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organic compounds
Effect of substitution on the dimensionality of supramolecular aggregation in dihydrobenzopyrazoloquinolines
aGrupo de Investigación de Compuestos Heterocíclicos, Departamento de Química, Universidad de Valle, AA 25360 Cali, Colombia, bDepartamento de Química Inorgánica y Orgánica, Universidad de Jaén, 23071 Jaén, Spain, cDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and dSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland
*Correspondence e-mail: cg@st-andrews.ac.uk
Molecules of 8-methyl-10-phenyl-6,10-dihydro-5H-benzo[h]pyrazolo[3,4-b]quinoline, C21H17N3, (I), are linked into cyclic centrosymmetric dimers by means of paired C—H⋯N hydrogen bonds. In each of 8-methyl-7,10-diphenyl-6,10-dihydro-5H-benzo[h]pyrazolo[3,4-b]quinoline, C27H21N3, (II)
, and 8-methyl-7-(4-methylphenyl)-10-phenyl-6,10-dihydro-5H-benzo[h]pyrazolo[3,4-b]quinoline, C28H23N3, (III)
, the molecules are linked by C—H⋯π(arene) hydrogen bonds into sheets, although the detailed construction of the sheets is entirely different in (II)
and (III)
. The molecules of 7-(4-methoxyphenyl)-8-methyl-10-phenyl-6,10-dihydro-5H-benzo[h]pyrazolo[3,4-b]quinoline, C28H23N3O, (IV)
, are linked into a complex three-dimensional framework structure by a combination of C—H⋯N, C—H⋯O and three independent C—H⋯π(arene) hydrogen bonds.
Comment
Pyrazolo[3,4-b]quinolines are of interest as possible antiviral and antimalarial agents, and because of their other biological properties, such as parasiticidic, bactericidal, vasodilator, and enzyme-inhibitory activity (Quiroga et al., 2001). We report here the structures of four dihydrobenzopyrazoloquinolines, (I)
–(IV)
(Figs. 1
–4
), synthesized by a simple solvent-free cyclocondensation, under microwave irradiation, of 5-amino-3-methyl-1-phenylpyrazole and the condensation products derived from 2-tetralone and a range of simple One objective of these structure determinations was the investigation of how the introduction of different simple aryl substituents at position 7 in compounds (II)
–(IV)
influences the supramolecular aggregation compared with that in the unsubstituted compound, (I)
. We have recently reported the structures of the isomorphous and isostructural chlorophenyl and bromophenyl analogues, compounds (V)
and (VI)
(Serrano et al., 2005a
,b
).
In each of compounds (I)–(IV)
, the bond distances within the fused heterocyclic components are consistent with aromatic delocalization within the pyridine ring, but with strong double-bond fixation in the C8—N9 bond of the pyrazole ring. The other distances and angles present no exceptional features. The non-aromatic carbocyclic ring adopts a nearly ideal screw-boat conformation (Evans & Boeyens, 1989
) in each compound, as shown by the ring-puckering parameters (Cremer & Pople, 1975
), given for the atom sequence C4a—C5—C6—C6a—C11a—C11b in Table 1
. For a six-membered ring with equal bond lengths throughout, the screw-boat conformation is characterized by θ = 67.5 or 112.5°, and φ = (60k + 30)° (k = integer).
Associated with the screw-boat conformation of the non-aromatic carbocyclic ring, the two aromatic rings linked by the bond C11a—C11b (Figs. 1–4
) are not parallel, and they make dihedral angles ranging from 11.11 (7)° in compound (III)
to 15.78 (7)° in compound (II)
(Table 1
). The dihedral angles between the pyridine ring and the pendent C71–C76 aryl ring are likewise very similar for compounds (II)
–(IV)
. On the other hand, the dihedral angles between the pyrazole ring and the pendent C101–C106 aryl ring show a rather larger variation. It may be noted here that rings C71–C76 and C101–C106 participate in the hydrogen bonding in each of (II)
–(IV)
, and that the hydrogen bonding may be an important factor in controlling these dihedral angles.
The supramolecular aggregation in compound (I) is extremely simple and involves just one hydrogen bond (Table 2
). Atom C5 in the molecule at (x, y, z) acts as hydrogen-bond donor, via the axial atom H5A, to pyrazole atom N9 in the molecule at (1 − x, 1 − y, 1 − z), so forming a centrosymmetric R22(16) dimer centred at (
,
,
) (Fig. 5
). The formation of this dimer is reinforced by a π–π stacking interaction involving the pyridine rings of the two component molecules. These rings are strictly parallel, with an interplanar spacing of 3.450 (2) Å. The ring-centroid separation is 3.729 (2) Å, corresponding to a nearly ideal ring offset of 1.415 (2) Å. There are no other direction-specific interactions between the molecules; in particular, C—H⋯π(arene) hydrogen bonds are absent. Hence, the structure of compound (I)
simply consists of isolated centrosymmetric dimers.
By contrast with the structure of (I), there are no C—H⋯N hydrogen bonds in the structures of either (II)
or (III)
. Instead, the molecules of (II)
and (III)
are linked into sheets by C—H⋯π(arene) hydrogen bonds, a type of interaction absent from the structure of (I)
. Despite crystallizing in the same namely P21/c, the formation of the hydrogen-bonded sheets differs considerably between (II)
and (III)
.
In compound (II), the pyridine ring and the pendent C101–C106 phenyl ring act as hydrogen-bond acceptors. In the shorter of the two hydrogen bonds (Table 2
), atom C73 in the molecule at (x, y, z) acts as donor to the C101–C106 aryl ring in the molecule at (1 − x, 1 − y, −z), so generating a cyclic and centrosymmetric dimeric motif centred at (
,
, 0). The second of the two hydrogen bonds then links this dimer at (
,
, 0) to four adjacent dimers. Atoms C4 in the molecules at (x, y, z) and (1 − x, 1 − y, −z) act as hydrogen-bond donors to the pyridine rings in the molecules at (x,
− y,
+ z) and (1 − x,
+ y, −
− z), respectively, which themselves form parts of the dimers centred at (
, 0,
) and (
, 1, −
), respectively. Similarly, the pyridine rings at (x, y, z) and (1 − x, 1 − y, −z) accept hydrogen bonds from the C4 atoms in the molecules at (x,
− y, z −
) and (1 − x,
+ y,
− z), which are themselves components of dimers centred at (
, 0, −
) and (
, 1,
). Propagation by the of these two hydrogen bonds, associated with an inversion and a c-glide plane, respectively, then generates a (100) sheet in which large and small rings alternate (Fig. 6
).
As in (II), the two-dimensional supramolecular structure of (III)
is built from two C—H⋯π(arene) hydrogen bonds (Table 2
), but now both are associated with translational symmetry operations and there are no directly connected pairs of molecules which are related by inversion. Again, unlike the hydrogen bonds in (II)
, for those in (III)
the two donors form parts of the same aryl ring, while the acceptors are the two aryl rings pendent from the fused ring system.
Aryl atom C73 in the molecule at (x, y, z) acts as hydrogen-bond donor to the C101–C106 ring in the molecule at (1 − x, y − ,
− z), thereby forming a chain running parallel to the [010] direction and generated by the 21 screw axis along (
, y,
) (Fig. 7
). In addition, atom C76 at (x, y, z) acts as hydrogen-bond donor to the C1/C2/C3/C4/C4a/C11b ring in the molecule at (x,
− y,
+ z), thus producing a chain parallel to the [001] direction and generated by the c-glide plane at y =
(Fig. 8
). The combination of these two chains generates a (100) sheet in the form of a (4,4)-net (Fig. 9
).
The constitution of compound (IV) differs from those of (I)
–(III)
in that it provides an additional acceptor of hydrogen bonds in the O atom of the methoxy substituent (Fig. 4
). In fact, the molecules of (IV)
are linked by a combination of C—H⋯N, C—H⋯O and C—H⋯π(arene) hydrogen bonds (Table 2
) into a rather complex three-dimensional framework. The formation of this framework can be analysed very straightforwardly in terms of the component one-dimensional substructures.
In the first such x, y, z) acts as hydrogen-bond donor to pyridine atom N11 in the molecule at (1 − x, 1 − y, 1 − z), thereby generating a centrosymmetric R22(14) ring centred at (,
,
). In addition, atom C2 at (x, y, z) acts as donor to atom O7 in the molecule at (1 + x, y, 1 + z), so generating by translation a C(12) chain running parallel to the [101] direction. The combination of these two hydrogen bonds then generates a chain of edge-fused rings, with R22(14) rings centred at (n +
,
, n +
) (n = zero or integer) and R44(22) rings centred at (n,
, n) (n = zero or integer) (Fig. 10
).
The second one-dimensional x, y, z) and (1 − x, 1 − y, 1 − z), which form the R22(14) dimer centred at (,
,
), act as hydrogen-bond donors to the C101–C106 rings in the molecules at (1 − x, 1 − y, −z) and (x, y, 1 + z), respectively, which themselves form part of the R22(14) dimers centred at (
,
, −
) and (
,
,
), respectively, so forming a chain of edge-fused centrosymmetric rings running parallel to the [001] direction (Fig. 11
).
In addition to this [001] chain of edge-fused rings generated by inversion, there is a second c-glide plane. Aryl atom C4 in the molecule at (x, y, z) acts as hydrogen-bond donor to the pyridine ring in the molecule at (x, − y,
+ z), producing an [001] chain generated by the c-glide plane at y =
(Fig. 12
).
In the final x, y, z) acts as hydrogen-bond donor to the pendent C71–C76 aryl ring in the molecule at (1 − x, y − ,
− z), so forming a chain running parallel to the [010] direction and generated by the 21 screw axis along (
, y,
) (Fig. 13
).
The combination of the chains along [010], [001] and [101] suffices to link all of the molecules into a single three-dimensional framework, the complexity of which arises largely from the occurrence in the structure of five independent hydrogen bonds (Table 2).
We briefly compare the supramolecular structures of compounds (I)–(IV)
reported here with those of the pair of compounds, (V)
and (VI)
(see scheme), containing 4-halogenophenyl substituents, where the molecular skeleton is a simple positional isomer of the skeleton in compounds (I)
–(IV)
, and which are themseleves strictly isostructural in P
, as reported recently (Serrano et al., 2005a
,b
). In these analogues, the molecules are linked by C—H⋯π(arene) hydrogen bonds into chains of edge-fused rings. Hence, within this rather compact group of compounds, viz. (I)
–(VI)
, the supramolecular aggregation ranges from finite (zero-dimensional) in compound (I)
, via one-dimensional in compounds (V)
and (VI)
and two-dimensional in compounds (II)
and (III)
, to three-dimensional in compound (IV)
.
The differences between the 4-methylphenyl compound, (III), and the 4-chlorophenyl compound, (V)
, in terms of both their space groups, namely P21/c for (III)
as opposed to P
for (V)
, and their supramolecular dimensionality, namely two-dimensional for (III)
as opposed to one-dimensional for (V)
, is unexpected, as methyl and chloro substituents on aryl rings are generally effectively isosteric. This is well illustrated, for example, by the related series of fused heterocycles (VII)
–(IX)
(see scheme) containing, respectively, 4-methylphenyl, 4-chlorophenyl and 4-bromophenyl substituents, which are all isomorphous and strictly isostructural (Portilla et al., 2005
).
![]() | Figure 1 The molecule of (I) ![]() |
![]() | Figure 2 The molecule of (II) ![]() |
![]() | Figure 3 The molecule of (III) ![]() |
![]() | Figure 4 The molecule of (IV) ![]() |
![]() | Figure 5 Part of the crystal structure of (I) ![]() |
![]() | Figure 6 A stereoview of part of the crystal structure of (II) ![]() |
![]() | Figure 7 A stereoview of part of the crystal structure of (III) ![]() |
![]() | Figure 8 A stereoview of part of the crystal structure of (III) ![]() |
![]() | Figure 9 A stereoview of part of the crystal structure of (III) ![]() |
![]() | Figure 10 A stereoview of part of the crystal structure of (IV) ![]() |
![]() | Figure 11 A stereoview of part of the crystal structure of (IV) ![]() |
![]() | Figure 12 Part of the crystal structure of (IV) ![]() ![]() ![]() ![]() ![]() |
![]() | Figure 13 Part of the crystal structure of (IV) ![]() ![]() ![]() ![]() ![]() |
Experimental
For the preparation of the title compounds, equimolar quantities of 5-amino-3-methyl-1-phenylpyrazole (1.0 mmol) and the corresponding methylene derivative (from 2-tetralone and the appropriate aldehyde) (1.0 mmol) were placed in open Pyrex glass vessels and irradiated in a domestic microwave oven for 3–5 min at 600 W. The reaction mixture was extracted with ethanol and the extract was evaporated. The solid residues were recrystallized from dimethylformamide to give crystals suitable for single-crystal X-ray : yellow crystals (m.p. 439–440 K, yield 60%), MS (30 eV) m/z (%) = 311 (100, M+), 296 (7); for (II)
: yellow crystals (m.p. 494–495 K, yield 78%), MS (30 eV) m/z (%) = 388 (36), 387 (100, M+), 372 (6); for (III)
: yellow crystals (m.p. 484–485 K, yield 75%), MS (30 eV) m/z (%) = 402 (36), 401 (100, M+), 386 (6); for (IV)
: pale-brown crystals (m.p. 484–485 K, yield 60%), MS (30 eV) m/z (%) = 418 (33), 417 (100, M+), 402 (6).
Compound (I)![[link]](../../../../../../logos/arrows/c_arr.gif)
Crystal data
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Data collection
Compound (II)![[link]](../../../../../../logos/arrows/c_arr.gif)
Crystal data
|
Data collection
Compound (III)![[link]](../../../../../../logos/arrows/c_arr.gif)
Crystal data
|
Data collection
Compound (IV)![[link]](../../../../../../logos/arrows/c_arr.gif)
Crystal data
|
Data collection
|
|
Crystals of compound (I) are triclinic; P
was selected and then confirmed by the successful structure analysis. For each of compounds (II)
–(IV)
, the P21/c was uniquely assigned from the All H atoms were located from difference maps and then treated as riding atoms, with C—H distances of 0.95 (aromatic), 0.98 (CH3) or 0.99 Å (CH2), and with Uiso(H) = 1.2Ueq(C), or 1.5Ueq(C) for the methyl groups. The crystals of compound (III)
were very fragile, and attempts to cut small fragments from larger crystals resulted in shattering.
For all compounds, data collection: COLLECT (Hooft, 1999); cell DENZO (Otwinowski & Minor, 1997
) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003
) and SHELXS97 (Sheldrick, 1997
); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997
); molecular graphics: PLATON (Spek, 2003
); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999
).
Supporting information
10.1107/S0108270105020093/sk1854sup1.cif
contains datablocks global, I, II, III, IV. DOI:Structure factors: contains datablock I. DOI: 10.1107/S0108270105020093/sk1854Isup2.hkl
Structure factors: contains datablock II. DOI: 10.1107/S0108270105020093/sk1854IIsup3.hkl
Structure factors: contains datablock III. DOI: 10.1107/S0108270105020093/sk1854IIIsup4.hkl
Structure factors: contains datablock IV. DOI: 10.1107/S0108270105020093/sk1854IVsup5.hkl
Equimolar quantities of 5-amino-3-methyl-1-phenylpyrazole (1.0 mmol) and the corresponding methylene derivative (from 2-tetralone and the appropriate aldehyde) (1.0 mmol) were placed in open Pyrex glass vessels and irradiated in a domestic microwave oven for 3–5 min at 600 W. The reaction mixture was extracted with ethanol and the extract was evaporated. The solid residues were recrystallized from dimethylformamide to give crystals suitable for single-crystal X-ray
for (I): yellow crystals (m.p. 439–440 K, yield 60%), MS (30 eV) m/z (%) = 311 (100, M+), 296 (7); for (II), yellow crystals (m.p. 494–495 K, yield 78%), MS (30 eV) m/z (%) = 388 (36), 387 (100, M+), 372 (6); for (III), yellow crystals (m.p. 484–485 K, yield 75%), MS (30 eV) m/z (%) = 402 (36), 401 (100, M+), 386 (6); for (IV), pale-brown crystals (m.p. 484–485 K, yield 60%), MS (30 eV) m/z (%) = 418 (33), 417 (100, M+), 402 (6).Crystals of compound (I) are triclinic; 1 was selected and then confirmed by the successful structure analysis. For each of compounds (II)–(IV), the P21/c was uniquely assigned from the All H atoms were located from difference maps and then treated as riding atoms, with C—H distances of 0.95 (aromatic), 0.98 (CH3) or 0.99 Å (CH2), and with Uiso(H) = 1.2Ueq(C), or 1.5Ueq(C) for the methyl groups. The crystals of compound (III) were very fragile, and attempts to cut small fragments from larger crystals resulted in shattering.
PFor all compounds, data collection: COLLECT (Hooft, 1999); cell
DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).C21H17N3 | Z = 2 |
Mr = 311.38 | F(000) = 328 |
Triclinic, P1 | Dx = 1.322 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.0870 (2) Å | Cell parameters from 3576 reflections |
b = 10.1321 (4) Å | θ = 3.1–27.6° |
c = 11.7977 (5) Å | µ = 0.08 mm−1 |
α = 87.501 (2)° | T = 120 K |
β = 73.171 (3)° | Rod, yellow |
γ = 74.828 (2)° | 0.50 × 0.10 × 0.10 mm |
V = 782.13 (5) Å3 |
Bruker Nonius KappaCCD area-detector diffractometer | 3576 independent reflections |
Radiation source: Bruker Nonius FR91 rotating anode | 2810 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.039 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.6°, θmin = 3.1° |
ϕ and ω scans | h = −8→9 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −12→13 |
Tmin = 0.954, Tmax = 0.992 | l = −15→15 |
15116 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0601P)2 + 0.1501P] where P = (Fo2 + 2Fc2)/3 |
3576 reflections | (Δ/σ)max < 0.001 |
218 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
C21H17N3 | γ = 74.828 (2)° |
Mr = 311.38 | V = 782.13 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.0870 (2) Å | Mo Kα radiation |
b = 10.1321 (4) Å | µ = 0.08 mm−1 |
c = 11.7977 (5) Å | T = 120 K |
α = 87.501 (2)° | 0.50 × 0.10 × 0.10 mm |
β = 73.171 (3)° |
Bruker Nonius KappaCCD area-detector diffractometer | 3576 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2810 reflections with I > 2σ(I) |
Tmin = 0.954, Tmax = 0.992 | Rint = 0.039 |
15116 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.23 e Å−3 |
3576 reflections | Δρmin = −0.28 e Å−3 |
218 parameters |
x | y | z | Uiso*/Ueq | ||
N9 | 0.83108 (15) | 0.57987 (10) | 0.28704 (9) | 0.0217 (2) | |
N10 | 0.83152 (15) | 0.44571 (10) | 0.31468 (9) | 0.0200 (2) | |
N11 | 0.76537 (15) | 0.31767 (10) | 0.49337 (9) | 0.0197 (2) | |
C1 | 0.77407 (18) | 0.07787 (13) | 0.62078 (11) | 0.0231 (3) | |
C2 | 0.7677 (2) | −0.04040 (14) | 0.68381 (12) | 0.0272 (3) | |
C3 | 0.6828 (2) | −0.03104 (14) | 0.80610 (12) | 0.0295 (3) | |
C4 | 0.6037 (2) | 0.09613 (14) | 0.86384 (12) | 0.0280 (3) | |
C4a | 0.61181 (19) | 0.21609 (14) | 0.80260 (11) | 0.0234 (3) | |
C5 | 0.5240 (2) | 0.35489 (14) | 0.86468 (11) | 0.0260 (3) | |
C6 | 0.6455 (2) | 0.45575 (14) | 0.80616 (11) | 0.0252 (3) | |
C6a | 0.68421 (18) | 0.45661 (13) | 0.67356 (11) | 0.0210 (3) | |
C7 | 0.70232 (18) | 0.57262 (13) | 0.60931 (11) | 0.0213 (3) | |
C7a | 0.75017 (17) | 0.56198 (12) | 0.48612 (11) | 0.0202 (3) | |
C8 | 0.78261 (18) | 0.64947 (13) | 0.38828 (11) | 0.0210 (3) | |
C10a | 0.78021 (17) | 0.43267 (13) | 0.43543 (11) | 0.0190 (3) | |
C11a | 0.71542 (17) | 0.33172 (13) | 0.61172 (11) | 0.0194 (3) | |
C11b | 0.69941 (17) | 0.20645 (13) | 0.67939 (11) | 0.0206 (3) | |
C81 | 0.7624 (2) | 0.79962 (13) | 0.38979 (13) | 0.0275 (3) | |
C101 | 0.86390 (18) | 0.34987 (12) | 0.22219 (11) | 0.0198 (3) | |
C102 | 0.78040 (18) | 0.23804 (13) | 0.24400 (11) | 0.0229 (3) | |
C103 | 0.8042 (2) | 0.15150 (13) | 0.15000 (12) | 0.0264 (3) | |
C104 | 0.9089 (2) | 0.17522 (14) | 0.03539 (12) | 0.0271 (3) | |
C105 | 0.9963 (2) | 0.28495 (13) | 0.01468 (12) | 0.0260 (3) | |
C106 | 0.97496 (19) | 0.37182 (13) | 0.10797 (11) | 0.0232 (3) | |
H1 | 0.8296 | 0.0716 | 0.5370 | 0.028* | |
H2 | 0.8210 | −0.1274 | 0.6436 | 0.033* | |
H3 | 0.6791 | −0.1117 | 0.8499 | 0.035* | |
H4 | 0.5425 | 0.1017 | 0.9472 | 0.034* | |
H5E | 0.5243 | 0.3461 | 0.9485 | 0.031* | |
H5A | 0.3806 | 0.3905 | 0.8633 | 0.031* | |
H6E | 0.5700 | 0.5488 | 0.8400 | 0.030* | |
H6A | 0.7780 | 0.4318 | 0.8244 | 0.030* | |
H7 | 0.6826 | 0.6574 | 0.6482 | 0.026* | |
H81A | 0.7887 | 0.8315 | 0.3085 | 0.041* | |
H81B | 0.8614 | 0.8186 | 0.4258 | 0.041* | |
H81C | 0.6239 | 0.8474 | 0.4361 | 0.041* | |
H103 | 0.7479 | 0.0749 | 0.1644 | 0.032* | |
H102 | 0.7080 | 0.2212 | 0.3223 | 0.027* | |
H104 | 0.9208 | 0.1168 | −0.0286 | 0.033* | |
H105 | 1.0708 | 0.3006 | −0.0634 | 0.031* | |
H106 | 1.0362 | 0.4462 | 0.0938 | 0.028* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N9 | 0.0234 (5) | 0.0204 (6) | 0.0224 (6) | −0.0077 (4) | −0.0070 (4) | 0.0028 (4) |
N10 | 0.0236 (5) | 0.0187 (5) | 0.0174 (5) | −0.0069 (4) | −0.0046 (4) | 0.0022 (4) |
N11 | 0.0193 (5) | 0.0223 (5) | 0.0167 (5) | −0.0051 (4) | −0.0043 (4) | 0.0016 (4) |
C1 | 0.0216 (6) | 0.0269 (7) | 0.0199 (6) | −0.0071 (5) | −0.0042 (5) | 0.0022 (5) |
C2 | 0.0278 (7) | 0.0250 (7) | 0.0285 (7) | −0.0072 (5) | −0.0077 (5) | 0.0026 (6) |
C3 | 0.0315 (7) | 0.0307 (8) | 0.0270 (7) | −0.0109 (6) | −0.0082 (6) | 0.0098 (6) |
C4 | 0.0290 (7) | 0.0364 (8) | 0.0190 (7) | −0.0116 (6) | −0.0058 (5) | 0.0059 (6) |
C4a | 0.0197 (6) | 0.0309 (7) | 0.0202 (7) | −0.0077 (5) | −0.0059 (5) | 0.0017 (5) |
C5 | 0.0262 (7) | 0.0320 (7) | 0.0191 (7) | −0.0072 (5) | −0.0058 (5) | 0.0008 (5) |
C6 | 0.0264 (7) | 0.0295 (7) | 0.0196 (7) | −0.0079 (5) | −0.0052 (5) | −0.0028 (5) |
C6a | 0.0165 (6) | 0.0264 (7) | 0.0190 (6) | −0.0056 (5) | −0.0032 (5) | −0.0019 (5) |
C7 | 0.0176 (6) | 0.0231 (6) | 0.0224 (7) | −0.0052 (5) | −0.0038 (5) | −0.0036 (5) |
C7a | 0.0150 (6) | 0.0221 (6) | 0.0227 (7) | −0.0045 (5) | −0.0043 (5) | −0.0008 (5) |
C8 | 0.0175 (6) | 0.0227 (6) | 0.0234 (7) | −0.0061 (5) | −0.0061 (5) | 0.0002 (5) |
C10a | 0.0146 (6) | 0.0237 (6) | 0.0179 (6) | −0.0046 (5) | −0.0036 (5) | 0.0005 (5) |
C11a | 0.0147 (6) | 0.0251 (7) | 0.0176 (6) | −0.0043 (5) | −0.0041 (5) | 0.0009 (5) |
C11b | 0.0162 (6) | 0.0272 (7) | 0.0190 (6) | −0.0068 (5) | −0.0055 (5) | 0.0030 (5) |
C81 | 0.0302 (7) | 0.0234 (7) | 0.0305 (8) | −0.0086 (5) | −0.0099 (6) | 0.0014 (6) |
C101 | 0.0201 (6) | 0.0209 (6) | 0.0181 (6) | −0.0034 (5) | −0.0067 (5) | 0.0001 (5) |
C102 | 0.0221 (6) | 0.0247 (7) | 0.0208 (7) | −0.0065 (5) | −0.0043 (5) | 0.0018 (5) |
C103 | 0.0299 (7) | 0.0233 (7) | 0.0282 (7) | −0.0091 (5) | −0.0097 (6) | 0.0008 (5) |
C104 | 0.0335 (7) | 0.0253 (7) | 0.0236 (7) | −0.0054 (6) | −0.0112 (6) | −0.0028 (5) |
C105 | 0.0316 (7) | 0.0262 (7) | 0.0185 (7) | −0.0060 (5) | −0.0060 (5) | 0.0020 (5) |
C106 | 0.0271 (7) | 0.0235 (7) | 0.0196 (7) | −0.0080 (5) | −0.0068 (5) | 0.0028 (5) |
C1—C2 | 1.3864 (18) | C8—N9 | 1.3233 (17) |
C1—C11b | 1.4004 (18) | C8—C81 | 1.4907 (18) |
C1—H1 | 0.95 | C81—H81A | 0.98 |
C2—C3 | 1.3900 (19) | C81—H81B | 0.98 |
C2—H2 | 0.95 | C81—H81C | 0.98 |
C3—C4 | 1.384 (2) | N9—N10 | 1.3834 (14) |
C3—H3 | 0.95 | N10—C10a | 1.3741 (16) |
C4—C4a | 1.3923 (18) | N10—C101 | 1.4202 (16) |
C4—H4 | 0.95 | C101—C106 | 1.3915 (17) |
C4a—C11b | 1.4022 (17) | C101—C102 | 1.3920 (17) |
C4a—C5 | 1.5064 (19) | C103—C104 | 1.3859 (19) |
C5—C6 | 1.5224 (18) | C103—C102 | 1.3879 (18) |
C5—H5E | 0.99 | C103—H103 | 0.95 |
C5—H5A | 0.99 | C102—H102 | 0.95 |
C6—C6a | 1.5080 (17) | C104—C105 | 1.3887 (18) |
C6—H6E | 0.99 | C104—H104 | 0.95 |
C6—H6A | 0.99 | C105—C106 | 1.3884 (18) |
C6a—C7 | 1.3848 (17) | C105—H105 | 0.95 |
C6a—C11a | 1.4223 (18) | C106—H106 | 0.95 |
C7—C7a | 1.3957 (17) | C10a—N11 | 1.3376 (16) |
C7—H7 | 0.95 | N11—C11a | 1.3415 (16) |
C7a—C10a | 1.4028 (17) | C11a—C11b | 1.4819 (17) |
C7a—C8 | 1.4266 (17) | ||
C2—C1—C11b | 120.64 (12) | C8—C81—H81A | 109.5 |
C2—C1—H1 | 119.7 | C8—C81—H81B | 109.5 |
C11b—C1—H1 | 119.7 | H81A—C81—H81B | 109.5 |
C1—C2—C3 | 119.65 (12) | C8—C81—H81C | 109.5 |
C1—C2—H2 | 120.2 | H81A—C81—H81C | 109.5 |
C3—C2—H2 | 120.2 | H81B—C81—H81C | 109.5 |
C4—C3—C2 | 119.81 (12) | C8—N9—N10 | 107.14 (10) |
C4—C3—H3 | 120.1 | C10a—N10—N9 | 110.09 (10) |
C2—C3—H3 | 120.1 | C10a—N10—C101 | 130.59 (10) |
C3—C4—C4a | 121.50 (12) | N9—N10—C101 | 119.05 (10) |
C3—C4—H4 | 119.2 | C106—C101—C102 | 120.18 (11) |
C4a—C4—H4 | 119.2 | C106—C101—N10 | 118.95 (11) |
C4—C4a—C11b | 118.62 (12) | C102—C101—N10 | 120.83 (11) |
C4—C4a—C5 | 121.78 (11) | C104—C103—C102 | 120.99 (12) |
C11b—C4a—C5 | 119.58 (11) | C104—C103—H103 | 119.5 |
C4a—C5—C6 | 111.57 (11) | C102—C103—H103 | 119.5 |
C4a—C5—H5E | 109.3 | C103—C102—C101 | 119.17 (12) |
C6—C5—H5E | 109.3 | C103—C102—H102 | 120.4 |
C4a—C5—H5A | 109.3 | C101—C102—H102 | 120.4 |
C6—C5—H5A | 109.3 | C103—C104—C105 | 119.54 (12) |
H5E—C5—H5A | 108.0 | C103—C104—H104 | 120.2 |
C6a—C6—C5 | 112.69 (10) | C105—C104—H104 | 120.2 |
C6a—C6—H6E | 109.1 | C106—C105—C104 | 120.10 (12) |
C5—C6—H6E | 109.1 | C106—C105—H105 | 120.0 |
C6a—C6—H6A | 109.1 | C104—C105—H105 | 120.0 |
C5—C6—H6A | 109.1 | C105—C106—C101 | 119.97 (12) |
H6E—C6—H6A | 107.8 | C105—C106—H106 | 120.0 |
C7—C6a—C11a | 118.89 (11) | C101—C106—H106 | 120.0 |
C7—C6a—C6 | 122.34 (11) | N11—C10a—N10 | 126.33 (11) |
C11a—C6a—C6 | 118.66 (11) | N11—C10a—C7a | 126.58 (11) |
C6a—C7—C7a | 118.42 (11) | N10—C10a—C7a | 107.08 (11) |
C6a—C7—H7 | 120.8 | C10a—N11—C11a | 114.72 (10) |
C7a—C7—H7 | 120.8 | N11—C11a—C6a | 124.08 (11) |
C7—C7a—C10a | 117.29 (11) | N11—C11a—C11b | 116.51 (11) |
C7—C7a—C8 | 137.65 (12) | C6a—C11a—C11b | 119.38 (11) |
C10a—C7a—C8 | 105.05 (11) | C1—C11b—C4a | 119.74 (11) |
N9—C8—C7a | 110.62 (11) | C1—C11b—C11a | 120.15 (11) |
N9—C8—C81 | 120.75 (11) | C4a—C11b—C11a | 120.10 (11) |
C7a—C8—C81 | 128.60 (12) | ||
C11b—C1—C2—C3 | 1.23 (18) | C103—C104—C105—C106 | −1.4 (2) |
C1—C2—C3—C4 | 0.58 (19) | C104—C105—C106—C101 | −0.73 (19) |
C2—C3—C4—C4a | −1.8 (2) | C102—C101—C106—C105 | 2.40 (18) |
C3—C4—C4a—C11b | 1.08 (19) | N10—C101—C106—C105 | −175.44 (11) |
C3—C4—C4a—C5 | 179.30 (12) | N9—N10—C10a—N11 | 179.88 (10) |
C4—C4a—C5—C6 | 147.22 (12) | C101—N10—C10a—N11 | 6.07 (19) |
C11b—C4a—C5—C6 | −34.57 (15) | N9—N10—C10a—C7a | −1.19 (13) |
C4a—C5—C6—C6a | 48.85 (14) | C101—N10—C10a—C7a | −175.00 (11) |
C5—C6—C6a—C7 | 149.47 (12) | C7—C7a—C10a—N11 | 0.84 (17) |
C5—C6—C6a—C11a | −34.42 (15) | C8—C7a—C10a—N11 | −179.85 (11) |
C11a—C6a—C7—C7a | 0.15 (17) | C7—C7a—C10a—N10 | −178.08 (10) |
C6—C6a—C7—C7a | 176.25 (11) | C8—C7a—C10a—N10 | 1.23 (12) |
C6a—C7—C7a—C10a | −1.05 (16) | N10—C10a—N11—C11a | 179.10 (10) |
C6a—C7—C7a—C8 | 179.93 (13) | C7a—C10a—N11—C11a | 0.38 (17) |
C7—C7a—C8—N9 | 178.21 (13) | C10a—N11—C11a—C6a | −1.40 (16) |
C10a—C7a—C8—N9 | −0.88 (13) | C10a—N11—C11a—C11b | −179.39 (9) |
C7—C7a—C8—C81 | −3.7 (2) | C7—C6a—C11a—N11 | 1.18 (17) |
C10a—C7a—C8—C81 | 177.22 (11) | C6—C6a—C11a—N11 | −175.07 (11) |
C7a—C8—N9—N10 | 0.17 (13) | C7—C6a—C11a—C11b | 179.12 (10) |
C81—C8—N9—N10 | −178.10 (10) | C6—C6a—C11a—C11b | 2.87 (16) |
C8—N9—N10—C10a | 0.64 (12) | C2—C1—C11b—C4a | −1.90 (18) |
C8—N9—N10—C101 | 175.27 (10) | C2—C1—C11b—C11a | 177.28 (11) |
C10a—N10—C101—C106 | −159.94 (12) | C4—C4a—C11b—C1 | 0.74 (17) |
N9—N10—C101—C106 | 26.70 (16) | C5—C4a—C11b—C1 | −177.53 (11) |
C10a—N10—C101—C102 | 22.24 (18) | C4—C4a—C11b—C11a | −178.43 (10) |
N9—N10—C101—C102 | −151.12 (11) | C5—C4a—C11b—C11a | 3.30 (17) |
C104—C103—C102—C101 | −0.20 (19) | N11—C11a—C11b—C1 | 12.73 (16) |
C106—C101—C102—C103 | −1.92 (18) | C6a—C11a—C11b—C1 | −165.36 (11) |
N10—C101—C102—C103 | 175.87 (11) | N11—C11a—C11b—C4a | −168.10 (10) |
C102—C103—C104—C105 | 1.8 (2) | C6a—C11a—C11b—C4a | 13.81 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5A···N9i | 0.99 | 2.60 | 3.407 (2) | 139 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
C27H21N3 | F(000) = 816 |
Mr = 387.47 | Dx = 1.294 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4539 reflections |
a = 11.5561 (4) Å | θ = 2.9–27.5° |
b = 17.6751 (7) Å | µ = 0.08 mm−1 |
c = 9.8469 (3) Å | T = 120 K |
β = 98.599 (2)° | Block, yellow |
V = 1988.67 (12) Å3 | 0.40 × 0.20 × 0.20 mm |
Z = 4 |
Bruker Nonius KappaCCD area-detector diffractometer | 4539 independent reflections |
Radiation source: Bruker Nonius FR91 rotating anode | 3236 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.053 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.9° |
ϕ and ω scans | h = −15→13 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −22→22 |
Tmin = 0.973, Tmax = 0.985 | l = −12→12 |
26788 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.126 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0639P)2 + 0.3388P] where P = (Fo2 + 2Fc2)/3 |
4539 reflections | (Δ/σ)max < 0.001 |
272 parameters | Δρmax = 0.28 e Å−3 |
0 restraints | Δρmin = −0.29 e Å−3 |
C27H21N3 | V = 1988.67 (12) Å3 |
Mr = 387.47 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.5561 (4) Å | µ = 0.08 mm−1 |
b = 17.6751 (7) Å | T = 120 K |
c = 9.8469 (3) Å | 0.40 × 0.20 × 0.20 mm |
β = 98.599 (2)° |
Bruker Nonius KappaCCD area-detector diffractometer | 4539 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 3236 reflections with I > 2σ(I) |
Tmin = 0.973, Tmax = 0.985 | Rint = 0.053 |
26788 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.126 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.28 e Å−3 |
4539 reflections | Δρmin = −0.29 e Å−3 |
272 parameters |
x | y | z | Uiso*/Ueq | ||
N9 | 0.43577 (11) | 0.58317 (7) | 0.12922 (12) | 0.0246 (3) | |
N10 | 0.34752 (10) | 0.54838 (7) | 0.18563 (12) | 0.0226 (3) | |
N11 | 0.33013 (10) | 0.44465 (7) | 0.34202 (11) | 0.0203 (3) | |
C1 | 0.21854 (13) | 0.35978 (9) | 0.52740 (15) | 0.0253 (3) | |
C2 | 0.15848 (14) | 0.31124 (9) | 0.60241 (16) | 0.0304 (4) | |
C3 | 0.21065 (15) | 0.24434 (10) | 0.65426 (16) | 0.0316 (4) | |
C4 | 0.32201 (14) | 0.22656 (9) | 0.62946 (16) | 0.0305 (4) | |
C4a | 0.38337 (13) | 0.27438 (8) | 0.55394 (15) | 0.0257 (3) | |
C5 | 0.50310 (15) | 0.25435 (9) | 0.52218 (19) | 0.0355 (4) | |
C6 | 0.57792 (13) | 0.32386 (9) | 0.51646 (16) | 0.0292 (4) | |
C6a | 0.51771 (13) | 0.38214 (8) | 0.41929 (14) | 0.0227 (3) | |
C7 | 0.57744 (13) | 0.42877 (9) | 0.33974 (16) | 0.0285 (4) | |
C7a | 0.51099 (12) | 0.48429 (8) | 0.25861 (14) | 0.0218 (3) | |
C8 | 0.53342 (13) | 0.54537 (8) | 0.17123 (14) | 0.0236 (3) | |
C10a | 0.39155 (12) | 0.48847 (8) | 0.26655 (13) | 0.0203 (3) | |
C11a | 0.39426 (12) | 0.39257 (8) | 0.41779 (13) | 0.0198 (3) | |
C11b | 0.33103 (12) | 0.34207 (8) | 0.50193 (13) | 0.0209 (3) | |
C71 | 0.70476 (13) | 0.41902 (8) | 0.33270 (15) | 0.0228 (3) | |
C72 | 0.74131 (13) | 0.39804 (9) | 0.20979 (15) | 0.0252 (3) | |
C73 | 0.85936 (13) | 0.38897 (9) | 0.20265 (16) | 0.0286 (4) | |
C74 | 0.94184 (13) | 0.40076 (9) | 0.31732 (16) | 0.0289 (4) | |
C75 | 0.90609 (13) | 0.42152 (9) | 0.43990 (16) | 0.0287 (4) | |
C76 | 0.78855 (13) | 0.43018 (8) | 0.44813 (15) | 0.0268 (3) | |
C81 | 0.64537 (13) | 0.57005 (9) | 0.12594 (16) | 0.0302 (4) | |
C101 | 0.23436 (12) | 0.58166 (8) | 0.16747 (14) | 0.0233 (3) | |
C102 | 0.22464 (14) | 0.66001 (9) | 0.15294 (15) | 0.0296 (4) | |
C103 | 0.11490 (15) | 0.69317 (10) | 0.13306 (16) | 0.0353 (4) | |
C104 | 0.01560 (15) | 0.64928 (10) | 0.12814 (16) | 0.0355 (4) | |
C105 | 0.02594 (14) | 0.57183 (11) | 0.14374 (17) | 0.0351 (4) | |
C106 | 0.13507 (13) | 0.53746 (9) | 0.16269 (15) | 0.0285 (4) | |
H1 | 0.1828 | 0.4057 | 0.4929 | 0.030* | |
H2 | 0.0817 | 0.3237 | 0.6184 | 0.036* | |
H3 | 0.1700 | 0.2110 | 0.7064 | 0.038* | |
H4 | 0.3573 | 0.1807 | 0.6648 | 0.037* | |
H5A | 0.4952 | 0.2277 | 0.4328 | 0.043* | |
H5E | 0.5419 | 0.2196 | 0.5937 | 0.043* | |
H6A | 0.5959 | 0.3461 | 0.6095 | 0.035* | |
H6E | 0.6528 | 0.3093 | 0.4864 | 0.035* | |
H72 | 0.6851 | 0.3899 | 0.1304 | 0.030* | |
H73 | 0.8837 | 0.3745 | 0.1184 | 0.034* | |
H74 | 1.0227 | 0.3946 | 0.3120 | 0.035* | |
H75 | 0.9627 | 0.4299 | 0.5189 | 0.034* | |
H76 | 0.7647 | 0.4438 | 0.5331 | 0.032* | |
H81A | 0.6669 | 0.5341 | 0.0581 | 0.045* | |
H81B | 0.7075 | 0.5717 | 0.2054 | 0.045* | |
H81C | 0.6351 | 0.6205 | 0.0846 | 0.045* | |
H102 | 0.2929 | 0.6904 | 0.1567 | 0.036* | |
H103 | 0.1079 | 0.7465 | 0.1227 | 0.042* | |
H104 | −0.0596 | 0.6723 | 0.1141 | 0.043* | |
H105 | −0.0424 | 0.5418 | 0.1415 | 0.042* | |
H106 | 0.1415 | 0.4841 | 0.1723 | 0.034* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N9 | 0.0258 (7) | 0.0241 (7) | 0.0243 (6) | −0.0023 (5) | 0.0052 (5) | 0.0026 (5) |
N10 | 0.0231 (6) | 0.0214 (6) | 0.0237 (6) | 0.0003 (5) | 0.0044 (5) | 0.0035 (5) |
N11 | 0.0225 (6) | 0.0198 (6) | 0.0189 (6) | 0.0024 (5) | 0.0046 (5) | 0.0007 (5) |
C1 | 0.0253 (8) | 0.0266 (8) | 0.0245 (7) | 0.0029 (6) | 0.0045 (6) | 0.0030 (6) |
C2 | 0.0267 (8) | 0.0352 (9) | 0.0309 (8) | 0.0013 (7) | 0.0094 (7) | 0.0033 (7) |
C3 | 0.0353 (9) | 0.0325 (9) | 0.0283 (8) | −0.0046 (7) | 0.0094 (7) | 0.0055 (7) |
C4 | 0.0343 (9) | 0.0248 (8) | 0.0330 (9) | 0.0015 (7) | 0.0065 (7) | 0.0085 (7) |
C4a | 0.0279 (8) | 0.0231 (8) | 0.0264 (8) | 0.0019 (6) | 0.0052 (6) | 0.0016 (6) |
C5 | 0.0318 (9) | 0.0262 (9) | 0.0510 (11) | 0.0064 (7) | 0.0141 (8) | 0.0098 (7) |
C6 | 0.0267 (8) | 0.0287 (8) | 0.0328 (8) | 0.0064 (7) | 0.0063 (6) | 0.0059 (7) |
C6a | 0.0219 (7) | 0.0227 (8) | 0.0233 (7) | 0.0004 (6) | 0.0021 (6) | 0.0014 (6) |
C7 | 0.0252 (8) | 0.0289 (8) | 0.0328 (8) | 0.0042 (7) | 0.0086 (6) | 0.0051 (7) |
C7a | 0.0229 (7) | 0.0232 (8) | 0.0194 (7) | 0.0017 (6) | 0.0038 (6) | −0.0001 (6) |
C8 | 0.0267 (8) | 0.0238 (8) | 0.0204 (7) | 0.0001 (6) | 0.0036 (6) | 0.0007 (6) |
C10a | 0.0250 (8) | 0.0192 (7) | 0.0164 (7) | 0.0020 (6) | 0.0024 (6) | −0.0001 (5) |
C11a | 0.0221 (7) | 0.0193 (7) | 0.0182 (7) | 0.0015 (6) | 0.0037 (6) | −0.0024 (5) |
C11b | 0.0234 (8) | 0.0226 (7) | 0.0168 (7) | −0.0008 (6) | 0.0032 (6) | −0.0014 (6) |
C71 | 0.0225 (7) | 0.0200 (7) | 0.0264 (8) | 0.0022 (6) | 0.0051 (6) | 0.0037 (6) |
C72 | 0.0245 (8) | 0.0279 (8) | 0.0224 (7) | −0.0012 (6) | 0.0012 (6) | 0.0014 (6) |
C73 | 0.0299 (9) | 0.0321 (9) | 0.0260 (8) | 0.0014 (7) | 0.0114 (6) | 0.0015 (7) |
C74 | 0.0185 (7) | 0.0314 (9) | 0.0373 (9) | −0.0001 (6) | 0.0057 (6) | 0.0058 (7) |
C75 | 0.0281 (8) | 0.0257 (8) | 0.0297 (8) | −0.0026 (7) | −0.0042 (6) | −0.0004 (6) |
C76 | 0.0329 (9) | 0.0239 (8) | 0.0235 (8) | 0.0044 (7) | 0.0042 (6) | −0.0014 (6) |
C81 | 0.0280 (9) | 0.0320 (9) | 0.0312 (8) | −0.0029 (7) | 0.0067 (7) | 0.0057 (7) |
C101 | 0.0247 (8) | 0.0266 (8) | 0.0182 (7) | 0.0049 (6) | 0.0021 (6) | 0.0011 (6) |
C102 | 0.0340 (9) | 0.0268 (8) | 0.0268 (8) | 0.0037 (7) | 0.0008 (6) | −0.0002 (6) |
C103 | 0.0451 (10) | 0.0311 (9) | 0.0287 (8) | 0.0144 (8) | 0.0022 (7) | −0.0012 (7) |
C104 | 0.0328 (9) | 0.0480 (11) | 0.0266 (8) | 0.0179 (8) | 0.0079 (7) | 0.0060 (7) |
C105 | 0.0267 (9) | 0.0466 (11) | 0.0328 (9) | 0.0033 (8) | 0.0066 (7) | 0.0095 (8) |
C106 | 0.0288 (8) | 0.0290 (9) | 0.0280 (8) | 0.0028 (7) | 0.0050 (6) | 0.0073 (6) |
C1—C2 | 1.384 (2) | C10a—N11 | 1.3467 (18) |
C1—C11b | 1.396 (2) | N11—C11a | 1.3370 (18) |
C1—H1 | 0.95 | C11a—C11b | 1.483 (2) |
C2—C3 | 1.389 (2) | C71—C72 | 1.391 (2) |
C2—H2 | 0.95 | C71—C76 | 1.393 (2) |
C3—C4 | 1.381 (2) | C72—C73 | 1.386 (2) |
C3—H3 | 0.95 | C72—H72 | 0.95 |
C4—C4a | 1.389 (2) | C73—C74 | 1.380 (2) |
C4—H4 | 0.95 | C73—H73 | 0.95 |
C4a—C11b | 1.402 (2) | C74—C75 | 1.383 (2) |
C4a—C5 | 1.506 (2) | C74—H74 | 0.95 |
C5—C6 | 1.508 (2) | C75—C76 | 1.381 (2) |
C5—H5A | 0.99 | C75—H75 | 0.95 |
C5—H5E | 0.99 | C76—H76 | 0.95 |
C6—C6a | 1.504 (2) | C81—H81A | 0.98 |
C6—H6A | 0.99 | C81—H81B | 0.98 |
C6—H6E | 0.99 | C81—H81C | 0.98 |
C6a—C7 | 1.390 (2) | C101—C106 | 1.383 (2) |
C6a—C11a | 1.436 (2) | C101—C102 | 1.395 (2) |
C7—C7a | 1.417 (2) | C102—C103 | 1.384 (2) |
C7—C71 | 1.493 (2) | C102—H102 | 0.95 |
C7a—C10a | 1.396 (2) | C103—C104 | 1.380 (3) |
C7a—C8 | 1.428 (2) | C103—H103 | 0.95 |
C8—N9 | 1.3234 (19) | C104—C105 | 1.381 (3) |
C8—C81 | 1.495 (2) | C104—H104 | 0.95 |
N9—N10 | 1.3769 (17) | C105—C106 | 1.387 (2) |
N10—C10a | 1.3762 (18) | C105—H105 | 0.95 |
N10—C101 | 1.4206 (18) | C106—H106 | 0.95 |
C2—C1—C11b | 120.77 (14) | N11—C11a—C11b | 116.61 (12) |
C2—C1—H1 | 119.6 | C6a—C11a—C11b | 119.25 (12) |
C11b—C1—H1 | 119.6 | C1—C11b—C4a | 119.22 (13) |
C1—C2—C3 | 119.92 (15) | C1—C11b—C11a | 121.02 (13) |
C1—C2—H2 | 120.0 | C4a—C11b—C11a | 119.73 (13) |
C3—C2—H2 | 120.0 | C72—C71—C76 | 118.92 (14) |
C4—C3—C2 | 119.55 (15) | C72—C71—C7 | 120.05 (13) |
C4—C3—H3 | 120.2 | C76—C71—C7 | 121.03 (13) |
C2—C3—H3 | 120.2 | C73—C72—C71 | 120.30 (14) |
C3—C4—C4a | 121.33 (15) | C73—C72—H72 | 119.9 |
C3—C4—H4 | 119.3 | C71—C72—H72 | 119.9 |
C4a—C4—H4 | 119.3 | C74—C73—C72 | 120.37 (14) |
C4—C4a—C11b | 119.20 (14) | C74—C73—H73 | 119.8 |
C4—C4a—C5 | 121.79 (14) | C72—C73—H73 | 119.8 |
C11b—C4a—C5 | 118.97 (13) | C73—C74—C75 | 119.63 (14) |
C4a—C5—C6 | 111.46 (13) | C73—C74—H74 | 120.2 |
C4a—C5—H5A | 109.3 | C75—C74—H74 | 120.2 |
C6—C5—H5A | 109.3 | C76—C75—C74 | 120.36 (14) |
C4a—C5—H5E | 109.3 | C76—C75—H75 | 119.8 |
C6—C5—H5E | 109.3 | C74—C75—H75 | 119.8 |
H5A—C5—H5E | 108.0 | C75—C76—C71 | 120.41 (14) |
C6a—C6—C5 | 111.62 (13) | C75—C76—H76 | 119.8 |
C6a—C6—H6A | 109.3 | C71—C76—H76 | 119.8 |
C5—C6—H6A | 109.3 | C8—C81—H81A | 109.5 |
C6a—C6—H6E | 109.3 | C8—C81—H81B | 109.5 |
C5—C6—H6E | 109.3 | H81A—C81—H81B | 109.5 |
H6A—C6—H6E | 108.0 | C8—C81—H81C | 109.5 |
C7—C6a—C11a | 119.63 (13) | H81A—C81—H81C | 109.5 |
C7—C6a—C6 | 122.91 (13) | H81B—C81—H81C | 109.5 |
C11a—C6a—C6 | 117.31 (13) | C106—C101—C102 | 120.23 (14) |
C6a—C7—C7a | 117.10 (14) | C106—C101—N10 | 120.92 (14) |
C6a—C7—C71 | 122.26 (13) | C102—C101—N10 | 118.85 (14) |
C7a—C7—C71 | 120.56 (13) | C103—C102—C101 | 119.54 (15) |
C10a—C7a—C7 | 117.52 (13) | C103—C102—H102 | 120.2 |
C10a—C7a—C8 | 105.29 (12) | C101—C102—H102 | 120.2 |
C7—C7a—C8 | 137.00 (14) | C104—C103—C102 | 120.42 (16) |
N9—C8—C7a | 110.29 (13) | C104—C103—H103 | 119.8 |
N9—C8—C81 | 119.67 (13) | C102—C103—H103 | 119.8 |
C7a—C8—C81 | 130.04 (13) | C103—C104—C105 | 119.72 (15) |
C8—N9—N10 | 107.27 (12) | C103—C104—H104 | 120.1 |
C10a—N10—N9 | 110.19 (11) | C105—C104—H104 | 120.1 |
C10a—N10—C101 | 130.18 (12) | C104—C105—C106 | 120.74 (16) |
N9—N10—C101 | 119.19 (12) | C104—C105—H105 | 119.6 |
N11—C10a—N10 | 125.61 (13) | C106—C105—H105 | 119.6 |
N11—C10a—C7a | 127.41 (13) | C101—C106—C105 | 119.35 (15) |
N10—C10a—C7a | 106.94 (12) | C101—C106—H106 | 120.3 |
C11a—N11—C10a | 114.20 (12) | C105—C106—H106 | 120.3 |
N11—C11a—C6a | 124.12 (13) | ||
C11b—C1—C2—C3 | 0.6 (2) | C7—C6a—C11a—N11 | 1.0 (2) |
C1—C2—C3—C4 | −0.5 (2) | C6—C6a—C11a—N11 | 176.62 (13) |
C2—C3—C4—C4a | 0.2 (2) | C7—C6a—C11a—C11b | 179.40 (13) |
C3—C4—C4a—C11b | 0.0 (2) | C6—C6a—C11a—C11b | −4.9 (2) |
C3—C4—C4a—C5 | −177.88 (15) | C2—C1—C11b—C4a | −0.3 (2) |
C4—C4a—C5—C6 | −147.16 (15) | C2—C1—C11b—C11a | 177.95 (13) |
C11b—C4a—C5—C6 | 34.9 (2) | C4—C4a—C11b—C1 | 0.1 (2) |
C4a—C5—C6—C6a | −53.40 (19) | C5—C4a—C11b—C1 | 178.00 (14) |
C5—C6—C6a—C7 | −145.07 (15) | C4—C4a—C11b—C11a | −178.27 (13) |
C5—C6—C6a—C11a | 39.42 (19) | C5—C4a—C11b—C11a | −0.3 (2) |
C11a—C6a—C7—C7a | −0.9 (2) | N11—C11a—C11b—C1 | −15.48 (19) |
C6—C6a—C7—C7a | −176.34 (14) | C6a—C11a—C11b—C1 | 165.96 (13) |
C11a—C6a—C7—C71 | −177.67 (13) | N11—C11a—C11b—C4a | 162.81 (13) |
C6—C6a—C7—C71 | 6.9 (2) | C6a—C11a—C11b—C4a | −15.75 (19) |
C6a—C7—C7a—C10a | 0.9 (2) | C6a—C7—C71—C72 | 114.74 (17) |
C71—C7—C7a—C10a | 177.72 (13) | C7a—C7—C71—C72 | −61.9 (2) |
C6a—C7—C7a—C8 | 175.16 (16) | C6a—C7—C71—C76 | −64.9 (2) |
C71—C7—C7a—C8 | −8.0 (3) | C7a—C7—C71—C76 | 118.49 (17) |
C10a—C7a—C8—N9 | −0.27 (16) | C76—C71—C72—C73 | −0.4 (2) |
C7—C7a—C8—N9 | −174.97 (17) | C7—C71—C72—C73 | 179.95 (14) |
C10a—C7a—C8—C81 | 179.29 (14) | C71—C72—C73—C74 | −0.1 (2) |
C7—C7a—C8—C81 | 4.6 (3) | C72—C73—C74—C75 | 0.2 (2) |
C7a—C8—N9—N10 | −0.51 (16) | C73—C74—C75—C76 | 0.3 (2) |
C81—C8—N9—N10 | 179.88 (12) | C74—C75—C76—C71 | −0.8 (2) |
C8—N9—N10—C10a | 1.13 (15) | C72—C71—C76—C75 | 0.9 (2) |
C8—N9—N10—C101 | 174.26 (12) | C7—C71—C76—C75 | −179.51 (14) |
N9—N10—C10a—N11 | 176.60 (13) | C10a—N10—C101—C106 | −38.4 (2) |
C101—N10—C10a—N11 | 4.4 (2) | N9—N10—C101—C106 | 150.00 (13) |
N9—N10—C10a—C7a | −1.29 (15) | C10a—N10—C101—C102 | 142.24 (15) |
C101—N10—C10a—C7a | −173.44 (13) | N9—N10—C101—C102 | −29.31 (19) |
C7—C7a—C10a—N11 | −1.0 (2) | C106—C101—C102—C103 | −0.3 (2) |
C8—C7a—C10a—N11 | −176.91 (13) | N10—C101—C102—C103 | 179.02 (13) |
C7—C7a—C10a—N10 | 176.86 (13) | C101—C102—C103—C104 | 0.3 (2) |
C8—C7a—C10a—N10 | 0.93 (15) | C102—C103—C104—C105 | 0.3 (2) |
N10—C10a—N11—C11a | −176.54 (13) | C103—C104—C105—C106 | −0.8 (2) |
C7a—C10a—N11—C11a | 0.9 (2) | C102—C101—C106—C105 | −0.2 (2) |
C10a—N11—C11a—C6a | −0.87 (19) | N10—C101—C106—C105 | −179.49 (13) |
C10a—N11—C11a—C11b | −179.35 (12) | C104—C105—C106—C101 | 0.7 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···Cg1i | 0.95 | 2.82 | 3.7461 (17) | 164 |
C73—H73···Cg2ii | 0.95 | 2.62 | 3.4852 (17) | 152 |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, −y+1, −z. |
C28H23N3 | F(000) = 848 |
Mr = 401.49 | Dx = 1.280 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4778 reflections |
a = 12.0313 (3) Å | θ = 3.2–27.5° |
b = 14.3347 (4) Å | µ = 0.08 mm−1 |
c = 12.7956 (3) Å | T = 120 K |
β = 109.3092 (14)° | Lath, yellow |
V = 2082.66 (9) Å3 | 0.66 × 0.42 × 0.14 mm |
Z = 4 |
Bruker Nonius KappaCCD area-detector diffractometer | 4778 independent reflections |
Radiation source: Bruker Nonius FR91 rotating anode | 3416 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.059 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.2° |
ϕ and ω scans | h = −15→15 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −18→18 |
Tmin = 0.956, Tmax = 0.989 | l = −16→16 |
38247 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.066P)2 + 0.5056P] where P = (Fo2 + 2Fc2)/3 |
4778 reflections | (Δ/σ)max < 0.001 |
282 parameters | Δρmax = 0.41 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
C28H23N3 | V = 2082.66 (9) Å3 |
Mr = 401.49 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.0313 (3) Å | µ = 0.08 mm−1 |
b = 14.3347 (4) Å | T = 120 K |
c = 12.7956 (3) Å | 0.66 × 0.42 × 0.14 mm |
β = 109.3092 (14)° |
Bruker Nonius KappaCCD area-detector diffractometer | 4778 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 3416 reflections with I > 2σ(I) |
Tmin = 0.956, Tmax = 0.989 | Rint = 0.059 |
38247 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.41 e Å−3 |
4778 reflections | Δρmin = −0.31 e Å−3 |
282 parameters |
x | y | z | Uiso*/Ueq | ||
N9 | 0.30634 (11) | 0.65547 (9) | 0.73214 (10) | 0.0258 (3) | |
N10 | 0.30409 (10) | 0.66474 (9) | 0.62375 (9) | 0.0240 (3) | |
N11 | 0.43992 (10) | 0.64102 (9) | 0.52311 (9) | 0.0226 (3) | |
C1 | 0.50934 (13) | 0.64311 (11) | 0.33420 (12) | 0.0267 (3) | |
C2 | 0.54058 (15) | 0.63637 (11) | 0.23984 (13) | 0.0304 (4) | |
C3 | 0.64913 (15) | 0.59966 (12) | 0.24608 (13) | 0.0322 (4) | |
C4 | 0.72493 (14) | 0.56801 (12) | 0.34689 (13) | 0.0317 (4) | |
C4a | 0.69491 (13) | 0.57393 (11) | 0.44258 (12) | 0.0264 (3) | |
C5 | 0.77415 (14) | 0.53670 (12) | 0.55198 (12) | 0.0314 (4) | |
C6 | 0.76520 (13) | 0.59487 (12) | 0.64686 (13) | 0.0315 (4) | |
C6a | 0.63895 (12) | 0.60365 (11) | 0.64328 (12) | 0.0244 (3) | |
C7 | 0.60599 (13) | 0.60251 (11) | 0.73788 (12) | 0.0243 (3) | |
C7a | 0.48778 (12) | 0.62315 (10) | 0.72366 (11) | 0.0219 (3) | |
C8 | 0.41448 (13) | 0.63049 (10) | 0.79173 (12) | 0.0239 (3) | |
C10a | 0.41290 (12) | 0.64386 (10) | 0.61634 (11) | 0.0217 (3) | |
C11a | 0.55248 (12) | 0.61967 (10) | 0.53789 (12) | 0.0217 (3) | |
C11b | 0.58595 (12) | 0.61283 (10) | 0.43662 (12) | 0.0226 (3) | |
C71 | 0.69221 (12) | 0.57974 (11) | 0.84904 (12) | 0.0247 (3) | |
C72 | 0.74078 (13) | 0.49082 (12) | 0.87080 (12) | 0.0294 (4) | |
C73 | 0.82076 (14) | 0.46872 (12) | 0.97366 (13) | 0.0315 (4) | |
C74 | 0.85460 (13) | 0.53490 (12) | 1.05790 (12) | 0.0297 (4) | |
C75 | 0.80652 (14) | 0.62366 (12) | 1.03547 (12) | 0.0302 (4) | |
C76 | 0.72639 (13) | 0.64641 (11) | 0.93260 (12) | 0.0274 (3) | |
C77 | 0.94094 (16) | 0.50995 (15) | 1.17000 (14) | 0.0450 (5) | |
C81 | 0.44431 (14) | 0.61437 (12) | 0.91309 (12) | 0.0296 (4) | |
C101 | 0.19686 (12) | 0.68698 (10) | 0.53990 (11) | 0.0235 (3) | |
C102 | 0.09135 (13) | 0.67465 (12) | 0.56059 (12) | 0.0285 (4) | |
C103 | −0.01409 (14) | 0.69713 (12) | 0.47966 (13) | 0.0328 (4) | |
C104 | −0.01591 (14) | 0.73023 (12) | 0.37762 (13) | 0.0343 (4) | |
C105 | 0.08906 (14) | 0.74071 (12) | 0.35707 (13) | 0.0329 (4) | |
C106 | 0.19587 (13) | 0.72066 (12) | 0.43766 (12) | 0.0289 (4) | |
H1 | 0.4349 | 0.6686 | 0.3295 | 0.032* | |
H2 | 0.4876 | 0.6569 | 0.1707 | 0.036* | |
H3 | 0.6715 | 0.5962 | 0.1816 | 0.039* | |
H4 | 0.7987 | 0.5418 | 0.3506 | 0.038* | |
H5A | 0.7519 | 0.4715 | 0.5612 | 0.038* | |
H5E | 0.8567 | 0.5367 | 0.5526 | 0.038* | |
H6A | 0.7978 | 0.6578 | 0.6433 | 0.038* | |
H6E | 0.8126 | 0.5658 | 0.7178 | 0.038* | |
H72 | 0.7188 | 0.4446 | 0.8144 | 0.035* | |
H73 | 0.8529 | 0.4076 | 0.9868 | 0.038* | |
H75 | 0.8289 | 0.6699 | 1.0918 | 0.036* | |
H76 | 0.6948 | 0.7077 | 0.9193 | 0.033* | |
H77A | 0.9695 | 0.5671 | 1.2124 | 0.068* | |
H77B | 1.0076 | 0.4759 | 1.1604 | 0.068* | |
H77C | 0.9018 | 0.4706 | 1.2099 | 0.068* | |
H81A | 0.4839 | 0.6696 | 0.9536 | 0.044* | |
H81B | 0.4967 | 0.5603 | 0.9352 | 0.044* | |
H81C | 0.3719 | 0.6026 | 0.9302 | 0.044* | |
H102 | 0.0916 | 0.6509 | 0.6300 | 0.034* | |
H103 | −0.0860 | 0.6897 | 0.4944 | 0.039* | |
H104 | −0.0885 | 0.7456 | 0.3223 | 0.041* | |
H105 | 0.0881 | 0.7620 | 0.2865 | 0.039* | |
H106 | 0.2676 | 0.7298 | 0.4232 | 0.035* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N9 | 0.0268 (7) | 0.0306 (8) | 0.0208 (6) | 0.0015 (5) | 0.0086 (5) | 0.0010 (5) |
N10 | 0.0213 (6) | 0.0305 (7) | 0.0201 (6) | 0.0029 (5) | 0.0067 (5) | 0.0015 (5) |
N11 | 0.0222 (6) | 0.0230 (7) | 0.0226 (6) | 0.0002 (5) | 0.0075 (5) | 0.0001 (5) |
C1 | 0.0291 (8) | 0.0245 (8) | 0.0263 (8) | 0.0012 (6) | 0.0091 (6) | 0.0000 (6) |
C2 | 0.0393 (9) | 0.0288 (9) | 0.0233 (8) | −0.0015 (7) | 0.0107 (7) | 0.0000 (6) |
C3 | 0.0385 (9) | 0.0350 (10) | 0.0276 (8) | −0.0067 (7) | 0.0169 (7) | −0.0057 (7) |
C4 | 0.0286 (8) | 0.0360 (10) | 0.0343 (9) | −0.0020 (7) | 0.0157 (7) | −0.0052 (7) |
C4a | 0.0271 (8) | 0.0252 (8) | 0.0276 (8) | −0.0030 (6) | 0.0101 (6) | −0.0024 (6) |
C5 | 0.0246 (8) | 0.0380 (10) | 0.0325 (8) | 0.0053 (7) | 0.0107 (6) | 0.0006 (7) |
C6 | 0.0244 (8) | 0.0404 (10) | 0.0287 (8) | 0.0021 (7) | 0.0075 (6) | 0.0025 (7) |
C6a | 0.0216 (7) | 0.0260 (8) | 0.0246 (7) | 0.0010 (6) | 0.0063 (6) | 0.0007 (6) |
C7 | 0.0241 (7) | 0.0241 (8) | 0.0235 (7) | 0.0007 (6) | 0.0063 (6) | 0.0002 (6) |
C7a | 0.0227 (7) | 0.0213 (8) | 0.0210 (7) | 0.0004 (6) | 0.0061 (6) | −0.0006 (6) |
C8 | 0.0245 (7) | 0.0236 (8) | 0.0231 (7) | 0.0011 (6) | 0.0070 (6) | 0.0007 (6) |
C10a | 0.0212 (7) | 0.0216 (8) | 0.0226 (7) | 0.0008 (6) | 0.0075 (6) | 0.0001 (6) |
C11a | 0.0218 (7) | 0.0182 (8) | 0.0247 (7) | −0.0013 (6) | 0.0075 (6) | −0.0002 (6) |
C11b | 0.0246 (7) | 0.0191 (8) | 0.0246 (7) | −0.0035 (6) | 0.0087 (6) | −0.0011 (6) |
C71 | 0.0196 (7) | 0.0317 (9) | 0.0225 (7) | 0.0010 (6) | 0.0067 (6) | 0.0020 (6) |
C72 | 0.0288 (8) | 0.0306 (9) | 0.0265 (8) | 0.0012 (7) | 0.0060 (6) | −0.0018 (6) |
C73 | 0.0311 (8) | 0.0310 (9) | 0.0313 (8) | 0.0069 (7) | 0.0090 (7) | 0.0082 (7) |
C74 | 0.0243 (8) | 0.0404 (10) | 0.0232 (7) | 0.0013 (7) | 0.0062 (6) | 0.0052 (7) |
C75 | 0.0290 (8) | 0.0352 (10) | 0.0236 (8) | −0.0017 (7) | 0.0052 (6) | −0.0023 (7) |
C76 | 0.0268 (8) | 0.0272 (9) | 0.0271 (8) | 0.0028 (6) | 0.0074 (6) | 0.0015 (6) |
C77 | 0.0407 (10) | 0.0597 (13) | 0.0278 (9) | 0.0106 (9) | 0.0022 (7) | 0.0075 (8) |
C81 | 0.0291 (8) | 0.0373 (10) | 0.0230 (7) | 0.0040 (7) | 0.0095 (6) | 0.0033 (6) |
C101 | 0.0212 (7) | 0.0236 (8) | 0.0232 (7) | 0.0025 (6) | 0.0043 (6) | −0.0012 (6) |
C102 | 0.0264 (8) | 0.0351 (9) | 0.0243 (8) | 0.0027 (7) | 0.0089 (6) | −0.0013 (6) |
C103 | 0.0229 (8) | 0.0421 (10) | 0.0325 (9) | 0.0019 (7) | 0.0079 (7) | −0.0029 (7) |
C104 | 0.0265 (8) | 0.0408 (10) | 0.0300 (8) | 0.0065 (7) | 0.0017 (6) | 0.0012 (7) |
C105 | 0.0337 (9) | 0.0358 (10) | 0.0264 (8) | 0.0054 (7) | 0.0062 (7) | 0.0064 (7) |
C106 | 0.0271 (8) | 0.0302 (9) | 0.0300 (8) | 0.0027 (7) | 0.0100 (6) | 0.0047 (6) |
C1—C2 | 1.381 (2) | C75—H75 | 0.95 |
C1—C11b | 1.399 (2) | C76—H76 | 0.95 |
C1—H1 | 0.95 | C77—H77A | 0.98 |
C2—C3 | 1.386 (2) | C77—H77B | 0.98 |
C2—H2 | 0.95 | C77—H77C | 0.98 |
C3—C4 | 1.387 (2) | C7a—C10a | 1.4026 (19) |
C3—H3 | 0.95 | C7a—C8 | 1.434 (2) |
C4—C4a | 1.389 (2) | C8—N9 | 1.3214 (19) |
C4—H4 | 0.95 | C8—C81 | 1.492 (2) |
C4a—C11b | 1.403 (2) | C81—H81A | 0.98 |
C4a—C5 | 1.507 (2) | C81—H81B | 0.98 |
C5—C6 | 1.506 (2) | C81—H81C | 0.98 |
C5—H5A | 0.99 | N9—N10 | 1.3845 (16) |
C5—H5E | 0.99 | N10—C10a | 1.3764 (18) |
C6—C6a | 1.510 (2) | N10—C101 | 1.4148 (18) |
C6—H6A | 0.99 | C101—C106 | 1.391 (2) |
C6—H6E | 0.99 | C101—C102 | 1.391 (2) |
C6a—C7 | 1.393 (2) | C102—C103 | 1.385 (2) |
C6a—C11a | 1.423 (2) | C102—H102 | 0.95 |
C7—C7a | 1.404 (2) | C103—C104 | 1.383 (2) |
C7—C71 | 1.4933 (19) | C103—H103 | 0.95 |
C71—C76 | 1.391 (2) | C104—C105 | 1.381 (2) |
C71—C72 | 1.391 (2) | C104—H104 | 0.95 |
C72—C73 | 1.386 (2) | C105—C106 | 1.386 (2) |
C72—H72 | 0.95 | C105—H105 | 0.95 |
C73—C74 | 1.392 (2) | C106—H106 | 0.95 |
C73—H73 | 0.95 | C10a—N11 | 1.3367 (18) |
C74—C75 | 1.388 (2) | N11—C11a | 1.3394 (18) |
C74—C77 | 1.510 (2) | C11a—C11b | 1.482 (2) |
C75—C76 | 1.389 (2) | ||
C2—C1—C11b | 120.78 (14) | C74—C77—H77A | 109.5 |
C2—C1—H1 | 119.6 | C74—C77—H77B | 109.5 |
C11b—C1—H1 | 119.6 | H77A—C77—H77B | 109.5 |
C1—C2—C3 | 119.99 (15) | C74—C77—H77C | 109.5 |
C1—C2—H2 | 120.0 | H77A—C77—H77C | 109.5 |
C3—C2—H2 | 120.0 | H77B—C77—H77C | 109.5 |
C2—C3—C4 | 119.69 (14) | C10a—C7a—C7 | 117.81 (13) |
C2—C3—H3 | 120.2 | C10a—C7a—C8 | 104.73 (12) |
C4—C3—H3 | 120.2 | C7—C7a—C8 | 137.46 (13) |
C3—C4—C4a | 121.14 (15) | N9—C8—C7a | 110.82 (12) |
C3—C4—H4 | 119.4 | N9—C8—C81 | 119.65 (13) |
C4a—C4—H4 | 119.4 | C7a—C8—C81 | 129.53 (13) |
C4—C4a—C11b | 119.14 (14) | C8—C81—H81A | 109.5 |
C4—C4a—C5 | 121.88 (14) | C8—C81—H81B | 109.5 |
C11b—C4a—C5 | 118.95 (13) | H81A—C81—H81B | 109.5 |
C6—C5—C4a | 111.16 (13) | C8—C81—H81C | 109.5 |
C6—C5—H5A | 109.4 | H81A—C81—H81C | 109.5 |
C4a—C5—H5A | 109.4 | H81B—C81—H81C | 109.5 |
C6—C5—H5E | 109.4 | C8—N9—N10 | 107.06 (12) |
C4a—C5—H5E | 109.4 | C10a—N10—N9 | 110.13 (11) |
H5A—C5—H5E | 108.0 | C10a—N10—C101 | 130.26 (12) |
C5—C6—C6a | 111.17 (13) | N9—N10—C101 | 119.49 (11) |
C5—C6—H6A | 109.4 | C106—C101—C102 | 119.91 (14) |
C6a—C6—H6A | 109.4 | C106—C101—N10 | 120.91 (13) |
C5—C6—H6E | 109.4 | C102—C101—N10 | 119.19 (13) |
C6a—C6—H6E | 109.4 | C103—C102—C101 | 119.75 (14) |
H6A—C6—H6E | 108.0 | C103—C102—H102 | 120.1 |
C7—C6a—C11a | 119.75 (13) | C101—C102—H102 | 120.1 |
C7—C6a—C6 | 123.05 (13) | C104—C103—C102 | 120.72 (15) |
C11a—C6a—C6 | 117.08 (13) | C104—C103—H103 | 119.6 |
C6a—C7—C7a | 116.88 (13) | C102—C103—H103 | 119.6 |
C6a—C7—C71 | 121.50 (13) | C105—C104—C103 | 119.16 (14) |
C7a—C7—C71 | 121.62 (13) | C105—C104—H104 | 120.4 |
C76—C71—C72 | 118.54 (14) | C103—C104—H104 | 120.4 |
C76—C71—C7 | 121.17 (14) | C104—C105—C106 | 121.14 (15) |
C72—C71—C7 | 120.29 (13) | C104—C105—H105 | 119.4 |
C73—C72—C71 | 120.87 (15) | C106—C105—H105 | 119.4 |
C73—C72—H72 | 119.6 | C105—C106—C101 | 119.30 (14) |
C71—C72—H72 | 119.6 | C105—C106—H106 | 120.4 |
C72—C73—C74 | 120.87 (15) | C101—C106—H106 | 120.4 |
C72—C73—H73 | 119.6 | N11—C10a—N10 | 125.85 (13) |
C74—C73—H73 | 119.6 | N11—C10a—C7a | 126.89 (13) |
C75—C74—C73 | 118.00 (14) | N10—C10a—C7a | 107.23 (12) |
C75—C74—C77 | 121.50 (15) | C10a—N11—C11a | 114.45 (12) |
C73—C74—C77 | 120.50 (16) | N11—C11a—C6a | 123.97 (13) |
C74—C75—C76 | 121.50 (15) | N11—C11a—C11b | 116.49 (12) |
C74—C75—H75 | 119.2 | C6a—C11a—C11b | 119.54 (13) |
C76—C75—H75 | 119.2 | C1—C11b—C4a | 119.25 (13) |
C75—C76—C71 | 120.22 (15) | C1—C11b—C11a | 120.89 (13) |
C75—C76—H76 | 119.9 | C4a—C11b—C11a | 119.85 (13) |
C71—C76—H76 | 119.9 | ||
C11b—C1—C2—C3 | −0.3 (2) | C8—N9—N10—C101 | 177.07 (13) |
C1—C2—C3—C4 | 1.4 (2) | C10a—N10—C101—C106 | −21.6 (2) |
C2—C3—C4—C4a | −1.2 (3) | N9—N10—C101—C106 | 162.93 (14) |
C3—C4—C4a—C11b | −0.1 (2) | C10a—N10—C101—C102 | 158.27 (15) |
C3—C4—C4a—C5 | 177.70 (15) | N9—N10—C101—C102 | −17.2 (2) |
C4—C4a—C5—C6 | 146.82 (15) | C106—C101—C102—C103 | −0.8 (2) |
C11b—C4a—C5—C6 | −35.4 (2) | N10—C101—C102—C103 | 179.28 (14) |
C4a—C5—C6—C6a | 54.16 (18) | C101—C102—C103—C104 | 1.1 (3) |
C5—C6—C6a—C7 | 141.78 (16) | C102—C103—C104—C105 | 0.0 (3) |
C5—C6—C6a—C11a | −42.3 (2) | C103—C104—C105—C106 | −1.5 (3) |
C11a—C6a—C7—C7a | −3.7 (2) | C104—C105—C106—C101 | 1.8 (3) |
C6—C6a—C7—C7a | 172.13 (14) | C102—C101—C106—C105 | −0.6 (2) |
C11a—C6a—C7—C71 | 175.89 (14) | N10—C101—C106—C105 | 179.29 (14) |
C6—C6a—C7—C71 | −8.3 (2) | N9—N10—C10a—N11 | 176.29 (14) |
C6a—C7—C71—C76 | 113.66 (17) | C101—N10—C10a—N11 | 0.5 (2) |
C7a—C7—C71—C76 | −66.8 (2) | N9—N10—C10a—C7a | −1.67 (16) |
C6a—C7—C71—C72 | −65.9 (2) | C101—N10—C10a—C7a | −177.45 (14) |
C7a—C7—C71—C72 | 113.63 (17) | C7—C7a—C10a—N11 | 4.2 (2) |
C76—C71—C72—C73 | 0.5 (2) | C8—C7a—C10a—N11 | −176.11 (14) |
C7—C71—C72—C73 | −179.90 (14) | C7—C7a—C10a—N10 | −177.89 (13) |
C71—C72—C73—C74 | 0.0 (2) | C8—C7a—C10a—N10 | 1.82 (16) |
C72—C73—C74—C75 | −0.5 (2) | N10—C10a—N11—C11a | 179.46 (14) |
C72—C73—C74—C77 | 179.44 (15) | C7a—C10a—N11—C11a | −3.0 (2) |
C73—C74—C75—C76 | 0.4 (2) | C10a—N11—C11a—C6a | −1.8 (2) |
C77—C74—C75—C76 | −179.49 (15) | C10a—N11—C11a—C11b | 178.21 (13) |
C74—C75—C76—C71 | 0.1 (2) | C7—C6a—C11a—N11 | 5.2 (2) |
C72—C71—C76—C75 | −0.6 (2) | C6—C6a—C11a—N11 | −170.92 (14) |
C7—C71—C76—C75 | 179.86 (14) | C7—C6a—C11a—C11b | −174.82 (14) |
C6a—C7—C7a—C10a | −0.5 (2) | C6—C6a—C11a—C11b | 9.1 (2) |
C71—C7—C7a—C10a | 179.94 (14) | C2—C1—C11b—C4a | −1.0 (2) |
C6a—C7—C7a—C8 | 179.93 (17) | C2—C1—C11b—C11a | −179.77 (14) |
C71—C7—C7a—C8 | 0.4 (3) | C4—C4a—C11b—C1 | 1.2 (2) |
C10a—C7a—C8—N9 | −1.42 (17) | C5—C4a—C11b—C1 | −176.71 (14) |
C7—C7a—C8—N9 | 178.20 (17) | C4—C4a—C11b—C11a | 179.97 (14) |
C10a—C7a—C8—C81 | 178.61 (15) | C5—C4a—C11b—C11a | 2.1 (2) |
C7—C7a—C8—C81 | −1.8 (3) | N11—C11a—C11b—C1 | 10.8 (2) |
C7a—C8—N9—N10 | 0.43 (17) | C6a—C11a—C11b—C1 | −169.21 (14) |
C81—C8—N9—N10 | −179.60 (13) | N11—C11a—C11b—C4a | −167.97 (14) |
C8—N9—N10—C10a | 0.77 (16) | C6a—C11a—C11b—C4a | 12.0 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C73—H73···Cg2i | 0.95 | 2.96 | 3.8991 (18) | 168 |
C76—H76···Cg3ii | 0.95 | 2.90 | 3.8349 (17) | 168 |
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) x, −y+3/2, z+1/2. |
C28H23N3O | F(000) = 880 |
Mr = 417.49 | Dx = 1.283 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4963 reflections |
a = 12.9148 (3) Å | θ = 3.3–27.5° |
b = 17.5938 (5) Å | µ = 0.08 mm−1 |
c = 9.8192 (2) Å | T = 120 K |
β = 104.3370 (17)° | Plate, pale brown |
V = 2161.64 (9) Å3 | 0.50 × 0.20 × 0.05 mm |
Z = 4 |
Bruker Nonius KappaCCD area-detector diffractometer | 4963 independent reflections |
Radiation source: Bruker Nonius FR91 rotating anode | 3449 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.062 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.3° |
ϕ and ω scans | h = −16→16 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −22→22 |
Tmin = 0.974, Tmax = 0.996 | l = −12→11 |
35681 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.112 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0534P)2 + 0.4296P] where P = (Fo2 + 2Fc2)/3 |
4963 reflections | (Δ/σ)max = 0.001 |
291 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
C28H23N3O | V = 2161.64 (9) Å3 |
Mr = 417.49 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.9148 (3) Å | µ = 0.08 mm−1 |
b = 17.5938 (5) Å | T = 120 K |
c = 9.8192 (2) Å | 0.50 × 0.20 × 0.05 mm |
β = 104.3370 (17)° |
Bruker Nonius KappaCCD area-detector diffractometer | 4963 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 3449 reflections with I > 2σ(I) |
Tmin = 0.974, Tmax = 0.996 | Rint = 0.062 |
35681 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.112 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.21 e Å−3 |
4963 reflections | Δρmin = −0.27 e Å−3 |
291 parameters |
x | y | z | Uiso*/Ueq | ||
O7 | −0.00309 (8) | 0.60663 (7) | 0.03830 (11) | 0.0377 (3) | |
N9 | 0.56190 (9) | 0.41506 (7) | 0.15846 (12) | 0.0237 (3) | |
N10 | 0.64399 (9) | 0.44956 (7) | 0.25661 (11) | 0.0209 (3) | |
N11 | 0.66123 (9) | 0.55376 (6) | 0.42113 (11) | 0.0198 (3) | |
C1 | 0.76553 (11) | 0.63739 (9) | 0.66044 (14) | 0.0250 (3) | |
C2 | 0.82021 (12) | 0.68454 (9) | 0.76705 (15) | 0.0298 (4) | |
C3 | 0.77204 (12) | 0.75040 (10) | 0.79858 (15) | 0.0322 (4) | |
C4 | 0.67023 (12) | 0.76916 (9) | 0.72270 (15) | 0.0300 (4) | |
C4a | 0.61388 (11) | 0.72238 (8) | 0.61543 (14) | 0.0244 (3) | |
C5 | 0.50473 (12) | 0.74353 (9) | 0.52858 (16) | 0.0308 (4) | |
C6 | 0.43597 (11) | 0.67437 (9) | 0.48495 (15) | 0.0261 (3) | |
C6a | 0.49047 (11) | 0.61550 (8) | 0.41528 (13) | 0.0203 (3) | |
C7 | 0.43553 (11) | 0.57136 (8) | 0.30262 (13) | 0.0202 (3) | |
C7a | 0.49543 (11) | 0.51598 (8) | 0.25225 (13) | 0.0198 (3) | |
C8 | 0.47405 (11) | 0.45416 (8) | 0.15370 (14) | 0.0221 (3) | |
C10a | 0.60502 (11) | 0.51027 (8) | 0.31725 (13) | 0.0192 (3) | |
C11a | 0.60280 (10) | 0.60557 (8) | 0.46939 (13) | 0.0189 (3) | |
C11b | 0.66193 (11) | 0.65542 (8) | 0.58432 (13) | 0.0208 (3) | |
C71 | 0.31912 (11) | 0.58090 (8) | 0.23634 (14) | 0.0206 (3) | |
C72 | 0.24315 (11) | 0.57061 (8) | 0.31310 (14) | 0.0233 (3) | |
C73 | 0.13443 (11) | 0.57765 (9) | 0.25071 (15) | 0.0254 (3) | |
C74 | 0.10111 (11) | 0.59604 (8) | 0.10945 (15) | 0.0245 (3) | |
C75 | 0.17600 (11) | 0.60728 (9) | 0.03142 (14) | 0.0255 (3) | |
C76 | 0.28378 (11) | 0.59988 (8) | 0.09389 (14) | 0.0236 (3) | |
C77 | −0.08224 (13) | 0.59641 (15) | 0.1150 (2) | 0.0576 (6) | |
C81 | 0.37100 (11) | 0.42962 (9) | 0.05751 (15) | 0.0273 (3) | |
C101 | 0.74468 (11) | 0.41267 (8) | 0.29682 (14) | 0.0217 (3) | |
C102 | 0.74869 (12) | 0.33419 (9) | 0.28130 (15) | 0.0285 (3) | |
C103 | 0.84610 (13) | 0.29716 (10) | 0.31932 (17) | 0.0365 (4) | |
C104 | 0.93899 (13) | 0.33738 (10) | 0.37330 (16) | 0.0357 (4) | |
C105 | 0.93435 (12) | 0.41570 (10) | 0.38817 (16) | 0.0330 (4) | |
C106 | 0.83735 (11) | 0.45363 (9) | 0.35031 (14) | 0.0258 (3) | |
H1 | 0.7987 | 0.5923 | 0.6388 | 0.030* | |
H2 | 0.8905 | 0.6718 | 0.8184 | 0.036* | |
H3 | 0.8090 | 0.7826 | 0.8723 | 0.039* | |
H4 | 0.6381 | 0.8148 | 0.7441 | 0.036* | |
H5A | 0.5118 | 0.7713 | 0.4437 | 0.037* | |
H5E | 0.4698 | 0.7778 | 0.5837 | 0.037* | |
H6A | 0.3681 | 0.6898 | 0.4190 | 0.031* | |
H6E | 0.4185 | 0.6517 | 0.5688 | 0.031* | |
H72 | 0.2659 | 0.5585 | 0.4102 | 0.028* | |
H73 | 0.0835 | 0.5699 | 0.3045 | 0.030* | |
H75 | 0.1530 | 0.6201 | −0.0654 | 0.031* | |
H76 | 0.3344 | 0.6077 | 0.0397 | 0.028* | |
H77A | −0.0808 | 0.5437 | 0.1474 | 0.086* | |
H77B | −0.1529 | 0.6079 | 0.0541 | 0.086* | |
H77C | −0.0675 | 0.6306 | 0.1962 | 0.086* | |
H81A | 0.3492 | 0.4667 | −0.0187 | 0.041* | |
H81B | 0.3159 | 0.4264 | 0.1102 | 0.041* | |
H81C | 0.3802 | 0.3797 | 0.0179 | 0.041* | |
H102 | 0.6849 | 0.3062 | 0.2448 | 0.034* | |
H103 | 0.8491 | 0.2436 | 0.3082 | 0.044* | |
H104 | 1.0056 | 0.3117 | 0.4001 | 0.043* | |
H105 | 0.9982 | 0.4435 | 0.4246 | 0.040* | |
H106 | 0.8345 | 0.5072 | 0.3610 | 0.031* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O7 | 0.0183 (5) | 0.0595 (8) | 0.0324 (6) | 0.0006 (5) | 0.0009 (4) | 0.0116 (5) |
N9 | 0.0242 (7) | 0.0253 (7) | 0.0209 (6) | −0.0027 (5) | 0.0042 (5) | −0.0026 (5) |
N10 | 0.0208 (6) | 0.0215 (6) | 0.0202 (6) | 0.0007 (5) | 0.0045 (5) | −0.0027 (5) |
N11 | 0.0215 (6) | 0.0196 (6) | 0.0181 (6) | 0.0010 (5) | 0.0048 (4) | 0.0019 (4) |
C1 | 0.0242 (8) | 0.0270 (8) | 0.0230 (7) | 0.0017 (6) | 0.0044 (6) | −0.0003 (6) |
C2 | 0.0255 (8) | 0.0369 (9) | 0.0244 (8) | −0.0017 (7) | 0.0013 (6) | 0.0002 (6) |
C3 | 0.0330 (9) | 0.0367 (10) | 0.0249 (8) | −0.0050 (7) | 0.0035 (6) | −0.0091 (6) |
C4 | 0.0328 (9) | 0.0282 (9) | 0.0284 (8) | 0.0018 (7) | 0.0065 (6) | −0.0073 (6) |
C4a | 0.0255 (8) | 0.0249 (8) | 0.0227 (7) | 0.0010 (6) | 0.0059 (6) | −0.0016 (6) |
C5 | 0.0282 (8) | 0.0265 (9) | 0.0349 (8) | 0.0064 (7) | 0.0025 (6) | −0.0059 (7) |
C6 | 0.0233 (8) | 0.0271 (9) | 0.0272 (8) | 0.0047 (6) | 0.0051 (6) | −0.0024 (6) |
C6a | 0.0216 (7) | 0.0201 (8) | 0.0186 (7) | 0.0020 (6) | 0.0041 (5) | 0.0027 (5) |
C7 | 0.0215 (7) | 0.0207 (7) | 0.0187 (7) | 0.0021 (6) | 0.0057 (5) | 0.0044 (5) |
C7a | 0.0206 (7) | 0.0213 (8) | 0.0174 (6) | −0.0003 (6) | 0.0045 (5) | 0.0024 (5) |
C10a | 0.0216 (7) | 0.0190 (7) | 0.0174 (6) | 0.0009 (6) | 0.0055 (5) | 0.0023 (5) |
C11a | 0.0219 (7) | 0.0184 (7) | 0.0167 (6) | 0.0015 (6) | 0.0052 (5) | 0.0038 (5) |
C11b | 0.0231 (7) | 0.0222 (8) | 0.0171 (6) | −0.0008 (6) | 0.0052 (5) | 0.0019 (5) |
C71 | 0.0208 (7) | 0.0194 (7) | 0.0209 (7) | 0.0005 (6) | 0.0040 (5) | −0.0007 (5) |
C72 | 0.0235 (7) | 0.0262 (8) | 0.0193 (7) | 0.0021 (6) | 0.0034 (6) | 0.0037 (6) |
C73 | 0.0216 (7) | 0.0295 (8) | 0.0259 (7) | −0.0014 (6) | 0.0076 (6) | 0.0036 (6) |
C74 | 0.0175 (7) | 0.0267 (8) | 0.0262 (8) | 0.0006 (6) | −0.0005 (6) | 0.0022 (6) |
C75 | 0.0267 (8) | 0.0308 (9) | 0.0171 (7) | 0.0013 (6) | 0.0017 (6) | 0.0020 (6) |
C76 | 0.0232 (7) | 0.0269 (8) | 0.0210 (7) | 0.0001 (6) | 0.0060 (5) | 0.0000 (6) |
C77 | 0.0208 (9) | 0.1029 (18) | 0.0480 (11) | −0.0027 (10) | 0.0062 (8) | 0.0209 (11) |
C8 | 0.0243 (7) | 0.0227 (8) | 0.0190 (7) | −0.0006 (6) | 0.0051 (5) | 0.0015 (5) |
C81 | 0.0260 (8) | 0.0281 (8) | 0.0263 (8) | −0.0015 (7) | 0.0033 (6) | −0.0037 (6) |
C101 | 0.0235 (7) | 0.0243 (8) | 0.0189 (7) | 0.0052 (6) | 0.0081 (5) | 0.0022 (5) |
C102 | 0.0301 (8) | 0.0259 (9) | 0.0321 (8) | 0.0015 (7) | 0.0124 (6) | 0.0017 (6) |
C103 | 0.0416 (10) | 0.0286 (9) | 0.0438 (9) | 0.0122 (8) | 0.0193 (8) | 0.0083 (7) |
C104 | 0.0322 (9) | 0.0428 (11) | 0.0330 (9) | 0.0161 (8) | 0.0093 (7) | 0.0075 (7) |
C105 | 0.0243 (8) | 0.0443 (11) | 0.0297 (8) | 0.0050 (7) | 0.0050 (6) | −0.0025 (7) |
C106 | 0.0263 (8) | 0.0274 (8) | 0.0245 (7) | 0.0031 (6) | 0.0080 (6) | −0.0023 (6) |
C1—C2 | 1.384 (2) | C75—H75 | 0.95 |
C1—C11b | 1.3980 (19) | C76—H76 | 0.95 |
C1—H1 | 0.95 | O7—C77 | 1.423 (2) |
C2—C3 | 1.386 (2) | C77—H77A | 0.98 |
C2—H2 | 0.95 | C77—H77B | 0.98 |
C3—C4 | 1.381 (2) | C77—H77C | 0.98 |
C3—H3 | 0.95 | C7a—C10a | 1.4047 (18) |
C4—C4a | 1.392 (2) | C7a—C8 | 1.4365 (19) |
C4—H4 | 0.95 | C8—N9 | 1.3177 (18) |
C4a—C11b | 1.400 (2) | C8—C81 | 1.4923 (19) |
C4a—C5 | 1.503 (2) | C81—H81A | 0.98 |
C5—C6 | 1.505 (2) | C81—H81B | 0.98 |
C5—H5A | 0.99 | C81—H81C | 0.98 |
C5—H5E | 0.99 | N9—N10 | 1.3840 (15) |
C6—C6a | 1.5082 (19) | N10—C10a | 1.3774 (17) |
C6—H6A | 0.99 | N10—C101 | 1.4191 (17) |
C6—H6E | 0.99 | C101—C106 | 1.384 (2) |
C6a—C7 | 1.3934 (19) | C101—C102 | 1.392 (2) |
C6a—C11a | 1.4268 (19) | C102—C103 | 1.383 (2) |
C7—C7a | 1.408 (2) | C102—H102 | 0.95 |
C7—C71 | 1.4925 (19) | C103—C104 | 1.381 (2) |
C71—C72 | 1.3892 (19) | C103—H103 | 0.95 |
C71—C76 | 1.4001 (19) | C104—C105 | 1.389 (2) |
C72—C73 | 1.3914 (19) | C104—H104 | 0.95 |
C72—H72 | 0.95 | C105—C106 | 1.387 (2) |
C73—C74 | 1.3850 (19) | C105—H105 | 0.95 |
C73—H73 | 0.95 | C106—H106 | 0.95 |
C74—O7 | 1.3668 (16) | C10a—N11 | 1.3365 (17) |
C74—C75 | 1.389 (2) | N11—C11a | 1.3423 (18) |
C75—C76 | 1.3812 (19) | C11a—C11b | 1.4830 (19) |
C2—C1—C11b | 120.64 (14) | C74—O7—C77 | 117.24 (12) |
C2—C1—H1 | 119.7 | O7—C77—H77A | 109.5 |
C11b—C1—H1 | 119.7 | O7—C77—H77B | 109.5 |
C1—C2—C3 | 119.79 (14) | H77A—C77—H77B | 109.5 |
C1—C2—H2 | 120.1 | O7—C77—H77C | 109.5 |
C3—C2—H2 | 120.1 | H77A—C77—H77C | 109.5 |
C4—C3—C2 | 119.95 (14) | H77B—C77—H77C | 109.5 |
C4—C3—H3 | 120.0 | C10a—C7a—C7 | 117.99 (12) |
C2—C3—H3 | 120.0 | C10a—C7a—C8 | 104.83 (12) |
C3—C4—C4a | 121.09 (14) | C7—C7a—C8 | 136.89 (13) |
C3—C4—H4 | 119.5 | N9—C8—C7a | 110.56 (12) |
C4a—C4—H4 | 119.5 | N9—C8—C81 | 119.77 (13) |
C4—C4a—C11b | 119.07 (13) | C7a—C8—C81 | 129.64 (13) |
C4—C4a—C5 | 121.62 (13) | C8—C81—H81A | 109.5 |
C11b—C4a—C5 | 119.26 (12) | C8—C81—H81B | 109.5 |
C4a—C5—C6 | 111.46 (12) | H81A—C81—H81B | 109.5 |
C4a—C5—H5A | 109.3 | C8—C81—H81C | 109.5 |
C6—C5—H5A | 109.3 | H81A—C81—H81C | 109.5 |
C4a—C5—H5E | 109.3 | H81B—C81—H81C | 109.5 |
C6—C5—H5E | 109.3 | C8—N9—N10 | 107.46 (11) |
H5A—C5—H5E | 108.0 | C10a—N10—N9 | 110.01 (11) |
C5—C6—C6a | 112.06 (12) | C10a—N10—C101 | 129.95 (11) |
C5—C6—H6A | 109.2 | N9—N10—C101 | 118.97 (11) |
C6a—C6—H6A | 109.2 | C106—C101—C102 | 120.40 (13) |
C5—C6—H6E | 109.2 | C106—C101—N10 | 120.93 (13) |
C6a—C6—H6E | 109.2 | C102—C101—N10 | 118.67 (13) |
H6A—C6—H6E | 107.9 | C103—C102—C101 | 119.59 (15) |
C7—C6a—C11a | 119.88 (12) | C103—C102—H102 | 120.2 |
C7—C6a—C6 | 122.67 (12) | C101—C102—H102 | 120.2 |
C11a—C6a—C6 | 117.45 (12) | C104—C103—C102 | 120.53 (16) |
C6a—C7—C7a | 116.65 (12) | C104—C103—H103 | 119.7 |
C6a—C7—C71 | 122.92 (12) | C102—C103—H103 | 119.7 |
C7a—C7—C71 | 120.43 (12) | C103—C104—C105 | 119.54 (15) |
C72—C71—C76 | 118.28 (12) | C103—C104—H104 | 120.2 |
C72—C71—C7 | 121.29 (12) | C105—C104—H104 | 120.2 |
C76—C71—C7 | 120.43 (12) | C106—C105—C104 | 120.61 (15) |
C71—C72—C73 | 121.39 (13) | C106—C105—H105 | 119.7 |
C71—C72—H72 | 119.3 | C104—C105—H105 | 119.7 |
C73—C72—H72 | 119.3 | C101—C106—C105 | 119.34 (15) |
C74—C73—C72 | 119.42 (13) | C101—C106—H106 | 120.3 |
C74—C73—H73 | 120.3 | C105—C106—H106 | 120.3 |
C72—C73—H73 | 120.3 | N11—C10a—N10 | 125.90 (12) |
O7—C74—C73 | 124.48 (13) | N11—C10a—C7a | 126.98 (12) |
O7—C74—C75 | 115.51 (12) | N10—C10a—C7a | 107.10 (11) |
C73—C74—C75 | 119.98 (13) | C10a—N11—C11a | 114.30 (11) |
C76—C75—C74 | 120.30 (13) | N11—C11a—C6a | 124.08 (12) |
C76—C75—H75 | 119.9 | N11—C11a—C11b | 116.21 (12) |
C74—C75—H75 | 119.9 | C6a—C11a—C11b | 119.70 (12) |
C75—C76—C71 | 120.63 (13) | C1—C11b—C4a | 119.44 (13) |
C75—C76—H76 | 119.7 | C1—C11b—C11a | 121.13 (12) |
C71—C76—H76 | 119.7 | C4a—C11b—C11a | 119.42 (12) |
C11b—C1—C2—C3 | −0.2 (2) | C8—N9—N10—C10a | 1.90 (15) |
C1—C2—C3—C4 | −0.7 (2) | C8—N9—N10—C101 | 171.27 (11) |
C2—C3—C4—C4a | 0.9 (2) | C10a—N10—C101—C106 | −37.2 (2) |
C3—C4—C4a—C11b | −0.2 (2) | N9—N10—C101—C106 | 155.87 (12) |
C3—C4—C4a—C5 | −177.71 (14) | C10a—N10—C101—C102 | 142.88 (14) |
C4—C4a—C5—C6 | −146.79 (14) | N9—N10—C101—C102 | −24.06 (18) |
C11b—C4a—C5—C6 | 35.72 (19) | C106—C101—C102—C103 | −0.2 (2) |
C4a—C5—C6—C6a | −52.28 (17) | N10—C101—C102—C103 | 179.74 (12) |
C5—C6—C6a—C7 | −142.94 (13) | C101—C102—C103—C104 | 0.4 (2) |
C5—C6—C6a—C11a | 37.32 (17) | C102—C103—C104—C105 | −0.6 (2) |
C11a—C6a—C7—C7a | 2.78 (19) | C103—C104—C105—C106 | 0.5 (2) |
C6—C6a—C7—C7a | −176.95 (13) | C102—C101—C106—C105 | 0.1 (2) |
C11a—C6a—C7—C71 | −177.20 (12) | N10—C101—C106—C105 | −179.84 (13) |
C6—C6a—C7—C71 | 3.1 (2) | C104—C105—C106—C101 | −0.2 (2) |
C6a—C7—C71—C72 | −60.70 (19) | N9—N10—C10a—N11 | 176.34 (12) |
C7a—C7—C71—C72 | 119.32 (15) | C101—N10—C10a—N11 | 8.5 (2) |
C6a—C7—C71—C76 | 119.91 (15) | N9—N10—C10a—C7a | −1.95 (14) |
C7a—C7—C71—C76 | −60.08 (19) | C101—N10—C10a—C7a | −169.80 (13) |
C76—C71—C72—C73 | 1.0 (2) | C7—C7a—C10a—N11 | −2.2 (2) |
C7—C71—C72—C73 | −178.41 (13) | C8—C7a—C10a—N11 | −177.04 (13) |
C71—C72—C73—C74 | −0.7 (2) | C7—C7a—C10a—N10 | 176.07 (12) |
C72—C73—C74—O7 | −177.97 (14) | C8—C7a—C10a—N10 | 1.23 (14) |
C72—C73—C74—C75 | 0.0 (2) | N10—C10a—N11—C11a | −174.93 (12) |
O7—C74—C75—C76 | 178.42 (13) | C7a—C10a—N11—C11a | 3.02 (19) |
C73—C74—C75—C76 | 0.3 (2) | C10a—N11—C11a—C6a | −0.86 (19) |
C74—C75—C76—C71 | 0.1 (2) | C10a—N11—C11a—C11b | −179.70 (11) |
C72—C71—C76—C75 | −0.7 (2) | C7—C6a—C11a—N11 | −2.0 (2) |
C7—C71—C76—C75 | 178.70 (13) | C6—C6a—C11a—N11 | 177.74 (13) |
C73—C74—O7—C77 | −1.3 (2) | C7—C6a—C11a—C11b | 176.79 (12) |
C75—C74—O7—C77 | −179.38 (16) | C6—C6a—C11a—C11b | −3.46 (18) |
C6a—C7—C7a—C10a | −0.91 (18) | C2—C1—C11b—C4a | 0.8 (2) |
C71—C7—C7a—C10a | 179.07 (12) | C2—C1—C11b—C11a | 179.66 (13) |
C6a—C7—C7a—C8 | 171.79 (15) | C4—C4a—C11b—C1 | −0.6 (2) |
C71—C7—C7a—C8 | −8.2 (2) | C5—C4a—C11b—C1 | 176.93 (13) |
C10a—C7a—C8—N9 | −0.09 (15) | C4—C4a—C11b—C11a | −179.49 (13) |
C7—C7a—C8—N9 | −173.42 (15) | C5—C4a—C11b—C11a | −1.9 (2) |
C10a—C7a—C8—C81 | 177.82 (13) | N11—C11a—C11b—C1 | −15.23 (19) |
C7—C7a—C8—C81 | 4.5 (3) | C6a—C11a—C11b—C1 | 165.87 (13) |
C7a—C8—N9—N10 | −1.09 (15) | N11—C11a—C11b—C4a | 163.62 (12) |
C81—C8—N9—N10 | −179.22 (12) | C6a—C11a—C11b—C4a | −15.28 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O7i | 0.95 | 2.53 | 3.3422 (18) | 144 |
C72—H72···N11ii | 0.95 | 2.60 | 3.3952 (17) | 142 |
C4—H4···Cg1iii | 0.95 | 2.84 | 3.7766 (17) | 168 |
C75—H75···Cg2iv | 0.95 | 2.67 | 3.5605 (15) | 157 |
C103—H103···Cg4v | 0.95 | 2.85 | 3.7417 (19) | 157 |
Symmetry codes: (i) x+1, y, z+1; (ii) −x+1, −y+1, −z+1; (iii) x, −y+3/2, z+1/2; (iv) −x+1, −y+1, −z; (v) −x+1, y−1/2, −z+1/2. |
Experimental details
(I) | (II) | (III) | (IV) | |
Crystal data | ||||
Chemical formula | C21H17N3 | C27H21N3 | C28H23N3 | C28H23N3O |
Mr | 311.38 | 387.47 | 401.49 | 417.49 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/c | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 120 | 120 | 120 | 120 |
a, b, c (Å) | 7.0870 (2), 10.1321 (4), 11.7977 (5) | 11.5561 (4), 17.6751 (7), 9.8469 (3) | 12.0313 (3), 14.3347 (4), 12.7956 (3) | 12.9148 (3), 17.5938 (5), 9.8192 (2) |
α, β, γ (°) | 87.501 (2), 73.171 (3), 74.828 (2) | 90, 98.599 (2), 90 | 90, 109.3092 (14), 90 | 90, 104.3370 (17), 90 |
V (Å3) | 782.13 (5) | 1988.67 (12) | 2082.66 (9) | 2161.64 (9) |
Z | 2 | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.08 | 0.08 | 0.08 | 0.08 |
Crystal size (mm) | 0.50 × 0.10 × 0.10 | 0.40 × 0.20 × 0.20 | 0.66 × 0.42 × 0.14 | 0.50 × 0.20 × 0.05 |
Data collection | ||||
Diffractometer | Bruker Nonius KappaCCD area-detector diffractometer | Bruker Nonius KappaCCD area-detector diffractometer | Bruker Nonius KappaCCD area-detector diffractometer | Bruker Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.954, 0.992 | 0.973, 0.985 | 0.956, 0.989 | 0.974, 0.996 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15116, 3576, 2810 | 26788, 4539, 3236 | 38247, 4778, 3416 | 35681, 4963, 3449 |
Rint | 0.039 | 0.053 | 0.059 | 0.062 |
(sin θ/λ)max (Å−1) | 0.651 | 0.650 | 0.650 | 0.650 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.114, 1.04 | 0.048, 0.126, 1.08 | 0.050, 0.129, 1.04 | 0.044, 0.112, 1.04 |
No. of reflections | 3576 | 4539 | 4778 | 4963 |
No. of parameters | 218 | 272 | 282 | 291 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.23, −0.28 | 0.28, −0.29 | 0.41, −0.31 | 0.21, −0.27 |
Computer programs: COLLECT (Hooft, 1999), DENZO (Otwinowski & Minor, 1997) and COLLECT, DENZO and COLLECT, OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997), OSCAIL and SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).
Parameter | (I) | (II) | (III) | (IV) |
Q | 0.423 (2) | 0.461 (2) | 0.460 (2) | 0.450 (2) |
θ | 63.9 (2) | 115.4 (2) | 61.5 (2) | 115.5 (2) |
ϕ | 89.6 (2) | 274.1 (2) | 96.6 (2) | 271.6 (2) |
(C1–C4,C4a,C11b)/pyridine | 13.84 (7) | 15.78 (7) | 11.11 (7) | 14.79 (7) |
(C71–C76)/pyridine | 63.45 (7) | 65.27 (7) | 60.88 (7) | |
(C101–C106)/pyrazole | 26.21 (7) | 33.16 (8) | 18.56 (8) | 30.30 (4) |
The ring-puckering parameters for the non-aromatic carbocyclic ring are calculated for the atom sequence C4a/C5/C6/C6a/C11a/C11b. |
Compound | D—H···A | D—H | H···A | D···A | D—H···A |
(I) | C5—H5A···N9i | 0.99 | 2.60 | 3.4070 (18) | 139 |
(II) | C4—H4···Cg1ii | 0.95 | 2.82 | 3.7461 (17) | 164 |
C73—H73···Cg2iii | 0.95 | 2.62 | 3.4852 (17) | 152 | |
(III) | C73—H73···Cg2iv | 0.95 | 2.96 | 3.8991 (18) | 168 |
C76—H76···Cg3v | 0.95 | 2.90 | 3.8349 (17) | 168 | |
(IV) | C2—H2···O7vi | 0.95 | 2.53 | 3.3422 (18) | 144 |
C72—H72···N11i | 0.95 | 2.60 | 3.3952 (17) | 142 | |
C4—H4···Cg1v | 0.95 | 2.84 | 3.7766 (17) | 168 | |
C75—H75···Cg2iii | 0.95 | 2.67 | 3.5605 (15) | 157 | |
C103—H103···Cg4vii | 0.95 | 2.85 | 3.7417 (19) | 157 |
Cg1–Cg4 are the centroids of the rings N11/C10a/C7a/C7/C6a/C11a, C101–C106, C1–C4/C4a/C11a and C71–C76, respectively. Symmetry codes: (i) 1 − x, 1 − y, 1 − z; (ii) x, 1/2 − y, 1/2 + z; (iii) 1 − x, 1 − y, −z; (iv) 1 − x, y − 1/2, 3/2 − z; (v) x, 3/2 − y, 1/2 + z; (vi) 1 + x, y, 1 + z; (vii) 1 − x, y − 1/2, 1/2 − z. |
Acknowledgements
The X-ray data were collected at the EPSRC X-ray Crystallographic Service, University of Southampton. JC thanks the Consejería de Innovación, Ciencia y Empresa (Junta de Andalucía, Spain) and the Universidad de Jaén for financial support. JQ and JP thank COLCIENCIAS and UNIVALLE (Universidad del Valle, Colombia) for financial support.
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Pyrazolo[3,4-b]quinolines are of interest as possible antiviral and antimalarial agents, and because of their other biological properties, such as parasiticidic, bactericidal, vasodilator, and enzyme-inhibitory activity (Quiroga et al., 2001). Here, we report the structures of four dihydrobenzopyrazoloquinolines, (I)–(IV) (Figs. 1–4), synthesized by a simple solvent-free cyclocondensation, under microwave irradiation, of 5-amino-3-methyl-1-phenylpyrazole and the condensation products derived from 2-tetralone and a range of simple aldehydes. One objective of these structure determinations was the investigation of how the introduction of different simple aryl substituents at position 7 in compounds (II)–(IV) influences the supramolecular aggregation compared with that in the unsubstituted compound, (I). We have recently reported the structures of the isomorphous and isostructural chlorophenyl and bromophenyl analogues, compounds (V) and (VI) (Serrano et al., 2005a,b).
In each of compounds (I)–(IV), the bond distances within the fused heterocyclic components are consistent with aromatic delocalization within the pyridine ring, but with strong double-bond fixation in the C8—N9 bond of the pyrazole ring. The other distances and angles present no exceptional features. The non-aromatic carbocyclic ring adopts a nearly ideal screw-boat conformation (Evans & Boeyens, 1989) in each compound, as shown by the ring-puckering parameters (Cremer & Pople, 1975), given for the atom sequence C4a/C5/C6/C6a/C11a/C11b in Table 1. For a six-membered ring with equal bond lengths throughout, the screw-boat conformation is characterized by θ = 67.5° or 112.5°, and ϕ = (60k + 30)° (k = integer).
Associated with the screw-boat conformation of the non-aromatic carbocyclic ring, the two aromatic rings linked by the bond C11a—C11b (Figs. 1–4) are not parallel, and they make dihedral angles ranging from 11.11 (7)° in compound (III) to 15.78 (7)° in compound (II) (Table 1). The dihedral angles between the pyridine ring and the pendent aryl ring C71–C76 are likewise very similar for compounds (II)–(IV). On the other hand, the dihedral angles between the pyrazole ring and the pendent aryl ring C101–C106 show a rather larger variation. It may be noted here that the rings C71–C76 and C101–C106 participate in the hydrogen bonding in each of (II)–(IV), and that the hydrogen bonding may be an important factor in controlling these dihedral angles.
The supramolecular aggregation in compound (I) is extremely simple and involves just one hydrogen bond (Table 2). Atom C5 in the molecule at (x, y, z) acts as hydrogen-bond donor, via the axial atom H5A, to pyrazole atom N9 in the molecule at (1 − x, 1 − y, 1 − z), so forming a centrosymmetric R22(16) dimer centred at (1/2, 1/2, 1/2) (Fig. 5). The formation of this dimer is reinforced by a π–π stacking interaction involving the pyridine rings of the two component molecules. These rings are strictly parallel, with an interplanar spacing of 3.450 (2) Å. The ring-centroid separation is 3.729 (2) Å, corresponding to a nearly ideal ring offset of 1.415 (2) Å. There are no other direction-specific interactions between the molecules; in particular, C—H···π(arene) hydrogen bonds are absent. Hence, the structure of compound (I) simply consists of isolated centrosymmetric dimers.
By contrast with the structure of (I), there are no C—H···N hydrogen bonds in the structures of either (II) or (III). Instead, the molecules of (II) and (III) are linked into sheets by C—H···π(arene) hydrogen bonds, a type of interaction absent from the structure of (I). Despite crystallizing in the same space group, P21/c, the formation of the hydrogen-bonded sheets differs considerably between (II) and (III).
In compound (II), the pyridine ring and the pendent phenyl ring C101–C106 act as hydrogen-bond acceptors. In the shorter of the two hydrogen bonds (Table 2), atom C73 in the molecule at (x, y, z) acts as donor to the aryl ring C101–C106 in the molecule at (1 − x, 1 − y, −z), so generating a cyclic and centrosymmetric dimeric motif centred at (1/2, 1/2, 0). The second of the two hydrogen bonds then links this dimer at (1/2, 1/2, 0) to four adjacent dimers. The atoms C4 in the molecules at (x, y, z) and (1 − x, 1 − y, −z) act as hydrogen-bond donors to the pyridine rings in the molecules at (x, 1/2 − y, 1/2 + z) and (1 − x, 1/2 + y, −1/2 − z), respectively, which themselves form parts of the dimers centred at (1/2, 0, 1/2) and (1/2, 1, −1/2), respectively. Similarly, the pyridine rings at (x, y, z) and (1 − x, 1 − y, −z) accept hydrogen bonds from the atoms C4 in the molecules at (x, 1/2 − y, z − 1/2) and (1 − x, 1/2 + y, 1/2 − z), which are themselves components of dimers centred at (1/2, 0, −1/2) and (1/2, 1, 1/2). Propagation by the space group of these two hydrogen bonds, associated with an inversion and a c-glide plane, respectively, then generates a (100) sheet in which large and small rings alternate (Fig. 6).
As in (II), the two-dimensional supramolecular structure of (III) is built from two C—H···π(arene) hydrogen bonds (Table 2), but now both are associated with translational symmetry operations and there are no directly connected pairs of molecules which are related by inversion. Again, unlike the hydrogen bonds in (II), for those in (III), the two donors form parts of the same aryl ring, while the acceptors are the two aryl rings pendent from the fused ring system.
Aryl atom C73 in the molecule at (x, y, z) acts as hydrogen-bond donor to the ring C101–C106 in the molecule at (1 − x, y − 1/2, 3/2 − z), thereby forming a chain running parallel to the [010] direction and generated by the 21 screw axis along (1/2, y, 3/4) (Fig. 7). In addition, atom C76 at (x, y, z) acts as hydrogen-bond donor to the C1/C2/C3/C4/C4a/C11b ring in the molecule at (x, 3/2 − y, 1/2 + z), thus producing a chain parallel to the [001] direction and generated by the c-glide plane at y = 3/4 (Fig. 8). The combination of these two chains generates a (100) sheet in the form of a (4,4) net (Fig. 9).
The constitution of compound (IV) differs from those of (I)–(III) in that it provides an additional acceptor of hydrogen bonds in the O atom of the methoxy substituent (Fig. 4). In fact, the molecules of (IV) are linked by a combination of C—H···N, C—H···O and C—H···π(arene) hydrogen bonds (Table 2) into a rather complex three-dimensional framework. The formation of this framework can be analysed very straightforwardly in terms of the component one-dimensional substructures.
In the first such substructure, the C—H···N and C—H···O hydrogen bonds combine to generate a chain of edge-fused rings. Aryl atom C72 in the molecule at (x, y, z) acts as hydrogen-bond donor to pyridine atom N11 in the molecule at (1 − x, 1 − y, 1 − z), thereby generating a centrosymmetric R22(14) ring centred at (1/2, 1/2, 1/2). In addition, atom C2 at (x, y, z) acts as donor to atom O7 in the molecule at (1 + x, y, 1 + z), so generating by translation a C(12) chain running parallel to the [101] direction. The combination of these two hydrogen bonds then generates a chain of edge-fused rings, with R22(14) rings centred at (n + 1/2, 1/2, n + 1/2) (n = zero or integer) and R44(22) rings centred at (n, 1/2, n) (n = zero or integer) (Fig. 10).
The second one-dimensional substructure also takes the form of a chain of edge-fused rings. Aryl atoms C75 in the molecules at (x, y, z) and (1 − x, 1 − y, 1 − z), which form the R22(14) dimer centred at (1/2, 1/2, 1/2), act as hydrogen-bond donors to the C101–C106 rings in the molecules at (1 − x, 1 − y, −z) and (x, y, 1 + z), respectively, which themselves form part of the R22(14) dimers centred at (1/2, 1/2, −1/2) and (1/2, 1/2, 3/2), respectively, so forming a chain of edge-fused centrosymmetric rings running parallel to the [001] direction (Fig. 11).
In addition to this [001] chain of edge-fused rings generated by inversion, there is a second substructure running parallel to [001] in the form of a simple chain generated by a c-glide plane. Aryl atom C4 in the molecule at (x, y, z) acts as hydrogen-bond donor to the pyridine ring in the molecule at (x, 3/2 − y, 1/2 + z), producing an [001] chain generated by the c-glide plane at y = 3/4 (Fig. 12).
In the final substructure, atom C103 in the molecule at (x, y, z) acts as hydrogen-bond donor to the pendent aryl ring C71–C76 in the molecule at (1 − x, y − 1/2, 1/2 − z), so forming a chain running parallel to the [010] direction and generated by the 21 screw axis along (1/2, y, 1/4) (Fig. 13).
The combination of the chains along [010], [001] and [101] suffices to link all of the molecules into a single three-dimensional framework, the complexity of which arises largely from the occurrence in the structure of five independent hydrogen bonds (Table 2).
We briefly compare the supramolecular structures of compounds (I)–(IV) reported here with those of the pair of compounds, (V) and (VI), containing 4-halogenophenyl substituents, where the molecular skeleton is a simple positional isomer of the skeleton in compounds (I)–(IV), and which are themseleves strictly isostructural in space group P1, as reported recently (Serrano et al., 2005a,b). In these analogues, the molecules are linked by C—H···π(arene) hydrogen bonds into chains of edge-fused rings. Hence, within this rather compact group of compounds, (I)–(VI), the supramolecular aggregation ranges from finite (zero-dimensional) in compound (I), via one-dimensional in compounds (V) and (VI) and two-dimensional in compounds (II) and (III), to three-dimensional in compound (IV).
The differences between the 4-methylphenyl compound, (III), and the 4-chlorophenyl compound, (V), in terms of both their space groups, namely P21/c for (III) as opposed to P1 for (V), and their supramolecular dimensionality, namely two-dimensional for (III) as opposed to one-dimensional for (V), is unexpected, as methyl and chloro substituents on aryl rings are generally effectively isosteric. This is well illustrated, for example by the related series of fused heterocycles (VII)–(IX) (see scheme) containing, respectively, 4-methylphenyl, 4-chlorophenyl and 4-bromophenyl substituents, which are all isomorphous and strictly isostructural (Portilla et al., 2005).