supplementary materials


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Acta Cryst. (2013). E69, o801    [ doi:10.1107/S1600536813010994 ]

7-Methyl-1-phenyl-1,10-dihydropyrazolo[3,4-a]carbazole

R. Archana, E. Yamuna, A. Thiruvalluvar, K. J. Rajendra Prasad, R. J. Butcher, S. K. Gupta and S. Öztürk Yildirim

Abstract top

In the title molecule, C20H15N3, the atoms in the carbazole unit deviate from planarity [maximum deviation from mean plane = 0.1082 (15) Å]. The pyrrole ring makes dihedral angles of 3.17 (8)/4.10 (9), 7.20 (9) and 44.62 (9)° with the fused benzene, pyrazole and phenyl rings, respectively. In the crystal, molecules are linked via N-H...N hydrogen bonds, forming an infinite chain along [010]. Molecules are further linked by nine [pi]-[pi] [centroid-centroid distances vary from 3.6864 (11) to 3.9802 (11) Å] and one C-H...[pi] interaction, forming a three-dimensional network.

Comment top

As part of our research (Archana et al., 2010, 2011), we have synthesized the title compound (I), and report its crystal structure here.

In the title molecule (Scheme I, Fig. 1), C20H15N3, the atoms in the carbazole unit deviate from planarity. Maximum deviation from carbazole mean plane = -0.1082 (15) Å for atom C4. The pyrrole ring makes dihedral angles of 3.17 (8), 4.10 (9), 7.20 (9) and 44.62 (9)° with the fused benzene rings, pyrazole and phenyl rings, respectively.

In the crystal structure, molecules are linked via a N10—H10···N2 interaction, forming an infinite one-dimensional chain with base vector [0 1 0] (Table 1, Fig. 2). Molecules are further linked by nine π-π [Cg1—Cg5i = Cg5—Cg1iii = 3.9802 (11), Cg1—Cg5iii = Cg5—Cg1i = 3.6864 (11), Cg2—Cg5i = Cg5—Cg2iii = 3.9402 (11), Cg3—Cg5i = 3.7920 (11), Cg4—Cg4ii = 3.8456 (9) and Cg5—Cg3iii = 3.7921 (11) Å, symmetry code (i): -x, -1/2 + y, 1/2 - z, (ii): 1 - x, 2 - y, 1 - z, (iii): -x, 1/2 + y, 1/2 - z where Cg1, Cg2, Cg3, Cg4 and Cg5 are the centroids of the pyrazole (N1/N2/C3/C3A/C10B), pyrrole (N10/C10A/C5A/C5B/C9A), benzene (C3A/C4/C5/C5A/C10A/C10B), benzene (C5B/C6—C9/C9A) and phenyl (C11—C16) rings, respectively (Fig. 3)] and one C17—H17B···π interactions to form a three-dimensional network (Table 1, Fig. 4).

Related literature top

For related structures and the biological and pharmacological activity of carbazole alkaloids, see: Archana et al. (2010, 2011).

Experimental top

A mixture of 2-(hydroxymethylene)-6-methyl-2,3,4,9-tetrahydro-1H- carbazol-1-one (0.227 g, 0.001 mol), phenyl hydrazine (0.540 g, 0.005 mol) and glacial acetic acid (5 ml) was refluxed at 393 K for 6 h. After completion of reaction it was then cooled and poured onto crushed ice, the solid thus separated out was filtered, washed with water, dried and purified by column chromatography over silica gel (eluting with a petroleum ether and ethyl acetate mixture, 95:5) to give the title compound (0.228 g, 77%). This pure compound was recrystallized from EtOAc and ethanol.

Refinement top

The H atom bonded to N10 was located in a difference Fourier map and refined freely; N10—H10 = 0.89 (2) Å. Other H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.95–0.98 Å, and with Uiso(H) = 1.2–1.5Ueq(parent atom).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and 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 the title compound, with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as small spheres of arbitrary radius.
[Figure 2] Fig. 2. The partial packing of the title compound, viewed approximately down the c axis. Dashed lines indicate hydrogen bonds. H atoms not involved in hydrogen bonding have been omitted.
[Figure 3] Fig. 3. The crystal structure of compound, showing the formation of π-π stacking interactions.
[Figure 4] Fig. 4. Part of the crystal structure of compound, showing the formation of C—H···π interactions. Symmetry code ii: 1 - x, 2 - y, 1 - z
7-Methyl-1-phenyl-1,10-dihydropyrazolo[3,4-a]carbazole top
Crystal data top
C20H15N3F(000) = 624
Mr = 297.35Dx = 1.319 Mg m3
Monoclinic, P21/cMelting point: 509 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 12.0727 (6) ÅCell parameters from 2152 reflections
b = 7.5934 (3) Åθ = 3.2–28.7°
c = 16.8355 (8) ŵ = 0.08 mm1
β = 104.087 (5)°T = 123 K
V = 1496.95 (12) Å3Block, colourless
Z = 40.43 × 0.35 × 0.30 mm
Data collection top
Agilent Xcalibur Ruby Gemini
diffractometer
3212 independent reflections
Radiation source: Enhance (Mo) X-ray Source2354 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.032
Detector resolution: 10.5081 pixels mm-1θmax = 28.8°, θmin = 3.2°
ω scansh = 1115
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2011)
k = 99
Tmin = 0.967, Tmax = 0.977l = 2217
6773 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)] = 0.051Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.115H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.0374P)2 + 0.6346P]
where P = (Fo2 + 2Fc2)/3
3212 reflections(Δ/σ)max = 0.001
213 parametersΔρmax = 0.24 e Å3
0 restraintsΔρmin = 0.25 e Å3
Crystal data top
C20H15N3V = 1496.95 (12) Å3
Mr = 297.35Z = 4
Monoclinic, P21/cMo Kα radiation
a = 12.0727 (6) ŵ = 0.08 mm1
b = 7.5934 (3) ÅT = 123 K
c = 16.8355 (8) Å0.43 × 0.35 × 0.30 mm
β = 104.087 (5)°
Data collection top
Agilent Xcalibur Ruby Gemini
diffractometer
3212 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2011)
2354 reflections with I > 2σ(I)
Tmin = 0.967, Tmax = 0.977Rint = 0.032
6773 measured reflectionsθmax = 28.8°
Refinement top
R[F2 > 2σ(F2)] = 0.051H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.115Δρmax = 0.24 e Å3
S = 1.03Δρmin = 0.25 e Å3
3212 reflectionsAbsolute structure: ?
213 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.02985 (12)1.03390 (19)0.21043 (9)0.0239 (4)
N20.00637 (13)1.1004 (2)0.13198 (9)0.0282 (5)
N100.20532 (12)0.85847 (19)0.37045 (9)0.0218 (5)
C30.08613 (15)1.1075 (2)0.10345 (11)0.0279 (6)
C3A0.18491 (15)1.0494 (2)0.16110 (10)0.0226 (5)
C40.30269 (15)1.0405 (3)0.16171 (11)0.0276 (6)
C50.37898 (16)0.9927 (3)0.23251 (11)0.0296 (6)
C5A0.33861 (14)0.9308 (2)0.30042 (11)0.0229 (5)
C5B0.39645 (14)0.8572 (2)0.37826 (10)0.0216 (5)
C60.51173 (15)0.8333 (2)0.41785 (11)0.0244 (5)
C70.54120 (15)0.7615 (2)0.49534 (11)0.0255 (5)
C80.45442 (16)0.7109 (2)0.53306 (11)0.0270 (6)
C90.33971 (15)0.7336 (2)0.49600 (11)0.0255 (6)
C9A0.31196 (14)0.8101 (2)0.41843 (10)0.0217 (5)
C10A0.22194 (14)0.9297 (2)0.29845 (10)0.0210 (5)
C10B0.14522 (14)1.0011 (2)0.22935 (10)0.0199 (5)
C110.04799 (14)1.0332 (2)0.26172 (11)0.0229 (5)
C120.01450 (16)1.0956 (2)0.34141 (11)0.0263 (5)
C130.09314 (17)1.0990 (3)0.38894 (12)0.0322 (6)
C140.20453 (17)1.0443 (3)0.35701 (13)0.0360 (7)
C150.23685 (17)0.9846 (3)0.27740 (13)0.0350 (7)
C160.15914 (15)0.9769 (2)0.22938 (12)0.0290 (6)
C170.66497 (15)0.7377 (3)0.54049 (12)0.0315 (6)
H30.086261.147320.049980.0334*
H40.327881.067290.113840.0331*
H50.458691.000540.236530.0355*
H60.569550.866510.391300.0292*
H80.475220.659130.585980.0324*
H90.282150.698470.522420.0306*
H100.1399 (17)0.809 (3)0.3743 (12)0.034 (6)*
H120.061461.135460.363040.0316*
H130.070561.139240.443950.0387*
H140.258361.047950.389800.0431*
H150.313470.948260.255320.0420*
H160.181510.933550.174870.0348*
H17A0.684180.612090.543270.0473*
H17B0.676870.785020.596090.0473*
H17C0.714010.800580.511360.0473*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0196 (7)0.0276 (8)0.0234 (8)0.0030 (7)0.0032 (6)0.0019 (6)
N20.0261 (8)0.0322 (9)0.0243 (8)0.0044 (7)0.0025 (7)0.0044 (7)
N100.0192 (8)0.0238 (8)0.0222 (8)0.0024 (7)0.0046 (7)0.0009 (6)
C30.0307 (10)0.0284 (10)0.0246 (10)0.0024 (9)0.0068 (8)0.0013 (8)
C3A0.0254 (9)0.0205 (9)0.0212 (9)0.0002 (8)0.0042 (8)0.0021 (7)
C40.0277 (10)0.0350 (11)0.0216 (9)0.0024 (9)0.0092 (8)0.0000 (8)
C50.0225 (9)0.0362 (11)0.0324 (11)0.0012 (9)0.0113 (9)0.0046 (9)
C5A0.0204 (9)0.0216 (9)0.0260 (10)0.0005 (8)0.0046 (8)0.0014 (7)
C5B0.0217 (9)0.0186 (8)0.0241 (9)0.0005 (8)0.0050 (8)0.0030 (7)
C60.0210 (9)0.0213 (9)0.0302 (10)0.0004 (8)0.0051 (8)0.0028 (8)
C70.0269 (9)0.0175 (9)0.0282 (10)0.0025 (8)0.0007 (8)0.0056 (7)
C80.0334 (10)0.0212 (9)0.0230 (10)0.0021 (8)0.0005 (8)0.0000 (8)
C90.0288 (10)0.0223 (9)0.0255 (10)0.0016 (8)0.0069 (8)0.0028 (8)
C9A0.0226 (9)0.0187 (9)0.0224 (9)0.0008 (8)0.0029 (8)0.0033 (7)
C10A0.0220 (9)0.0199 (9)0.0211 (9)0.0006 (7)0.0052 (8)0.0017 (7)
C10B0.0170 (9)0.0196 (9)0.0223 (9)0.0000 (7)0.0031 (7)0.0032 (7)
C110.0215 (9)0.0197 (9)0.0279 (10)0.0037 (8)0.0069 (8)0.0032 (8)
C120.0244 (9)0.0232 (9)0.0311 (10)0.0003 (8)0.0062 (8)0.0014 (8)
C130.0381 (11)0.0279 (10)0.0342 (11)0.0022 (9)0.0155 (9)0.0014 (9)
C140.0351 (11)0.0308 (11)0.0488 (13)0.0008 (9)0.0234 (10)0.0013 (10)
C150.0230 (10)0.0297 (10)0.0532 (14)0.0016 (9)0.0109 (10)0.0030 (10)
C160.0233 (10)0.0268 (10)0.0348 (11)0.0008 (8)0.0030 (8)0.0007 (8)
C170.0282 (10)0.0279 (10)0.0324 (11)0.0064 (9)0.0044 (9)0.0059 (8)
Geometric parameters (Å, º) top
N1—N21.382 (2)C10A—C10B1.407 (2)
N1—C10B1.374 (2)C11—C161.387 (3)
N1—C111.423 (2)C11—C121.387 (2)
N2—C31.320 (2)C12—C131.383 (3)
N10—C9A1.392 (2)C13—C141.385 (3)
N10—C10A1.386 (2)C14—C151.378 (3)
N10—H100.89 (2)C15—C161.381 (3)
C3—C3A1.413 (2)C3—H30.9500
C3A—C41.421 (3)C4—H40.9500
C3A—C10B1.397 (2)C5—H50.9500
C4—C51.366 (3)C6—H60.9500
C5—C5A1.427 (3)C8—H80.9500
C5A—C5B1.439 (2)C9—H90.9500
C5A—C10A1.401 (2)C12—H120.9500
C5B—C9A1.401 (2)C13—H130.9500
C5B—C61.401 (3)C14—H140.9500
C6—C71.378 (2)C15—H150.9500
C7—C81.404 (3)C16—H160.9500
C7—C171.513 (3)C17—H17A0.9800
C8—C91.384 (3)C17—H17B0.9800
C9—C9A1.394 (2)C17—H17C0.9800
N2—N1—C10B110.79 (14)C12—C11—C16120.75 (17)
N2—N1—C11118.65 (14)N1—C11—C16118.80 (16)
C10B—N1—C11129.85 (15)C11—C12—C13119.11 (18)
N1—N2—C3105.30 (15)C12—C13—C14120.56 (18)
C9A—N10—C10A107.47 (14)C13—C14—C15119.63 (19)
C9A—N10—H10123.9 (14)C14—C15—C16120.76 (19)
C10A—N10—H10123.2 (13)C11—C16—C15119.17 (18)
N2—C3—C3A112.63 (16)N2—C3—H3124.00
C4—C3A—C10B121.63 (16)C3A—C3—H3124.00
C3—C3A—C4134.09 (16)C3A—C4—H4121.00
C3—C3A—C10B104.23 (16)C5—C4—H4121.00
C3A—C4—C5118.68 (17)C4—C5—H5120.00
C4—C5—C5A119.82 (18)C5A—C5—H5120.00
C5B—C5A—C10A106.35 (15)C5B—C6—H6120.00
C5—C5A—C10A121.36 (16)C7—C6—H6120.00
C5—C5A—C5B132.27 (17)C7—C8—H8119.00
C5A—C5B—C6133.56 (16)C9—C8—H8119.00
C5A—C5B—C9A106.85 (15)C8—C9—H9121.00
C6—C5B—C9A119.55 (15)C9A—C9—H9121.00
C5B—C6—C7119.95 (17)C11—C12—H12120.00
C8—C7—C17119.62 (16)C13—C12—H12120.00
C6—C7—C8119.15 (17)C12—C13—H13120.00
C6—C7—C17121.23 (17)C14—C13—H13120.00
C7—C8—C9122.46 (16)C13—C14—H14120.00
C8—C9—C9A117.40 (16)C15—C14—H14120.00
N10—C9A—C9129.13 (16)C14—C15—H15120.00
N10—C9A—C5B109.38 (14)C16—C15—H15120.00
C5B—C9A—C9121.45 (16)C11—C16—H16120.00
C5A—C10A—C10B118.22 (15)C15—C16—H16120.00
N10—C10A—C10B131.84 (16)C7—C17—H17A109.00
N10—C10A—C5A109.90 (15)C7—C17—H17B109.00
N1—C10B—C3A107.04 (14)C7—C17—H17C109.00
N1—C10B—C10A133.44 (16)H17A—C17—H17B109.00
C3A—C10B—C10A119.50 (16)H17A—C17—H17C109.00
N1—C11—C12120.38 (16)H17B—C17—H17C109.00
C10B—N1—N2—C30.15 (18)C5—C5A—C10A—N10178.07 (16)
C11—N1—N2—C3171.43 (14)C5—C5A—C10A—C10B3.7 (2)
N2—N1—C10B—C3A0.50 (18)C5B—C5A—C10A—N100.41 (18)
N2—N1—C10B—C10A177.71 (17)C5B—C5A—C10A—C10B177.85 (14)
C11—N1—C10B—C3A169.53 (15)C5A—C5B—C6—C7178.06 (17)
C11—N1—C10B—C10A12.3 (3)C9A—C5B—C6—C70.9 (2)
N2—N1—C11—C12132.06 (16)C5A—C5B—C9A—N102.61 (18)
N2—N1—C11—C1644.9 (2)C5A—C5B—C9A—C9179.74 (14)
C10B—N1—C11—C1237.3 (2)C6—C5B—C9A—N10175.22 (14)
C10B—N1—C11—C16145.69 (17)C6—C5B—C9A—C92.4 (2)
N1—N2—C3—C3A0.76 (18)C5B—C6—C7—C80.9 (2)
C10A—N10—C9A—C5B2.37 (18)C5B—C6—C7—C17178.63 (16)
C10A—N10—C9A—C9179.78 (16)C6—C7—C8—C91.3 (2)
C9A—N10—C10A—C5A1.18 (18)C17—C7—C8—C9178.20 (16)
C9A—N10—C10A—C10B179.12 (16)C7—C8—C9—C9A0.1 (2)
N2—C3—C3A—C4176.18 (19)C8—C9—C9A—N10175.15 (16)
N2—C3—C3A—C10B1.05 (18)C8—C9—C9A—C5B2.0 (2)
C3—C3A—C4—C5173.19 (19)N10—C10A—C10B—N14.0 (3)
C10B—C3A—C4—C53.7 (3)N10—C10A—C10B—C3A174.02 (16)
C3—C3A—C10B—N10.89 (17)C5A—C10A—C10B—N1173.79 (17)
C3—C3A—C10B—C10A177.62 (14)C5A—C10A—C10B—C3A8.2 (2)
C4—C3A—C10B—N1176.78 (16)N1—C11—C12—C13177.78 (16)
C4—C3A—C10B—C10A4.7 (2)C16—C11—C12—C130.8 (2)
C3A—C4—C5—C5A8.2 (3)N1—C11—C16—C15176.60 (16)
C4—C5—C5A—C5B173.34 (19)C12—C11—C16—C150.4 (2)
C4—C5—C5A—C10A4.7 (3)C11—C12—C13—C141.3 (3)
C5—C5A—C5B—C66.2 (3)C12—C13—C14—C150.6 (3)
C5—C5A—C5B—C9A176.42 (19)C13—C14—C15—C160.7 (3)
C10A—C5A—C5B—C6175.56 (17)C14—C15—C16—C111.2 (3)
C10A—C5A—C5B—C9A1.83 (17)
Hydrogen-bond geometry (Å, º) top
Cg2 is the centroid of the N10/C10A/C5A/C5B/C9A pyrrole ring.
D—H···AD—HH···AD···AD—H···A
N10—H10···N2i0.89 (2)2.24 (2)3.092 (2)159 (2)
C17—H17B···Cg2ii0.982.703.401 (2)129
Symmetry codes: (i) x, y1/2, z+1/2; (ii) x+1, y+2, z+1.
Hydrogen-bond geometry (Å, º) top
Cg2 is the centroid of the N10/C10A/C5A/C5B/C9A pyrrole ring.
D—H···AD—HH···AD···AD—H···A
N10—H10···N2i0.89 (2)2.24 (2)3.092 (2)159 (2)
C17—H17B···Cg2ii0.982.703.401 (2)129
Symmetry codes: (i) x, y1/2, z+1/2; (ii) x+1, y+2, z+1.
Acknowledgements top

RJB acknowledges the NSF–MRI program (grant No. CHE0619278) for funds to purchase the X-ray diffractometer. SKG wishes to acknowledge the USIEF for the award of a Fulbright–Nehru Senior Research Fellowship.

references
References top

Agilent (2011). CrysAlis PRO. Agilent Technologies, Yarnton, England.

Archana, R., Prabakaran, K., Rajendra Prasad, K. J., Thiruvalluvar, A. & Butcher, R. J. (2010). Acta Cryst. E66, o3146.

Archana, R., Yamuna, E., Rajendra Prasad, K. J., Thiruvalluvar, A. & Butcher, R. J. (2011). Acta Cryst. E67, o1799.

Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Spek, A. L. (2009). Acta Cryst. D65, 148–155.