4-(4-Bromo-phen-yl)-4,5,6,7-tetra-hydro-3-methyl-6-oxo-1-phenyl-1H-pyrazolo[3,4-b]pyridine-5-carbonitrile ethanol solvate.

In the structure of the title compound, C(20)H(15)BrN(4)O·C(2)H(6)O, the hydrogenated pyridinone ring adopts an envelope conformation. The dihedral angle between the bromo-substituted phenyl ring and the pyrazole ring is 79.6 (1)°, and that between the non-substituted phenyl ring and the pyrazole ring is 51.2 (1)°. In the crystal structure, mol-ecules are linked via inter-molecular N-H⋯O and O-H⋯N hydrogen bonds. A short inter-molecular N⋯Br contact [3.213 (4) Å] is present in the crystal structure.

Related literature

For general background, see: Falcó et al. (2005 ▶); Kung & Wager (2007 ▶).

Experimental

Crystal data

C20H15BrN4O·C2H6O

M = 453.34

Monoclinic,

a = 21.871 (9) Å

b = 9.209 (4) Å

c = 10.552 (5) Å

β = 90.370 (5)°

V = 2125.4 (15) Å3

Z = 4

Mo Kα radiation

μ = 1.96 mm−1

T = 295 (2) K

0.31 × 0.24 × 0.14 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1997 ▶) T min = 0.586, T max = 0.770

10428 measured reflections

3947 independent reflections

2414 reflections with I > 2σ(I)

R int = 0.035

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.121

S = 1.01

3947 reflections

265 parameters

H-atom parameters constrained

Δρmax = 0.53 e Å−3

Δρmin = −0.51 e Å−3

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); 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, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808028638/xu2452sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808028638/xu2452Isup2.hkl

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

C20H15BrN4O·C2H6O	F(000) = 928
Mr = 453.34	Dx = 1.417 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2154 reflections
a = 21.871 (9) Å	θ = 2.4–22.3°
b = 9.209 (4) Å	µ = 1.96 mm−1
c = 10.552 (5) Å	T = 295 K
β = 90.370 (5)°	Block, colourless
V = 2125.4 (15) Å3	0.31 × 0.24 × 0.14 mm
Z = 4

Bruker SMART CCD area-detector diffractometer	3947 independent reflections
Radiation source: fine-focus sealed tube	2414 reflections with I > 2σ(I)
graphite	Rint = 0.035
φ and ω scans	θmax = 25.5°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −26→26
Tmin = 0.586, Tmax = 0.770	k = −11→9
10428 measured reflections	l = −12→12

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.121	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.0415P)2 + 1.3425P] where P = (Fo2 + 2Fc2)/3
3947 reflections	(Δ/σ)max = 0.001
265 parameters	Δρmax = 0.53 e Å−3
0 restraints	Δρmin = −0.51 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
Br1	0.449857 (19)	0.58567 (7)	0.18723 (5)	0.1023 (3)
O1	0.77687 (11)	0.8095 (2)	0.2363 (2)	0.0553 (6)
O2	0.83439 (11)	0.5202 (3)	0.0508 (2)	0.0558 (6)
H2	0.8220	0.4430	0.0218	0.084*
N1	0.77906 (13)	0.2474 (3)	0.4696 (2)	0.0478 (7)
N2	0.80852 (12)	0.3344 (3)	0.3832 (2)	0.0431 (6)
N3	0.79796 (12)	0.5800 (3)	0.2978 (2)	0.0434 (6)
H3D	0.8174	0.5606	0.2174	0.065*
N4	0.67632 (15)	0.9759 (4)	0.4375 (3)	0.0732 (9)
C1	0.73512 (15)	0.3303 (4)	0.5195 (3)	0.0442 (8)
C2	0.73547 (14)	0.4703 (3)	0.4646 (3)	0.0404 (7)
C3	0.69597 (14)	0.6023 (3)	0.4808 (3)	0.0414 (8)
H3	0.6870	0.6128	0.5712	0.050*
C4	0.73741 (14)	0.7328 (3)	0.4401 (3)	0.0407 (8)
H4	0.7688	0.7432	0.5061	0.049*
C5	0.77157 (14)	0.7129 (4)	0.3138 (3)	0.0418 (8)
C6	0.78163 (14)	0.4672 (3)	0.3795 (3)	0.0387 (7)
C7	0.70350 (16)	0.8703 (4)	0.4370 (3)	0.0487 (8)
C8	0.69393 (18)	0.2752 (4)	0.6197 (3)	0.0648 (10)
H8A	0.6546	0.2537	0.5833	0.097*
H8B	0.6895	0.3477	0.6843	0.097*
H8C	0.7110	0.1886	0.6561	0.097*
C9	0.63578 (14)	0.5971 (3)	0.4089 (3)	0.0426 (8)
C10	0.58214 (16)	0.6426 (4)	0.4648 (3)	0.0628 (10)
H10	0.5830	0.6750	0.5482	0.075*
C11	0.52737 (17)	0.6412 (5)	0.3997 (4)	0.0771 (13)
H11	0.4918	0.6721	0.4391	0.092*
C12	0.52561 (16)	0.5939 (4)	0.2764 (4)	0.0626 (10)
C13	0.57776 (16)	0.5502 (4)	0.2179 (3)	0.0661 (11)
H13	0.5765	0.5189	0.1341	0.079*
C14	0.63241 (16)	0.5528 (4)	0.2835 (3)	0.0586 (10)
H14	0.6680	0.5240	0.2427	0.070*
C15	0.85626 (15)	0.2756 (4)	0.3081 (3)	0.0456 (8)
C16	0.84675 (18)	0.1459 (4)	0.2460 (3)	0.0559 (9)
H16	0.8097	0.0969	0.2529	0.067*
C17	0.8936 (2)	0.0902 (5)	0.1732 (4)	0.0769 (13)
H17	0.8880	0.0026	0.1309	0.092*
C18	0.9477 (2)	0.1616 (6)	0.1624 (4)	0.0854 (14)
H18	0.9786	0.1231	0.1125	0.103*
C19	0.95680 (19)	0.2899 (6)	0.2249 (4)	0.0816 (13)
H19	0.9939	0.3384	0.2175	0.098*
C20	0.91114 (17)	0.3477 (4)	0.2990 (4)	0.0627 (10)
H20	0.9174	0.4344	0.3423	0.075*
C21	0.89214 (19)	0.5522 (5)	−0.0008 (4)	0.0750 (12)
H21A	0.8879	0.5692	−0.0911	0.090*
H21B	0.9192	0.4699	0.0114	0.090*
C22	0.9183 (3)	0.6785 (6)	0.0587 (6)	0.128 (2)
H22A	0.8972	0.7637	0.0298	0.192*
H22B	0.9607	0.6855	0.0371	0.192*
H22C	0.9144	0.6704	0.1490	0.192*

	U11	U22	U33	U12	U13	U23
Br1	0.0484 (3)	0.1630 (6)	0.0952 (4)	0.0022 (3)	−0.0134 (2)	−0.0219 (3)
O1	0.0811 (17)	0.0401 (14)	0.0446 (13)	−0.0010 (13)	0.0004 (11)	0.0073 (11)
O2	0.0628 (16)	0.0541 (16)	0.0508 (13)	−0.0062 (13)	0.0098 (11)	−0.0147 (12)
N1	0.0548 (17)	0.0385 (16)	0.0503 (16)	−0.0019 (14)	0.0086 (13)	0.0083 (13)
N2	0.0485 (16)	0.0365 (16)	0.0444 (14)	0.0022 (14)	0.0089 (12)	0.0029 (13)
N3	0.0540 (16)	0.0375 (16)	0.0387 (14)	0.0027 (13)	0.0093 (12)	0.0032 (12)
N4	0.065 (2)	0.049 (2)	0.105 (3)	0.0064 (18)	−0.0053 (18)	−0.0055 (19)
C1	0.0478 (19)	0.039 (2)	0.0458 (18)	−0.0049 (17)	0.0068 (15)	0.0041 (16)
C2	0.0456 (18)	0.039 (2)	0.0366 (16)	0.0001 (16)	0.0007 (14)	0.0015 (14)
C3	0.0476 (18)	0.042 (2)	0.0344 (15)	−0.0009 (16)	0.0043 (13)	−0.0030 (14)
C4	0.0491 (18)	0.0367 (19)	0.0364 (16)	0.0024 (16)	−0.0051 (14)	−0.0046 (14)
C5	0.0486 (19)	0.040 (2)	0.0371 (16)	−0.0037 (16)	−0.0039 (14)	0.0000 (16)
C6	0.0447 (18)	0.0332 (19)	0.0383 (16)	0.0012 (15)	0.0017 (14)	0.0015 (14)
C7	0.052 (2)	0.040 (2)	0.054 (2)	−0.0029 (18)	−0.0030 (16)	−0.0052 (16)
C8	0.074 (3)	0.053 (2)	0.068 (2)	−0.001 (2)	0.024 (2)	0.0119 (19)
C9	0.0445 (18)	0.0367 (19)	0.0466 (18)	0.0004 (15)	0.0051 (14)	−0.0050 (15)
C10	0.055 (2)	0.084 (3)	0.049 (2)	−0.001 (2)	0.0105 (17)	−0.0201 (19)
C11	0.043 (2)	0.117 (4)	0.072 (3)	0.004 (2)	0.0126 (19)	−0.022 (3)
C12	0.043 (2)	0.075 (3)	0.069 (2)	−0.001 (2)	−0.0050 (18)	−0.009 (2)
C13	0.054 (2)	0.087 (3)	0.057 (2)	0.005 (2)	−0.0018 (18)	−0.025 (2)
C14	0.047 (2)	0.073 (3)	0.056 (2)	0.0102 (19)	0.0020 (16)	−0.0236 (19)
C15	0.050 (2)	0.043 (2)	0.0433 (17)	0.0105 (17)	0.0019 (15)	0.0024 (16)
C16	0.071 (2)	0.046 (2)	0.051 (2)	0.0061 (19)	0.0051 (18)	−0.0011 (17)
C17	0.119 (4)	0.052 (3)	0.060 (2)	0.021 (3)	0.017 (2)	−0.004 (2)
C18	0.091 (4)	0.086 (4)	0.080 (3)	0.038 (3)	0.034 (3)	0.012 (3)
C19	0.054 (3)	0.093 (4)	0.098 (3)	0.008 (3)	0.017 (2)	0.007 (3)
C20	0.054 (2)	0.062 (3)	0.072 (2)	0.002 (2)	0.0058 (19)	−0.001 (2)
C21	0.071 (3)	0.079 (3)	0.075 (3)	−0.010 (2)	0.016 (2)	−0.015 (2)
C22	0.105 (4)	0.127 (5)	0.152 (5)	−0.062 (4)	0.036 (4)	−0.049 (4)

Br1—C12	1.901 (4)	C9—C14	1.386 (4)
O1—C5	1.215 (3)	C10—C11	1.377 (5)
O2—C21	1.409 (4)	C10—H10	0.9300
O2—H2	0.8200	C11—C12	1.373 (5)
N1—C1	1.338 (4)	C11—H11	0.9300
N1—N2	1.377 (3)	C12—C13	1.361 (5)
N2—C6	1.357 (4)	C13—C14	1.378 (5)
N2—C15	1.422 (4)	C13—H13	0.9300
N3—C5	1.364 (4)	C14—H14	0.9300
N3—C6	1.398 (4)	C15—C20	1.376 (5)
N3—H3D	0.9687	C15—C16	1.377 (5)
N4—C7	1.140 (4)	C16—C17	1.383 (5)
C1—C2	1.414 (4)	C16—H16	0.9300
C1—C8	1.482 (4)	C17—C18	1.359 (6)
C2—C6	1.356 (4)	C17—H17	0.9300
C2—C3	1.502 (4)	C18—C19	1.367 (6)
C3—C9	1.516 (4)	C18—H18	0.9300
C3—C4	1.567 (4)	C19—C20	1.379 (5)
C3—H3	0.9800	C19—H19	0.9300
C4—C7	1.468 (5)	C20—H20	0.9300
C4—C5	1.544 (4)	C21—C22	1.438 (6)
C4—H4	0.9800	C21—H21A	0.9700
C8—H8A	0.9600	C21—H21B	0.9700
C8—H8B	0.9600	C22—H22A	0.9600
C8—H8C	0.9600	C22—H22B	0.9600
C9—C10	1.381 (5)	C22—H22C	0.9600
C21—O2—H2	109.5	C9—C10—H10	119.2
C1—N1—N2	105.7 (2)	C12—C11—C10	119.6 (3)
C6—N2—N1	109.8 (2)	C12—C11—H11	120.2
C6—N2—C15	130.3 (3)	C10—C11—H11	120.2
N1—N2—C15	119.7 (3)	C13—C12—C11	120.4 (3)
C5—N3—C6	118.8 (3)	C13—C12—Br1	119.6 (3)
C5—N3—H3D	117.5	C11—C12—Br1	120.0 (3)
C6—N3—H3D	121.2	C12—C13—C14	119.6 (3)
N1—C1—C2	110.6 (3)	C12—C13—H13	120.2
N1—C1—C8	121.8 (3)	C14—C13—H13	120.2
C2—C1—C8	127.5 (3)	C13—C14—C9	121.7 (3)
C6—C2—C1	105.0 (3)	C13—C14—H14	119.1
C6—C2—C3	121.6 (3)	C9—C14—H14	119.1
C1—C2—C3	133.4 (3)	C20—C15—C16	121.0 (3)
C2—C3—C9	114.6 (3)	C20—C15—N2	120.0 (3)
C2—C3—C4	104.8 (2)	C16—C15—N2	119.1 (3)
C9—C3—C4	112.9 (2)	C15—C16—C17	118.4 (4)
C2—C3—H3	108.1	C15—C16—H16	120.8
C9—C3—H3	108.1	C17—C16—H16	120.8
C4—C3—H3	108.1	C18—C17—C16	121.0 (4)
C7—C4—C5	109.3 (3)	C18—C17—H17	119.5
C7—C4—C3	112.0 (3)	C16—C17—H17	119.5
C5—C4—C3	115.4 (2)	C17—C18—C19	120.1 (4)
C7—C4—H4	106.5	C17—C18—H18	119.9
C5—C4—H4	106.5	C19—C18—H18	119.9
C3—C4—H4	106.5	C18—C19—C20	120.2 (4)
O1—C5—N3	122.1 (3)	C18—C19—H19	119.9
O1—C5—C4	122.9 (3)	C20—C19—H19	119.9
N3—C5—C4	114.9 (3)	C15—C20—C19	119.3 (4)
C2—C6—N2	108.9 (3)	C15—C20—H20	120.4
C2—C6—N3	125.9 (3)	C19—C20—H20	120.4
N2—C6—N3	125.1 (3)	O2—C21—C22	110.8 (3)
N4—C7—C4	178.1 (4)	O2—C21—H21A	109.5
C1—C8—H8A	109.5	C22—C21—H21A	109.5
C1—C8—H8B	109.5	O2—C21—H21B	109.5
H8A—C8—H8B	109.5	C22—C21—H21B	109.5
C1—C8—H8C	109.5	H21A—C21—H21B	108.1
H8A—C8—H8C	109.5	C21—C22—H22A	109.5
H8B—C8—H8C	109.5	C21—C22—H22B	109.5
C10—C9—C14	117.1 (3)	H22A—C22—H22B	109.5
C10—C9—C3	121.0 (3)	C21—C22—H22C	109.5
C14—C9—C3	121.8 (3)	H22A—C22—H22C	109.5
C11—C10—C9	121.6 (3)	H22B—C22—H22C	109.5
C11—C10—H10	119.2
C1—N1—N2—C6	−1.3 (3)	C5—N3—C6—C2	9.3 (4)
C1—N1—N2—C15	−176.8 (3)	C5—N3—C6—N2	−172.9 (3)
N2—N1—C1—C2	0.7 (3)	C5—C4—C7—N4	168 (11)
N2—N1—C1—C8	−178.6 (3)	C3—C4—C7—N4	39 (12)
N1—C1—C2—C6	0.0 (3)	C2—C3—C9—C10	137.1 (3)
C8—C1—C2—C6	179.4 (3)	C4—C3—C9—C10	−103.1 (4)
N1—C1—C2—C3	177.5 (3)	C2—C3—C9—C14	−45.7 (4)
C8—C1—C2—C3	−3.1 (6)	C4—C3—C9—C14	74.2 (4)
C6—C2—C3—C9	97.3 (3)	C14—C9—C10—C11	1.3 (6)
C1—C2—C3—C9	−79.9 (4)	C3—C9—C10—C11	178.7 (4)
C6—C2—C3—C4	−27.0 (4)	C9—C10—C11—C12	−0.1 (7)
C1—C2—C3—C4	155.8 (3)	C10—C11—C12—C13	−0.8 (7)
C2—C3—C4—C7	173.7 (2)	C10—C11—C12—Br1	178.0 (3)
C9—C3—C4—C7	48.4 (3)	C11—C12—C13—C14	0.5 (6)
C2—C3—C4—C5	47.8 (3)	Br1—C12—C13—C14	−178.4 (3)
C9—C3—C4—C5	−77.5 (3)	C12—C13—C14—C9	0.8 (6)
C6—N3—C5—O1	−169.4 (3)	C10—C9—C14—C13	−1.7 (6)
C6—N3—C5—C4	13.4 (4)	C3—C9—C14—C13	−179.0 (3)
C7—C4—C5—O1	11.5 (4)	C6—N2—C15—C20	54.7 (5)
C3—C4—C5—O1	138.8 (3)	N1—N2—C15—C20	−130.8 (3)
C7—C4—C5—N3	−171.3 (3)	C6—N2—C15—C16	−125.7 (4)
C3—C4—C5—N3	−44.0 (4)	N1—N2—C15—C16	48.7 (4)
C1—C2—C6—N2	−0.8 (3)	C20—C15—C16—C17	−0.6 (5)
C3—C2—C6—N2	−178.7 (3)	N2—C15—C16—C17	179.9 (3)
C1—C2—C6—N3	177.2 (3)	C15—C16—C17—C18	−0.2 (6)
C3—C2—C6—N3	−0.6 (5)	C16—C17—C18—C19	0.6 (7)
N1—N2—C6—C2	1.3 (3)	C17—C18—C19—C20	−0.1 (7)
C15—N2—C6—C2	176.2 (3)	C16—C15—C20—C19	1.0 (5)
N1—N2—C6—N3	−176.7 (3)	N2—C15—C20—C19	−179.5 (3)
C15—N2—C6—N3	−1.8 (5)	C18—C19—C20—C15	−0.7 (6)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N1i	0.82	2.06	2.874 (4)	171.
N3—H3D···O2	0.97	1.84	2.786 (3)	166.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯N1i	0.82	2.06	2.874 (4)	171
N3—H3D⋯O2	0.97	1.84	2.786 (3)	166

Symmetry code: (i) .