6-Amino-3,4-dimethyl-4-phenyl-2H,4H-pyrano[2,3-c]pyrazole-5-carbonitrile.

In the title compound, C(15)H(14)N(4)O, the pyrazole ring is aligned at 88.23 (4)° with respect to the aromatic ring and at 3.75 (4)° with respect to the pyran ring. In the crystal, N-H⋯N hydrogen bonds link adjacent mol-ecules into a linear chain motif. C-H⋯N inter-actions are also observed.

Related literature

For the synthesis, see: Vasuki & Kumaravel (2008 ▶). For the use of related compounds in organic synthesis, see: Liang et al. (2009 ▶). For related structures, see: Kannan et al. (2010 ▶).

Experimental

Crystal data

C15H14N4O

M = 266.3

Triclinic,

a = 6.682 (5) Å

b = 9.347 (5) Å

c = 11.078 (5) Å

α = 99.213 (5)°

β = 102.740 (5)°

γ = 97.767 (5)°

V = 655.6 (7) Å3

Z = 2

Mo Kα radiation

μ = 0.09 mm−1

T = 293 K

0.22 × 0.20 × 0.16 mm

Data collection

Bruker APEXII Kappa CCD detector diffractometer

18424 measured reflections

4996 independent reflections

3169 reflections with I > 2σ(I)

R int = 0.036

Refinement

R[F 2 > 2σ(F 2)] = 0.057

wR(F 2) = 0.173

S = 0.99

4996 reflections

183 parameters

H-atom parameters constrained

Δρmax = 0.30 e Å−3

Δρmin = −0.29 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811009354/ng5120sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811009354/ng5120Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C15H14N4O	Z = 2
Mr = 266.3	F(000) = 280
Triclinic, P1	Dx = 1.349 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71069 Å
a = 6.682 (5) Å	Cell parameters from 4350 reflections
b = 9.347 (5) Å	θ = 1.9–33.3°
c = 11.078 (5) Å	µ = 0.09 mm−1
α = 99.213 (5)°	T = 293 K
β = 102.740 (5)°	Prism, colourless
γ = 97.767 (5)°	0.22 × 0.20 × 0.16 mm
V = 655.6 (7) Å3

Bruker APEXII Kappa CCD-detector diffractometer	3169 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.036
graphite	θmax = 33.3°, θmin = 1.9°
Detector resolution: 0 pixels mm-1	h = −10→9
ω and φ scans	k = −14→14
18424 measured reflections	l = −17→16
4996 independent reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.173	H-atom parameters constrained
S = 0.99	w = 1/[σ2(Fo2) + (0.0847P)2 + 0.1309P] where P = (Fo2 + 2Fc2)/3
4996 reflections	(Δ/σ)max = 0.014
183 parameters	Δρmax = 0.30 e Å−3
0 restraints	Δρmin = −0.29 e Å−3

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

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 > σ(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.

	x	y	z	Uiso*/Ueq
O1	0.22065 (13)	0.57205 (11)	0.58851 (9)	0.0380 (2)
C2	0.52515 (18)	0.74174 (14)	0.57658 (11)	0.0306 (3)
N1	0.23543 (18)	0.67259 (14)	0.41251 (11)	0.0406 (3)
C6	0.64969 (18)	0.74989 (14)	0.70869 (12)	0.0304 (2)
C5	0.52503 (19)	0.63581 (14)	0.76101 (12)	0.0315 (3)
C7	0.6205 (2)	0.60943 (15)	0.88018 (13)	0.0377 (3)
C4	0.32984 (19)	0.55767 (14)	0.70373 (12)	0.0315 (3)
C3	0.32497 (19)	0.66098 (15)	0.52808 (12)	0.0320 (3)
C8	0.6664 (2)	0.90474 (14)	0.78630 (12)	0.0332 (3)
N3	0.21879 (18)	0.45814 (14)	0.74817 (12)	0.0439 (3)
H3A	0.0968	0.4142	0.7044	0.053*
H3B	0.2692	0.4379	0.8206	0.053*
N2	0.38757 (19)	0.76374 (15)	0.38430 (11)	0.0432 (3)
H2	0.3736	0.7912	0.3129	0.052*
N4	0.7004 (2)	0.59058 (17)	0.97741 (14)	0.0571 (4)
C1	0.5621 (2)	0.80702 (16)	0.47848 (13)	0.0376 (3)
C14	0.8640 (2)	0.70915 (18)	0.70847 (16)	0.0438 (3)
H14A	0.8467	0.6116	0.6599	0.066*
H14B	0.9397	0.7124	0.7936	0.066*
H14C	0.9401	0.7779	0.6718	0.066*
C13	0.4882 (2)	0.95084 (17)	0.81184 (15)	0.0442 (3)
H13	0.3617	0.8859	0.7841	0.053*
C9	0.8513 (3)	1.00406 (18)	0.82993 (17)	0.0517 (4)
H9	0.9738	0.9768	0.8150	0.062*
C10	0.8558 (3)	1.1452 (2)	0.89631 (18)	0.0639 (5)
H10	0.9817	1.2109	0.9251	0.077*
C15	0.7477 (3)	0.9053 (2)	0.46603 (16)	0.0536 (4)
H15A	0.8448	0.8469	0.4411	0.080*
H15B	0.8130	0.9701	0.5456	0.080*
H15C	0.7051	0.9625	0.4033	0.080*
C12	0.4943 (3)	1.0905 (2)	0.87732 (17)	0.0568 (4)
H12	0.3727	1.1186	0.8930	0.068*
C11	0.6797 (4)	1.18818 (19)	0.91953 (16)	0.0595 (5)
H11	0.6843	1.2826	0.9635	0.071*

	U11	U22	U33	U12	U13	U23
O1	0.0256 (4)	0.0500 (6)	0.0318 (5)	−0.0082 (4)	−0.0019 (3)	0.0142 (4)
C2	0.0260 (5)	0.0314 (6)	0.0302 (6)	−0.0015 (4)	0.0032 (4)	0.0049 (4)
N1	0.0346 (6)	0.0480 (7)	0.0319 (6)	−0.0072 (5)	−0.0007 (4)	0.0116 (5)
C6	0.0233 (5)	0.0309 (6)	0.0322 (6)	−0.0011 (4)	0.0012 (4)	0.0056 (4)
C5	0.0272 (5)	0.0296 (6)	0.0320 (6)	−0.0019 (4)	−0.0014 (4)	0.0073 (5)
C7	0.0308 (6)	0.0350 (7)	0.0397 (7)	−0.0061 (5)	−0.0026 (5)	0.0109 (5)
C4	0.0266 (5)	0.0338 (6)	0.0303 (6)	0.0004 (4)	0.0013 (4)	0.0072 (5)
C3	0.0273 (5)	0.0362 (6)	0.0290 (6)	−0.0015 (4)	0.0029 (4)	0.0073 (5)
C8	0.0330 (6)	0.0318 (6)	0.0286 (6)	−0.0033 (5)	−0.0005 (5)	0.0066 (5)
N3	0.0331 (6)	0.0509 (7)	0.0396 (6)	−0.0111 (5)	−0.0038 (5)	0.0191 (5)
N2	0.0415 (6)	0.0517 (7)	0.0308 (6)	−0.0082 (5)	0.0030 (5)	0.0144 (5)
N4	0.0472 (7)	0.0635 (9)	0.0477 (8)	−0.0143 (6)	−0.0114 (6)	0.0260 (7)
C1	0.0327 (6)	0.0407 (7)	0.0352 (7)	−0.0031 (5)	0.0057 (5)	0.0075 (5)
C14	0.0271 (6)	0.0477 (8)	0.0529 (9)	0.0045 (5)	0.0052 (6)	0.0076 (7)
C13	0.0464 (8)	0.0385 (8)	0.0450 (8)	0.0025 (6)	0.0122 (6)	0.0034 (6)
C9	0.0384 (7)	0.0422 (8)	0.0600 (10)	−0.0085 (6)	−0.0025 (7)	0.0016 (7)
C10	0.0682 (12)	0.0430 (9)	0.0577 (11)	−0.0165 (8)	−0.0087 (9)	−0.0007 (8)
C15	0.0450 (8)	0.0609 (10)	0.0498 (9)	−0.0142 (7)	0.0090 (7)	0.0193 (8)
C12	0.0746 (12)	0.0457 (9)	0.0514 (10)	0.0136 (8)	0.0213 (9)	0.0032 (7)
C11	0.0922 (14)	0.0371 (8)	0.0405 (8)	0.0039 (9)	0.0083 (9)	−0.0001 (6)

O1—C4	1.3602 (16)	N2—C1	1.3465 (19)
O1—C3	1.3611 (16)	N2—H2	0.8600
C2—C1	1.3799 (19)	C1—C15	1.486 (2)
C2—C3	1.3885 (18)	C14—H14A	0.9600
C2—C6	1.5001 (18)	C14—H14B	0.9600
N1—C3	1.3164 (17)	C14—H14C	0.9600
N1—N2	1.3595 (17)	C13—C12	1.379 (2)
C6—C5	1.5289 (18)	C13—H13	0.9300
C6—C14	1.531 (2)	C9—C10	1.397 (3)
C6—C8	1.5369 (19)	C9—H9	0.9300
C5—C4	1.3661 (18)	C10—C11	1.357 (3)
C5—C7	1.4091 (19)	C10—H10	0.9300
C7—N4	1.1440 (19)	C15—H15A	0.9600
C4—N3	1.3340 (17)	C15—H15B	0.9600
C8—C9	1.380 (2)	C15—H15C	0.9600
C8—C13	1.390 (2)	C12—C11	1.374 (3)
N3—H3A	0.8600	C12—H12	0.9300
N3—H3B	0.8600	C11—H11	0.9300
C4—O1—C3	115.59 (10)	N2—C1—C2	106.17 (12)
C1—C2—C3	103.33 (11)	N2—C1—C15	122.22 (14)
C1—C2—C6	133.30 (11)	C2—C1—C15	131.61 (13)
C3—C2—C6	123.33 (11)	C6—C14—H14A	109.5
C3—N1—N2	101.74 (11)	C6—C14—H14B	109.5
C2—C6—C5	105.36 (10)	H14A—C14—H14B	109.5
C2—C6—C14	110.78 (11)	C6—C14—H14C	109.5
C5—C6—C14	109.28 (12)	H14A—C14—H14C	109.5
C2—C6—C8	109.09 (10)	H14B—C14—H14C	109.5
C5—C6—C8	109.98 (11)	C12—C13—C8	121.64 (15)
C14—C6—C8	112.12 (10)	C12—C13—H13	119.2
C4—C5—C7	116.92 (12)	C8—C13—H13	119.2
C4—C5—C6	126.31 (11)	C8—C9—C10	120.50 (17)
C7—C5—C6	116.77 (11)	C8—C9—H9	119.8
N4—C7—C5	178.69 (15)	C10—C9—H9	119.8
N3—C4—O1	110.00 (11)	C11—C10—C9	121.11 (17)
N3—C4—C5	127.07 (12)	C11—C10—H10	119.4
O1—C4—C5	122.93 (12)	C9—C10—H10	119.4
N1—C3—O1	119.33 (11)	C1—C15—H15A	109.5
N1—C3—C2	114.94 (12)	C1—C15—H15B	109.5
O1—C3—C2	125.71 (12)	H15A—C15—H15B	109.5
C9—C8—C13	117.40 (14)	C1—C15—H15C	109.5
C9—C8—C6	123.01 (13)	H15A—C15—H15C	109.5
C13—C8—C6	119.57 (11)	H15B—C15—H15C	109.5
C4—N3—H3A	120.0	C11—C12—C13	120.16 (18)
C4—N3—H3B	120.0	C11—C12—H12	119.9
H3A—N3—H3B	120.0	C13—C12—H12	119.9
C1—N2—N1	113.80 (12)	C10—C11—C12	119.19 (17)
C1—N2—H2	123.1	C10—C11—H11	120.4
N1—N2—H2	123.1	C12—C11—H11	120.4
C1—C2—C6—C5	−173.79 (14)	C6—C2—C3—N1	176.69 (12)
C3—C2—C6—C5	8.91 (17)	C1—C2—C3—O1	177.46 (13)
C1—C2—C6—C14	−55.7 (2)	C6—C2—C3—O1	−4.6 (2)
C3—C2—C6—C14	126.98 (14)	C2—C6—C8—C9	−111.80 (15)
C1—C2—C6—C8	68.17 (18)	C5—C6—C8—C9	133.10 (14)
C3—C2—C6—C8	−109.13 (14)	C14—C6—C8—C9	11.29 (19)
C2—C6—C5—C4	−7.33 (18)	C2—C6—C8—C13	66.30 (15)
C14—C6—C5—C4	−126.40 (15)	C5—C6—C8—C13	−48.80 (16)
C8—C6—C5—C4	110.12 (15)	C14—C6—C8—C13	−170.61 (13)
C2—C6—C5—C7	173.06 (12)	C3—N1—N2—C1	−0.42 (17)
C14—C6—C5—C7	53.99 (16)	N1—N2—C1—C2	−0.34 (18)
C8—C6—C5—C7	−69.50 (15)	N1—N2—C1—C15	179.23 (15)
C4—C5—C7—N4	−158 (8)	C3—C2—C1—N2	0.91 (15)
C6—C5—C7—N4	21 (8)	C6—C2—C1—N2	−176.77 (14)
C3—O1—C4—N3	−174.36 (12)	C3—C2—C1—C15	−178.61 (17)
C3—O1—C4—C5	5.24 (19)	C6—C2—C1—C15	3.7 (3)
C7—C5—C4—N3	−0.2 (2)	C9—C8—C13—C12	0.5 (2)
C6—C5—C4—N3	−179.80 (13)	C6—C8—C13—C12	−177.74 (14)
C7—C5—C4—O1	−179.72 (12)	C13—C8—C9—C10	−0.4 (2)
C6—C5—C4—O1	0.7 (2)	C6—C8—C9—C10	177.75 (15)
N2—N1—C3—O1	−177.77 (12)	C8—C9—C10—C11	0.0 (3)
N2—N1—C3—C2	1.06 (17)	C8—C13—C12—C11	−0.2 (3)
C4—O1—C3—N1	175.29 (12)	C9—C10—C11—C12	0.3 (3)
C4—O1—C3—C2	−3.4 (2)	C13—C12—C11—C10	−0.2 (3)
C1—C2—C3—N1	−1.29 (17)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N1i	0.86	2.27	3.129 (2)	173
N3—H3B···N4ii	0.86	2.26	3.087 (2)	160
C10—H10···N4iii	0.93	2.53	3.455 (3)	172
C14—H14A···N1iv	0.96	2.59	3.522 (3)	163

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯N1i	0.86	2.27	3.129 (2)	173
N3—H3B⋯N4ii	0.86	2.26	3.087 (2)	160
C10—H10⋯N4iii	0.93	2.53	3.455 (3)	172
C14—H14A⋯N1iv	0.96	2.59	3.522 (3)	163

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .