9-(Thio-phen-2-yl)-8,9-dihydro-3H-pyrazolo-[4,3-f]quinolin-7(6H)-one ethanol monosolvate.

In the title compound, C(14)H(11)N(3)OS·C(2)H(5)OH, the dihedral angle between the pyridine N-C(fused)-C(fused)-C(thio-phene) plane and the plane of the thio-phene ring is 81.9 (3)°, indicating that they are close to perpendicular. The dihedral angle between this pyridine plane and the benzene ring is 1.3 (3)°. The thio-phene ring is disordered over two coplanar orientations with an occupancy ratio of 0.692 (7):0.308 (7), while the ethanol solvent mol-ecule is also disordered over two sets of site in a 0.66 (4):0.34 (4) ratio. In the crystal, chains are formed along the b axis by N-H⋯O and O-H⋯N inter-actions with adjacent chains being connected through C-H⋯N and C-H⋯S inter-actions.

Related literature

For background to the biological activity of quinolinone derivatives, see: Larsen et al. (1996 ▶); Chackal et al. (2002 ▶); Kalluraya & Sreenivasa (1998 ▶); Xu et al. (2000 ▶). For the synthesis of quinolino­nes, see: Suarez et al. (1999 ▶).

Experimental

Crystal data

C14H11N3OS·C2H6O

M = 315.39

Monoclinic,

a = 9.3831 (10) Å

b = 19.138 (2) Å

c = 8.7490 (9) Å

β = 99.412 (1)°

V = 1549.9 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.22 mm−1

T = 298 K

0.38 × 0.19 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.921, T max = 0.974

7663 measured reflections

2707 independent reflections

1526 reflections with I > 2σ(I)

R int = 0.041

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.154

S = 1.02

2707 reflections

248 parameters

?

Δρmax = 0.28 e Å−3

Δρmin = −0.26 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1999 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812033533/zq2174sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812033533/zq2174Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812033533/zq2174Isup3.cml

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

C14H11N3OS·C2H6O	F(000) = 664
Mr = 315.39	Dx = 1.352 Mg m−3
Monoclinic, P21/c	Melting point = 553–554 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 9.3831 (10) Å	Cell parameters from 1612 reflections
b = 19.138 (2) Å	θ = 2.4–25.1°
c = 8.7490 (9) Å	µ = 0.22 mm−1
β = 99.412 (1)°	T = 298 K
V = 1549.9 (3) Å3	Block, colourless
Z = 4	0.38 × 0.19 × 0.12 mm

Bruker SMART CCD area-detector diffractometer	2707 independent reflections
Radiation source: fine-focus sealed tube	1526 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
phi and ω scans	θmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→8
Tmin = 0.921, Tmax = 0.974	k = −19→22
7663 measured reflections	l = −10→10

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.154	w = 1/[σ2(Fo2) + (0.0595P)2 + 0.7752P] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max = 0.001
2707 reflections	Δρmax = 0.28 e Å−3
248 parameters	Δρmin = −0.26 e Å−3
0 restraints

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	Occ. (<1)
N1	0.4885 (3)	0.37278 (15)	0.4386 (3)	0.0564 (8)
H1	0.4232	0.4008	0.4606	0.068*
N2	0.6055 (4)	0.39328 (15)	0.3787 (3)	0.0602 (8)
N3	0.5568 (3)	0.08861 (13)	0.4727 (3)	0.0482 (7)
H3	0.5116	0.0647	0.5330	0.058*
O1	0.6492 (3)	−0.01035 (12)	0.3895 (3)	0.0661 (8)
O2	0.7049 (18)	0.5320 (7)	0.454 (2)	0.074 (3)	0.66 (4)
H2	0.6727	0.4921	0.4459	0.111*	0.66 (4)
S1	0.9693 (10)	0.2364 (5)	0.5804 (11)	0.0641 (12)	0.692 (7)
O2'	0.660 (4)	0.5360 (13)	0.388 (4)	0.074 (6)	0.34 (4)
H2'	0.6242	0.4973	0.3696	0.111*	0.34 (4)
C12'	0.969 (8)	0.219 (3)	0.588 (9)	0.064 (17)	0.308 (7)
H12'	0.9461	0.2658	0.5743	0.077*	0.308 (7)
C1	0.6784 (4)	0.33555 (18)	0.3592 (4)	0.0523 (9)
H1A	0.7642	0.3344	0.3190	0.063*
C2	0.6089 (3)	0.27598 (15)	0.4074 (3)	0.0414 (8)
C3	0.4862 (3)	0.30217 (17)	0.4600 (4)	0.0454 (8)
C4	0.3889 (4)	0.25971 (18)	0.5179 (4)	0.0519 (9)
H4	0.3085	0.2782	0.5529	0.062*
C5	0.4155 (3)	0.18913 (17)	0.5218 (4)	0.0478 (9)
H5	0.3522	0.1592	0.5609	0.057*
C6	0.5368 (3)	0.16138 (16)	0.4678 (4)	0.0400 (8)
C7	0.6358 (3)	0.20320 (16)	0.4120 (3)	0.0396 (8)
C8	0.7669 (3)	0.17000 (16)	0.3616 (4)	0.0437 (8)
H8	0.7972	0.1994	0.2809	0.052*
C9	0.7228 (4)	0.09839 (17)	0.2912 (4)	0.0509 (9)
H9A	0.6628	0.1052	0.1910	0.061*
H9B	0.8090	0.0736	0.2744	0.061*
C10	0.6422 (4)	0.05399 (18)	0.3891 (4)	0.0487 (9)
C11	0.8917 (3)	0.16488 (19)	0.4956 (4)	0.0466 (8)
C12	0.963 (4)	0.106 (2)	0.569 (4)	0.076 (10)	0.692 (7)
H12	0.9395	0.0605	0.5401	0.091*	0.692 (7)
S1'	0.962 (3)	0.0921 (16)	0.570 (3)	0.076 (3)	0.308 (7)
C13	1.0754 (5)	0.1238 (3)	0.6916 (6)	0.0920 (15)
H13	1.1337	0.0921	0.7536	0.110*
C14	1.0840 (4)	0.1937 (3)	0.7042 (5)	0.0813 (14)
H14	1.1510	0.2159	0.7785	0.098*
C15	0.749 (2)	0.5536 (8)	0.306 (3)	0.114 (5)	0.66 (4)
H15A	0.7454	0.5140	0.2359	0.137*	0.66 (4)
H15B	0.6848	0.5897	0.2562	0.137*	0.66 (4)
C16	0.896 (2)	0.5801 (13)	0.344 (3)	0.142 (6)	0.66 (4)
H16A	0.9040	0.6091	0.4347	0.213*	0.66 (4)
H16B	0.9190	0.6072	0.2589	0.213*	0.66 (4)
H16C	0.9621	0.5417	0.3639	0.213*	0.66 (4)
C15'	0.813 (5)	0.5334 (19)	0.378 (5)	0.114 (10)	0.34 (4)
H15C	0.8377	0.4902	0.3306	0.137*	0.34 (4)
H15D	0.8723	0.5385	0.4788	0.137*	0.34 (4)
C16'	0.827 (5)	0.595 (3)	0.276 (5)	0.142 (12)	0.34 (4)
H16D	0.7802	0.5855	0.1720	0.214*	0.34 (4)
H16E	0.9277	0.6047	0.2752	0.214*	0.34 (4)
H16F	0.7831	0.6354	0.3145	0.214*	0.34 (4)

	U11	U22	U33	U12	U13	U23
N1	0.0542 (19)	0.0485 (18)	0.065 (2)	0.0099 (15)	0.0051 (16)	0.0007 (15)
N2	0.072 (2)	0.0467 (18)	0.062 (2)	0.0014 (16)	0.0107 (17)	0.0047 (14)
N3	0.0484 (16)	0.0392 (16)	0.0604 (18)	−0.0001 (13)	0.0187 (14)	0.0006 (13)
O1	0.0662 (17)	0.0407 (15)	0.097 (2)	−0.0024 (12)	0.0311 (15)	−0.0068 (13)
O2	0.087 (7)	0.059 (3)	0.085 (8)	−0.006 (4)	0.041 (6)	0.000 (5)
S1	0.0519 (16)	0.067 (3)	0.0727 (19)	−0.0077 (14)	0.0084 (13)	−0.0134 (15)
O2'	0.087 (14)	0.059 (7)	0.085 (15)	−0.006 (8)	0.041 (11)	0.000 (9)
C12'	0.052 (16)	0.07 (4)	0.073 (18)	−0.008 (19)	0.008 (12)	−0.01 (2)
C1	0.059 (2)	0.045 (2)	0.053 (2)	0.0024 (18)	0.0121 (17)	0.0042 (17)
C2	0.0448 (19)	0.0381 (19)	0.0393 (18)	−0.0010 (15)	0.0010 (15)	0.0022 (14)
C3	0.043 (2)	0.043 (2)	0.048 (2)	0.0020 (16)	−0.0002 (16)	0.0005 (16)
C4	0.0376 (19)	0.056 (2)	0.061 (2)	0.0068 (17)	0.0045 (17)	−0.0076 (18)
C5	0.0383 (19)	0.050 (2)	0.056 (2)	−0.0058 (15)	0.0100 (16)	−0.0019 (16)
C6	0.0370 (17)	0.0382 (18)	0.0446 (19)	0.0009 (15)	0.0057 (15)	0.0011 (15)
C7	0.0387 (18)	0.0425 (19)	0.0369 (18)	0.0004 (15)	0.0043 (14)	0.0013 (14)
C8	0.0468 (19)	0.0450 (19)	0.0421 (19)	0.0006 (16)	0.0159 (15)	0.0040 (15)
C9	0.051 (2)	0.056 (2)	0.047 (2)	0.0009 (17)	0.0125 (17)	−0.0040 (16)
C10	0.045 (2)	0.047 (2)	0.053 (2)	−0.0033 (17)	0.0078 (17)	−0.0086 (17)
C11	0.0355 (17)	0.061 (2)	0.047 (2)	0.0016 (18)	0.0153 (15)	0.0003 (18)
C12	0.075 (10)	0.061 (19)	0.087 (11)	0.008 (9)	−0.002 (7)	0.001 (9)
S1'	0.075 (5)	0.061 (7)	0.087 (6)	0.008 (3)	−0.002 (4)	0.001 (3)
C13	0.063 (3)	0.125 (5)	0.084 (4)	0.026 (3)	0.001 (3)	0.018 (3)
C14	0.048 (3)	0.127 (4)	0.069 (3)	−0.014 (3)	0.008 (2)	−0.022 (3)
C15	0.108 (11)	0.121 (9)	0.110 (12)	−0.022 (8)	0.009 (10)	0.038 (8)
C16	0.101 (13)	0.188 (16)	0.144 (15)	−0.013 (11)	0.041 (10)	0.031 (11)
C15'	0.11 (2)	0.121 (18)	0.111 (19)	−0.021 (17)	0.009 (18)	0.038 (17)
C16'	0.10 (3)	0.19 (3)	0.14 (3)	−0.01 (2)	0.04 (2)	0.03 (2)

N1—N2	1.350 (4)	C7—C8	1.512 (4)
N1—C3	1.365 (4)	C8—C11	1.519 (4)
N1—H1	0.8600	C8—C9	1.531 (4)
N2—C1	1.325 (4)	C8—H8	0.9800
N3—C10	1.345 (4)	C9—C10	1.496 (5)
N3—C6	1.405 (4)	C9—H9A	0.9700
N3—H3	0.8600	C9—H9B	0.9700
O1—C10	1.233 (4)	C11—C12	1.41 (4)
O2—C15	1.48 (3)	C11—S1'	1.63 (3)
O2—H2	0.8200	C12—C13	1.41 (4)
S1—C14	1.618 (12)	C12—H12	0.9300
S1—C11	1.667 (10)	S1'—C13	1.50 (3)
O2'—C15'	1.45 (6)	C13—C14	1.343 (6)
O2'—H2'	0.8200	C13—H13	0.9300
C12'—C11	1.43 (6)	C14—H14	0.9300
C12'—C14	1.44 (7)	C15—C16	1.46 (4)
C12'—H12'	0.9300	C15—H15A	0.9700
C1—C2	1.412 (4)	C15—H15B	0.9700
C1—H1A	0.9300	C16—H16A	0.9600
C2—C3	1.400 (5)	C16—H16B	0.9600
C2—C7	1.415 (4)	C16—H16C	0.9600
C3—C4	1.379 (5)	C15'—C16'	1.51 (8)
C4—C5	1.373 (4)	C15'—H15C	0.9700
C4—H4	0.9300	C15'—H15D	0.9700
C5—C6	1.406 (4)	C16'—H16D	0.9600
C5—H5	0.9300	C16'—H16E	0.9600
C6—C7	1.375 (4)	C16'—H16F	0.9600
N2—N1—C3	111.9 (3)	H9A—C9—H9B	107.6
N2—N1—H1	124.1	O1—C10—N3	121.8 (3)
C3—N1—H1	124.1	O1—C10—C9	122.5 (3)
C1—N2—N1	106.1 (3)	N3—C10—C9	115.7 (3)
C10—N3—C6	124.1 (3)	C12—C11—C12'	99 (3)
C10—N3—H3	118.0	C12—C11—C8	130.9 (17)
C6—N3—H3	118.0	C12'—C11—C8	130 (3)
C15—O2—H2	109.5	C12'—C11—S1'	105 (3)
C14—S1—C11	94.4 (5)	C8—C11—S1'	125.1 (10)
C15'—O2'—H2'	109.5	C12—C11—S1	108.0 (18)
C11—C12'—C14	114 (4)	C8—C11—S1	121.1 (4)
C11—C12'—H12'	122.8	S1'—C11—S1	113.8 (10)
C14—C12'—H12'	122.8	C11—C12—C13	113 (3)
N2—C1—C2	111.2 (3)	C11—C12—H12	123.3
N2—C1—H1A	124.4	C13—C12—H12	123.3
C2—C1—H1A	124.4	C13—S1'—C11	97.5 (17)
C3—C2—C1	104.7 (3)	C14—C13—C12	109.0 (16)
C3—C2—C7	119.7 (3)	C14—C13—S1'	119.1 (12)
C1—C2—C7	135.6 (3)	C14—C13—H13	125.5
N1—C3—C4	131.3 (3)	C12—C13—H13	125.5
N1—C3—C2	106.1 (3)	S1'—C13—H13	115.4
C4—C3—C2	122.6 (3)	C13—C14—C12'	104 (2)
C5—C4—C3	117.4 (3)	C13—C14—S1	115.1 (5)
C5—C4—H4	121.3	C13—C14—H14	122.4
C3—C4—H4	121.3	C12'—C14—H14	133.3
C4—C5—C6	121.1 (3)	S1—C14—H14	122.4
C4—C5—H5	119.4	C16—C15—O2	106 (3)
C6—C5—H5	119.4	C16—C15—H15A	110.4
C7—C6—N3	119.6 (3)	O2—C15—H15A	110.4
C7—C6—C5	122.1 (3)	C16—C15—H15B	110.4
N3—C6—C5	118.4 (3)	O2—C15—H15B	110.4
C6—C7—C2	117.1 (3)	H15A—C15—H15B	108.6
C6—C7—C8	119.2 (3)	O2'—C15'—C16'	101 (6)
C2—C7—C8	123.7 (3)	O2'—C15'—H15C	111.5
C7—C8—C11	111.3 (3)	C16'—C15'—H15C	111.5
C7—C8—C9	108.3 (3)	O2'—C15'—H15D	111.5
C11—C8—C9	112.1 (3)	C16'—C15'—H15D	111.5
C7—C8—H8	108.4	H15C—C15'—H15D	109.3
C11—C8—H8	108.4	C15'—C16'—H16D	109.5
C9—C8—H8	108.4	C15'—C16'—H16E	109.5
C10—C9—C8	114.0 (3)	H16D—C16'—H16E	109.5
C10—C9—H9A	108.8	C15'—C16'—H16F	109.5
C8—C9—H9A	108.8	H16D—C16'—H16F	109.5
C10—C9—H9B	108.8	H16E—C16'—H16F	109.5
C8—C9—H9B	108.8
C3—N1—N2—C1	0.9 (4)	C14—C12'—C11—C8	−179 (2)
N1—N2—C1—C2	−0.2 (4)	C14—C12'—C11—S1'	4 (5)
N2—C1—C2—C3	−0.4 (4)	C14—C12'—C11—S1	−163 (25)
N2—C1—C2—C7	179.4 (3)	C7—C8—C11—C12	116 (2)
N2—N1—C3—C4	179.6 (3)	C9—C8—C11—C12	−5 (2)
N2—N1—C3—C2	−1.2 (3)	C7—C8—C11—C12'	−61 (4)
C1—C2—C3—N1	0.9 (3)	C9—C8—C11—C12'	177 (4)
C7—C2—C3—N1	−178.9 (3)	C7—C8—C11—S1'	115.6 (12)
C1—C2—C3—C4	−179.8 (3)	C9—C8—C11—S1'	−5.9 (12)
C7—C2—C3—C4	0.3 (5)	C7—C8—C11—S1	−64.4 (5)
N1—C3—C4—C5	178.6 (3)	C9—C8—C11—S1	174.2 (5)
C2—C3—C4—C5	−0.5 (5)	C14—S1—C11—C12	−1.0 (18)
C3—C4—C5—C6	−0.4 (5)	C14—S1—C11—C12'	14 (20)
C10—N3—C6—C7	−19.3 (4)	C14—S1—C11—C8	179.7 (3)
C10—N3—C6—C5	161.2 (3)	C14—S1—C11—S1'	−0.3 (12)
C4—C5—C6—C7	1.5 (5)	C12'—C11—C12—C13	−1 (4)
C4—C5—C6—N3	−179.0 (3)	C8—C11—C12—C13	−179.7 (11)
N3—C6—C7—C2	179.0 (3)	S1'—C11—C12—C13	−173 (28)
C5—C6—C7—C2	−1.5 (4)	S1—C11—C12—C13	1 (3)
N3—C6—C7—C8	−1.9 (4)	C12—C11—S1'—C13	7 (24)
C5—C6—C7—C8	177.6 (3)	C12'—C11—S1'—C13	−3 (3)
C3—C2—C7—C6	0.6 (4)	C8—C11—S1'—C13	179.8 (6)
C1—C2—C7—C6	−179.2 (3)	S1—C11—S1'—C13	−0.2 (17)
C3—C2—C7—C8	−178.5 (3)	C11—C12—C13—C14	−1 (3)
C1—C2—C7—C8	1.7 (5)	C11—C12—C13—S1'	175 (17)
C6—C7—C8—C11	−89.4 (3)	C11—S1'—C13—C14	0.8 (17)
C2—C7—C8—C11	89.7 (3)	C11—S1'—C13—C12	−4 (14)
C6—C7—C8—C9	34.2 (4)	C12—C13—C14—C12'	2 (4)
C2—C7—C8—C9	−146.7 (3)	S1'—C13—C14—C12'	1 (3)
C7—C8—C9—C10	−49.2 (4)	C12—C13—C14—S1	−0.3 (18)
C11—C8—C9—C10	74.0 (4)	S1'—C13—C14—S1	−1.1 (14)
C6—N3—C10—O1	−175.2 (3)	C11—C12'—C14—C13	−3 (5)
C6—N3—C10—C9	2.4 (4)	C11—C12'—C14—S1	165 (21)
C8—C9—C10—O1	−149.4 (3)	C11—S1—C14—C13	0.8 (7)
C8—C9—C10—N3	33.0 (4)	C11—S1—C14—C12'	−12 (17)
C14—C12'—C11—C12	3 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2i	0.86	1.99	2.838 (16)	170
N3—H3···O1ii	0.86	2.04	2.863 (4)	160
O2—H2···N2	0.82	2.05	2.855 (14)	167
C8—H8···S1iii	0.98	2.86	3.802 (6)	162
C9—H9A···N1iii	0.97	2.56	3.529 (7)	175

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2i	0.86	1.99	2.838 (16)	170
N3—H3⋯O1ii	0.86	2.04	2.863 (4)	160
O2—H2⋯N2	0.82	2.05	2.855 (14)	167
C8—H8⋯S1iii	0.98	2.86	3.802 (6)	162
C9—H9A⋯N1iii	0.97	2.56	3.529 (7)	175

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