Crystal structure of 3-methyl-1-phenyl-5-(1H-pyrrol-1-yl)-1H-pyrazole-4-carbaldehyde.

In the title compound, C15H13N3O, the pyrrolyl and phenyl rings make dihedral angles of 58.99 (5) and 34.95 (5)°, respectively, with the central pyrazole ring. In the crystal, weak, pairwise C-H⋯O inter-actions across centers of symmetry form dimers, which are further associated into corrugated sheets running approximately parallel to (100) via weak C-H⋯N inter-actions.

Related literature

For the biological activity of pyrazoline-containing compounds see: Nauduri & Reddy (1998 ▶); Korgaokar et al. (1996 ▶); Taylor & Patel (1992 ▶); Ozdemir et al. (2007 ▶); Ruhoğlu et al. (2005 ▶); Palaska et al. (2001 ▶); Rajendra Prasad et al. (2005 ▶); Udupi et al. (1998 ▶). For synthetic and industrial applications of pyrazolo­[3,4-b]pyrazines see: Rangnekar & Dhamnaskar (1990 ▶); Kopp et al. (2001 ▶); Farghaly & El-Kashef (2005 ▶).

Experimental

Crystal data

C15H13N3O

M = 251.28

Monoclinic,

a = 9.5807 (8) Å

b = 15.1720 (13) Å

c = 8.7370 (8) Å

β = 93.6180 (11)°

V = 1267.46 (19) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 150 K

0.29 × 0.17 × 0.04 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2014 ▶) T min = 0.98, T max = 1.00

26282 measured reflections

3321 independent reflections

2527 reflections with I > 2σ(I)

R int = 0.053

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.114

S = 1.07

3321 reflections

173 parameters

H-atom parameters constrained

Δρmax = 0.31 e Å−3

Δρmin = −0.25 e Å−3

Data collection: APEX2 (Bruker, 2014 ▶); cell refinement: SAINT (Bruker, 2014 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXT (Bruker, 2014 ▶); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2012 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814020984/sj5428sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814020984/sj5428Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814020984/sj5428Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S1600536814020984/sj5428fig1.tif

Perspective view of the title mol­ecule with labeling scheme and 50% probability ellipsoids for non-H atoms.

Click here for additional data file.

c . DOI: 10.1107/S1600536814020984/sj5428fig2.tif

Packing viewed down the c axis showing an edge view of one corrugated sheet with hydrogen bonds drawn as red and blue dashed lines.

Click here for additional data file.

a . DOI: 10.1107/S1600536814020984/sj5428fig3.tif

Packing viewed down the a axis showing the C—H⋯O and C—H⋯N inter­actions as red and blue dashed lines, respectively.

CCDC reference: 1025251

Additional supporting information: crystallographic information; 3D view; checkCIF report

C15H13N3O	F(000) = 528
Mr = 251.28	Dx = 1.317 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.5807 (8) Å	Cell parameters from 6992 reflections
b = 15.1720 (13) Å	θ = 2.5–29.1°
c = 8.7370 (8) Å	µ = 0.09 mm−1
β = 93.6180 (11)°	T = 150 K
V = 1267.46 (19) Å3	Plate, colourless
Z = 4	0.29 × 0.17 × 0.04 mm

Bruker SMART APEX CCD diffractometer	3321 independent reflections
Radiation source: fine-focus sealed tube	2527 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.053
Detector resolution: 8.3660 pixels mm-1	θmax = 29.2°, θmin = 2.1°
φ and ω scans	h = −13→13
Absorption correction: multi-scan (SADABS; Bruker, 2014)	k = −20→20
Tmin = 0.98, Tmax = 1.00	l = −11→11
26282 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) = 0.114	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0533P)2 + 0.2193P] where P = (Fo2 + 2Fc2)/3
3321 reflections	(Δ/σ)max < 0.001
173 parameters	Δρmax = 0.31 e Å−3
0 restraints	Δρmin = −0.25 e Å−3

Experimental. The diffraction data were collected in three sets of400 frames (0.5° width in ω) at φ = 0, 120and 240°. A scan time of 80 sec/frame was used.

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

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR andgoodness of fit S are based on F2, conventional R-factors R are basedon F, with F set to zero for negative F2. The threshold expression ofF2 > σ(F2) is used only for calculating R-factors(gt) etc. and isnot relevant to the choice of reflections for refinement. R-factors basedon F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. H-atoms attached to carbonwere placed in calculated positions (C—H = 0.95 - 0.98 Å). All wereincluded as riding contributions with isotropic displacement parameters1.2 - 1.5 times those of the attached atoms.

	x	y	z	Uiso*/Ueq
O1	0.33317 (10)	0.54403 (7)	0.91467 (11)	0.0336 (2)
N1	0.59037 (11)	0.76421 (7)	0.80193 (12)	0.0234 (2)
N2	0.67710 (11)	0.71108 (7)	0.72255 (12)	0.0211 (2)
N3	0.70035 (11)	0.55911 (6)	0.64732 (12)	0.0210 (2)
C1	0.63304 (13)	0.62637 (8)	0.72276 (14)	0.0208 (3)
C2	0.51547 (13)	0.62272 (8)	0.80704 (14)	0.0217 (3)
C3	0.49451 (13)	0.71148 (8)	0.85367 (14)	0.0230 (3)
C4	0.38179 (14)	0.74728 (10)	0.94605 (16)	0.0306 (3)
H4A	0.3977	0.8103	0.9644	0.046*
H4B	0.3827	0.7162	1.0445	0.046*
H4C	0.2909	0.7388	0.8901	0.046*
C5	0.43357 (14)	0.54534 (9)	0.83563 (15)	0.0253 (3)
H5	0.4597	0.4916	0.7896	0.030*
C6	0.79899 (13)	0.74965 (8)	0.66330 (14)	0.0206 (3)
C7	0.92330 (13)	0.70303 (8)	0.66282 (14)	0.0242 (3)
H7	0.9285	0.6441	0.6997	0.029*
C8	1.03977 (14)	0.74327 (9)	0.60798 (15)	0.0269 (3)
H8	1.1251	0.7115	0.6063	0.032*
C9	1.03304 (14)	0.82956 (9)	0.55550 (15)	0.0276 (3)
H9	1.1131	0.8567	0.5172	0.033*
C10	0.90846 (15)	0.87586 (9)	0.55948 (15)	0.0276 (3)
H10	0.9040	0.9354	0.5256	0.033*
C11	0.79111 (13)	0.83644 (8)	0.61199 (15)	0.0240 (3)
H11	0.7057	0.8682	0.6132	0.029*
C12	0.76608 (14)	0.48753 (8)	0.71948 (15)	0.0250 (3)
H12	0.7625	0.4720	0.8245	0.030*
C13	0.83647 (15)	0.44366 (9)	0.61277 (15)	0.0288 (3)
H13	0.8913	0.3920	0.6299	0.035*
C14	0.81336 (14)	0.48874 (9)	0.47146 (15)	0.0276 (3)
H14	0.8493	0.4722	0.3767	0.033*
C15	0.73103 (14)	0.55959 (8)	0.49470 (14)	0.0240 (3)
H15	0.7001	0.6018	0.4198	0.029*

	U11	U22	U33	U12	U13	U23
O1	0.0322 (5)	0.0361 (6)	0.0335 (5)	−0.0085 (4)	0.0099 (4)	0.0015 (4)
N1	0.0209 (5)	0.0216 (5)	0.0282 (6)	0.0022 (4)	0.0048 (4)	−0.0046 (4)
N2	0.0209 (5)	0.0177 (5)	0.0251 (5)	0.0001 (4)	0.0044 (4)	−0.0023 (4)
N3	0.0249 (5)	0.0171 (5)	0.0214 (5)	0.0011 (4)	0.0038 (4)	−0.0007 (4)
C1	0.0233 (6)	0.0172 (6)	0.0216 (6)	−0.0004 (5)	0.0002 (5)	−0.0002 (4)
C2	0.0217 (6)	0.0222 (6)	0.0211 (6)	−0.0005 (5)	0.0012 (5)	−0.0007 (5)
C3	0.0214 (6)	0.0242 (6)	0.0232 (6)	0.0006 (5)	0.0007 (5)	−0.0024 (5)
C4	0.0258 (7)	0.0327 (7)	0.0341 (7)	0.0010 (6)	0.0071 (6)	−0.0065 (6)
C5	0.0274 (6)	0.0254 (6)	0.0229 (6)	−0.0033 (5)	0.0008 (5)	0.0006 (5)
C6	0.0218 (6)	0.0197 (6)	0.0204 (6)	−0.0025 (5)	0.0033 (5)	−0.0022 (5)
C7	0.0249 (6)	0.0208 (6)	0.0270 (6)	0.0007 (5)	0.0028 (5)	−0.0009 (5)
C8	0.0234 (6)	0.0277 (7)	0.0299 (7)	−0.0003 (5)	0.0044 (5)	−0.0049 (5)
C9	0.0279 (7)	0.0279 (7)	0.0275 (7)	−0.0077 (5)	0.0067 (5)	−0.0042 (5)
C10	0.0331 (7)	0.0214 (6)	0.0284 (7)	−0.0041 (5)	0.0026 (5)	0.0005 (5)
C11	0.0253 (6)	0.0192 (6)	0.0272 (6)	0.0010 (5)	0.0005 (5)	−0.0011 (5)
C12	0.0315 (7)	0.0184 (6)	0.0250 (6)	0.0016 (5)	0.0002 (5)	0.0021 (5)
C13	0.0342 (7)	0.0209 (6)	0.0313 (7)	0.0062 (5)	0.0012 (6)	−0.0015 (5)
C14	0.0318 (7)	0.0276 (7)	0.0238 (6)	0.0024 (5)	0.0043 (5)	−0.0041 (5)
C15	0.0294 (7)	0.0234 (6)	0.0195 (6)	0.0012 (5)	0.0028 (5)	0.0002 (5)

O1—C5	1.2191 (16)	C6—C11	1.3915 (17)
N1—C3	1.3191 (16)	C7—C8	1.3838 (18)
N1—N2	1.3762 (14)	C7—H7	0.9500
N2—C1	1.3529 (15)	C8—C9	1.3873 (19)
N2—C6	1.4319 (15)	C8—H8	0.9500
N3—C15	1.3835 (16)	C9—C10	1.3873 (19)
N3—C12	1.3869 (16)	C9—H9	0.9500
N3—C1	1.3946 (15)	C10—C11	1.3775 (18)
C1—C2	1.3852 (17)	C10—H10	0.9500
C2—C3	1.4248 (17)	C11—H11	0.9500
C2—C5	1.4427 (17)	C12—C13	1.3589 (19)
C3—C4	1.4909 (17)	C12—H12	0.9500
C4—H4A	0.9800	C13—C14	1.4165 (19)
C4—H4B	0.9800	C13—H13	0.9500
C4—H4C	0.9800	C14—C15	1.3562 (18)
C5—H5	0.9500	C14—H14	0.9500
C6—C7	1.3854 (17)	C15—H15	0.9500
C3—N1—N2	105.85 (10)	C8—C7—C6	119.21 (12)
C1—N2—N1	110.94 (10)	C8—C7—H7	120.4
C1—N2—C6	130.57 (10)	C6—C7—H7	120.4
N1—N2—C6	118.36 (10)	C7—C8—C9	120.60 (12)
C15—N3—C12	108.92 (10)	C7—C8—H8	119.7
C15—N3—C1	125.76 (10)	C9—C8—H8	119.7
C12—N3—C1	124.63 (10)	C10—C9—C8	119.45 (12)
N2—C1—C2	107.63 (10)	C10—C9—H9	120.3
N2—C1—N3	122.74 (11)	C8—C9—H9	120.3
C2—C1—N3	129.63 (11)	C11—C10—C9	120.67 (12)
C1—C2—C3	104.38 (11)	C11—C10—H10	119.7
C1—C2—C5	126.44 (11)	C9—C10—H10	119.7
C3—C2—C5	129.17 (12)	C10—C11—C6	119.30 (12)
N1—C3—C2	111.19 (11)	C10—C11—H11	120.4
N1—C3—C4	120.56 (11)	C6—C11—H11	120.4
C2—C3—C4	128.25 (12)	C13—C12—N3	107.60 (11)
C3—C4—H4A	109.5	C13—C12—H12	126.2
C3—C4—H4B	109.5	N3—C12—H12	126.2
H4A—C4—H4B	109.5	C12—C13—C14	107.73 (12)
C3—C4—H4C	109.5	C12—C13—H13	126.1
H4A—C4—H4C	109.5	C14—C13—H13	126.1
H4B—C4—H4C	109.5	C15—C14—C13	108.21 (12)
O1—C5—C2	124.65 (12)	C15—C14—H14	125.9
O1—C5—H5	117.7	C13—C14—H14	125.9
C2—C5—H5	117.7	C14—C15—N3	107.53 (11)
C7—C6—C11	120.75 (11)	C14—C15—H15	126.2
C7—C6—N2	120.88 (11)	N3—C15—H15	126.2
C11—C6—N2	118.31 (11)
C3—N1—N2—C1	1.28 (13)	C3—C2—C5—O1	−4.1 (2)
C3—N1—N2—C6	−174.98 (10)	C1—N2—C6—C7	−32.38 (19)
N1—N2—C1—C2	−1.18 (13)	N1—N2—C6—C7	143.01 (12)
C6—N2—C1—C2	174.49 (11)	C1—N2—C6—C11	150.22 (13)
N1—N2—C1—N3	178.45 (10)	N1—N2—C6—C11	−34.39 (16)
C6—N2—C1—N3	−5.88 (19)	C11—C6—C7—C8	−1.13 (19)
C15—N3—C1—N2	−53.33 (18)	N2—C6—C7—C8	−178.47 (11)
C12—N3—C1—N2	116.10 (14)	C6—C7—C8—C9	0.68 (19)
C15—N3—C1—C2	126.21 (14)	C7—C8—C9—C10	0.54 (19)
C12—N3—C1—C2	−64.36 (19)	C8—C9—C10—C11	−1.3 (2)
N2—C1—C2—C3	0.59 (13)	C9—C10—C11—C6	0.87 (19)
N3—C1—C2—C3	−179.00 (12)	C7—C6—C11—C10	0.37 (19)
N2—C1—C2—C5	179.33 (11)	N2—C6—C11—C10	177.77 (11)
N3—C1—C2—C5	−0.3 (2)	C15—N3—C12—C13	−0.26 (15)
N2—N1—C3—C2	−0.88 (14)	C1—N3—C12—C13	−171.20 (11)
N2—N1—C3—C4	−179.99 (11)	N3—C12—C13—C14	−0.27 (15)
C1—C2—C3—N1	0.20 (14)	C12—C13—C14—C15	0.71 (16)
C5—C2—C3—N1	−178.50 (12)	C13—C14—C15—N3	−0.86 (15)
C1—C2—C3—C4	179.21 (12)	C12—N3—C15—C14	0.70 (15)
C5—C2—C3—C4	0.5 (2)	C1—N3—C15—C14	171.52 (12)
C1—C2—C5—O1	177.49 (13)

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15···N1i	0.95	2.48	3.3931 (17)	161
C12—H12···O1ii	0.95	2.52	3.4255 (17)	159

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C15—H15⋯N1i	0.95	2.48	3.3931 (17)	161
C12—H12⋯O1ii	0.95	2.52	3.4255 (17)	159

Symmetry codes: (i) ; (ii) .