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In 6-(4-bromo­phen­yl)-3-methyl-1-phenyl-4,5-dihydro-1H-pyrazolo[3,4-b]pyridine, C19H16BrN3, the reduced pyridine ring adopts a conformation that is close to a screw-boat form. Mol­ecules are linked by pairs of symmetry-related C—H...π(arene) hydrogen bonds into cyclic centrosymmetric dimers. Mol­ecules of 3-(4-nitro­phen­yl)-4-phenyl-1H-pyrazolo[3,4-b]pyridine, C18H12N4O2, are linked into centrosymmetric R22(8) dimers by pairs of symmetry-related N—H...N hydrogen bonds, and these dimers are linked by pairs of C—H...π(pyridine) hydrogen bonds to form a chain of edge-fused rings, or a mol­ecular ladder, along [100]. The mol­ecular aggregation in this compound is completed by two weak C—H...O hydrogen bonds, one of which links the chains along [100] into sheets.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110006451/eg3040sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110006451/eg3040Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110006451/eg3040IIsup3.hkl
Contains datablock II

CCDC references: 774892; 774893

Comment top

4,5-Dihydropyrazolo[3,4-b]pyridines and their derivatives are useful synthetic intermediates as position 5 is active in, for example, Vilsmeier formylation reactions. The analogous 6,7-dihydropyrazolo[1,5-a]pyrimidines, which are purine analogues, are of potential pharmacological value (Novinson et al., 1976; Senga et al., 1981). Here we report the molecular and supramolecular structures of two pyrazolo[3,4-b]pyridine derivatives, namely 6-(4-bromophenyl)-4,5-dihydro-3-methyl-1-phenyl-1H- pyrazolo[3,4-b]pyridine, (I), and 3-(4-nitrophenyl)-4-phenyl-1H-pyrazolo[3,4-b]pyridine, (II) (Figs. 1 and 2), each of which was obtained from a cyclization reaction between a substituted 5-aminopyrazole and a 3-(dimethylamino)propiophenone derivative, but involving different regiochemistry in the two cases.

The synthesis of compound (I) involved a cyclization reaction between 5-amino-3-methyl-1-phenylpyrazole and a bromo-substituted 3-(dimethylamino)propiophenone hydrochloride to give the product (I) in 75% yield (see scheme). In this cyclization, the amino group of the pyrazole component reacts with the carbonyl group of the propiophenone component, while atom C4 of the pyrazole reacts at position 3 of the propiophenone. By contrast, in the corresponding reaction between 5-amino-3-(4-nitrophenyl)-1H-pyrazole and neutral 3-(dimethylamino)propiophenone, the formation of compound (II) involves the opposite regiochemistry, with atom C4 of the pyrazole reacting with the carbonyl group and the amino group of the pyrazole attacking at position 3 of the propiophenone. Compound (II) was, in fact, formed as a very minor product, and the major product of this reaction resulted from a cyclization utilising both the NH2 and the NH functions of the pyrazole component to yield 2-(4-nitrophenyl)-6,7-dihydro-5-phenylpyrazolo[1,5-a]pyrimidine, (III), in 80% yield (see scheme). Compounds (I) and (II) thus differ in several respects: the oxidation level of the six-membered heterocyclic ring; the location of the aryl substituent in this ring; and the presence in (II), but not in (I), of an NH group available for hydrogen-bond formation. However, because of the very similar processes by which they are formed, differing primarily in the regiochemistry of the reaction rather than in the reactants themselves, it is appropriate to consider them at the same time. Compounds (IV) and (V) (see scheme) are close analogues of compounds (I) and (II), respectively whose structures have been published, and these two compounds are discussed following the discussion of compounds (I) and (II).

Within the molecule of compound (I), the reduced pyridine ring is nonplanar with ring-puckering angles (Cremer & Pople, 1975) θ = 62.0 (5)° and ϕ = 161.7 (6)°; these values indicate a ring conformation that is close to the screw-boat form, where the idealized ring-puckering angles are θ = 67.5° and ϕ = (60k + 30)° (k represents an integer). The rest of the molecular conformation in (I) can be defined in terms of just two torsion angles (Table 1). The molecular conformation of compound (II) can be defined in terms of three torsion angles (Table 1) or, alternatively, in terms of three interplanar angles. The substituted and unsubstituted aryl rings in (II) make dihedral angles with their neighbouring heterocyclic rings of 46.1 (2) and 46.4 (2)°, respectively, while the nitro group makes a dihedral angle of 11.3 (2)° with the adjacent phenyl ring. The molecules of compounds (I) and (II) thus have no internal symmetry, and so they are conformationally chiral; however, the centrosymmetric space groups accommodate equal numbers of the two conformational enantiomers in each case. The bond distances in the fused heterocyclic systems (Table 1) are consistent with a modest degree of electronic delocalization in the pyrazole ring of (I) and with a delocalized pyridine system in (II).

The supramolecular aggregation is very simple in (I) and more complex in (II). In (I), pairs of molecules related by inversion are linked by pairs of symmetry-related C—H···π(arene) hydrogen bonds (Table 2) to form a cyclic centrosymmetric dimers (Fig. 3), but there are no significant direction-specific interactions between the dimers.

The molecules of compound (II) are linked into a chain of edge-fused rings, or a molecular ladder, by a combination of N—H···N and C—H···π(pyridine) hydrogen bonds (Table 2). Pairs of molecules related by inversion are linked by pairs of symmetry-related, nearly linear N—H···N hydrogen bonds to form cyclic dimers characterised by an R22(8) (Bernstein et al., 1995) motif (Fig. 4). In addition, the phenyl atom C45 in the molecule at (x, y, z) acts as hydrogen-bond donor to the pyridine ring of the molecule at (x + 1, y, z), so linking cyclic dimers into a chain of edge-fused rings running parallel to the [100] direction. In this chain, the centosymmetric R22(8) rings are centred at (n, 0, 1), where n represents an integer. These alternate with the larger centrosymmetric rings formed by the C—H···π(pyridine) hydrogen bonds and centred at (n + 1/2, 0, 1), where n again represents an integer (Fig. 4).

Within this chain of rings, pairs of pyrazolopyridine rings related by inversion across (n + 1/2, 0, 1) have an interplanar spacing of 3.663 (2) Å between the pyridine rings, whose ring-centroid separation is 3.827 (2) Å, corresponding to a ring-centroid offset of 1.106 (2)°. The interplanar spacing and the ring-centroid separation are both quite large, and it is possible that this contact is an adventitious consequence of the hydrogen bonding, rather than being of structural significance in itself. Nonetheless, any attractive interaction associated with this contact will reinforce, albeit weakly, the formation of the chain of rings parallel to [100].

There are also two short intermolecular C—H···O contacts in the crystal structure of (II), both involving the nitro atom O2 (Table 2). One of these contacts, involving atom C32, is between molecules related by translation along the [100] direction so that, if this contact is regarded as a weak hydrogen bond, its role is to reinforce the chain along [100]. The second contact, involving atom C6, is between molecules related by translation along [101]; if this contact is regarded as a weak hydrogen bond, then its role is to link the chains along [100] into a sheet parallel to (010).

The structure of the 4-chlorophenyl analogue of (I), compound (IV) (see scheme) was reported some years ago on a proof of constitution basis, without discussion [Cambridge Structural Database (CSD; Allen, 2002) refcode LABDAT (Quiroga et al., 1998)]. It is clear from the unit-cell dimensions for (IV) [a = 8.113 (1) Å, b = 17.315 (1) Å, c = 11.789 (1) Å, β = 104.77 (1)° in space group P21/n (incorrectly reported as P21/c)] that compounds (I) and (IV) are by no means isomorphous, as might possibly have been expected. However, since no H-atom coordinates for (IV) have been deposited, very little can be deduced about any supramolecular aggregation in the structure of (IV). Somewhat similar to compound (II), and obtained in a somewhat similar way, is compound (V), which was also reported on a proof of constitution basis without discussion (CSD refcode DEZQII; Quiroga et al., 1999), although this appears to be the only previously reported example of a 1H-pyrazolo[3,4-b]pyridine carrying two aryl substituents at the 3- and 4-positions. Examination of the crystal structure of (V) using the deposited atomic coordinates shows the presence of two hydrogen bonds, one each of N—H···N and C—H···N types, where the acceptors are, respectively, the pyridine ring N atom and the nitrile N atom. Inversion-related pairs of molecules are linked by pairs of N—H···N hydrogen bonds to form centrosymmetric R22(8) dimers, just as in (II). However, in (V) these dimers are linked by the C—H···N hydrogen bond to form a sheet lying parallel to (101) and built from centrosymmetric R22(8) and centrosymmetric R66(44) rings arranged in a chessboard fashion (Fig. 5). Unlike the structure of (II), that of (V) contains no C—H···π(arene) hydrogen bonds.

Related literature top

For related literature, see: Allen (2002); Bernstein et al. (1995); Cremer & Pople (1975); Novinson et al. (1976); Quiroga et al. (1998, 1999); Senga et al. (1981).

Experimental top

For the synthesis of (I), a solution of 5-amino-1-phenyl-3-methylpyrazole (0.5 mmole and 1-(4-bromophenyl)-3-(dimethylamino)propan-1-one hydrochloride (0.5 mmol) in pyridine (2 ml) was heated under reflux for 20 min. The mixture was cooled to ambient temperature and the product was isolated by filtration, washed with ethanol and dried prior to purification by column chromatography on silica gel using chloroform as eluant (yield 75%, m.p. 420-422 K). MS (70 eV) m/z (%) 365 (M+, 100), 364 (41), 183 (31), 143 (18), 102 (50), 77 (79), 51 (48); HR–MS found 365.0535, C19H16BrN3 requires 365.0528. Yellow crystals suitable for single-crystal X-ray diffraction were obtained by slow evaporation, at ambient temperature and in air, of a solution in dimethylformamide.

For the synthesis of (II), a solution of 5-amino-3-(4-nitrophenyl)-1H-pyrazole (1.9 mmol) and 3-dimethylaminopropiophenone (1.9 mmol) in pyridine (0.5 ml) was heated under reflux for 20 min. The solution was cooled to ambient temperature and the product mixture was collected by filtration, washed with ethanol and dried in air. The two components were separated by column chromatography on alumina using chloroform as the eluant. The main product was 2-(4-nitrophenyl)-6,7-dihydro-5-phenylpyrazolo[1,5-a]pyrimidine, (III), isolated as a yellow solid (yield 80%, m.p. 552-544 K). HR–MS found 318.0959, C18H14N4O2 requires 318.0960. Crystallization from ethanol–dimethylformamide (1:1, v/v) of the impure column fractions gave just a few crystals of compound (II) that proved to be suitable for single-crystal X-ray diffraction.

Refinement top

All H atoms were located in difference maps and then treated as riding atoms in geometrically idealized positions with C—H distances of 0.95 (aromatic or pyridyl), 0.98 (CH3) or 0.99 Å (CH2) and N—H distances of 0.88 Å, and with Uiso(H) = kUeq(carrier), where k = 1.5 for the methyl group in (I), which was permitted to rotate but not to tilt, and k = 1.2 for all other H atoms.

Computing details top

For both compounds, data collection: COLLECT (Hooft, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: Sir2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) showing the atom labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. The molecular structure of (II) showing the atom labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 3] Fig. 3. Part of the crystal structure of (I), showing the formation of a centrosymmetric hydrogen-bonded dimer. For the sake of clarity, H atoms not involved in the motif shown have been omitted. The atom marked with an asterisk (*) is at the symmetry position (-x, 1 - y, 1 - z).
[Figure 4] Fig. 4. A stereoview of part of the crystal structure of (II), showing the formation of a chain of hydrogen-bonded rings along [100] built from N—H···N and C—H···π(pyridine) interactions. For the sake of clarity, H atoms not involved in the motif shown have been omitted.
[Figure 5] Fig. 5. A stereoview of part of the crystal structure of (V), showing the formation of a hydrogen-bonded sheet parallel to (101). The original atomic coordinates (Quiroga et al., 1999) have been used and, for the sake of clarity, H atoms not involved in the motifs shown have been omitted.
(I) 6-(4-bromophenyl)-3-methyl-1-phenyl-4,5-dihydro-1H- pyrazolo[3,4-b]pyridine top
Crystal data top
C19H16BrN3F(000) = 744
Mr = 366.26Dx = 1.571 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3058 reflections
a = 7.5165 (1) Åθ = 3.2–26.1°
b = 11.6572 (3) ŵ = 2.66 mm1
c = 17.6917 (5) ÅT = 120 K
β = 92.701 (2)°Needle, yellow
V = 1548.45 (6) Å30.20 × 0.06 × 0.04 mm
Z = 4
Data collection top
Bruker–Nonius KappaCCD
diffractometer
3058 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode2597 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.048
Detector resolution: 9.091 pixels mm-1θmax = 26.1°, θmin = 3.2°
ϕ & ω scansh = 89
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1414
Tmin = 0.685, Tmax = 0.901l = 2121
21038 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.069H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0284P)2 + 1.0784P]
where P = (Fo2 + 2Fc2)/3
3058 reflections(Δ/σ)max = 0.001
209 parametersΔρmax = 0.26 e Å3
0 restraintsΔρmin = 0.51 e Å3
Crystal data top
C19H16BrN3V = 1548.45 (6) Å3
Mr = 366.26Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.5165 (1) ŵ = 2.66 mm1
b = 11.6572 (3) ÅT = 120 K
c = 17.6917 (5) Å0.20 × 0.06 × 0.04 mm
β = 92.701 (2)°
Data collection top
Bruker–Nonius KappaCCD
diffractometer
3058 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
2597 reflections with I > 2σ(I)
Tmin = 0.685, Tmax = 0.901Rint = 0.048
21038 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0290 restraints
wR(F2) = 0.069H-atom parameters constrained
S = 1.05Δρmax = 0.26 e Å3
3058 reflectionsΔρmin = 0.51 e Å3
209 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.1491 (2)0.57039 (14)0.57944 (10)0.0166 (4)
N20.0955 (2)0.68300 (15)0.58020 (10)0.0192 (4)
C30.1460 (3)0.72732 (18)0.51492 (12)0.0196 (4)
C3A0.2321 (3)0.64486 (18)0.47129 (11)0.0168 (4)
C40.3286 (3)0.64703 (19)0.39950 (12)0.0222 (5)
H4A0.44810.68120.40900.027*
H4B0.26220.69500.36160.027*
C50.3472 (3)0.52481 (18)0.36877 (12)0.0193 (4)
H5A0.24690.51050.33170.023*
H5B0.45840.52080.34110.023*
C60.3506 (3)0.42890 (18)0.42673 (11)0.0159 (4)
N70.2959 (2)0.43926 (14)0.49501 (10)0.0161 (4)
C7A0.2298 (3)0.54648 (17)0.51320 (11)0.0158 (4)
C110.1298 (3)0.50223 (18)0.64513 (11)0.0170 (4)
C120.1356 (3)0.38296 (19)0.64202 (12)0.0196 (5)
H120.15410.34510.59550.024*
C130.1142 (3)0.3197 (2)0.70750 (12)0.0237 (5)
H130.11990.23840.70540.028*
C140.0847 (3)0.3729 (2)0.77579 (12)0.0242 (5)
H140.06800.32890.82010.029*
C150.0802 (3)0.4915 (2)0.77804 (13)0.0265 (5)
H150.06070.52900.82460.032*
C160.1036 (3)0.55689 (19)0.71364 (12)0.0231 (5)
H160.10180.63830.71630.028*
C310.1059 (3)0.85022 (19)0.49562 (14)0.0265 (5)
H31A0.00340.85380.45940.040*
H31B0.20970.88510.47320.040*
H31C0.07850.89200.54170.040*
C610.4087 (3)0.31249 (18)0.40482 (11)0.0162 (4)
C620.5062 (3)0.29113 (19)0.34087 (11)0.0195 (4)
H620.53540.35290.30870.023*
C630.5609 (3)0.18080 (19)0.32385 (12)0.0219 (5)
H630.62920.16720.28090.026*
C640.5154 (3)0.09143 (19)0.36966 (12)0.0202 (5)
Br640.59123 (3)0.060800 (19)0.348270 (13)0.02834 (9)
C650.4155 (3)0.10903 (19)0.43266 (12)0.0210 (5)
H650.38320.04630.46340.025*
C660.3639 (3)0.21905 (19)0.44977 (12)0.0206 (5)
H660.29640.23180.49310.025*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0184 (9)0.0155 (9)0.0158 (9)0.0010 (7)0.0017 (7)0.0015 (7)
N20.0222 (9)0.0141 (9)0.0211 (9)0.0013 (7)0.0006 (7)0.0017 (7)
C30.0205 (11)0.0169 (11)0.0211 (11)0.0005 (8)0.0033 (8)0.0002 (9)
C3A0.0174 (10)0.0160 (11)0.0168 (10)0.0006 (8)0.0005 (8)0.0007 (8)
C40.0278 (12)0.0203 (12)0.0184 (11)0.0018 (9)0.0016 (9)0.0039 (9)
C50.0226 (11)0.0203 (11)0.0149 (10)0.0003 (8)0.0017 (8)0.0026 (9)
C60.0136 (10)0.0187 (11)0.0152 (10)0.0028 (8)0.0005 (8)0.0000 (8)
N70.0167 (9)0.0161 (9)0.0157 (9)0.0011 (7)0.0022 (7)0.0012 (7)
C7A0.0146 (10)0.0187 (11)0.0139 (10)0.0014 (8)0.0002 (8)0.0019 (8)
C110.0145 (10)0.0205 (12)0.0161 (10)0.0007 (8)0.0021 (8)0.0003 (8)
C120.0218 (11)0.0200 (12)0.0176 (11)0.0007 (8)0.0053 (8)0.0031 (9)
C130.0268 (12)0.0184 (12)0.0264 (12)0.0015 (9)0.0058 (9)0.0030 (9)
C140.0254 (12)0.0295 (13)0.0179 (11)0.0015 (9)0.0035 (9)0.0049 (9)
C150.0319 (13)0.0307 (14)0.0174 (12)0.0011 (10)0.0059 (9)0.0047 (10)
C160.0276 (12)0.0208 (12)0.0211 (12)0.0003 (9)0.0034 (9)0.0038 (9)
C310.0312 (12)0.0166 (12)0.0315 (13)0.0032 (9)0.0008 (10)0.0028 (10)
C610.0158 (10)0.0184 (11)0.0145 (10)0.0024 (8)0.0004 (8)0.0021 (8)
C620.0221 (11)0.0208 (12)0.0156 (11)0.0026 (8)0.0015 (8)0.0006 (9)
C630.0249 (11)0.0241 (12)0.0170 (10)0.0001 (9)0.0051 (9)0.0023 (9)
C640.0246 (11)0.0191 (11)0.0167 (11)0.0008 (8)0.0018 (9)0.0039 (9)
Br640.04297 (16)0.01933 (14)0.02316 (14)0.00488 (10)0.00611 (10)0.00395 (9)
C650.0273 (12)0.0169 (11)0.0188 (11)0.0043 (9)0.0027 (9)0.0018 (9)
C660.0224 (11)0.0231 (12)0.0169 (11)0.0014 (9)0.0061 (8)0.0008 (9)
Geometric parameters (Å, º) top
N1—C7A1.373 (3)C13—C141.385 (3)
N1—N21.373 (2)C13—H130.9500
N1—C111.421 (3)C14—C151.384 (3)
N2—C31.336 (3)C14—H140.9500
C3—C3A1.409 (3)C15—C161.389 (3)
C3—C311.500 (3)C15—H150.9500
C3A—C7A1.366 (3)C16—H160.9500
C3A—C41.492 (3)C31—H31A0.9800
C4—C51.534 (3)C31—H31B0.9800
C4—H4A0.9900C31—H31C0.9800
C4—H4B0.9900C61—C661.399 (3)
C5—C61.516 (3)C61—C621.399 (3)
C5—H5A0.9900C62—C631.388 (3)
C5—H5B0.9900C62—H620.9500
C6—N71.300 (3)C63—C641.373 (3)
C6—C611.483 (3)C63—H630.9500
N7—C7A1.388 (3)C64—C651.388 (3)
C11—C161.391 (3)C64—Br641.907 (2)
C11—C121.392 (3)C65—C661.378 (3)
C12—C131.389 (3)C65—H650.9500
C12—H120.9500C66—H660.9500
C7A—N1—N2110.12 (16)C14—C13—H13119.3
C7A—N1—C11130.61 (17)C12—C13—H13119.3
N2—N1—C11119.01 (16)C15—C14—C13118.5 (2)
C3—N2—N1105.40 (17)C15—C14—H14120.7
N2—C3—C3A111.48 (18)C13—C14—H14120.7
N2—C3—C31120.25 (19)C14—C15—C16121.4 (2)
C3A—C3—C31128.3 (2)C14—C15—H15119.3
C7A—C3A—C3104.93 (18)C16—C15—H15119.3
C7A—C3A—C4119.68 (19)C15—C16—C11119.5 (2)
C3—C3A—C4135.1 (2)C15—C16—H16120.3
C3A—C4—C5110.00 (18)C11—C16—H16120.3
C3A—C4—H4A109.7C3—C31—H31A109.5
C5—C4—H4A109.7C3—C31—H31B109.5
C3A—C4—H4B109.7H31A—C31—H31B109.5
C5—C4—H4B109.7C3—C31—H31C109.5
H4A—C4—H4B108.2H31A—C31—H31C109.5
C6—C5—C4116.37 (17)H31B—C31—H31C109.5
C6—C5—H5A108.2C66—C61—C62118.06 (19)
C4—C5—H5A108.2C66—C61—C6118.82 (18)
C6—C5—H5B108.2C62—C61—C6123.12 (19)
C4—C5—H5B108.2C63—C62—C61120.8 (2)
H5A—C5—H5B107.3C63—C62—H62119.6
N7—C6—C61115.98 (18)C61—C62—H62119.6
N7—C6—C5124.32 (19)C64—C63—C62119.39 (19)
C61—C6—C5119.59 (17)C64—C63—H63120.3
C6—N7—C7A115.56 (17)C62—C63—H63120.3
C3A—C7A—N1108.06 (18)C63—C64—C65121.4 (2)
C3A—C7A—N7128.04 (18)C63—C64—Br64120.25 (16)
N1—C7A—N7123.90 (18)C65—C64—Br64118.34 (16)
C16—C11—C12119.86 (19)C66—C65—C64118.8 (2)
C16—C11—N1118.72 (19)C66—C65—H65120.6
C12—C11—N1121.43 (18)C64—C65—H65120.6
C13—C12—C11119.5 (2)C65—C66—C61121.47 (19)
C13—C12—H12120.3C65—C66—H66119.3
C11—C12—H12120.3C61—C66—H66119.3
C14—C13—C12121.3 (2)
C7A—N1—N2—C30.8 (2)N2—N1—C11—C1617.2 (3)
C11—N1—N2—C3173.92 (17)C7A—N1—C11—C1224.0 (3)
N1—N2—C3—C3A0.1 (2)N2—N1—C11—C12162.54 (18)
N1—N2—C3—C31178.99 (18)C16—C11—C12—C130.4 (3)
N2—C3—C3A—C7A0.7 (2)N1—C11—C12—C13179.33 (19)
C31—C3—C3A—C7A178.1 (2)C11—C12—C13—C140.9 (3)
N2—C3—C3A—C4173.2 (2)C12—C13—C14—C151.2 (3)
C31—C3—C3A—C48.0 (4)C13—C14—C15—C160.3 (3)
C7A—C3A—C4—C522.7 (3)C14—C15—C16—C110.9 (3)
C3—C3A—C4—C5164.1 (2)C12—C11—C16—C151.2 (3)
C3A—C4—C5—C627.5 (3)N1—C11—C16—C15178.50 (19)
C4—C5—C6—N717.9 (3)N7—C6—C61—C6614.6 (3)
C4—C5—C6—C61166.16 (18)C5—C6—C61—C66161.72 (19)
C61—C6—N7—C7A175.57 (17)N7—C6—C61—C62165.64 (19)
C5—C6—N7—C7A0.5 (3)C5—C6—C61—C6218.1 (3)
C3—C3A—C7A—N11.2 (2)C66—C61—C62—C631.7 (3)
C4—C3A—C7A—N1173.88 (18)C6—C61—C62—C63178.49 (19)
C3—C3A—C7A—N7179.06 (19)C61—C62—C63—C641.3 (3)
C4—C3A—C7A—N75.9 (3)C62—C63—C64—C650.1 (3)
N2—N1—C7A—C3A1.3 (2)C62—C63—C64—Br64179.25 (16)
C11—N1—C7A—C3A172.66 (19)C63—C64—C65—C661.0 (3)
N2—N1—C7A—N7178.93 (17)Br64—C64—C65—C66178.34 (16)
C11—N1—C7A—N77.1 (3)C64—C65—C66—C610.6 (3)
C6—N7—C7A—C3A7.3 (3)C62—C61—C66—C650.8 (3)
C6—N7—C7A—N1172.91 (19)C6—C61—C66—C65179.42 (19)
C7A—N1—C11—C16156.3 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5—H5A···Cg1i0.992.803.662 (2)146
Symmetry code: (i) x, y+1, z+1.
(II) 3-(4-nitrophenyl)-4-phenyl-1H-pyrazolo[3,4-b]pyridine top
Crystal data top
C18H12N4O2Z = 2
Mr = 316.32F(000) = 328
Triclinic, P1Dx = 1.406 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.0408 (1) ÅCell parameters from 2938 reflections
b = 9.6360 (3) Åθ = 3.5–26.1°
c = 11.1961 (3) ŵ = 0.10 mm1
α = 84.906 (1)°T = 120 K
β = 89.177 (2)°Plate, yellow
γ = 81.012 (2)°0.24 × 0.20 × 0.06 mm
V = 747.31 (3) Å3
Data collection top
Bruker–Nonius KappaCCD
diffractometer
2938 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode2447 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.038
Detector resolution: 9.091 pixels mm-1θmax = 26.1°, θmin = 3.5°
ϕ & ω scansh = 88
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1111
Tmin = 0.974, Tmax = 0.994l = 1313
13461 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.101H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0487P)2 + 0.2645P]
where P = (Fo2 + 2Fc2)/3
2938 reflections(Δ/σ)max = 0.001
217 parametersΔρmax = 0.20 e Å3
0 restraintsΔρmin = 0.34 e Å3
Crystal data top
C18H12N4O2γ = 81.012 (2)°
Mr = 316.32V = 747.31 (3) Å3
Triclinic, P1Z = 2
a = 7.0408 (1) ÅMo Kα radiation
b = 9.6360 (3) ŵ = 0.10 mm1
c = 11.1961 (3) ÅT = 120 K
α = 84.906 (1)°0.24 × 0.20 × 0.06 mm
β = 89.177 (2)°
Data collection top
Bruker–Nonius KappaCCD
diffractometer
2938 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
2447 reflections with I > 2σ(I)
Tmin = 0.974, Tmax = 0.994Rint = 0.038
13461 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.101H-atom parameters constrained
S = 1.06Δρmax = 0.20 e Å3
2938 reflectionsΔρmin = 0.34 e Å3
217 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.14822 (16)0.02507 (12)0.86334 (10)0.0174 (3)
H10.05230.02140.88200.021*
N20.23027 (16)0.03444 (12)0.75281 (10)0.0177 (3)
C30.37039 (18)0.11149 (14)0.76011 (12)0.0152 (3)
C3A0.37809 (18)0.15793 (14)0.87802 (12)0.0149 (3)
C40.47665 (18)0.24722 (14)0.93931 (12)0.0155 (3)
C50.42734 (19)0.25808 (15)1.05886 (12)0.0189 (3)
H50.49200.31431.10510.023*
C60.28394 (19)0.18771 (15)1.11298 (13)0.0190 (3)
H60.25750.19791.19550.023*
N70.18203 (16)0.10750 (12)1.05670 (10)0.0173 (3)
C7A0.23280 (18)0.09634 (14)0.94114 (12)0.0152 (3)
C310.49462 (19)0.13361 (14)0.65465 (12)0.0148 (3)
C320.41393 (19)0.17295 (15)0.54097 (12)0.0181 (3)
H320.27880.18150.53050.022*
C330.53012 (19)0.19956 (15)0.44359 (12)0.0183 (3)
H330.47610.22670.36620.022*
C340.72658 (19)0.18583 (14)0.46111 (12)0.0155 (3)
C350.81192 (19)0.14082 (14)0.57121 (12)0.0163 (3)
H350.94770.12740.58010.020*
C360.69376 (19)0.11592 (14)0.66806 (12)0.0166 (3)
H360.74910.08640.74480.020*
N340.84861 (16)0.22220 (12)0.35935 (10)0.0180 (3)
O10.77058 (15)0.28314 (11)0.26739 (9)0.0258 (3)
O21.02401 (14)0.19188 (12)0.37097 (9)0.0260 (3)
C410.61947 (19)0.32961 (14)0.88097 (12)0.0170 (3)
C420.5819 (2)0.40547 (15)0.76971 (13)0.0213 (3)
H420.46140.40810.73180.026*
C430.7203 (2)0.47722 (16)0.71405 (15)0.0294 (4)
H430.69440.52800.63790.035*
C440.8960 (2)0.47499 (16)0.76927 (16)0.0321 (4)
H440.99120.52260.73040.039*
C450.9319 (2)0.40323 (16)0.88105 (15)0.0287 (4)
H451.05130.40310.91960.034*
C460.7945 (2)0.33129 (15)0.93734 (14)0.0214 (3)
H460.81980.28301.01450.026*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0156 (6)0.0238 (6)0.0151 (6)0.0096 (5)0.0038 (4)0.0038 (5)
N20.0167 (6)0.0226 (6)0.0151 (6)0.0067 (5)0.0033 (4)0.0028 (5)
C30.0132 (6)0.0174 (7)0.0151 (7)0.0033 (5)0.0000 (5)0.0010 (5)
C3A0.0129 (6)0.0168 (7)0.0146 (7)0.0015 (5)0.0009 (5)0.0006 (5)
C40.0132 (6)0.0165 (7)0.0165 (7)0.0018 (5)0.0001 (5)0.0018 (5)
C50.0180 (7)0.0234 (7)0.0169 (7)0.0070 (6)0.0004 (5)0.0043 (6)
C60.0180 (7)0.0259 (8)0.0140 (7)0.0052 (6)0.0011 (5)0.0032 (6)
N70.0167 (6)0.0216 (6)0.0144 (6)0.0053 (5)0.0019 (4)0.0020 (5)
C7A0.0129 (6)0.0174 (7)0.0153 (7)0.0029 (5)0.0008 (5)0.0014 (5)
C310.0158 (7)0.0149 (7)0.0147 (7)0.0047 (5)0.0026 (5)0.0038 (5)
C320.0134 (7)0.0245 (7)0.0174 (7)0.0053 (5)0.0001 (5)0.0039 (6)
C330.0195 (7)0.0219 (7)0.0136 (7)0.0038 (5)0.0022 (5)0.0007 (6)
C340.0171 (7)0.0161 (7)0.0141 (7)0.0048 (5)0.0044 (5)0.0021 (5)
C350.0121 (7)0.0193 (7)0.0179 (7)0.0029 (5)0.0006 (5)0.0025 (5)
C360.0177 (7)0.0189 (7)0.0132 (7)0.0032 (5)0.0009 (5)0.0005 (5)
N340.0193 (6)0.0206 (6)0.0154 (6)0.0066 (5)0.0026 (5)0.0022 (5)
O10.0282 (6)0.0332 (6)0.0161 (5)0.0090 (4)0.0007 (4)0.0056 (4)
O20.0166 (5)0.0381 (6)0.0231 (6)0.0058 (4)0.0049 (4)0.0005 (5)
C410.0172 (7)0.0156 (7)0.0195 (7)0.0043 (5)0.0041 (5)0.0050 (5)
C420.0250 (8)0.0175 (7)0.0220 (8)0.0043 (6)0.0018 (6)0.0032 (6)
C430.0429 (10)0.0174 (8)0.0273 (9)0.0050 (6)0.0100 (7)0.0009 (6)
C440.0299 (9)0.0218 (8)0.0469 (11)0.0111 (7)0.0179 (7)0.0053 (7)
C450.0186 (8)0.0251 (8)0.0447 (10)0.0083 (6)0.0044 (7)0.0072 (7)
C460.0188 (7)0.0208 (7)0.0258 (8)0.0052 (6)0.0012 (6)0.0043 (6)
Geometric parameters (Å, º) top
N1—C7A1.3543 (17)C33—H330.9500
N1—N21.3599 (15)C34—C351.3833 (19)
N1—H10.8800C34—N341.4677 (17)
N2—C31.3316 (17)C35—C361.3841 (19)
C3—C3A1.4354 (19)C35—H350.9500
C3—C311.4794 (18)C36—H360.9500
C3A—C7A1.4116 (18)N34—O21.2299 (15)
C3A—C41.4135 (19)N34—O11.2308 (15)
C4—C51.3868 (19)C41—C421.394 (2)
C4—C411.4854 (18)C41—C461.396 (2)
C5—C61.4034 (19)C42—C431.390 (2)
C5—H50.9500C42—H420.9500
C6—N71.3350 (18)C43—C441.387 (2)
C6—H60.9500C43—H430.9500
N7—C7A1.3463 (17)C44—C451.382 (2)
C31—C361.3944 (19)C44—H440.9500
C31—C321.3980 (19)C45—C461.389 (2)
C32—C331.3835 (19)C45—H450.9500
C32—H320.9500C46—H460.9500
C33—C341.3840 (19)
C7A—N1—N2111.45 (11)C34—C33—H33120.6
C7A—N1—H1124.3C35—C34—C33122.49 (12)
N2—N1—H1124.3C35—C34—N34118.79 (12)
C3—N2—N1106.65 (11)C33—C34—N34118.71 (12)
N2—C3—C3A110.78 (11)C34—C35—C36118.09 (12)
N2—C3—C31119.39 (12)C34—C35—H35121.0
C3A—C3—C31129.80 (12)C36—C35—H35121.0
C7A—C3A—C4117.54 (12)C35—C36—C31120.95 (12)
C7A—C3A—C3103.56 (11)C35—C36—H36119.5
C4—C3A—C3138.78 (12)C31—C36—H36119.5
C5—C4—C3A115.72 (12)O2—N34—O1123.32 (11)
C5—C4—C41120.84 (12)O2—N34—C34118.23 (11)
C3A—C4—C41123.40 (12)O1—N34—C34118.44 (11)
C4—C5—C6121.39 (13)C42—C41—C46119.07 (13)
C4—C5—H5119.3C42—C41—C4120.93 (12)
C6—C5—H5119.3C46—C41—C4120.00 (13)
N7—C6—C5124.60 (13)C43—C42—C41120.22 (14)
N7—C6—H6117.7C43—C42—H42119.9
C5—C6—H6117.7C41—C42—H42119.9
C6—N7—C7A113.47 (11)C44—C43—C42120.27 (15)
N7—C7A—N1125.29 (12)C44—C43—H43119.9
N7—C7A—C3A127.17 (12)C42—C43—H43119.9
N1—C7A—C3A107.52 (11)C45—C44—C43119.77 (14)
C36—C31—C32119.39 (12)C45—C44—H44120.1
C36—C31—C3120.12 (12)C43—C44—H44120.1
C32—C31—C3120.49 (12)C44—C45—C46120.34 (15)
C33—C32—C31120.24 (13)C44—C45—H45119.8
C33—C32—H32119.9C46—C45—H45119.8
C31—C32—H32119.9C45—C46—C41120.29 (14)
C32—C33—C34118.73 (13)C45—C46—H46119.9
C32—C33—H33120.6C41—C46—H46119.9
C7A—N1—N2—C30.60 (15)C36—C31—C32—C332.6 (2)
N1—N2—C3—C3A1.66 (15)C3—C31—C32—C33177.14 (12)
N1—N2—C3—C31176.51 (11)C31—C32—C33—C340.3 (2)
N2—C3—C3A—C7A2.04 (15)C32—C33—C34—C352.8 (2)
C31—C3—C3A—C7A175.88 (13)C32—C33—C34—N34176.39 (12)
N2—C3—C3A—C4173.67 (15)C33—C34—C35—C363.4 (2)
C31—C3—C3A—C48.4 (3)N34—C34—C35—C36175.78 (12)
C7A—C3A—C4—C53.82 (18)C34—C35—C36—C311.0 (2)
C3—C3A—C4—C5179.11 (15)C32—C31—C36—C351.9 (2)
C7A—C3A—C4—C41174.04 (12)C3—C31—C36—C35177.77 (12)
C3—C3A—C4—C411.2 (2)C35—C34—N34—O210.49 (18)
C3A—C4—C5—C61.97 (19)C33—C34—N34—O2170.30 (12)
C41—C4—C5—C6175.95 (12)C35—C34—N34—O1168.53 (12)
C4—C5—C6—N70.9 (2)C33—C34—N34—O110.69 (18)
C5—C6—N7—C7A1.6 (2)C5—C4—C41—C42132.24 (14)
C6—N7—C7A—N1177.81 (13)C3A—C4—C41—C4245.51 (19)
C6—N7—C7A—C3A0.6 (2)C5—C4—C41—C4648.04 (19)
N2—N1—C7A—N7179.36 (12)C3A—C4—C41—C46134.20 (14)
N2—N1—C7A—C3A0.70 (15)C46—C41—C42—C432.4 (2)
C4—C3A—C7A—N73.4 (2)C4—C41—C42—C43177.32 (13)
C3—C3A—C7A—N7179.78 (13)C41—C42—C43—C440.6 (2)
C4—C3A—C7A—N1175.21 (11)C42—C43—C44—C451.2 (2)
C3—C3A—C7A—N11.59 (14)C43—C44—C45—C461.2 (2)
N2—C3—C31—C36133.34 (14)C44—C45—C46—C410.6 (2)
C3A—C3—C31—C3644.4 (2)C42—C41—C46—C452.4 (2)
N2—C3—C31—C3246.95 (18)C4—C41—C46—C45177.30 (13)
C3A—C3—C31—C32135.29 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N7i0.882.042.916 (2)171
C6—H6···O2ii0.952.553.397 (2)149
C32—H32···O2iii0.952.533.335 (2)142
C45—H45···Cg2iv0.952.793.472 (2)129
Symmetry codes: (i) x, y, z+2; (ii) x1, y, z+1; (iii) x1, y, z; (iv) x+1, y, z.

Experimental details

(I)(II)
Crystal data
Chemical formulaC19H16BrN3C18H12N4O2
Mr366.26316.32
Crystal system, space groupMonoclinic, P21/cTriclinic, P1
Temperature (K)120120
a, b, c (Å)7.5165 (1), 11.6572 (3), 17.6917 (5)7.0408 (1), 9.6360 (3), 11.1961 (3)
α, β, γ (°)90, 92.701 (2), 9084.906 (1), 89.177 (2), 81.012 (2)
V3)1548.45 (6)747.31 (3)
Z42
Radiation typeMo KαMo Kα
µ (mm1)2.660.10
Crystal size (mm)0.20 × 0.06 × 0.040.24 × 0.20 × 0.06
Data collection
DiffractometerBruker–Nonius KappaCCD
diffractometer
Bruker–Nonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.685, 0.9010.974, 0.994
No. of measured, independent and
observed [I > 2σ(I)] reflections
21038, 3058, 2597 13461, 2938, 2447
Rint0.0480.038
(sin θ/λ)max1)0.6180.618
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.069, 1.05 0.038, 0.101, 1.06
No. of reflections30582938
No. of parameters209217
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.26, 0.510.20, 0.34

Computer programs: COLLECT (Hooft, 1999), DIRAX/LSQ (Duisenberg et al., 2000), EVALCCD (Duisenberg et al., 2003), Sir2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Selected geometric parameters (Å, °) for compounds (I) and (II) top
Parameter(I)(II)
N1—N21.373 (2)1.3599 (15)
N2—C31.336 (3)1.3316 (17)
C3—C3A1.409 (3)1.4354 (19)
C3A—C41.492 (3)1.4135 (19)
C4—C51.534 (3)1.3868 (19)
C5—C61.516 (3)1.4034 (19)
C6—N71.300 (3)1.3350 (18)
N7—C7A1.388 (3)1.3463 (17)
C7A—N11.373 (3)1.3543 (17)
C3A—C7A1.366 (2)1.4116 (18)
N2—N1—C11—C12162.54 (18)
N2—C3—C31—C3246.95 (18)
N7—C6—C61—C62-165.64 (19)
C3A—C4—C41—C4245.51 (19)
C33—C34—N34—O110.69 (18)
Hydrogen bonds and short intermolecular contacts (Å, °) for compounds (I) and (II) top
CompoundD—H···AD—HH···AD···AD—H···A
(I)C5—H5A···Cg1a,i0.992.803.662 (2)146
(II)N1—H1···N7ii0.882.042.916 (2)171
C6—H6···O2iii0.952.553.397 (2)149
C32—H32···O2iv0.952.533.335 (2)142
C45—H45···Cg2b,v0.952.793.472 (2)129
Cg1 and Cg2 represent the centroids of the C11–C16 and C3A/C4/C5/C6/N7/C7A rings, respectively. Symmetry codes: (i) -x, -y+1, -z+1; (ii) -x, -y, -z+2; (iii) x-1, y, z+1; (iv) x-1, y, z; (v) x+1, y, z.
 

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