Crystal structure of 3-{1-[(1-allyl-1H-indazol-6-yl)amino]-ethyl-idene}-6-methyl-2H-pyran-2,4(3H)-dione.

In the title compound, C18H17N3O3, the dihedral angle between the planes of the indazole ring system [maximum deviation = 0.012 (1) Å] and the pyran-2,4-dione ring is 54.03 (6)°. An intra-molecular N-H⋯O hydrogen bond closes an S(6) ring. The same H atom also participates in an inter-molecular N-H⋯O hydrogen bond, which generates an inversion dimer. The dimers are linked by weak C-H⋯O contacts, thereby forming a three-dimensional network.

Related literature

For pharmacological activities of indazole derivatives, see: Cerecetto et al. (2005 ▶); Jennings & Tennant (2007 ▶); Sun et al. (1997 ▶). For innovative methods in their synthesis, see: Paul et al. (2014 ▶).

Experimental

Crystal data

C18H17N3O3

M = 323.35

Triclinic,

a = 6.7708 (11) Å

b = 10.5761 (17) Å

c = 11.9643 (17) Å

α = 88.239 (9)°

β = 81.123 (9)°

γ = 79.140 (9)°

V = 831.3 (2) Å3

Z = 2

Mo Kα radiation

μ = 0.09 mm−1

T = 296 K

0.39 × 0.34 × 0.29 mm

Data collection

Bruker X8 APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.685, T max = 0.746

11752 measured reflections

3929 independent reflections

2930 reflections with I > 2σ(I)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.131

S = 1.04

3929 reflections

217 parameters

H-atom parameters constrained

Δρmax = 0.19 e Å−3

Δρmin = −0.19 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; 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 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶) and publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814024520/hb7311sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814024520/hb7311Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814024520/hb7311Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S1600536814024520/hb7311fig1.tif

Mol­ecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.

Click here for additional data file.

N A . DOI: 10.1107/S1600536814024520/hb7311fig2.tif

Partial crystal packing for the title compound showing N3—H3N⋯O3, C6—H6⋯O1 and C8—H8A⋯O1 hydrogen bonds as dashed lines.

CCDC reference: 1033266

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

C18H17N3O3	Z = 2
Mr = 323.35	F(000) = 340
Triclinic, P1	Dx = 1.292 Mg m−3
Hall symbol: -P 1	Melting point: 392 K
a = 6.7708 (11) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.5761 (17) Å	Cell parameters from 3929 reflections
c = 11.9643 (17) Å	θ = 2.6–27.9°
α = 88.239 (9)°	µ = 0.09 mm−1
β = 81.123 (9)°	T = 296 K
γ = 79.140 (9)°	Block, yellow
V = 831.3 (2) Å3	0.39 × 0.34 × 0.29 mm

Bruker X8 APEX CCD diffractometer	3929 independent reflections
Radiation source: fine-focus sealed tube	2930 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
φ and ω scans	θmax = 27.9°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −8→8
Tmin = 0.685, Tmax = 0.746	k = −12→13
11752 measured reflections	l = −15→15

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) = 0.131	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0634P)2 + 0.1441P] where P = (Fo2 + 2Fc2)/3
3929 reflections	(Δ/σ)max < 0.001
217 parameters	Δρmax = 0.19 e Å−3
0 restraints	Δρmin = −0.19 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
C1	−0.2126 (2)	0.27561 (17)	0.19077 (14)	0.0535 (4)
H1	−0.3315	0.2495	0.1792	0.064*
C2	−0.1187 (2)	0.24555 (13)	0.28909 (11)	0.0394 (3)
C3	−0.1571 (2)	0.17674 (15)	0.38933 (12)	0.0453 (4)
H3	−0.2704	0.1375	0.4040	0.054*
C4	−0.0230 (2)	0.16880 (14)	0.46546 (11)	0.0419 (3)
H4	−0.0454	0.1230	0.5324	0.050*
C5	0.14799 (19)	0.22876 (12)	0.44391 (10)	0.0327 (3)
C6	0.1916 (2)	0.29707 (12)	0.34631 (10)	0.0347 (3)
H6	0.3054	0.3358	0.3323	0.042*
C7	0.0533 (2)	0.30446 (12)	0.26930 (10)	0.0352 (3)
C8	0.2094 (3)	0.42381 (18)	0.10121 (14)	0.0664 (5)
H8A	0.2818	0.4594	0.1529	0.080*
H8B	0.1464	0.4943	0.0572	0.080*
C9	0.3587 (4)	0.3318 (3)	0.02309 (16)	0.0820 (7)
H9	0.4607	0.3652	−0.0227	0.098*
C10	0.3598 (3)	0.2112 (3)	0.01307 (18)	0.0866 (7)
H10A	0.2609	0.1733	0.0570	0.104*
H10B	0.4595	0.1616	−0.0382	0.104*
C11	0.3460 (2)	0.29146 (12)	0.58397 (10)	0.0349 (3)
C12	0.4993 (2)	0.24657 (12)	0.65330 (10)	0.0341 (3)
C13	0.5675 (2)	0.11088 (13)	0.66967 (10)	0.0359 (3)
C14	0.7230 (2)	0.07406 (14)	0.74087 (11)	0.0429 (3)
H14	0.7646	−0.0126	0.7568	0.051*
C15	0.8078 (2)	0.16072 (16)	0.78399 (12)	0.0474 (4)
C16	0.5936 (3)	0.33761 (15)	0.70210 (12)	0.0482 (4)
C17	0.2422 (3)	0.42837 (15)	0.57937 (16)	0.0671 (6)
H17A	0.1140	0.4326	0.5532	0.101*
H17B	0.3260	0.4753	0.5284	0.101*
H17C	0.2197	0.4655	0.6535	0.101*
C18	0.9761 (3)	0.1362 (2)	0.85373 (18)	0.0806 (6)
H18A	0.9316	0.1796	0.9250	0.121*
H18C	1.0918	0.1679	0.8145	0.121*
H18B	1.0133	0.0454	0.8665	0.121*
N1	0.0511 (2)	0.36448 (12)	0.16653 (10)	0.0472 (3)
N2	−0.1112 (2)	0.34456 (14)	0.11844 (11)	0.0574 (4)
N3	0.28794 (17)	0.20639 (10)	0.52426 (9)	0.0350 (3)
H3N	0.3443	0.1235	0.5379	0.042*
O1	0.5633 (3)	0.45366 (11)	0.69316 (13)	0.0832 (5)
O2	0.74794 (18)	0.28942 (11)	0.76619 (9)	0.0567 (3)
O3	0.50060 (18)	0.02513 (9)	0.62444 (9)	0.0538 (3)

	U11	U22	U33	U12	U13	U23
C1	0.0429 (9)	0.0691 (11)	0.0520 (9)	−0.0058 (8)	−0.0233 (7)	−0.0044 (8)
C2	0.0330 (7)	0.0437 (8)	0.0413 (7)	−0.0003 (6)	−0.0124 (5)	−0.0057 (6)
C3	0.0325 (7)	0.0595 (9)	0.0459 (8)	−0.0136 (6)	−0.0057 (6)	−0.0009 (7)
C4	0.0404 (8)	0.0494 (8)	0.0360 (7)	−0.0096 (6)	−0.0055 (6)	0.0045 (6)
C5	0.0351 (7)	0.0320 (6)	0.0313 (6)	−0.0016 (5)	−0.0108 (5)	−0.0025 (5)
C6	0.0392 (7)	0.0317 (6)	0.0362 (6)	−0.0083 (5)	−0.0128 (5)	0.0005 (5)
C7	0.0413 (7)	0.0306 (6)	0.0340 (6)	−0.0015 (5)	−0.0130 (5)	−0.0012 (5)
C8	0.1033 (15)	0.0663 (11)	0.0490 (9)	−0.0470 (11)	−0.0384 (10)	0.0265 (8)
C9	0.0885 (15)	0.130 (2)	0.0434 (9)	−0.0647 (15)	−0.0069 (10)	0.0047 (11)
C10	0.0708 (14)	0.125 (2)	0.0651 (12)	−0.0253 (14)	0.0001 (10)	−0.0205 (13)
C11	0.0409 (7)	0.0328 (7)	0.0307 (6)	−0.0022 (5)	−0.0090 (5)	−0.0023 (5)
C12	0.0401 (7)	0.0347 (7)	0.0288 (6)	−0.0061 (5)	−0.0099 (5)	−0.0020 (5)
C13	0.0405 (7)	0.0375 (7)	0.0298 (6)	−0.0037 (6)	−0.0102 (5)	−0.0011 (5)
C14	0.0483 (8)	0.0446 (8)	0.0344 (6)	0.0024 (6)	−0.0160 (6)	0.0005 (6)
C15	0.0472 (9)	0.0594 (9)	0.0366 (7)	−0.0040 (7)	−0.0163 (6)	−0.0006 (6)
C16	0.0641 (10)	0.0441 (8)	0.0438 (8)	−0.0155 (7)	−0.0247 (7)	0.0010 (6)
C17	0.0909 (14)	0.0388 (8)	0.0736 (11)	0.0151 (8)	−0.0484 (10)	−0.0163 (8)
C18	0.0723 (13)	0.1046 (16)	0.0736 (12)	−0.0078 (12)	−0.0479 (11)	−0.0039 (11)
N1	0.0629 (8)	0.0466 (7)	0.0385 (6)	−0.0134 (6)	−0.0258 (6)	0.0080 (5)
N2	0.0622 (9)	0.0659 (9)	0.0493 (7)	−0.0067 (7)	−0.0324 (7)	0.0040 (6)
N3	0.0408 (6)	0.0308 (5)	0.0347 (5)	−0.0014 (5)	−0.0159 (5)	0.0006 (4)
O1	0.1312 (13)	0.0405 (7)	0.1001 (10)	−0.0286 (7)	−0.0724 (10)	0.0073 (6)
O2	0.0669 (7)	0.0579 (7)	0.0567 (6)	−0.0191 (6)	−0.0349 (6)	−0.0013 (5)
O3	0.0747 (8)	0.0333 (5)	0.0610 (7)	−0.0055 (5)	−0.0394 (6)	−0.0006 (4)

C1—N2	1.311 (2)	C11—N3	1.3166 (16)
C1—C2	1.4215 (19)	C11—C12	1.4309 (18)
C1—H1	0.9300	C11—C17	1.4890 (19)
C2—C3	1.399 (2)	C12—C16	1.4339 (18)
C2—C7	1.407 (2)	C12—C13	1.4394 (18)
C3—C4	1.3723 (19)	C13—O3	1.2575 (16)
C3—H3	0.9300	C13—C14	1.4447 (18)
C4—C5	1.408 (2)	C14—C15	1.325 (2)
C4—H4	0.9300	C14—H14	0.9300
C5—C6	1.3765 (18)	C15—O2	1.3649 (19)
C5—N3	1.4355 (15)	C15—C18	1.494 (2)
C6—C7	1.4022 (17)	C16—O1	1.2099 (19)
C6—H6	0.9300	C16—O2	1.4010 (18)
C7—N1	1.3672 (17)	C17—H17A	0.9600
C8—N1	1.456 (2)	C17—H17B	0.9600
C8—C9	1.495 (3)	C17—H17C	0.9600
C8—H8A	0.9700	C18—H18A	0.9600
C8—H8B	0.9700	C18—H18C	0.9600
C9—C10	1.284 (3)	C18—H18B	0.9600
C9—H9	0.9300	N1—N2	1.3684 (18)
C10—H10A	0.9300	N3—H3N	0.9090
C10—H10B	0.9300
N2—C1—C2	111.83 (14)	C11—C12—C16	119.56 (12)
N2—C1—H1	124.1	C11—C12—C13	120.72 (11)
C2—C1—H1	124.1	C16—C12—C13	119.64 (12)
C3—C2—C7	119.78 (12)	O3—C13—C12	123.39 (12)
C3—C2—C1	136.29 (14)	O3—C13—C14	119.55 (12)
C7—C2—C1	103.93 (13)	C12—C13—C14	117.06 (12)
C4—C3—C2	118.11 (13)	C15—C14—C13	121.62 (13)
C4—C3—H3	120.9	C15—C14—H14	119.2
C2—C3—H3	120.9	C13—C14—H14	119.2
C3—C4—C5	121.11 (13)	C14—C15—O2	121.58 (13)
C3—C4—H4	119.4	C14—C15—C18	127.34 (16)
C5—C4—H4	119.4	O2—C15—C18	111.07 (14)
C6—C5—C4	122.61 (12)	O1—C16—O2	113.34 (13)
C6—C5—N3	120.24 (12)	O1—C16—C12	128.87 (14)
C4—C5—N3	116.93 (11)	O2—C16—C12	117.75 (13)
C5—C6—C7	115.68 (12)	C11—C17—H17A	109.5
C5—C6—H6	122.2	C11—C17—H17B	109.5
C7—C6—H6	122.2	H17A—C17—H17B	109.5
N1—C7—C6	130.43 (13)	C11—C17—H17C	109.5
N1—C7—C2	106.87 (12)	H17A—C17—H17C	109.5
C6—C7—C2	122.70 (12)	H17B—C17—H17C	109.5
N1—C8—C9	113.14 (15)	C15—C18—H18A	109.5
N1—C8—H8A	109.0	C15—C18—H18C	109.5
C9—C8—H8A	109.0	H18A—C18—H18C	109.5
N1—C8—H8B	109.0	C15—C18—H18B	109.5
C9—C8—H8B	109.0	H18A—C18—H18B	109.5
H8A—C8—H8B	107.8	H18C—C18—H18B	109.5
C10—C9—C8	126.33 (19)	C7—N1—N2	110.85 (13)
C10—C9—H9	116.8	C7—N1—C8	128.13 (13)
C8—C9—H9	116.8	N2—N1—C8	120.20 (12)
C9—C10—H10A	120.0	C1—N2—N1	106.50 (12)
C9—C10—H10B	120.0	C11—N3—C5	128.38 (11)
H10A—C10—H10B	120.0	C11—N3—H3N	113.9
N3—C11—C12	118.25 (11)	C5—N3—H3N	117.7
N3—C11—C17	118.15 (12)	C15—O2—C16	122.25 (11)
C12—C11—C17	123.55 (12)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···O3	0.91	1.77	2.5567 (15)	143
N3—H3N···O3i	0.91	2.51	3.0612 (16)	120
C6—H6···O1ii	0.93	2.54	3.3554 (19)	146
C8—H8A···O1ii	0.97	2.53	3.495 (2)	173

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N3H3NO3	0.91	1.77	2.5567(15)	143
N3H3NO3i	0.91	2.51	3.0612(16)	120
C6H6O1ii	0.93	2.54	3.3554(19)	146
C8H8AO1ii	0.97	2.53	3.495(2)	173

Symmetry codes: (i) ; (ii) .