 40.6, 47.7, 199.9, 120.9, 121.0, 121.6, 121.8, 126.0, 126.1, 126.5, 130.2, 130.7, 130.8, 136.0, 136.1, 139.7, 141.0, 146.9, 147.9, 148.0, 153.7, 153.9, 162.2, 203.0, 205.0; IR (KBr, cm-1): 3429 (OH), 1682 (C═O); analysis found: C 60.2, H 3.9, N 6.0%; C35H27Br2N3O3 requires: C 60.3, H 3.9, N 6.0%. Crystals of (I)–(III) suitable for single-crystal X-ray diffraction were grown by slow evaporation, at ambient temperature and in the presence of air, of solutions in acetone.
Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms in the cycohexanol components were located in difference maps and then treated as riding atoms. H atoms bonded to C atoms were treated as riding atoms in geometrically idealized positions, with C—H = 0.95 (aromatic and heteroaromatic), 0.99 (CH2) or 1.00 Å (aliphatic), and with Uiso(H) = 1.2Ueq(C). H atoms bonded to O atoms were permitted to ride at the positions located in difference maps, with Uiso(H) = 1.5Ueq(O), giving the O—H distances shown in Table 3. Chloro compound (II) crystallizes as an acetone solvate where the solvent molecules are over two sets of atomic sites. For the minor component, the bonded distances and the one-angle nonbonded distances were restrained to the corresponding values in the major component, subject to variations of 0.005 and 0.01 Å, respectively. In addition, the anisotropic displacement parameters for atoms C71 and C81 were constrained to be identical, as were those of atoms O71 and O81, and those of methyl atoms C72, C73, C82 and C83. The H atoms for both components of the acetone component were included in calculated positions as riding atoms, with C—H = 0.95 Å and Uiso(H) = 1.5Ueq(C). Subject to these conditions, the occupancies of the major and minor components refined to 0.690 (13) and 0.261 (13), respectively. The correct orientation of the structure of (II) with respect to the polar-axis direction was determined using the Flack x parameter (Flack, 1983), calculated using 613 quotients of the type [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013), although this has no chemical significance. Examination of the refined structures using PLATON (Spek, 2009) showed that none of them contained any solvent-accessible voids.
Although all of the cyclohexanols reported here, (I)–(III), were recrystallized from acetone, fluoro and bromo derivatives (I) and (III) crystallized in solvent-free form but chloro derivative (II) crystallized as a nonstoichiometric acetone solvate, in which the acetone solvent component is disordered over two adjacent sets of atomic sites having occupancies of 0.690 (13) and 0.261 (13) in the crystal selected for data collection. In addition to the contrast between solvate (II) and solvent-free forms (I) and (III), all of these compounds crystallize in different space groups, viz. Pbca, Fdd2 and P1, respectively, for compounds (I), (II) and (III), despite the very small differences in their overall molecular constitutions. This behaviour contrasts with the isomorphous behaviour sometimes seen in compounds which differ only in the identity of their halogen substituents (e.g. Glidewell et al., 2005; Nayak et al., 2014). Compound (IV) crystallizes in the space group P21/c as a stoichiometric 1:1 solvate with butanone, although the reported synthetic procedure for (IV) specifies that the compound was crystallized from acetone (Fun et al., 2012).
The cyclohexanol components in compounds (I)–(III) contain five stereogenic centres and, for each compound, the reference molecule was selected as one having the R configuration at atom C1 (Figs. 1–3). On this basis, the reference molecules all have the configuration (1R,2S,3S,4R,5R) and the space groups confirm that all three compounds crystallize as racemic mixtures. Compound (IV) has exactly the same stereochemistry, although this aspect of its structure was not mentioned in the original structure report (Fun et al., 2012). The isolated yields of the (1RS,2SR,3SR,4RS,5RS) forms for compounds (I)–(IV), in the range 64–74%, suggest a high degree of stereoselectivity in the formation of the substituted cyclohexane ring.
The formation of these polysubstituted cyclohexanols from very simple precursors can be envisaged as starting with a condensation reaction between the substituted benzaldehyde, ArCHO, and 2-acetylpyridine, MeCOPy, to form a chalcone intermediate (A) (see Scheme 2). This step is followed by two Michael additions, the first of which is addition of MeCOPy to the chalcone (A) to form the intermediate (B), and the second addition is that of (B) to a further molecule of (A) giving (C). Finally, an intramolecular aldol reaction converts intermediate (C) to the cyclohexanol product. The formation of intermediate (B) introduces a stereogenic centre, at the site which will eventually become atom C5 of the cyclohexane ring (cf. Figs 1–3). Intermediate (B) is necessary racemic, as no component in the initial reaction mixtures is capable of inducing enantioselectivity. However, the presence of a stereogenic centre in (B) appears to control the relative stereochemistry at the remaining stereogenic centres subsequently formed at the final positions C1, C2, C3 and C4. This reaction scheme accounts for the reaction stoichiometry, the formation of five adjacent stereogenic centres and the formation of the final products as racemic mixtures, but it must be emphasized that this scheme is largely conjectural, albeit firmly based on the straightforward application of simple organic processes.
Within the cyclohexanol components, the cyclohexane rings all adopt chair conformations and the ring-puckering angles θ, calculated (Cremer & Pople, 1975) for the atom sequence C1–C2–C3–C4–C5–C6 are 5.36 (17), 5.5 (3) and 0.0 (3)° for compounds (I), (II) and (III), respectively; the corresponding value for compound (IV) is 4.69 (15)°. The ideal value for a perfect chair conformation is θ = 0.0° (Boeyens, 1978). The organic substituents at atoms C1, C2, C3 and C5 all occupy equatorial sites, and both the hydroxy group at atom C1 and the acyl substituent at atom C4 occupy axial sites.
In each of compounds (I)–(III) there is an intramolecular O—H···N hydrogen bond (Table 3), which may serve effectively to lock the orientation of the pyridine ring bonded to atom C1. The overall molecular conformation can be conveniently summarized in terms of the dihedral angles between the successive rings bonded to the central cyclohexane ring (Table 2); the corresponding values for (I)–(III) are in general similar, although with some small differences in detail. The overall similarity between compounds (I)–(III) in terms of their molecular constitutions, stereochemistry and molecular conformations makes their marked differences in crystallization behavior difficult to understand.
The supramolecular assembly in compounds (I)–(III) is fairly simple for molecules of this complexity. Thus, for example, despite the presence in each cyclohexanol molecule of five independent aryl or pyridyl rings, there are no π–π interactions in the structure of (I) and only one such interaction in each of (II) and (III). Similarly, there are no C—H···π interactions in the structures of (I) and (III), while the single interaction of this type in (II) has long H···Cg and C···Cg distances (Table 3), and it is not considered to be structurally significant. The principal intermolecular interactions are thus C—H···N and C—H···O hydrogen bonds, augmented by the π–π interactions in (II) and (III). In the structure of compound (I), a combination of two C—H···O hydrogen bonds (Table 3) links molecules related by a b-glide plane to form a C(5)C(10)[R22(15)] chain of rings (Bernstein et al., 1995) running parallel to the [010] direction (Fig. 4).
There are several C—H···O contacts between the molecular components in compound (II) (Table 3). Within the selected asymmetric unit, the cyclohexanol molecule forms rather long C—H···O contacts with the two partial-occupancy components of the disordered acetone molecule, one of them with an H···O distance beyond the sum (2.65 Å) of the van der Waals radii for H and O (Rowland & Taylor, 1996). A third such contact has a C—H···O angle of only 129°, so that this contact is probably not structurally significant (Wood et al., 2009). The weak bonding of the acetone to the cyclohexanol component may account for the nonstoichiometric nature of the solvation, for the positional disorder of the solvent molecule, and for the relatively large displacement parameters for the solvent component. Subject to these provisos, and that mentioned above concerning the C—H···π contact, the sole significant intermolecular hydrogen bond, of C—H···N type, links cyclohexanol molecules related by the d-glide plane at y = 0.375 to form a simple C(4) chain running parallel to the [101] direction (Fig. 5). These simple chains are linked into sheets by a single π–π stacking interaction. The pyridyl rings containing atoms N11 and N41 in the molecules at (x, y, z) and (x+1/2, y, z+1/2), respectively, make a dihedral angle of 4.7 (2)°. The ring-centroid separation is 3.846 (2) Å and the shortest perpendicular distance from the centroid of one ring to the plane of the other is 3.3909 (17) Å, corresponding to a nearly ideal ring-centroid offset of ca 1.52 Å. This interaction links cyclohexanol molecules related by translation to form a π-stacked chain running parallel to the [101] direction (Fig. 6). The combination of the hydrogen-bonded chains along [101] and the π-stacked chains along [101] links the cyclohexanol molecules into a sheet parallel to (010) to which the acetone molecules are linked only weakly, if at all.
A combination of one C—H···N hydrogen bond and one C—H···O hydrogen bond links the molecules of compound (III) into a chain of centrosymmetric rings running parallel to the [011] direction (Fig. 7). Inversion-related pairs of C—H···N hydrogen bonds link pairs of molecules into R22(18) rings centred at (0, 0.5-n, n), where n represents an integer, and these rings alternate with R22(16) rings containing inversion-related pairs of C—H···O hydrogen bonds which are centred at (0, n, 0.5-n), where n again represents an integer. There is a single π–π interaction in this structure; the pyridine rings containing atom N21 in the molecules at (x, y, z) and (-x+1, -y, -z+1) are parallel. The interplanar spacing is 3.555 (2) Å, the ring-centroid separation is 3.680 (3) and the ring-centroid offset is 0.951 (3) Å, and the effect of this interaction is to link the hydrogen-bonded chain into a sheet parallel to (011).
In the structure of compound (III), there is a short intermolecular Br···Br contact between inversion-related molecules, with Br54···Br54i = 3.3802 (6) Å and C54—Br54···Br54i= 159.23 (9)° [symmetry code: (i) -x, -y+1, -z]. A database study of the angular distribution of such contacts (Ramasubbu et al., 1986) has shown that the C—X···X angles (where X = Cl, Br or I) are clustered either around 100° or around 165°, and the angle observed in compound (III) is consistent with this finding. Although the observed Br···Br distance in (III) is shorter that the conventional sum of van der Waals radii (3.70 Å; Rowland & Taylor, 1996), a database study of the non-bonded distances in such contacts (Nyburg & Faerman, 1985) found that atoms such as halogens bonded to C atoms do not behave in this context as though they were spherical but instead they behave as oblate ellipsoids, with the major axis normal to the direction of the C—X bond and the minor axis parallel to the C—X bond. For Br, these characteristic radii were found to be 2.01 and 1.64 Å, respectively, and, on this basis, the observed Br···Br distance in compound (III) does not seem to be exceptional.
In compound (IV) (Fun et al., 2012), the supramolecular assembly consists of C(5) chains built from a single C—H···O hydrogen bond, to which the butanone solvent molecules are linked, also via C—H···O hydrogen bonds. Although the presence of a π–π stacking interaction was mentioned in the original structure report, no discussion of its action was given. In fact, this interaction links the hydrogen-bonded chains into a sheet lying parallel to (100) (Fig. 8).
For related literature, see: Bernstein et al. (1995); Boeyens (1978); Cremer & Pople (1975); Fischer et al. (2008); Flack (1983); Fun et al. (2010a, 2010b, 2012); Glidewell et al. (2005); Jasinski, Guild, Samshuddin, Narayana & Yathirajan (2010); Jasinski, Pek, Samshuddin, Narayana & Yathirajan (2010); Nayak et al. (2014); Nyburg & Faerman (1985); Parsons et al. (2013); Ramasubbu et al. (1986); Ravindran et al. (2008); Rowland & Taylor (1996); Samshuddin et al. (2010); Spek (2009); Tabba et al. (1995); Wood et al. (2009).
For all compounds, data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis RED (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2014); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2014) and PLATON (Spek, 2009).
C35H27F2N3O3 | Dx = 1.282 Mg m−3 |
Mr = 575.60 | Cu Kα radiation, λ = 1.54178 Å |
Orthorhombic, Pbca | Cell parameters from 5754 reflections |
a = 21.8864 (9) Å | θ = 3.6–71.2° |
b = 11.2268 (4) Å | µ = 0.75 mm−1 |
c = 24.2670 (9) Å | T = 200 K |
V = 5962.7 (4) Å3 | Needle, colourless |
Z = 8 | 0.40 × 0.09 × 0.08 mm |
F(000) = 2400 |
Agilent Eos Gemini diffractometer | 4489 reflections with I > 2σ(I) |
Radiation source: Enhance (Cu) X-ray Source | Rint = 0.036 |
ω scans | θmax = 71.2°, θmin = 3.6° |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | h = −18→26 |
Tmin = 0.693, Tmax = 0.942 | k = −13→13 |
37077 measured reflections | l = −27→29 |
5754 independent reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.131 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0634P)2 + 1.1285P] where P = (Fo2 + 2Fc2)/3 |
5754 reflections | (Δ/σ)max < 0.001 |
388 parameters | Δρmax = 0.19 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
C35H27F2N3O3 | V = 5962.7 (4) Å3 |
Mr = 575.60 | Z = 8 |
Orthorhombic, Pbca | Cu Kα radiation |
a = 21.8864 (9) Å | µ = 0.75 mm−1 |
b = 11.2268 (4) Å | T = 200 K |
c = 24.2670 (9) Å | 0.40 × 0.09 × 0.08 mm |
Agilent Eos Gemini diffractometer | 5754 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | 4489 reflections with I > 2σ(I) |
Tmin = 0.693, Tmax = 0.942 | Rint = 0.036 |
37077 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.131 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.19 e Å−3 |
5754 reflections | Δρmin = −0.20 e Å−3 |
388 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.19695 (8) | 0.56058 (14) | 0.29755 (6) | 0.0469 (4) | |
O11 | 0.20061 (6) | 0.43914 (10) | 0.28039 (5) | 0.0587 (3) | |
H11 | 0.1716 | 0.4286 | 0.2598 | 0.088* | |
C2 | 0.15217 (7) | 0.57345 (13) | 0.34750 (6) | 0.0436 (3) | |
H2 | 0.1509 | 0.6589 | 0.3590 | 0.052* | |
C3 | 0.17385 (7) | 0.49773 (13) | 0.39661 (6) | 0.0434 (3) | |
H3 | 0.1731 | 0.4128 | 0.3842 | 0.052* | |
C4 | 0.24067 (7) | 0.52586 (13) | 0.41351 (6) | 0.0433 (3) | |
H4 | 0.2539 | 0.4617 | 0.4395 | 0.052* | |
C5 | 0.28430 (7) | 0.52110 (13) | 0.36324 (7) | 0.0463 (3) | |
H5 | 0.2842 | 0.4368 | 0.3500 | 0.056* | |
C6 | 0.26119 (7) | 0.59731 (15) | 0.31527 (7) | 0.0495 (4) | |
H6A | 0.2609 | 0.6821 | 0.3265 | 0.059* | |
H6B | 0.2894 | 0.5890 | 0.2836 | 0.059* | |
N11 | 0.13521 (8) | 0.57704 (16) | 0.21601 (6) | 0.0662 (4) | |
C12 | 0.17203 (8) | 0.63612 (16) | 0.25019 (7) | 0.0513 (4) | |
C13 | 0.18284 (11) | 0.75631 (19) | 0.24506 (9) | 0.0716 (5) | |
H13 | 0.2101 | 0.7960 | 0.2694 | 0.086* | |
C14 | 0.15306 (14) | 0.8180 (2) | 0.20361 (11) | 0.0942 (8) | |
H14 | 0.1597 | 0.9010 | 0.1990 | 0.113* | |
C15 | 0.11414 (13) | 0.7586 (3) | 0.16938 (10) | 0.0927 (8) | |
H15 | 0.0927 | 0.7995 | 0.1411 | 0.111* | |
C16 | 0.10686 (12) | 0.6393 (3) | 0.17684 (9) | 0.0853 (7) | |
H16 | 0.0800 | 0.5980 | 0.1527 | 0.102* | |
C27 | 0.08834 (8) | 0.53511 (15) | 0.33041 (7) | 0.0493 (4) | |
O27 | 0.07514 (6) | 0.43068 (11) | 0.32607 (6) | 0.0646 (3) | |
N21 | 0.05596 (9) | 0.74111 (16) | 0.32838 (8) | 0.0758 (5) | |
C22 | 0.04146 (8) | 0.62888 (18) | 0.31706 (7) | 0.0573 (4) | |
C23 | −0.01306 (10) | 0.5955 (3) | 0.29329 (10) | 0.0846 (7) | |
H23 | −0.0222 | 0.5142 | 0.2861 | 0.102* | |
C24 | −0.05428 (13) | 0.6857 (4) | 0.28028 (13) | 0.1123 (10) | |
H24 | −0.0920 | 0.6669 | 0.2630 | 0.135* | |
C25 | −0.04035 (15) | 0.8010 (3) | 0.29238 (13) | 0.1112 (10) | |
H25 | −0.0684 | 0.8633 | 0.2847 | 0.133* | |
C26 | 0.01477 (14) | 0.8246 (3) | 0.31575 (11) | 0.1002 (9) | |
H26 | 0.0246 | 0.9052 | 0.3236 | 0.120* | |
C31 | 0.13233 (7) | 0.50623 (14) | 0.44664 (7) | 0.0473 (4) | |
C32 | 0.10194 (9) | 0.60966 (17) | 0.46100 (8) | 0.0604 (4) | |
H32 | 0.1041 | 0.6769 | 0.4373 | 0.072* | |
C33 | 0.06841 (10) | 0.6169 (2) | 0.50932 (9) | 0.0737 (6) | |
H33 | 0.0479 | 0.6885 | 0.5190 | 0.088* | |
C34 | 0.06538 (10) | 0.5205 (2) | 0.54226 (9) | 0.0771 (6) | |
F34 | 0.03235 (8) | 0.52803 (18) | 0.58975 (6) | 0.1177 (6) | |
C35 | 0.09327 (12) | 0.4160 (2) | 0.52967 (9) | 0.0830 (7) | |
H35 | 0.0899 | 0.3491 | 0.5535 | 0.100* | |
C36 | 0.12679 (10) | 0.40895 (18) | 0.48118 (8) | 0.0649 (5) | |
H36 | 0.1462 | 0.3362 | 0.4716 | 0.078* | |
C47 | 0.24466 (7) | 0.64265 (13) | 0.44453 (7) | 0.0456 (3) | |
O47 | 0.23444 (6) | 0.73801 (9) | 0.42281 (5) | 0.0575 (3) | |
N41 | 0.28713 (11) | 0.54117 (16) | 0.52388 (8) | 0.0865 (6) | |
C42 | 0.26141 (9) | 0.63990 (15) | 0.50466 (7) | 0.0561 (4) | |
C43 | 0.25094 (12) | 0.73865 (19) | 0.53713 (8) | 0.0764 (6) | |
H43 | 0.2322 | 0.8079 | 0.5223 | 0.092* | |
C44 | 0.26832 (17) | 0.7342 (3) | 0.59181 (10) | 0.1086 (10) | |
H44 | 0.2610 | 0.8002 | 0.6154 | 0.130* | |
C45 | 0.29594 (18) | 0.6346 (3) | 0.61140 (11) | 0.1234 (12) | |
H45 | 0.3091 | 0.6302 | 0.6486 | 0.148* | |
C46 | 0.30429 (18) | 0.5414 (3) | 0.57659 (12) | 0.1228 (12) | |
H46 | 0.3236 | 0.4719 | 0.5907 | 0.147* | |
C51 | 0.34937 (7) | 0.54824 (14) | 0.38108 (7) | 0.0481 (4) | |
C52 | 0.37957 (9) | 0.46579 (17) | 0.41399 (9) | 0.0653 (5) | |
H52 | 0.3597 | 0.3934 | 0.4234 | 0.078* | |
C53 | 0.43805 (9) | 0.48691 (19) | 0.43340 (9) | 0.0705 (5) | |
H53 | 0.4584 | 0.4302 | 0.4560 | 0.085* | |
C54 | 0.46566 (8) | 0.59140 (18) | 0.41921 (8) | 0.0598 (4) | |
F54 | 0.52375 (5) | 0.61192 (12) | 0.43809 (5) | 0.0820 (4) | |
C55 | 0.43852 (8) | 0.67500 (17) | 0.38715 (8) | 0.0621 (5) | |
H55 | 0.4592 | 0.7468 | 0.3780 | 0.074* | |
C56 | 0.37968 (8) | 0.65291 (15) | 0.36802 (8) | 0.0550 (4) | |
H56 | 0.3599 | 0.7106 | 0.3456 | 0.066* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0533 (9) | 0.0418 (8) | 0.0455 (8) | 0.0003 (6) | −0.0003 (7) | −0.0037 (7) |
O11 | 0.0640 (7) | 0.0490 (6) | 0.0631 (7) | 0.0062 (5) | −0.0044 (6) | −0.0149 (6) |
C2 | 0.0496 (8) | 0.0366 (7) | 0.0447 (8) | 0.0021 (6) | −0.0022 (6) | −0.0004 (6) |
C3 | 0.0501 (8) | 0.0328 (7) | 0.0474 (8) | 0.0012 (6) | −0.0015 (6) | 0.0008 (6) |
C4 | 0.0496 (8) | 0.0340 (7) | 0.0462 (8) | 0.0013 (6) | −0.0034 (6) | 0.0028 (6) |
C5 | 0.0495 (9) | 0.0381 (7) | 0.0514 (8) | 0.0022 (6) | −0.0018 (7) | −0.0023 (6) |
C6 | 0.0483 (9) | 0.0523 (9) | 0.0478 (8) | 0.0008 (7) | 0.0011 (7) | 0.0016 (7) |
N11 | 0.0690 (10) | 0.0781 (11) | 0.0516 (8) | −0.0047 (8) | −0.0112 (7) | −0.0038 (8) |
C12 | 0.0541 (9) | 0.0577 (10) | 0.0421 (8) | −0.0008 (7) | 0.0008 (7) | −0.0011 (7) |
C13 | 0.0880 (14) | 0.0628 (12) | 0.0641 (12) | −0.0082 (10) | −0.0169 (10) | 0.0112 (9) |
C14 | 0.119 (2) | 0.0785 (15) | 0.0852 (16) | −0.0030 (14) | −0.0186 (15) | 0.0296 (13) |
C15 | 0.0962 (18) | 0.116 (2) | 0.0661 (14) | 0.0048 (15) | −0.0201 (12) | 0.0294 (14) |
C16 | 0.0844 (15) | 0.113 (2) | 0.0583 (12) | −0.0039 (14) | −0.0201 (11) | 0.0039 (12) |
C27 | 0.0525 (9) | 0.0505 (9) | 0.0450 (8) | −0.0014 (7) | 0.0009 (7) | 0.0017 (7) |
O27 | 0.0643 (8) | 0.0548 (7) | 0.0748 (8) | −0.0110 (6) | −0.0088 (6) | 0.0017 (6) |
N21 | 0.0841 (12) | 0.0654 (11) | 0.0780 (11) | 0.0245 (9) | −0.0153 (9) | −0.0006 (9) |
C22 | 0.0535 (9) | 0.0708 (12) | 0.0476 (9) | 0.0096 (8) | 0.0003 (7) | 0.0047 (8) |
C23 | 0.0627 (12) | 0.1074 (18) | 0.0838 (15) | 0.0044 (12) | −0.0151 (11) | 0.0066 (13) |
C24 | 0.0685 (15) | 0.160 (3) | 0.109 (2) | 0.0285 (18) | −0.0282 (14) | 0.014 (2) |
C25 | 0.104 (2) | 0.126 (3) | 0.104 (2) | 0.058 (2) | −0.0170 (17) | 0.0143 (19) |
C26 | 0.112 (2) | 0.0883 (17) | 0.1003 (18) | 0.0465 (16) | −0.0226 (16) | 0.0019 (14) |
C31 | 0.0469 (8) | 0.0490 (8) | 0.0461 (8) | −0.0031 (7) | −0.0036 (7) | 0.0001 (7) |
C32 | 0.0650 (11) | 0.0566 (10) | 0.0595 (10) | 0.0019 (8) | 0.0082 (8) | −0.0039 (8) |
C33 | 0.0722 (13) | 0.0803 (14) | 0.0686 (12) | −0.0002 (11) | 0.0124 (10) | −0.0182 (11) |
C34 | 0.0707 (13) | 0.1070 (18) | 0.0534 (11) | −0.0127 (12) | 0.0120 (9) | −0.0094 (11) |
F34 | 0.1163 (12) | 0.1697 (16) | 0.0670 (8) | −0.0229 (11) | 0.0383 (8) | −0.0117 (9) |
C35 | 0.0904 (16) | 0.0956 (17) | 0.0630 (12) | −0.0111 (13) | 0.0090 (11) | 0.0248 (12) |
C36 | 0.0704 (12) | 0.0625 (11) | 0.0619 (11) | 0.0012 (9) | 0.0033 (9) | 0.0128 (9) |
C47 | 0.0474 (8) | 0.0381 (8) | 0.0513 (8) | −0.0013 (6) | 0.0000 (7) | 0.0017 (7) |
O47 | 0.0793 (8) | 0.0351 (6) | 0.0580 (7) | 0.0012 (5) | −0.0048 (6) | 0.0018 (5) |
N41 | 0.1270 (17) | 0.0641 (11) | 0.0682 (11) | 0.0086 (10) | −0.0376 (11) | 0.0004 (9) |
C42 | 0.0673 (11) | 0.0477 (9) | 0.0531 (9) | −0.0099 (8) | −0.0066 (8) | 0.0002 (7) |
C43 | 0.1111 (18) | 0.0619 (12) | 0.0562 (11) | −0.0032 (11) | 0.0002 (11) | −0.0056 (9) |
C44 | 0.173 (3) | 0.0959 (19) | 0.0572 (13) | −0.0161 (19) | −0.0056 (16) | −0.0175 (13) |
C45 | 0.196 (4) | 0.112 (2) | 0.0613 (15) | −0.022 (2) | −0.0468 (19) | 0.0030 (15) |
C46 | 0.196 (4) | 0.0907 (19) | 0.0821 (17) | 0.010 (2) | −0.066 (2) | 0.0076 (15) |
C51 | 0.0480 (9) | 0.0433 (8) | 0.0529 (9) | 0.0031 (6) | 0.0018 (7) | −0.0014 (7) |
C52 | 0.0575 (10) | 0.0523 (10) | 0.0862 (13) | −0.0029 (8) | −0.0101 (9) | 0.0141 (9) |
C53 | 0.0605 (11) | 0.0714 (13) | 0.0795 (13) | 0.0020 (9) | −0.0142 (10) | 0.0209 (10) |
C54 | 0.0480 (9) | 0.0718 (12) | 0.0597 (10) | −0.0051 (8) | −0.0060 (8) | −0.0029 (9) |
F54 | 0.0588 (6) | 0.1041 (9) | 0.0831 (8) | −0.0149 (6) | −0.0181 (6) | 0.0077 (7) |
C55 | 0.0576 (10) | 0.0542 (10) | 0.0744 (12) | −0.0093 (8) | −0.0008 (9) | 0.0043 (9) |
C56 | 0.0523 (9) | 0.0492 (9) | 0.0634 (10) | 0.0012 (7) | −0.0025 (8) | 0.0062 (8) |
C1—O11 | 1.4279 (19) | C25—C26 | 1.359 (4) |
C1—C6 | 1.527 (2) | C25—H25 | 0.9500 |
C1—C12 | 1.529 (2) | C26—H26 | 0.9500 |
C1—C2 | 1.565 (2) | C31—C36 | 1.382 (2) |
O11—H11 | 0.8158 | C31—C32 | 1.383 (2) |
C2—C27 | 1.519 (2) | C32—C33 | 1.386 (3) |
C2—C3 | 1.539 (2) | C32—H32 | 0.9500 |
C2—H2 | 1.0000 | C33—C34 | 1.347 (3) |
C3—C31 | 1.520 (2) | C33—H33 | 0.9500 |
C3—C4 | 1.551 (2) | C34—C35 | 1.357 (4) |
C3—H3 | 1.0000 | C34—F34 | 1.363 (2) |
C4—C47 | 1.514 (2) | C35—C36 | 1.389 (3) |
C4—C5 | 1.550 (2) | C35—H35 | 0.9500 |
C4—H4 | 1.0000 | C36—H36 | 0.9500 |
C5—C51 | 1.519 (2) | C47—O47 | 1.2140 (19) |
C5—C6 | 1.531 (2) | C47—C42 | 1.505 (2) |
C5—H5 | 1.0000 | N41—C42 | 1.328 (3) |
C6—H6A | 0.9900 | N41—C46 | 1.333 (3) |
C6—H6B | 0.9900 | C42—C43 | 1.379 (3) |
N11—C12 | 1.333 (2) | C43—C44 | 1.381 (3) |
N11—C16 | 1.333 (3) | C43—H43 | 0.9500 |
C12—C13 | 1.376 (3) | C44—C45 | 1.357 (4) |
C13—C14 | 1.384 (3) | C44—H44 | 0.9500 |
C13—H13 | 0.9500 | C45—C46 | 1.357 (4) |
C14—C15 | 1.364 (4) | C45—H45 | 0.9500 |
C14—H14 | 0.9500 | C46—H46 | 0.9500 |
C15—C16 | 1.361 (4) | C51—C56 | 1.386 (2) |
C15—H15 | 0.9500 | C51—C52 | 1.390 (2) |
C16—H16 | 0.9500 | C52—C53 | 1.384 (3) |
C27—O27 | 1.212 (2) | C52—H52 | 0.9500 |
C27—C22 | 1.505 (2) | C53—C54 | 1.364 (3) |
N21—C22 | 1.328 (3) | C53—H53 | 0.9500 |
N21—C26 | 1.336 (3) | C54—C55 | 1.356 (3) |
C22—C23 | 1.378 (3) | C54—F54 | 1.371 (2) |
C23—C24 | 1.393 (4) | C55—C56 | 1.391 (2) |
C23—H23 | 0.9500 | C55—H55 | 0.9500 |
C24—C25 | 1.362 (4) | C56—H56 | 0.9500 |
C24—H24 | 0.9500 | ||
O11—C1—C6 | 106.76 (13) | C25—C24—H24 | 120.1 |
O11—C1—C12 | 109.29 (13) | C23—C24—H24 | 120.1 |
C6—C1—C12 | 112.97 (13) | C26—C25—C24 | 118.3 (2) |
O11—C1—C2 | 110.43 (13) | C26—C25—H25 | 120.9 |
C6—C1—C2 | 109.49 (13) | C24—C25—H25 | 120.9 |
C12—C1—C2 | 107.91 (13) | N21—C26—C25 | 123.9 (3) |
C1—O11—H11 | 105.9 | N21—C26—H26 | 118.0 |
C27—C2—C3 | 109.78 (12) | C25—C26—H26 | 118.0 |
C27—C2—C1 | 109.77 (13) | C36—C31—C32 | 117.94 (17) |
C3—C2—C1 | 110.82 (12) | C36—C31—C3 | 119.17 (15) |
C27—C2—H2 | 108.8 | C32—C31—C3 | 122.80 (15) |
C3—C2—H2 | 108.8 | C31—C32—C33 | 121.13 (19) |
C1—C2—H2 | 108.8 | C31—C32—H32 | 119.4 |
C31—C3—C2 | 113.55 (13) | C33—C32—H32 | 119.4 |
C31—C3—C4 | 109.86 (12) | C34—C33—C32 | 118.8 (2) |
C2—C3—C4 | 112.52 (12) | C34—C33—H33 | 120.6 |
C31—C3—H3 | 106.8 | C32—C33—H33 | 120.6 |
C2—C3—H3 | 106.8 | C33—C34—C35 | 122.59 (19) |
C4—C3—H3 | 106.8 | C33—C34—F34 | 118.6 (2) |
C47—C4—C5 | 112.67 (12) | C35—C34—F34 | 118.9 (2) |
C47—C4—C3 | 111.22 (12) | C34—C35—C36 | 118.5 (2) |
C5—C4—C3 | 111.44 (12) | C34—C35—H35 | 120.7 |
C47—C4—H4 | 107.1 | C36—C35—H35 | 120.7 |
C5—C4—H4 | 107.1 | C31—C36—C35 | 121.0 (2) |
C3—C4—H4 | 107.1 | C31—C36—H36 | 119.5 |
C51—C5—C6 | 114.48 (13) | C35—C36—H36 | 119.5 |
C51—C5—C4 | 110.25 (13) | O47—C47—C42 | 118.94 (15) |
C6—C5—C4 | 112.07 (13) | O47—C47—C4 | 122.49 (14) |
C51—C5—H5 | 106.5 | C42—C47—C4 | 118.56 (13) |
C6—C5—H5 | 106.5 | C42—N41—C46 | 117.1 (2) |
C4—C5—H5 | 106.5 | N41—C42—C43 | 122.75 (18) |
C1—C6—C5 | 111.55 (13) | N41—C42—C47 | 117.45 (16) |
C1—C6—H6A | 109.3 | C43—C42—C47 | 119.79 (17) |
C5—C6—H6A | 109.3 | C42—C43—C44 | 118.3 (2) |
C1—C6—H6B | 109.3 | C42—C43—H43 | 120.9 |
C5—C6—H6B | 109.3 | C44—C43—H43 | 120.9 |
H6A—C6—H6B | 108.0 | C45—C44—C43 | 119.3 (3) |
C12—N11—C16 | 117.64 (19) | C45—C44—H44 | 120.4 |
N11—C12—C13 | 122.39 (17) | C43—C44—H44 | 120.4 |
N11—C12—C1 | 114.04 (15) | C44—C45—C46 | 118.5 (2) |
C13—C12—C1 | 123.42 (16) | C44—C45—H45 | 120.7 |
C12—C13—C14 | 118.4 (2) | C46—C45—H45 | 120.7 |
C12—C13—H13 | 120.8 | N41—C46—C45 | 124.1 (3) |
C14—C13—H13 | 120.8 | N41—C46—H46 | 118.0 |
C15—C14—C13 | 119.5 (2) | C45—C46—H46 | 118.0 |
C15—C14—H14 | 120.3 | C56—C51—C52 | 117.92 (16) |
C13—C14—H14 | 120.3 | C56—C51—C5 | 123.61 (15) |
C16—C15—C14 | 118.2 (2) | C52—C51—C5 | 118.43 (15) |
C16—C15—H15 | 120.9 | C53—C52—C51 | 121.41 (18) |
C14—C15—H15 | 120.9 | C53—C52—H52 | 119.3 |
N11—C16—C15 | 123.8 (2) | C51—C52—H52 | 119.3 |
N11—C16—H16 | 118.1 | C54—C53—C52 | 118.12 (18) |
C15—C16—H16 | 118.1 | C54—C53—H53 | 120.9 |
O27—C27—C22 | 119.69 (16) | C52—C53—H53 | 120.9 |
O27—C27—C2 | 121.13 (15) | C55—C54—C53 | 123.09 (17) |
C22—C27—C2 | 119.16 (15) | C55—C54—F54 | 118.79 (17) |
C22—N21—C26 | 117.2 (2) | C53—C54—F54 | 118.11 (17) |
N21—C22—C23 | 123.49 (19) | C54—C55—C56 | 118.26 (17) |
N21—C22—C27 | 117.14 (16) | C54—C55—H55 | 120.9 |
C23—C22—C27 | 119.36 (19) | C56—C55—H55 | 120.9 |
C22—C23—C24 | 117.3 (3) | C51—C56—C55 | 121.20 (16) |
C22—C23—H23 | 121.4 | C51—C56—H56 | 119.4 |
C24—C23—H23 | 121.4 | C55—C56—H56 | 119.4 |
C25—C24—C23 | 119.8 (3) | ||
O11—C1—C2—C27 | −61.80 (16) | C22—C23—C24—C25 | −1.5 (4) |
C6—C1—C2—C27 | −179.08 (13) | C23—C24—C25—C26 | 1.7 (5) |
C12—C1—C2—C27 | 57.59 (16) | C22—N21—C26—C25 | 0.1 (4) |
O11—C1—C2—C3 | 59.62 (16) | C24—C25—C26—N21 | −1.0 (5) |
C6—C1—C2—C3 | −57.65 (16) | C2—C3—C31—C36 | 148.77 (15) |
C12—C1—C2—C3 | 179.02 (13) | C4—C3—C31—C36 | −84.24 (18) |
C27—C2—C3—C31 | −58.61 (16) | C2—C3—C31—C32 | −34.7 (2) |
C1—C2—C3—C31 | 179.97 (12) | C4—C3—C31—C32 | 92.30 (18) |
C27—C2—C3—C4 | 175.80 (12) | C36—C31—C32—C33 | 1.9 (3) |
C1—C2—C3—C4 | 54.37 (16) | C3—C31—C32—C33 | −174.72 (17) |
C31—C3—C4—C47 | −51.99 (16) | C31—C32—C33—C34 | −0.5 (3) |
C2—C3—C4—C47 | 75.59 (16) | C32—C33—C34—C35 | −0.8 (4) |
C31—C3—C4—C5 | −178.62 (12) | C32—C33—C34—F34 | 180.0 (2) |
C2—C3—C4—C5 | −51.05 (16) | C33—C34—C35—C36 | 0.7 (4) |
C47—C4—C5—C51 | 54.51 (16) | F34—C34—C35—C36 | 179.9 (2) |
C3—C4—C5—C51 | −179.66 (12) | C32—C31—C36—C35 | −1.9 (3) |
C47—C4—C5—C6 | −74.26 (16) | C3—C31—C36—C35 | 174.78 (19) |
C3—C4—C5—C6 | 51.57 (16) | C34—C35—C36—C31 | 0.7 (3) |
O11—C1—C6—C5 | −60.66 (17) | C5—C4—C47—O47 | 58.7 (2) |
C12—C1—C6—C5 | 179.18 (13) | C3—C4—C47—O47 | −67.30 (19) |
C2—C1—C6—C5 | 58.90 (17) | C5—C4—C47—C42 | −121.88 (15) |
C51—C5—C6—C1 | 176.87 (13) | C3—C4—C47—C42 | 112.16 (16) |
C4—C5—C6—C1 | −56.61 (17) | C46—N41—C42—C43 | −1.6 (4) |
C16—N11—C12—C13 | −2.1 (3) | C46—N41—C42—C47 | 177.1 (3) |
C16—N11—C12—C1 | 173.54 (18) | O47—C47—C42—N41 | −163.26 (19) |
O11—C1—C12—N11 | 28.5 (2) | C4—C47—C42—N41 | 17.3 (3) |
C6—C1—C12—N11 | 147.25 (15) | O47—C47—C42—C43 | 15.5 (3) |
C2—C1—C12—N11 | −91.57 (17) | C4—C47—C42—C43 | −164.01 (18) |
O11—C1—C12—C13 | −155.82 (18) | N41—C42—C43—C44 | 0.3 (4) |
C6—C1—C12—C13 | −37.1 (2) | C47—C42—C43—C44 | −178.3 (2) |
C2—C1—C12—C13 | 84.1 (2) | C42—C43—C44—C45 | 1.2 (5) |
N11—C12—C13—C14 | 1.6 (3) | C43—C44—C45—C46 | −1.4 (6) |
C1—C12—C13—C14 | −173.7 (2) | C42—N41—C46—C45 | 1.4 (5) |
C12—C13—C14—C15 | 0.1 (4) | C44—C45—C46—N41 | 0.1 (6) |
C13—C14—C15—C16 | −1.1 (4) | C6—C5—C51—C56 | 18.5 (2) |
C12—N11—C16—C15 | 1.0 (4) | C4—C5—C51—C56 | −108.96 (18) |
C14—C15—C16—N11 | 0.6 (4) | C6—C5—C51—C52 | −163.96 (16) |
C3—C2—C27—O27 | −45.1 (2) | C4—C5—C51—C52 | 68.6 (2) |
C1—C2—C27—O27 | 76.93 (19) | C56—C51—C52—C53 | 0.1 (3) |
C3—C2—C27—C22 | 136.74 (14) | C5—C51—C52—C53 | −177.57 (19) |
C1—C2—C27—C22 | −101.21 (16) | C51—C52—C53—C54 | −0.2 (3) |
C26—N21—C22—C23 | 0.1 (3) | C52—C53—C54—C55 | 0.0 (3) |
C26—N21—C22—C27 | 179.0 (2) | C52—C53—C54—F54 | −179.53 (19) |
O27—C27—C22—N21 | 172.63 (17) | C53—C54—C55—C56 | 0.2 (3) |
C2—C27—C22—N21 | −9.2 (2) | F54—C54—C55—C56 | 179.70 (17) |
O27—C27—C22—C23 | −8.4 (3) | C52—C51—C56—C55 | 0.1 (3) |
C2—C27—C22—C23 | 169.76 (18) | C5—C51—C56—C55 | 177.62 (16) |
N21—C22—C23—C24 | 0.6 (4) | C54—C55—C56—C51 | −0.2 (3) |
C27—C22—C23—C24 | −178.2 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H11···N11 | 0.82 | 2.13 | 2.624 (2) | 119 |
C13—H13···O11i | 0.95 | 2.54 | 3.385 (3) | 148 |
C55—H55···O27i | 0.95 | 2.53 | 3.244 (2) | 132 |
Symmetry code: (i) −x+1/2, y+1/2, z. |
C35H27Cl2N3O3·0.951C3H6O | Dx = 1.280 Mg m−3 |
Mr = 663.73 | Cu Kα radiation, λ = 1.54178 Å |
Orthorhombic, Fdd2 | Cell parameters from 4224 reflections |
a = 16.5446 (6) Å | θ = 4.6–70.1° |
b = 53.4204 (17) Å | µ = 2.05 mm−1 |
c = 15.5857 (4) Å | T = 200 K |
V = 13774.9 (8) Å3 | Block, colourless |
Z = 16 | 0.30 × 0.25 × 0.20 mm |
F(000) = 5543 |
Agilent Xcalibur Ruby Gemini diffractometer | 3490 reflections with I > 2σ(I) |
Radiation source: Enhance (Cu) X-ray Source | Rint = 0.027 |
ω scans | θmax = 70.1°, θmin = 4.6° |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | h = −19→20 |
Tmin = 0.388, Tmax = 0.664 | k = −56→64 |
9544 measured reflections | l = −18→6 |
4224 independent reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.039 | H-atom parameters constrained |
wR(F2) = 0.109 | w = 1/[σ2(Fo2) + (0.0744P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.97 | (Δ/σ)max = 0.001 |
4224 reflections | Δρmax = 0.16 e Å−3 |
436 parameters | Δρmin = −0.16 e Å−3 |
7 restraints | Absolute structure: Flack x determined using 613 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013). |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.089 (18) |
C35H27Cl2N3O3·0.951C3H6O | V = 13774.9 (8) Å3 |
Mr = 663.73 | Z = 16 |
Orthorhombic, Fdd2 | Cu Kα radiation |
a = 16.5446 (6) Å | µ = 2.05 mm−1 |
b = 53.4204 (17) Å | T = 200 K |
c = 15.5857 (4) Å | 0.30 × 0.25 × 0.20 mm |
Agilent Xcalibur Ruby Gemini diffractometer | 4224 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | 3490 reflections with I > 2σ(I) |
Tmin = 0.388, Tmax = 0.664 | Rint = 0.027 |
9544 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | H-atom parameters constrained |
wR(F2) = 0.109 | Δρmax = 0.16 e Å−3 |
S = 0.97 | Δρmin = −0.16 e Å−3 |
4224 reflections | Absolute structure: Flack x determined using 613 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013). |
436 parameters | Absolute structure parameter: 0.089 (18) |
7 restraints |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 0.25172 (19) | 0.35490 (6) | 0.4632 (2) | 0.0505 (6) | |
O11 | 0.20607 (15) | 0.35606 (5) | 0.54074 (15) | 0.0647 (6) | |
H11 | 0.2379 | 0.3467 | 0.5731 | 0.097* | |
C2 | 0.21280 (17) | 0.33568 (5) | 0.40064 (19) | 0.0481 (6) | |
H2 | 0.2440 | 0.3357 | 0.3457 | 0.058* | |
C3 | 0.12475 (17) | 0.34306 (5) | 0.38147 (19) | 0.0460 (6) | |
H3 | 0.0962 | 0.3435 | 0.4380 | 0.055* | |
C4 | 0.11812 (16) | 0.36986 (5) | 0.34352 (19) | 0.0454 (6) | |
H4 | 0.0596 | 0.3745 | 0.3438 | 0.054* | |
C5 | 0.16302 (18) | 0.38897 (5) | 0.4017 (2) | 0.0489 (6) | |
H5 | 0.1336 | 0.3891 | 0.4577 | 0.059* | |
C6 | 0.24983 (19) | 0.38087 (5) | 0.4218 (2) | 0.0526 (6) | |
H6A | 0.2818 | 0.3806 | 0.3681 | 0.063* | |
H6B | 0.2750 | 0.3932 | 0.4611 | 0.063* | |
N11 | 0.3517 (2) | 0.33975 (6) | 0.5638 (2) | 0.0679 (7) | |
C12 | 0.33845 (19) | 0.34663 (6) | 0.4829 (2) | 0.0546 (7) | |
C13 | 0.3972 (2) | 0.34512 (7) | 0.4207 (3) | 0.0649 (8) | |
H13 | 0.3865 | 0.3509 | 0.3642 | 0.078* | |
C14 | 0.4712 (2) | 0.33528 (9) | 0.4409 (3) | 0.0809 (11) | |
H14 | 0.5121 | 0.3338 | 0.3984 | 0.097* | |
C15 | 0.4854 (3) | 0.32758 (9) | 0.5246 (4) | 0.0876 (13) | |
H15 | 0.5356 | 0.3204 | 0.5407 | 0.105* | |
C16 | 0.4251 (3) | 0.33070 (9) | 0.5827 (3) | 0.0862 (13) | |
H16 | 0.4357 | 0.3262 | 0.6405 | 0.103* | |
C27 | 0.21686 (19) | 0.30956 (6) | 0.4398 (2) | 0.0541 (7) | |
O27 | 0.16848 (16) | 0.30235 (5) | 0.4917 (2) | 0.0735 (7) | |
N21 | 0.3165 (2) | 0.29660 (7) | 0.3350 (3) | 0.0837 (10) | |
C22 | 0.2864 (2) | 0.29305 (6) | 0.4138 (3) | 0.0620 (8) | |
C23 | 0.3160 (3) | 0.27562 (7) | 0.4698 (4) | 0.0841 (12) | |
H23 | 0.2924 | 0.2736 | 0.5249 | 0.101* | |
C24 | 0.3807 (4) | 0.26106 (10) | 0.4446 (5) | 0.1104 (18) | |
H24 | 0.4038 | 0.2492 | 0.4829 | 0.132* | |
C25 | 0.4108 (4) | 0.26401 (11) | 0.3641 (5) | 0.116 (2) | |
H25 | 0.4540 | 0.2537 | 0.3445 | 0.139* | |
C26 | 0.3785 (3) | 0.28192 (12) | 0.3115 (4) | 0.1066 (17) | |
H26 | 0.4009 | 0.2841 | 0.2559 | 0.128* | |
C31 | 0.08089 (18) | 0.32368 (6) | 0.3270 (2) | 0.0513 (6) | |
C32 | 0.1182 (2) | 0.31044 (7) | 0.2615 (3) | 0.0637 (8) | |
H32 | 0.1729 | 0.3141 | 0.2477 | 0.076* | |
C33 | 0.0783 (2) | 0.29211 (8) | 0.2158 (3) | 0.0746 (10) | |
H33 | 0.1049 | 0.2832 | 0.1712 | 0.090* | |
C34 | −0.0008 (3) | 0.28699 (7) | 0.2360 (3) | 0.0757 (10) | |
Cl34 | −0.05239 (11) | 0.26346 (3) | 0.18053 (12) | 0.1225 (6) | |
C35 | −0.0399 (2) | 0.29974 (8) | 0.2996 (3) | 0.0764 (11) | |
H35 | −0.0946 | 0.2960 | 0.3126 | 0.092* | |
C36 | 0.0003 (2) | 0.31802 (7) | 0.3446 (3) | 0.0631 (8) | |
H36 | −0.0272 | 0.3269 | 0.3884 | 0.076* | |
C47 | 0.14717 (16) | 0.37140 (5) | 0.25098 (19) | 0.0451 (6) | |
O47 | 0.21661 (12) | 0.36662 (5) | 0.23092 (16) | 0.0607 (6) | |
N41 | 0.01329 (16) | 0.38537 (6) | 0.2066 (2) | 0.0646 (7) | |
C42 | 0.08830 (17) | 0.37945 (5) | 0.1827 (2) | 0.0488 (6) | |
C43 | 0.1135 (2) | 0.38102 (7) | 0.0983 (2) | 0.0618 (8) | |
H43 | 0.1672 | 0.3765 | 0.0831 | 0.074* | |
C44 | 0.0603 (2) | 0.38919 (8) | 0.0363 (3) | 0.0751 (10) | |
H44 | 0.0768 | 0.3907 | −0.0218 | 0.090* | |
C45 | −0.0167 (3) | 0.39508 (8) | 0.0603 (3) | 0.0782 (11) | |
H45 | −0.0553 | 0.4005 | 0.0192 | 0.094* | |
C46 | −0.0367 (2) | 0.39294 (9) | 0.1454 (3) | 0.0794 (11) | |
H46 | −0.0903 | 0.3972 | 0.1616 | 0.095* | |
C51 | 0.15672 (19) | 0.41541 (6) | 0.3660 (2) | 0.0508 (6) | |
C52 | 0.0822 (2) | 0.42707 (7) | 0.3642 (3) | 0.0706 (10) | |
H52 | 0.0362 | 0.4185 | 0.3856 | 0.085* | |
C53 | 0.0733 (3) | 0.45099 (8) | 0.3318 (4) | 0.0804 (11) | |
H53 | 0.0215 | 0.4587 | 0.3302 | 0.096* | |
C54 | 0.1397 (3) | 0.46354 (7) | 0.3021 (3) | 0.0725 (10) | |
Cl54 | 0.12896 (10) | 0.49384 (2) | 0.26117 (12) | 0.1142 (5) | |
C55 | 0.2146 (3) | 0.45280 (7) | 0.3033 (3) | 0.0726 (10) | |
H55 | 0.2603 | 0.4617 | 0.2825 | 0.087* | |
C56 | 0.2225 (2) | 0.42862 (6) | 0.3355 (3) | 0.0623 (8) | |
H56 | 0.2744 | 0.4210 | 0.3366 | 0.075* | |
C71 | 0.6495 (16) | 0.2977 (7) | 0.2767 (10) | 0.125 (3) | 0.690 (13) |
O71 | 0.5974 (5) | 0.3120 (2) | 0.2778 (8) | 0.159 (4) | 0.690 (13) |
C72 | 0.7036 (14) | 0.2906 (3) | 0.2035 (9) | 0.174 (5) | 0.690 (13) |
H72A | 0.7137 | 0.2726 | 0.2047 | 0.261* | 0.690 (13) |
H72B | 0.7550 | 0.2996 | 0.2087 | 0.261* | 0.690 (13) |
H72C | 0.6776 | 0.2951 | 0.1492 | 0.261* | 0.690 (13) |
C73 | 0.6809 (14) | 0.2869 (3) | 0.3563 (8) | 0.174 (5) | 0.690 (13) |
H73A | 0.7396 | 0.2893 | 0.3587 | 0.261* | 0.690 (13) |
H73B | 0.6686 | 0.2690 | 0.3581 | 0.261* | 0.690 (13) |
H73C | 0.6557 | 0.2953 | 0.4055 | 0.261* | 0.690 (13) |
C81 | 0.664 (4) | 0.293 (2) | 0.285 (2) | 0.125 (3) | 0.261 (11) |
O81 | 0.6093 (14) | 0.2987 (6) | 0.326 (2) | 0.159 (4) | 0.261 (11) |
C82 | 0.680 (3) | 0.2969 (10) | 0.1916 (17) | 0.174 (5) | 0.261 (11) |
H82A | 0.7179 | 0.2841 | 0.1711 | 0.261* | 0.261 (11) |
H82B | 0.7035 | 0.3135 | 0.1825 | 0.261* | 0.261 (11) |
H82C | 0.6291 | 0.2956 | 0.1599 | 0.261* | 0.261 (11) |
C83 | 0.731 (2) | 0.2787 (7) | 0.323 (2) | 0.174 (5) | 0.261 (11) |
H83A | 0.7726 | 0.2758 | 0.2799 | 0.261* | 0.261 (11) |
H83B | 0.7101 | 0.2626 | 0.3440 | 0.261* | 0.261 (11) |
H83C | 0.7539 | 0.2881 | 0.3714 | 0.261* | 0.261 (11) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0563 (14) | 0.0556 (15) | 0.0397 (13) | 0.0015 (13) | 0.0020 (13) | 0.0001 (12) |
O11 | 0.0749 (13) | 0.0745 (14) | 0.0445 (12) | 0.0068 (12) | 0.0082 (11) | −0.0015 (11) |
C2 | 0.0501 (13) | 0.0502 (13) | 0.0440 (14) | 0.0029 (12) | 0.0040 (12) | 0.0005 (12) |
C3 | 0.0469 (13) | 0.0504 (13) | 0.0409 (13) | 0.0026 (11) | 0.0056 (11) | 0.0026 (11) |
C4 | 0.0413 (12) | 0.0505 (14) | 0.0443 (14) | 0.0055 (11) | 0.0058 (11) | 0.0000 (12) |
C5 | 0.0552 (14) | 0.0497 (13) | 0.0419 (13) | 0.0031 (12) | 0.0075 (13) | −0.0010 (11) |
C6 | 0.0576 (15) | 0.0507 (14) | 0.0495 (15) | −0.0007 (13) | −0.0049 (13) | −0.0007 (13) |
N11 | 0.0849 (19) | 0.0655 (15) | 0.0533 (15) | 0.0078 (15) | −0.0128 (16) | 0.0091 (13) |
C12 | 0.0625 (16) | 0.0502 (14) | 0.0512 (16) | −0.0030 (13) | −0.0109 (15) | 0.0016 (13) |
C13 | 0.0551 (16) | 0.080 (2) | 0.0597 (19) | −0.0013 (16) | −0.0068 (16) | 0.0029 (17) |
C14 | 0.0621 (19) | 0.092 (3) | 0.088 (3) | 0.0039 (19) | −0.008 (2) | 0.002 (2) |
C15 | 0.074 (2) | 0.086 (3) | 0.104 (3) | 0.015 (2) | −0.029 (3) | 0.006 (3) |
C16 | 0.105 (3) | 0.084 (3) | 0.070 (2) | 0.019 (2) | −0.030 (3) | 0.015 (2) |
C27 | 0.0583 (15) | 0.0555 (15) | 0.0485 (15) | −0.0016 (13) | −0.0029 (14) | 0.0026 (13) |
O27 | 0.0774 (14) | 0.0687 (14) | 0.0743 (17) | 0.0041 (12) | 0.0120 (14) | 0.0199 (13) |
N21 | 0.088 (2) | 0.093 (2) | 0.070 (2) | 0.0334 (19) | 0.0021 (18) | −0.0136 (18) |
C22 | 0.0672 (17) | 0.0499 (15) | 0.069 (2) | 0.0054 (14) | −0.0081 (17) | −0.0079 (15) |
C23 | 0.097 (3) | 0.0609 (19) | 0.094 (3) | 0.019 (2) | −0.003 (3) | 0.011 (2) |
C24 | 0.123 (4) | 0.077 (3) | 0.131 (5) | 0.042 (3) | −0.014 (4) | 0.004 (3) |
C25 | 0.122 (4) | 0.102 (4) | 0.123 (5) | 0.061 (3) | −0.013 (4) | −0.039 (4) |
C26 | 0.110 (3) | 0.128 (4) | 0.081 (3) | 0.047 (3) | 0.011 (3) | −0.030 (3) |
C31 | 0.0516 (14) | 0.0498 (14) | 0.0526 (16) | 0.0002 (12) | −0.0016 (13) | 0.0070 (13) |
C32 | 0.0637 (16) | 0.0635 (17) | 0.064 (2) | 0.0005 (15) | −0.0012 (17) | −0.0067 (16) |
C33 | 0.086 (2) | 0.067 (2) | 0.071 (2) | 0.0000 (18) | −0.016 (2) | −0.0121 (18) |
C34 | 0.090 (2) | 0.0581 (17) | 0.079 (3) | −0.0081 (18) | −0.031 (2) | 0.0038 (18) |
Cl34 | 0.1446 (11) | 0.0949 (8) | 0.1281 (12) | −0.0398 (8) | −0.0502 (10) | −0.0146 (8) |
C35 | 0.0620 (18) | 0.081 (2) | 0.086 (3) | −0.0154 (19) | −0.0148 (19) | 0.014 (2) |
C36 | 0.0564 (16) | 0.0667 (19) | 0.066 (2) | −0.0026 (15) | −0.0054 (16) | 0.0083 (17) |
C47 | 0.0442 (13) | 0.0472 (12) | 0.0440 (15) | 0.0009 (11) | 0.0069 (12) | −0.0014 (11) |
O47 | 0.0481 (10) | 0.0849 (15) | 0.0491 (11) | 0.0098 (10) | 0.0084 (10) | 0.0015 (11) |
N41 | 0.0513 (13) | 0.0835 (18) | 0.0588 (16) | 0.0139 (13) | 0.0057 (13) | 0.0086 (15) |
C42 | 0.0477 (13) | 0.0507 (13) | 0.0479 (15) | −0.0038 (11) | 0.0003 (13) | 0.0001 (12) |
C43 | 0.0542 (16) | 0.082 (2) | 0.0494 (17) | −0.0068 (15) | 0.0071 (15) | 0.0027 (16) |
C44 | 0.079 (2) | 0.093 (3) | 0.0528 (19) | −0.010 (2) | −0.0045 (18) | 0.0080 (19) |
C45 | 0.080 (2) | 0.083 (2) | 0.072 (2) | 0.003 (2) | −0.022 (2) | 0.016 (2) |
C46 | 0.0548 (17) | 0.101 (3) | 0.083 (3) | 0.0193 (19) | −0.0018 (19) | 0.014 (2) |
C51 | 0.0590 (15) | 0.0487 (14) | 0.0448 (14) | 0.0031 (13) | 0.0035 (13) | −0.0028 (12) |
C52 | 0.0645 (18) | 0.0581 (17) | 0.089 (3) | 0.0055 (16) | 0.0117 (19) | 0.0037 (18) |
C53 | 0.076 (2) | 0.062 (2) | 0.103 (3) | 0.0158 (18) | −0.003 (2) | 0.008 (2) |
C54 | 0.098 (3) | 0.0495 (16) | 0.070 (2) | 0.0066 (18) | −0.007 (2) | 0.0090 (16) |
Cl54 | 0.1386 (10) | 0.0630 (5) | 0.1409 (12) | 0.0055 (6) | −0.0158 (10) | 0.0338 (6) |
C55 | 0.084 (2) | 0.0572 (17) | 0.077 (2) | −0.0077 (18) | 0.006 (2) | 0.0091 (17) |
C56 | 0.0596 (16) | 0.0565 (16) | 0.071 (2) | 0.0020 (14) | 0.0073 (17) | 0.0020 (16) |
C71 | 0.138 (11) | 0.106 (16) | 0.132 (7) | −0.032 (6) | 0.022 (7) | 0.008 (6) |
O71 | 0.130 (5) | 0.161 (8) | 0.186 (11) | 0.012 (5) | 0.014 (6) | 0.015 (7) |
C72 | 0.286 (14) | 0.131 (8) | 0.104 (5) | −0.013 (8) | 0.028 (7) | 0.016 (4) |
C73 | 0.286 (14) | 0.131 (8) | 0.104 (5) | −0.013 (8) | 0.028 (7) | 0.016 (4) |
C81 | 0.138 (11) | 0.106 (16) | 0.132 (7) | −0.032 (6) | 0.022 (7) | 0.008 (6) |
O81 | 0.130 (5) | 0.161 (8) | 0.186 (11) | 0.012 (5) | 0.014 (6) | 0.015 (7) |
C82 | 0.286 (14) | 0.131 (8) | 0.104 (5) | −0.013 (8) | 0.028 (7) | 0.016 (4) |
C83 | 0.286 (14) | 0.131 (8) | 0.104 (5) | −0.013 (8) | 0.028 (7) | 0.016 (4) |
C1—O11 | 1.426 (4) | C34—C35 | 1.365 (7) |
C1—C6 | 1.531 (4) | C34—Cl34 | 1.748 (4) |
C1—C12 | 1.533 (4) | C35—C36 | 1.374 (6) |
C1—C2 | 1.556 (4) | C35—H35 | 0.9500 |
O11—H11 | 0.8847 | C36—H36 | 0.9500 |
C2—C27 | 1.524 (4) | C47—O47 | 1.218 (3) |
C2—C3 | 1.539 (4) | C47—C42 | 1.506 (4) |
C2—H2 | 1.0000 | N41—C46 | 1.326 (5) |
C3—C31 | 1.523 (4) | N41—C42 | 1.334 (4) |
C3—C4 | 1.552 (4) | C42—C43 | 1.382 (5) |
C3—H3 | 1.0000 | C43—C44 | 1.378 (5) |
C4—C47 | 1.523 (4) | C43—H43 | 0.9500 |
C4—C5 | 1.555 (4) | C44—C45 | 1.364 (6) |
C4—H4 | 1.0000 | C44—H44 | 0.9500 |
C5—C51 | 1.521 (4) | C45—C46 | 1.372 (7) |
C5—C6 | 1.532 (4) | C45—H45 | 0.9500 |
C5—H5 | 1.0000 | C46—H46 | 0.9500 |
C6—H6A | 0.9900 | C51—C52 | 1.381 (5) |
C6—H6B | 0.9900 | C51—C56 | 1.382 (5) |
N11—C12 | 1.331 (5) | C52—C53 | 1.382 (5) |
N11—C16 | 1.340 (5) | C52—H52 | 0.9500 |
C12—C13 | 1.375 (5) | C53—C54 | 1.368 (6) |
C13—C14 | 1.370 (6) | C53—H53 | 0.9500 |
C13—H13 | 0.9500 | C54—C55 | 1.365 (6) |
C14—C15 | 1.387 (8) | C54—Cl54 | 1.749 (4) |
C14—H14 | 0.9500 | C55—C56 | 1.392 (5) |
C15—C16 | 1.357 (7) | C55—H55 | 0.9500 |
C15—H15 | 0.9500 | C56—H56 | 0.9500 |
C16—H16 | 0.9500 | C71—O71 | 1.151 (13) |
C27—O27 | 1.201 (4) | C71—C73 | 1.464 (17) |
C27—C22 | 1.506 (5) | C71—C72 | 1.498 (14) |
N21—C22 | 1.338 (6) | C72—H72A | 0.9800 |
N21—C26 | 1.342 (5) | C72—H72B | 0.9800 |
C22—C23 | 1.366 (6) | C72—H72C | 0.9800 |
C23—C24 | 1.380 (7) | C73—H73A | 0.9800 |
C23—H23 | 0.9500 | C73—H73B | 0.9800 |
C24—C25 | 1.360 (10) | C73—H73C | 0.9800 |
C24—H24 | 0.9500 | C81—O81 | 1.150 (13) |
C25—C26 | 1.369 (9) | C81—C83 | 1.463 (18) |
C25—H25 | 0.9500 | C81—C82 | 1.497 (15) |
C26—H26 | 0.9500 | C82—H82A | 0.9800 |
C31—C32 | 1.386 (5) | C82—H82B | 0.9800 |
C31—C36 | 1.394 (5) | C82—H82C | 0.9800 |
C32—C33 | 1.380 (5) | C83—H83A | 0.9800 |
C32—H32 | 0.9500 | C83—H83B | 0.9800 |
C33—C34 | 1.373 (6) | C83—H83C | 0.9800 |
C33—H33 | 0.9500 | ||
O11—C1—C6 | 107.9 (2) | C34—C33—H33 | 120.7 |
O11—C1—C12 | 109.8 (3) | C32—C33—H33 | 120.7 |
C6—C1—C12 | 111.4 (3) | C35—C34—C33 | 121.2 (4) |
O11—C1—C2 | 109.9 (2) | C35—C34—Cl34 | 119.1 (3) |
C6—C1—C2 | 109.0 (2) | C33—C34—Cl34 | 119.6 (4) |
C12—C1—C2 | 108.8 (2) | C34—C35—C36 | 119.7 (3) |
C1—O11—H11 | 98.2 | C34—C35—H35 | 120.1 |
C27—C2—C3 | 110.7 (2) | C36—C35—H35 | 120.1 |
C27—C2—C1 | 109.6 (2) | C35—C36—C31 | 121.1 (4) |
C3—C2—C1 | 110.1 (2) | C35—C36—H36 | 119.5 |
C27—C2—H2 | 108.8 | C31—C36—H36 | 119.5 |
C3—C2—H2 | 108.8 | O47—C47—C42 | 119.2 (3) |
C1—C2—H2 | 108.8 | O47—C47—C4 | 122.0 (3) |
C31—C3—C2 | 112.6 (2) | C42—C47—C4 | 118.8 (2) |
C31—C3—C4 | 112.4 (2) | C46—N41—C42 | 116.8 (3) |
C2—C3—C4 | 112.2 (2) | N41—C42—C43 | 122.2 (3) |
C31—C3—H3 | 106.4 | N41—C42—C47 | 118.1 (3) |
C2—C3—H3 | 106.4 | C43—C42—C47 | 119.6 (3) |
C4—C3—H3 | 106.4 | C44—C43—C42 | 119.5 (3) |
C47—C4—C3 | 112.9 (2) | C44—C43—H43 | 120.2 |
C47—C4—C5 | 111.5 (2) | C42—C43—H43 | 120.2 |
C3—C4—C5 | 110.5 (2) | C45—C44—C43 | 118.6 (4) |
C47—C4—H4 | 107.2 | C45—C44—H44 | 120.7 |
C3—C4—H4 | 107.2 | C43—C44—H44 | 120.7 |
C5—C4—H4 | 107.2 | C44—C45—C46 | 118.1 (4) |
C51—C5—C6 | 113.7 (2) | C44—C45—H45 | 121.0 |
C51—C5—C4 | 111.3 (2) | C46—C45—H45 | 121.0 |
C6—C5—C4 | 112.4 (2) | N41—C46—C45 | 124.8 (4) |
C51—C5—H5 | 106.3 | N41—C46—H46 | 117.6 |
C6—C5—H5 | 106.3 | C45—C46—H46 | 117.6 |
C4—C5—H5 | 106.3 | C52—C51—C56 | 117.7 (3) |
C1—C6—C5 | 111.2 (2) | C52—C51—C5 | 119.2 (3) |
C1—C6—H6A | 109.4 | C56—C51—C5 | 123.1 (3) |
C5—C6—H6A | 109.4 | C51—C52—C53 | 121.4 (4) |
C1—C6—H6B | 109.4 | C51—C52—H52 | 119.3 |
C5—C6—H6B | 109.4 | C53—C52—H52 | 119.3 |
H6A—C6—H6B | 108.0 | C54—C53—C52 | 119.4 (4) |
C12—N11—C16 | 117.2 (4) | C54—C53—H53 | 120.3 |
N11—C12—C13 | 122.3 (3) | C52—C53—H53 | 120.3 |
N11—C12—C1 | 115.1 (3) | C55—C54—C53 | 121.2 (3) |
C13—C12—C1 | 122.5 (3) | C55—C54—Cl54 | 119.1 (3) |
C14—C13—C12 | 119.5 (4) | C53—C54—Cl54 | 119.7 (3) |
C14—C13—H13 | 120.3 | C54—C55—C56 | 118.7 (4) |
C12—C13—H13 | 120.3 | C54—C55—H55 | 120.6 |
C13—C14—C15 | 118.7 (5) | C56—C55—H55 | 120.6 |
C13—C14—H14 | 120.6 | C51—C56—C55 | 121.6 (3) |
C15—C14—H14 | 120.6 | C51—C56—H56 | 119.2 |
C16—C15—C14 | 117.8 (4) | C55—C56—H56 | 119.2 |
C16—C15—H15 | 121.1 | O71—C71—C73 | 120.9 (14) |
C14—C15—H15 | 121.1 | O71—C71—C72 | 128.7 (13) |
N11—C16—C15 | 124.3 (4) | C73—C71—C72 | 109.5 (11) |
N11—C16—H16 | 117.8 | C71—C72—H72A | 109.5 |
C15—C16—H16 | 117.8 | C71—C72—H72B | 109.5 |
O27—C27—C22 | 120.2 (3) | H72A—C72—H72B | 109.5 |
O27—C27—C2 | 122.2 (3) | C71—C72—H72C | 109.5 |
C22—C27—C2 | 117.5 (3) | H72A—C72—H72C | 109.5 |
C22—N21—C26 | 116.8 (4) | H72B—C72—H72C | 109.5 |
N21—C22—C23 | 123.3 (4) | C71—C73—H73A | 109.5 |
N21—C22—C27 | 116.6 (3) | C71—C73—H73B | 109.5 |
C23—C22—C27 | 120.1 (4) | H73A—C73—H73B | 109.5 |
C22—C23—C24 | 118.7 (5) | C71—C73—H73C | 109.5 |
C22—C23—H23 | 120.6 | H73A—C73—H73C | 109.5 |
C24—C23—H23 | 120.6 | H73B—C73—H73C | 109.5 |
C25—C24—C23 | 118.8 (5) | O81—C81—C83 | 120.7 (17) |
C25—C24—H24 | 120.6 | O81—C81—C82 | 129.5 (16) |
C23—C24—H24 | 120.6 | C83—C81—C82 | 109.7 (13) |
C24—C25—C26 | 119.3 (5) | C81—C82—H82A | 109.5 |
C24—C25—H25 | 120.3 | C81—C82—H82B | 109.5 |
C26—C25—H25 | 120.3 | H82A—C82—H82B | 109.5 |
N21—C26—C25 | 123.0 (6) | C81—C82—H82C | 109.5 |
N21—C26—H26 | 118.5 | H82A—C82—H82C | 109.5 |
C25—C26—H26 | 118.5 | H82B—C82—H82C | 109.5 |
C32—C31—C36 | 117.4 (3) | C81—C83—H83A | 109.5 |
C32—C31—C3 | 123.0 (3) | C81—C83—H83B | 109.5 |
C36—C31—C3 | 119.5 (3) | H83A—C83—H83B | 109.5 |
C33—C32—C31 | 121.9 (3) | C81—C83—H83C | 109.5 |
C33—C32—H32 | 119.0 | H83A—C83—H83C | 109.5 |
C31—C32—H32 | 119.0 | H83B—C83—H83C | 109.5 |
C34—C33—C32 | 118.6 (4) | ||
O11—C1—C2—C27 | −63.9 (3) | C22—C23—C24—C25 | −2.2 (8) |
C6—C1—C2—C27 | 178.1 (2) | C23—C24—C25—C26 | 2.5 (10) |
C12—C1—C2—C27 | 56.4 (3) | C22—N21—C26—C25 | 0.0 (8) |
O11—C1—C2—C3 | 58.2 (3) | C24—C25—C26—N21 | −1.4 (10) |
C6—C1—C2—C3 | −59.9 (3) | C2—C3—C31—C32 | −36.8 (4) |
C12—C1—C2—C3 | 178.5 (2) | C4—C3—C31—C32 | 91.0 (4) |
C27—C2—C3—C31 | −53.4 (3) | C2—C3—C31—C36 | 140.7 (3) |
C1—C2—C3—C31 | −174.8 (2) | C4—C3—C31—C36 | −91.4 (3) |
C27—C2—C3—C4 | 178.6 (2) | C36—C31—C32—C33 | −0.8 (5) |
C1—C2—C3—C4 | 57.3 (3) | C3—C31—C32—C33 | 176.8 (3) |
C31—C3—C4—C47 | −55.0 (3) | C31—C32—C33—C34 | 0.2 (6) |
C2—C3—C4—C47 | 73.1 (3) | C32—C33—C34—C35 | 0.3 (6) |
C31—C3—C4—C5 | 179.5 (2) | C32—C33—C34—Cl34 | −178.8 (3) |
C2—C3—C4—C5 | −52.4 (3) | C33—C34—C35—C36 | −0.1 (6) |
C47—C4—C5—C51 | 54.1 (3) | Cl34—C34—C35—C36 | 179.0 (3) |
C3—C4—C5—C51 | −179.6 (2) | C34—C35—C36—C31 | −0.6 (6) |
C47—C4—C5—C6 | −74.7 (3) | C32—C31—C36—C35 | 1.0 (5) |
C3—C4—C5—C6 | 51.6 (3) | C3—C31—C36—C35 | −176.7 (3) |
O11—C1—C6—C5 | −59.7 (3) | C3—C4—C47—O47 | −61.9 (4) |
C12—C1—C6—C5 | 179.7 (3) | C5—C4—C47—O47 | 63.1 (4) |
C2—C1—C6—C5 | 59.6 (3) | C3—C4—C47—C42 | 119.0 (3) |
C51—C5—C6—C1 | 176.0 (3) | C5—C4—C47—C42 | −116.0 (3) |
C4—C5—C6—C1 | −56.4 (3) | C46—N41—C42—C43 | −0.1 (5) |
C16—N11—C12—C13 | −1.2 (5) | C46—N41—C42—C47 | 178.5 (3) |
C16—N11—C12—C1 | 175.4 (3) | O47—C47—C42—N41 | −177.8 (3) |
O11—C1—C12—N11 | 6.8 (4) | C4—C47—C42—N41 | 1.3 (4) |
C6—C1—C12—N11 | 126.3 (3) | O47—C47—C42—C43 | 0.8 (4) |
C2—C1—C12—N11 | −113.6 (3) | C4—C47—C42—C43 | 179.9 (3) |
O11—C1—C12—C13 | −176.6 (3) | N41—C42—C43—C44 | 0.7 (5) |
C6—C1—C12—C13 | −57.1 (4) | C47—C42—C43—C44 | −177.9 (3) |
C2—C1—C12—C13 | 63.1 (4) | C42—C43—C44—C45 | −1.1 (6) |
N11—C12—C13—C14 | 2.7 (6) | C43—C44—C45—C46 | 1.0 (7) |
C1—C12—C13—C14 | −173.7 (4) | C42—N41—C46—C45 | 0.0 (7) |
C12—C13—C14—C15 | −1.4 (7) | C44—C45—C46—N41 | −0.5 (7) |
C13—C14—C15—C16 | −1.3 (7) | C6—C5—C51—C52 | −165.0 (3) |
C12—N11—C16—C15 | −1.7 (7) | C4—C5—C51—C52 | 66.9 (4) |
C14—C15—C16—N11 | 2.9 (8) | C6—C5—C51—C56 | 14.5 (4) |
C3—C2—C27—O27 | −39.9 (4) | C4—C5—C51—C56 | −113.6 (3) |
C1—C2—C27—O27 | 81.8 (4) | C56—C51—C52—C53 | 1.0 (6) |
C3—C2—C27—C22 | 142.5 (3) | C5—C51—C52—C53 | −179.5 (4) |
C1—C2—C27—C22 | −95.8 (3) | C51—C52—C53—C54 | −0.9 (7) |
C26—N21—C22—C23 | 0.3 (7) | C52—C53—C54—C55 | 0.4 (7) |
C26—N21—C22—C27 | −179.9 (4) | C52—C53—C54—Cl54 | −179.9 (4) |
O27—C27—C22—N21 | 152.5 (4) | C53—C54—C55—C56 | 0.0 (7) |
C2—C27—C22—N21 | −29.9 (5) | Cl54—C54—C55—C56 | −179.7 (3) |
O27—C27—C22—C23 | −27.8 (5) | C52—C51—C56—C55 | −0.5 (6) |
C2—C27—C22—C23 | 149.9 (4) | C5—C51—C56—C55 | 180.0 (4) |
N21—C22—C23—C24 | 0.8 (7) | C54—C55—C56—C51 | 0.0 (6) |
C27—C22—C23—C24 | −178.9 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H11···N11 | 0.88 | 1.92 | 2.587 (4) | 130 |
C14—H14···O71 | 0.95 | 2.62 | 3.517 (12) | 157 |
C14—H14···O81 | 0.95 | 2.72 | 3.499 (12) | 140 |
C43—H43···N41i | 0.95 | 2.61 | 3.433 (4) | 145 |
C45—H45···O71ii | 0.95 | 2.57 | 3.251 (11) | 129 |
C16—H16···Cg1iii | 0.95 | 3.00 | 3.869 (5) | 153 |
Symmetry codes: (i) x+1/4, −y+3/4, z−1/4; (ii) x−3/4, −y+3/4, z−1/4; (iii) x+1/2, y, z+1/2. |
C35H27Br2N3O3 | Z = 2 |
Mr = 697.41 | F(000) = 704 |
Triclinic, P1 | Dx = 1.471 Mg m−3 |
a = 9.5741 (4) Å | Cu Kα radiation, λ = 1.54178 Å |
b = 10.7061 (3) Å | Cell parameters from 5922 reflections |
c = 15.9952 (6) Å | θ = 4.8–70.0° |
α = 92.863 (3)° | µ = 3.58 mm−1 |
β = 97.443 (3)° | T = 200 K |
γ = 103.618 (3)° | Block, colourless |
V = 1574.49 (10) Å3 | 0.25 × 0.20 × 0.15 mm |
Agilent Xcalibur Ruby Gemini diffractometer | 4948 reflections with I > 2σ(I) |
Radiation source: Enhance (Cu) X-ray Source | Rint = 0.026 |
ω scans | θmax = 70.0°, θmin = 4.8° |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | h = −10→11 |
Tmin = 0.109, Tmax = 0.584 | k = −13→13 |
11667 measured reflections | l = −19→19 |
5922 independent reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.141 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0808P)2 + 0.8269P] where P = (Fo2 + 2Fc2)/3 |
5922 reflections | (Δ/σ)max < 0.001 |
388 parameters | Δρmax = 0.67 e Å−3 |
0 restraints | Δρmin = −0.64 e Å−3 |
C35H27Br2N3O3 | γ = 103.618 (3)° |
Mr = 697.41 | V = 1574.49 (10) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.5741 (4) Å | Cu Kα radiation |
b = 10.7061 (3) Å | µ = 3.58 mm−1 |
c = 15.9952 (6) Å | T = 200 K |
α = 92.863 (3)° | 0.25 × 0.20 × 0.15 mm |
β = 97.443 (3)° |
Agilent Xcalibur Ruby Gemini diffractometer | 5922 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | 4948 reflections with I > 2σ(I) |
Tmin = 0.109, Tmax = 0.584 | Rint = 0.026 |
11667 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.141 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.67 e Å−3 |
5922 reflections | Δρmin = −0.64 e Å−3 |
388 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.1094 (3) | 0.2890 (3) | 0.37522 (18) | 0.0469 (6) | |
O11 | −0.0179 (2) | 0.1914 (2) | 0.34356 (14) | 0.0597 (5) | |
H11 | −0.0388 | 0.1511 | 0.3839 | 0.075* | |
C2 | 0.2459 (3) | 0.2500 (3) | 0.34883 (17) | 0.0431 (6) | |
H2 | 0.3345 | 0.3181 | 0.3736 | 0.052* | |
C3 | 0.2393 (3) | 0.2382 (2) | 0.25268 (17) | 0.0423 (5) | |
H3 | 0.1509 | 0.1686 | 0.2300 | 0.051* | |
C4 | 0.2191 (3) | 0.3631 (3) | 0.21229 (17) | 0.0428 (6) | |
H4 | 0.2020 | 0.3448 | 0.1494 | 0.051* | |
C5 | 0.0830 (3) | 0.3990 (3) | 0.23934 (18) | 0.0474 (6) | |
H5 | −0.0014 | 0.3245 | 0.2185 | 0.057* | |
C6 | 0.0928 (3) | 0.4136 (3) | 0.33570 (19) | 0.0505 (6) | |
H6A | 0.0040 | 0.4358 | 0.3508 | 0.061* | |
H6B | 0.1771 | 0.4851 | 0.3592 | 0.061* | |
N11 | 0.0326 (3) | 0.2241 (3) | 0.50752 (18) | 0.0679 (8) | |
C12 | 0.1245 (3) | 0.3091 (3) | 0.47110 (19) | 0.0496 (6) | |
C13 | 0.2307 (4) | 0.4069 (4) | 0.5184 (2) | 0.0618 (8) | |
H13 | 0.2964 | 0.4669 | 0.4914 | 0.074* | |
C14 | 0.2392 (4) | 0.4156 (4) | 0.6059 (2) | 0.0722 (9) | |
H14 | 0.3110 | 0.4819 | 0.6396 | 0.087* | |
C15 | 0.1442 (4) | 0.3286 (5) | 0.6429 (2) | 0.0778 (11) | |
H15 | 0.1477 | 0.3333 | 0.7026 | 0.093* | |
C16 | 0.0443 (5) | 0.2349 (5) | 0.5928 (2) | 0.0857 (13) | |
H16 | −0.0211 | 0.1735 | 0.6190 | 0.103* | |
C27 | 0.2561 (3) | 0.1226 (3) | 0.38517 (19) | 0.0489 (6) | |
O27 | 0.1950 (3) | 0.0192 (2) | 0.34738 (15) | 0.0666 (6) | |
N21 | 0.4626 (4) | 0.2257 (3) | 0.4895 (2) | 0.0679 (8) | |
C22 | 0.3450 (4) | 0.1270 (3) | 0.4699 (2) | 0.0541 (7) | |
C23 | 0.3069 (5) | 0.0303 (4) | 0.5227 (3) | 0.0768 (11) | |
H23 | 0.2229 | −0.0384 | 0.5068 | 0.092* | |
C24 | 0.3957 (7) | 0.0364 (6) | 0.6000 (3) | 0.1017 (17) | |
H24 | 0.3722 | −0.0276 | 0.6384 | 0.122* | |
C25 | 0.5172 (7) | 0.1359 (5) | 0.6197 (3) | 0.0977 (17) | |
H25 | 0.5802 | 0.1416 | 0.6715 | 0.117* | |
C26 | 0.5455 (6) | 0.2268 (4) | 0.5633 (3) | 0.0884 (14) | |
H26 | 0.6300 | 0.2954 | 0.5776 | 0.106* | |
C31 | 0.3678 (3) | 0.1972 (2) | 0.22351 (17) | 0.0439 (6) | |
C32 | 0.5090 (3) | 0.2443 (3) | 0.2641 (2) | 0.0550 (7) | |
H32 | 0.5266 | 0.2992 | 0.3148 | 0.066* | |
C33 | 0.6256 (3) | 0.2124 (3) | 0.2318 (2) | 0.0597 (8) | |
H33 | 0.7222 | 0.2468 | 0.2593 | 0.072* | |
C34 | 0.5991 (4) | 0.1310 (3) | 0.1601 (2) | 0.0575 (7) | |
Br34 | 0.75694 (5) | 0.09296 (5) | 0.11223 (4) | 0.0979 (2) | |
C35 | 0.4591 (4) | 0.0767 (4) | 0.1205 (2) | 0.0655 (9) | |
H35 | 0.4417 | 0.0171 | 0.0721 | 0.079* | |
C36 | 0.3452 (4) | 0.1110 (3) | 0.1528 (2) | 0.0561 (7) | |
H36 | 0.2487 | 0.0745 | 0.1257 | 0.067* | |
C47 | 0.3521 (3) | 0.4760 (3) | 0.23542 (18) | 0.0441 (6) | |
O47 | 0.4088 (2) | 0.5068 (2) | 0.30802 (13) | 0.0568 (5) | |
N41 | 0.3478 (4) | 0.5267 (3) | 0.0881 (2) | 0.0725 (8) | |
C42 | 0.4133 (3) | 0.5553 (3) | 0.1677 (2) | 0.0512 (6) | |
C43 | 0.5344 (4) | 0.6559 (4) | 0.1917 (3) | 0.0752 (10) | |
H43 | 0.5767 | 0.6742 | 0.2495 | 0.090* | |
C44 | 0.5924 (6) | 0.7290 (5) | 0.1310 (4) | 0.1031 (17) | |
H44 | 0.6775 | 0.7971 | 0.1456 | 0.124* | |
C45 | 0.5261 (6) | 0.7024 (6) | 0.0496 (4) | 0.113 (2) | |
H45 | 0.5621 | 0.7530 | 0.0064 | 0.135* | |
C46 | 0.4060 (6) | 0.6008 (6) | 0.0310 (3) | 0.1027 (17) | |
H46 | 0.3615 | 0.5822 | −0.0263 | 0.123* | |
C51 | 0.0525 (3) | 0.5151 (3) | 0.19609 (18) | 0.0466 (6) | |
C52 | −0.0392 (4) | 0.4954 (3) | 0.1203 (2) | 0.0611 (8) | |
H52 | −0.0860 | 0.4096 | 0.0980 | 0.073* | |
C53 | −0.0653 (4) | 0.5979 (3) | 0.0755 (2) | 0.0643 (8) | |
H53 | −0.1278 | 0.5828 | 0.0229 | 0.077* | |
C54 | 0.0009 (3) | 0.7206 (3) | 0.1089 (2) | 0.0544 (7) | |
Br54 | −0.03457 (5) | 0.86020 (4) | 0.04693 (3) | 0.07606 (16) | |
C55 | 0.0917 (4) | 0.7454 (3) | 0.1847 (2) | 0.0577 (7) | |
H55 | 0.1369 | 0.8315 | 0.2068 | 0.069* | |
C56 | 0.1159 (4) | 0.6418 (3) | 0.2283 (2) | 0.0553 (7) | |
H56 | 0.1772 | 0.6578 | 0.2813 | 0.066* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0392 (13) | 0.0497 (15) | 0.0488 (15) | 0.0037 (11) | 0.0059 (11) | 0.0116 (11) |
O11 | 0.0459 (11) | 0.0660 (13) | 0.0585 (12) | −0.0037 (10) | 0.0042 (9) | 0.0149 (10) |
C2 | 0.0421 (13) | 0.0399 (13) | 0.0450 (14) | 0.0050 (10) | 0.0043 (10) | 0.0108 (10) |
C3 | 0.0393 (13) | 0.0383 (12) | 0.0457 (14) | 0.0030 (10) | 0.0023 (10) | 0.0102 (10) |
C4 | 0.0433 (13) | 0.0421 (13) | 0.0408 (13) | 0.0061 (11) | 0.0027 (10) | 0.0114 (10) |
C5 | 0.0409 (14) | 0.0458 (14) | 0.0525 (15) | 0.0062 (11) | 0.0005 (11) | 0.0126 (11) |
C6 | 0.0473 (15) | 0.0552 (16) | 0.0536 (16) | 0.0161 (12) | 0.0129 (12) | 0.0159 (13) |
N11 | 0.0625 (17) | 0.0764 (19) | 0.0571 (16) | −0.0042 (14) | 0.0157 (13) | 0.0159 (13) |
C12 | 0.0454 (15) | 0.0543 (16) | 0.0517 (16) | 0.0126 (12) | 0.0119 (12) | 0.0139 (12) |
C13 | 0.0581 (18) | 0.0651 (19) | 0.0566 (18) | 0.0054 (15) | 0.0049 (14) | 0.0089 (14) |
C14 | 0.063 (2) | 0.085 (3) | 0.063 (2) | 0.0140 (18) | 0.0011 (16) | −0.0032 (18) |
C15 | 0.068 (2) | 0.114 (3) | 0.0501 (19) | 0.018 (2) | 0.0123 (16) | 0.0069 (19) |
C16 | 0.079 (3) | 0.113 (3) | 0.057 (2) | −0.004 (2) | 0.0232 (19) | 0.022 (2) |
C27 | 0.0526 (16) | 0.0413 (14) | 0.0510 (15) | 0.0072 (12) | 0.0066 (12) | 0.0116 (11) |
O27 | 0.0818 (16) | 0.0433 (11) | 0.0637 (14) | −0.0001 (11) | −0.0038 (12) | 0.0116 (10) |
N21 | 0.077 (2) | 0.0548 (15) | 0.0665 (18) | 0.0189 (14) | −0.0131 (15) | 0.0022 (13) |
C22 | 0.0646 (19) | 0.0483 (15) | 0.0513 (16) | 0.0208 (14) | 0.0012 (13) | 0.0073 (12) |
C23 | 0.096 (3) | 0.068 (2) | 0.067 (2) | 0.020 (2) | 0.0048 (19) | 0.0260 (18) |
C24 | 0.148 (5) | 0.104 (4) | 0.064 (2) | 0.053 (4) | 0.004 (3) | 0.037 (2) |
C25 | 0.133 (4) | 0.095 (3) | 0.066 (2) | 0.056 (3) | −0.031 (3) | −0.006 (2) |
C26 | 0.102 (3) | 0.069 (2) | 0.083 (3) | 0.028 (2) | −0.033 (2) | −0.008 (2) |
C31 | 0.0465 (14) | 0.0387 (13) | 0.0453 (14) | 0.0083 (11) | 0.0038 (11) | 0.0105 (10) |
C32 | 0.0480 (16) | 0.0565 (17) | 0.0559 (17) | 0.0096 (13) | 0.0012 (12) | −0.0086 (13) |
C33 | 0.0432 (15) | 0.0594 (18) | 0.073 (2) | 0.0076 (13) | 0.0068 (14) | −0.0022 (15) |
C34 | 0.0583 (18) | 0.0496 (16) | 0.0683 (19) | 0.0139 (13) | 0.0215 (15) | 0.0060 (14) |
Br34 | 0.0719 (3) | 0.0935 (3) | 0.1280 (4) | 0.0138 (2) | 0.0402 (3) | −0.0285 (3) |
C35 | 0.070 (2) | 0.0626 (19) | 0.0597 (19) | 0.0105 (16) | 0.0115 (16) | −0.0109 (15) |
C36 | 0.0533 (17) | 0.0572 (17) | 0.0509 (16) | 0.0043 (13) | 0.0014 (13) | −0.0014 (13) |
C47 | 0.0407 (13) | 0.0398 (13) | 0.0507 (16) | 0.0072 (10) | 0.0049 (11) | 0.0102 (11) |
O47 | 0.0561 (12) | 0.0521 (11) | 0.0518 (12) | −0.0030 (9) | −0.0009 (9) | 0.0071 (9) |
N41 | 0.0667 (18) | 0.081 (2) | 0.0631 (18) | 0.0009 (15) | 0.0096 (14) | 0.0287 (15) |
C42 | 0.0459 (15) | 0.0511 (15) | 0.0564 (17) | 0.0085 (12) | 0.0079 (12) | 0.0181 (13) |
C43 | 0.064 (2) | 0.068 (2) | 0.084 (3) | −0.0065 (17) | 0.0105 (18) | 0.0255 (19) |
C44 | 0.085 (3) | 0.093 (3) | 0.115 (4) | −0.020 (3) | 0.021 (3) | 0.045 (3) |
C45 | 0.098 (4) | 0.121 (4) | 0.113 (4) | −0.007 (3) | 0.033 (3) | 0.068 (3) |
C46 | 0.099 (3) | 0.128 (4) | 0.071 (3) | −0.002 (3) | 0.013 (2) | 0.049 (3) |
C51 | 0.0423 (14) | 0.0468 (14) | 0.0518 (15) | 0.0126 (11) | 0.0049 (11) | 0.0117 (11) |
C52 | 0.065 (2) | 0.0478 (16) | 0.0630 (19) | 0.0093 (14) | −0.0101 (15) | 0.0076 (14) |
C53 | 0.071 (2) | 0.0616 (19) | 0.0572 (18) | 0.0187 (16) | −0.0089 (15) | 0.0128 (15) |
C54 | 0.0542 (17) | 0.0510 (16) | 0.0645 (18) | 0.0192 (13) | 0.0126 (14) | 0.0249 (14) |
Br54 | 0.0745 (3) | 0.0655 (2) | 0.0962 (3) | 0.02530 (19) | 0.0135 (2) | 0.0409 (2) |
C55 | 0.0626 (19) | 0.0443 (15) | 0.0655 (19) | 0.0107 (13) | 0.0079 (15) | 0.0117 (13) |
C56 | 0.0569 (17) | 0.0517 (16) | 0.0535 (17) | 0.0111 (13) | −0.0026 (13) | 0.0080 (13) |
C1—O11 | 1.422 (3) | C25—C26 | 1.364 (7) |
C1—C12 | 1.521 (4) | C25—H25 | 0.9500 |
C1—C6 | 1.537 (4) | C26—H26 | 0.9500 |
C1—C2 | 1.563 (4) | C31—C36 | 1.384 (4) |
O11—H11 | 0.8144 | C31—C32 | 1.387 (4) |
C2—C27 | 1.528 (4) | C32—C33 | 1.394 (4) |
C2—C3 | 1.529 (4) | C32—H32 | 0.9500 |
C2—H2 | 1.0000 | C33—C34 | 1.363 (5) |
C3—C31 | 1.519 (4) | C33—H33 | 0.9500 |
C3—C4 | 1.555 (3) | C34—C35 | 1.383 (5) |
C3—H3 | 1.0000 | C34—Br34 | 1.896 (3) |
C4—C47 | 1.526 (4) | C35—C36 | 1.381 (5) |
C4—C5 | 1.548 (4) | C35—H35 | 0.9500 |
C4—H4 | 1.0000 | C36—H36 | 0.9500 |
C5—C51 | 1.521 (4) | C47—O47 | 1.211 (4) |
C5—C6 | 1.530 (4) | C47—C42 | 1.503 (4) |
C5—H5 | 1.0000 | N41—C46 | 1.330 (5) |
C6—H6A | 0.9900 | N41—C42 | 1.331 (4) |
C6—H6B | 0.9900 | C42—C43 | 1.382 (5) |
N11—C12 | 1.322 (4) | C43—C44 | 1.369 (6) |
N11—C16 | 1.351 (5) | C43—H43 | 0.9500 |
C12—C13 | 1.387 (5) | C44—C45 | 1.358 (8) |
C13—C14 | 1.388 (5) | C44—H44 | 0.9500 |
C13—H13 | 0.9500 | C45—C46 | 1.373 (7) |
C14—C15 | 1.357 (6) | C45—H45 | 0.9500 |
C14—H14 | 0.9500 | C46—H46 | 0.9500 |
C15—C16 | 1.353 (6) | C51—C52 | 1.377 (4) |
C15—H15 | 0.9500 | C51—C56 | 1.391 (4) |
C16—H16 | 0.9500 | C52—C53 | 1.394 (4) |
C27—O27 | 1.213 (4) | C52—H52 | 0.9500 |
C27—C22 | 1.496 (4) | C53—C54 | 1.364 (5) |
N21—C26 | 1.333 (5) | C53—H53 | 0.9500 |
N21—C22 | 1.341 (5) | C54—C55 | 1.372 (5) |
C22—C23 | 1.381 (5) | C54—Br54 | 1.905 (3) |
C23—C24 | 1.397 (6) | C55—C56 | 1.388 (4) |
C23—H23 | 0.9500 | C55—H55 | 0.9500 |
C24—C25 | 1.369 (8) | C56—H56 | 0.9500 |
C24—H24 | 0.9500 | ||
O11—C1—C12 | 110.1 (2) | C25—C24—H24 | 120.5 |
O11—C1—C6 | 107.2 (2) | C23—C24—H24 | 120.5 |
C12—C1—C6 | 109.9 (2) | C26—C25—C24 | 118.5 (4) |
O11—C1—C2 | 109.9 (2) | C26—C25—H25 | 120.7 |
C12—C1—C2 | 110.0 (2) | C24—C25—H25 | 120.7 |
C6—C1—C2 | 109.7 (2) | N21—C26—C25 | 124.4 (4) |
C1—O11—H11 | 105.3 | N21—C26—H26 | 117.8 |
C27—C2—C3 | 110.6 (2) | C25—C26—H26 | 117.8 |
C27—C2—C1 | 108.8 (2) | C36—C31—C32 | 117.9 (3) |
C3—C2—C1 | 111.4 (2) | C36—C31—C3 | 119.4 (3) |
C27—C2—H2 | 108.6 | C32—C31—C3 | 122.7 (3) |
C3—C2—H2 | 108.6 | C31—C32—C33 | 121.1 (3) |
C1—C2—H2 | 108.6 | C31—C32—H32 | 119.4 |
C31—C3—C2 | 113.6 (2) | C33—C32—H32 | 119.4 |
C31—C3—C4 | 110.4 (2) | C34—C33—C32 | 119.0 (3) |
C2—C3—C4 | 112.4 (2) | C34—C33—H33 | 120.5 |
C31—C3—H3 | 106.7 | C32—C33—H33 | 120.5 |
C2—C3—H3 | 106.7 | C33—C34—C35 | 121.4 (3) |
C4—C3—H3 | 106.7 | C33—C34—Br34 | 119.6 (3) |
C47—C4—C5 | 110.4 (2) | C35—C34—Br34 | 119.0 (3) |
C47—C4—C3 | 112.7 (2) | C36—C35—C34 | 118.6 (3) |
C5—C4—C3 | 109.4 (2) | C36—C35—H35 | 120.7 |
C47—C4—H4 | 108.1 | C34—C35—H35 | 120.7 |
C5—C4—H4 | 108.1 | C35—C36—C31 | 121.8 (3) |
C3—C4—H4 | 108.1 | C35—C36—H36 | 119.1 |
C51—C5—C6 | 113.8 (3) | C31—C36—H36 | 119.1 |
C51—C5—C4 | 111.2 (2) | O47—C47—C42 | 118.1 (2) |
C6—C5—C4 | 111.4 (2) | O47—C47—C4 | 121.7 (2) |
C51—C5—H5 | 106.6 | C42—C47—C4 | 120.1 (2) |
C6—C5—H5 | 106.6 | C46—N41—C42 | 116.2 (4) |
C4—C5—H5 | 106.6 | N41—C42—C43 | 123.2 (3) |
C5—C6—C1 | 111.5 (3) | N41—C42—C47 | 118.9 (3) |
C5—C6—H6A | 109.3 | C43—C42—C47 | 117.9 (3) |
C1—C6—H6A | 109.3 | C44—C43—C42 | 118.9 (4) |
C5—C6—H6B | 109.3 | C44—C43—H43 | 120.6 |
C1—C6—H6B | 109.3 | C42—C43—H43 | 120.6 |
H6A—C6—H6B | 108.0 | C45—C44—C43 | 118.7 (4) |
C12—N11—C16 | 118.2 (3) | C45—C44—H44 | 120.6 |
N11—C12—C13 | 121.5 (3) | C43—C44—H44 | 120.6 |
N11—C12—C1 | 115.7 (3) | C44—C45—C46 | 118.7 (4) |
C13—C12—C1 | 122.7 (3) | C44—C45—H45 | 120.7 |
C12—C13—C14 | 118.8 (3) | C46—C45—H45 | 120.7 |
C12—C13—H13 | 120.6 | N41—C46—C45 | 124.2 (5) |
C14—C13—H13 | 120.6 | N41—C46—H46 | 117.9 |
C15—C14—C13 | 119.4 (4) | C45—C46—H46 | 117.9 |
C15—C14—H14 | 120.3 | C52—C51—C56 | 117.8 (3) |
C13—C14—H14 | 120.3 | C52—C51—C5 | 119.1 (3) |
C16—C15—C14 | 118.5 (4) | C56—C51—C5 | 123.2 (3) |
C16—C15—H15 | 120.7 | C51—C52—C53 | 121.7 (3) |
C14—C15—H15 | 120.7 | C51—C52—H52 | 119.2 |
N11—C16—C15 | 123.5 (4) | C53—C52—H52 | 119.2 |
N11—C16—H16 | 118.2 | C54—C53—C52 | 118.6 (3) |
C15—C16—H16 | 118.2 | C54—C53—H53 | 120.7 |
O27—C27—C22 | 119.5 (3) | C52—C53—H53 | 120.7 |
O27—C27—C2 | 122.0 (3) | C53—C54—C55 | 122.0 (3) |
C22—C27—C2 | 118.4 (2) | C53—C54—Br54 | 118.3 (2) |
C26—N21—C22 | 116.9 (4) | C55—C54—Br54 | 119.8 (2) |
N21—C22—C23 | 123.1 (3) | C54—C55—C56 | 118.5 (3) |
N21—C22—C27 | 116.8 (3) | C54—C55—H55 | 120.7 |
C23—C22—C27 | 120.1 (3) | C56—C55—H55 | 120.7 |
C22—C23—C24 | 118.1 (4) | C55—C56—C51 | 121.5 (3) |
C22—C23—H23 | 121.0 | C55—C56—H56 | 119.3 |
C24—C23—H23 | 121.0 | C51—C56—H56 | 119.3 |
C25—C24—C23 | 119.0 (4) | ||
O11—C1—C2—C27 | −59.6 (3) | C22—C23—C24—C25 | −1.0 (8) |
C12—C1—C2—C27 | 61.8 (3) | C23—C24—C25—C26 | 1.0 (8) |
C6—C1—C2—C27 | −177.2 (2) | C22—N21—C26—C25 | −0.9 (7) |
O11—C1—C2—C3 | 62.6 (3) | C24—C25—C26—N21 | 0.0 (8) |
C12—C1—C2—C3 | −176.0 (2) | C2—C3—C31—C36 | 140.5 (3) |
C6—C1—C2—C3 | −55.0 (3) | C4—C3—C31—C36 | −92.2 (3) |
C27—C2—C3—C31 | −57.4 (3) | C2—C3—C31—C32 | −40.6 (4) |
C1—C2—C3—C31 | −178.5 (2) | C4—C3—C31—C32 | 86.7 (3) |
C27—C2—C3—C4 | 176.4 (2) | C36—C31—C32—C33 | 4.0 (5) |
C1—C2—C3—C4 | 55.2 (3) | C3—C31—C32—C33 | −174.9 (3) |
C31—C3—C4—C47 | −59.7 (3) | C31—C32—C33—C34 | −1.6 (5) |
C2—C3—C4—C47 | 68.3 (3) | C32—C33—C34—C35 | −1.9 (5) |
C31—C3—C4—C5 | 177.1 (2) | C32—C33—C34—Br34 | 177.0 (3) |
C2—C3—C4—C5 | −54.9 (3) | C33—C34—C35—C36 | 2.9 (6) |
C47—C4—C5—C51 | 59.7 (3) | Br34—C34—C35—C36 | −176.1 (3) |
C3—C4—C5—C51 | −175.8 (2) | C34—C35—C36—C31 | −0.3 (5) |
C47—C4—C5—C6 | −68.5 (3) | C32—C31—C36—C35 | −3.0 (5) |
C3—C4—C5—C6 | 56.0 (3) | C3—C31—C36—C35 | 175.9 (3) |
C51—C5—C6—C1 | 174.7 (2) | C5—C4—C47—O47 | 72.3 (3) |
C4—C5—C6—C1 | −58.6 (3) | C3—C4—C47—O47 | −50.3 (4) |
O11—C1—C6—C5 | −62.5 (3) | C5—C4—C47—C42 | −105.5 (3) |
C12—C1—C6—C5 | 177.9 (2) | C3—C4—C47—C42 | 131.9 (3) |
C2—C1—C6—C5 | 56.8 (3) | C46—N41—C42—C43 | 0.4 (6) |
C16—N11—C12—C13 | 0.1 (6) | C46—N41—C42—C47 | 179.4 (4) |
C16—N11—C12—C1 | 177.9 (4) | O47—C47—C42—N41 | −176.7 (3) |
O11—C1—C12—N11 | 8.8 (4) | C4—C47—C42—N41 | 1.3 (4) |
C6—C1—C12—N11 | 126.6 (3) | O47—C47—C42—C43 | 2.5 (5) |
C2—C1—C12—N11 | −112.5 (3) | C4—C47—C42—C43 | −179.6 (3) |
O11—C1—C12—C13 | −173.5 (3) | N41—C42—C43—C44 | −1.3 (7) |
C6—C1—C12—C13 | −55.7 (4) | C47—C42—C43—C44 | 179.7 (4) |
C2—C1—C12—C13 | 65.2 (4) | C42—C43—C44—C45 | 2.0 (9) |
N11—C12—C13—C14 | −0.4 (5) | C43—C44—C45—C46 | −1.9 (10) |
C1—C12—C13—C14 | −178.0 (3) | C42—N41—C46—C45 | −0.3 (9) |
C12—C13—C14—C15 | 0.1 (6) | C44—C45—C46—N41 | 1.1 (11) |
C13—C14—C15—C16 | 0.5 (7) | C6—C5—C51—C52 | −141.5 (3) |
C12—N11—C16—C15 | 0.6 (7) | C4—C5—C51—C52 | 91.7 (3) |
C14—C15—C16—N11 | −0.9 (8) | C6—C5—C51—C56 | 40.2 (4) |
C3—C2—C27—O27 | −34.8 (4) | C4—C5—C51—C56 | −86.7 (4) |
C1—C2—C27—O27 | 88.0 (4) | C56—C51—C52—C53 | 1.9 (5) |
C3—C2—C27—C22 | 145.0 (3) | C5—C51—C52—C53 | −176.6 (3) |
C1—C2—C27—C22 | −92.3 (3) | C51—C52—C53—C54 | −0.9 (6) |
C26—N21—C22—C23 | 0.9 (6) | C52—C53—C54—C55 | 0.0 (6) |
C26—N21—C22—C27 | −177.2 (4) | C52—C53—C54—Br54 | 179.7 (3) |
O27—C27—C22—N21 | 146.8 (3) | C53—C54—C55—C56 | −0.1 (5) |
C2—C27—C22—N21 | −32.9 (4) | Br54—C54—C55—C56 | −179.8 (3) |
O27—C27—C22—C23 | −31.3 (5) | C54—C55—C56—C51 | 1.1 (5) |
C2—C27—C22—C23 | 148.9 (3) | C52—C51—C56—C55 | −2.0 (5) |
N21—C22—C23—C24 | 0.1 (7) | C5—C51—C56—C55 | 176.4 (3) |
C27—C22—C23—C24 | 178.1 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H11···N11 | 0.81 | 2.06 | 2.595 (4) | 123 |
C16—H16···O27i | 0.95 | 2.46 | 3.385 (6) | 165 |
C53—H53···N41ii | 0.95 | 2.57 | 3.473 (5) | 158 |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x, −y+1, −z. |
Experimental details
(I) | (II) | (III) | |
Crystal data | |||
Chemical formula | C35H27F2N3O3 | C35H27Cl2N3O3·0.951C3H6O | C35H27Br2N3O3 |
Mr | 575.60 | 663.73 | 697.41 |
Crystal system, space group | Orthorhombic, Pbca | Orthorhombic, Fdd2 | Triclinic, P1 |
Temperature (K) | 200 | 200 | 200 |
a, b, c (Å) | 21.8864 (9), 11.2268 (4), 24.2670 (9) | 16.5446 (6), 53.4204 (17), 15.5857 (4) | 9.5741 (4), 10.7061 (3), 15.9952 (6) |
α, β, γ (°) | 90, 90, 90 | 90, 90, 90 | 92.863 (3), 97.443 (3), 103.618 (3) |
V (Å3) | 5962.7 (4) | 13774.9 (8) | 1574.49 (10) |
Z | 8 | 16 | 2 |
Radiation type | Cu Kα | Cu Kα | Cu Kα |
µ (mm−1) | 0.75 | 2.05 | 3.58 |
Crystal size (mm) | 0.40 × 0.09 × 0.08 | 0.30 × 0.25 × 0.20 | 0.25 × 0.20 × 0.15 |
Data collection | |||
Diffractometer | Agilent Eos Gemini diffractometer | Agilent Xcalibur Ruby Gemini diffractometer | Agilent Xcalibur Ruby Gemini diffractometer |
Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2012) | Multi-scan (CrysAlis PRO; Agilent, 2012) | Multi-scan (CrysAlis PRO; Agilent, 2012) |
Tmin, Tmax | 0.693, 0.942 | 0.388, 0.664 | 0.109, 0.584 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 37077, 5754, 4489 | 9544, 4224, 3490 | 11667, 5922, 4948 |
Rint | 0.036 | 0.027 | 0.026 |
(sin θ/λ)max (Å−1) | 0.614 | 0.610 | 0.610 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.131, 1.03 | 0.039, 0.109, 0.97 | 0.046, 0.141, 1.05 |
No. of reflections | 5754 | 4224 | 5922 |
No. of parameters | 388 | 436 | 388 |
No. of restraints | 0 | 7 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.20 | 0.16, −0.16 | 0.67, −0.64 |
Absolute structure | ? | Flack x determined using 613 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013). | ? |
Absolute structure parameter | ? | 0.089 (18) | ? |
Computer programs: CrysAlis PRO (Agilent, 2012), CrysAlis RED (Agilent, 2012), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2014) and PLATON (Spek, 2009).
Compound | θ1 | θ2 | θ3 | θ4 | θ5 |
(I) | 30.80 (12) | 85.33 (11) | 44.19 (13) | 67.09 (13) | 28.94 (10) |
(II) | 24.3 (2) | 88.0 (2) | 62.66 (19) | 57.3 (2) | 53.3 (2) |
(III) | 31.5 (2) | 79.4 (2) | 63.9 (2) | 42.5 (2) | 49.05 (18) |
Notes: θ1 represents the dihedral angle between the N11/C12–C16) and N21/C22–C26 planes; θ2 represents the dihedral angle between the N21/C22–C26 and C31–C36 planes; θ3 represents the dihedral angle between the C31–C36 and N41/C42–C46 planes; θ4 represents the dihedral angle between the N41/C42–C46 and C51–C56 planes; θ5 represents the dihedral angle between the C51–C56 and N11/C12–C16 planes. |
Compound | D—H···A | D—H | H···A | D···A | D—H···A | |
(I) | O11—H11···N11 | 0.82 | 2.13 | 2.624 (2) | 119 | |
C13—H13···O11i | 0.95 | 2.54 | 3.385 (3) | 148 | ||
C55—H55···O27i | 0.95 | 2.53 | 3.244 (2) | 132 | ||
(I) | O11—H11···N11 | 0.88 | 1.92 | 2.587 (4) | 130 | |
C14—H14···O71 | 0.95 | 2.62 | 3.517 (12) | 157 | ||
C14—H14···O81 | 0.95 | 2.72 | 3.499 (12) | 140 | ||
C43—H43···N41ii | 0.95 | 2.61 | 3.433 (4) | 145 | ||
C45—H45···O71iii | 0.95 | 2.57 | 3.251 (11) | 129 | ||
C16—H16···Cg1iv | 0.95 | 3.00 | 3.869 (5) | 153 | ||
(I) | O11—H11···N11 | 0.81 | 2.06 | 2.595 (4) | 123 | |
C16—H16···O27v | 0.95 | 2.46 | 3.385 (6) | 165 | ||
C53—H53···N41vi | 0.95 | 2.57 | 3.473 (5) | 158 |
Symmetry codes: (i) -x+1/2, y+1/2, z;
(ii) x+1/4, -y+3/4, z-1/4;
(iii) x-3/4, -y+3/4, z-1/4;
(iv) x+1/2, y, z+1/2;
(v) -x, -y, -z+1;
(vi) -x, -y+1, -z. Cg1 represents the centroid of the C31–C36 ring. |
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