Crystal structure of 13-(2-meth-oxy-phenyl)-3,4-di-hydro-2H-indazolo[1,2-b]phthalazine-1,6,11(13H)-trione.

In the title compound, C22H18N2O4, the three fused rings of the pyrazolo-phthalazine moiety are coplanar (r.m.s. deviation = 0.027 Å). The cyclo-hexene ring fused to the pyrazolidine ring, so forming the indazolophthalazine unit, has a half-chair conformation. The benzene ring is almost normal to the mean plane of the pyrazolo-phthalazine moiety, with a dihedral angle of 87.21 (6)° between their planes. In the crystal, mol-ecules are linked by pairs of C-H⋯O hydrogen bonds forming inversion dimers. The dimers are linked via C-H⋯π inter-actions, forming slabs parallel to (100). Between the slabs there are weak π-π inter-actions [shortest inter-centroid distance = 3.6664 (9) Å], leading to the formation of a three-dimensional structure.

Related literature

For the synthesis of phthalazine derivatives, see: Hasaninejed et al., (2012 ▸); Keshipour et al., (2012 ▸). For applications of this class of compounds, see: Soliman et al. (1981 ▸); Nomoto et al. (1990 ▸); Abd El-Wahab et al. (2013 ▸); Cashman & Ghirmai (2009 ▸); Hall et al. (1992 ▸, 2001 ▸). For the synthesis of the title compound, see: Khurana & Magoo (2009 ▸). For similar condensation reactions as used here, see: Atar et al. (2015 ▸). For the Cambridge Structural Database, see: Groom & Allen (2014 ▸).

Experimental

Crystal data

C22H18N2O4

M = 374.38

Monoclinic,

a = 8.5839 (2) Å

b = 11.8474 (2) Å

c = 17.5317 (4) Å

β = 102.199 (1)°

V = 1742.66 (6) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 295 K

0.15 × 0.11 × 0.08 mm

Data collection

Bruker APEXII diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2011 ▸) T min = 0.983, T max = 0.991

17655 measured reflections

5142 independent reflections

3865 reflections with I > 2σ(I)

R int = 0.02

Refinement

R[F 2 > 2σ(F 2)] = 0.056

wR(F 2) = 0.163

S = 1.03

5142 reflections

254 parameters

H-atom parameters constrained

Δρmax = 0.56 e Å−3

Δρmin = −0.41 e Å−3

Data collection: APEX2 (Bruker, 2011 ▸); cell refinement: SAINT (Bruker, 2011 ▸); data reduction: SAINT; program(s) used to solve structure: SIR2002 (Burla et al., 2005 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸) and DIAMOND (Brandenburg & Berndt, 2001 ▸); software used to prepare material for publication: WinGX (Farrugia, 2012 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015013894/su5175sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015013894/su5175Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015013894/su5175Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015013894/su5175fig1.tif

The mol­ecule structure of the title compound, showing the atom labelling. Displacement are drawn at the 50% probability level.

Click here for additional data file.

b . DOI: 10.1107/S2056989015013894/su5175fig2.tif

A view along the b axis of the crystal packing of the title compound.

CCDC reference: 1414255

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

C22H18N2O4	F(000) = 784
Mr = 374.38	Dx = 1.427 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7478 reflections
a = 8.5839 (2) Å	θ = 3.0–30.1°
b = 11.8474 (2) Å	µ = 0.10 mm−1
c = 17.5317 (4) Å	T = 295 K
β = 102.199 (1)°	Prism, colourless
V = 1742.66 (6) Å3	0.15 × 0.11 × 0.08 mm
Z = 4

Bruker APEXII diffractometer	5142 independent reflections
Radiation source: Enraf Nonius FR590	3865 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.02
CCD rotation images, thick slices scans	θmax = 30.2°, θmin = 3.4°
Absorption correction: multi-scan (SADABS; Bruker, 2011)	h = −11→12
Tmin = 0.983, Tmax = 0.991	k = −15→16
17655 measured reflections	l = −24→24

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.163	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0781P)2 + 0.6856P] where P = (Fo2 + 2Fc2)/3
5142 reflections	(Δ/σ)max < 0.001
254 parameters	Δρmax = 0.56 e Å−3
0 restraints	Δρmin = −0.41 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	0.74930 (19)	0.02215 (12)	0.50539 (9)	0.0359 (3)
C2	0.68942 (17)	−0.04887 (12)	0.56184 (8)	0.0337 (3)
C3	0.6996 (2)	−0.16641 (14)	0.55560 (10)	0.0430 (4)
H3	0.7435	−0.198	0.5163	0.052*
C4	0.6449 (2)	−0.23529 (15)	0.60752 (12)	0.0490 (4)
H4	0.6524	−0.3133	0.6034	0.059*
C5	0.5787 (2)	−0.18879 (16)	0.66597 (11)	0.0489 (4)
H5	0.5424	−0.2357	0.701	0.059*
C6	0.5665 (2)	−0.07285 (16)	0.67227 (10)	0.0447 (4)
H6	0.5217	−0.0421	0.7115	0.054*
C7	0.62115 (17)	−0.00193 (13)	0.61993 (9)	0.0341 (3)
C8	0.60256 (17)	0.12191 (13)	0.62625 (9)	0.0352 (3)
C9	0.65657 (17)	0.30813 (12)	0.56789 (8)	0.0320 (3)
H9	0.5459	0.3345	0.5569	0.038*
C10	0.72602 (18)	0.32444 (12)	0.49673 (8)	0.0333 (3)
C11	0.7440 (2)	0.43077 (15)	0.45874 (11)	0.0485 (4)
C12	0.8116 (5)	0.4197 (2)	0.38642 (18)	0.0957 (11)
H12A	0.7232	0.4177	0.3416	0.115*
H12B	0.8726	0.4873	0.3818	0.115*
C13	0.9104 (4)	0.3247 (2)	0.38186 (19)	0.0949 (11)
H13A	1.0142	0.3395	0.4148	0.114*
H13B	0.9251	0.3193	0.3286	0.114*
C14	0.8543 (2)	0.21095 (15)	0.40457 (10)	0.0430 (4)
H14A	0.782	0.1775	0.3603	0.052*
H14B	0.9448	0.1608	0.4201	0.052*
C15	0.77157 (17)	0.22582 (12)	0.47050 (8)	0.0320 (3)
C16	0.74875 (17)	0.36667 (12)	0.64012 (8)	0.0315 (3)
C17	0.67423 (19)	0.44961 (13)	0.67530 (9)	0.0382 (3)
H17	0.5667	0.4645	0.6562	0.046*
C18	0.7569 (2)	0.51077 (14)	0.73840 (10)	0.0435 (4)
H18	0.7055	0.5664	0.7612	0.052*
C19	0.9162 (2)	0.48835 (14)	0.76704 (9)	0.0422 (4)
H19	0.9725	0.5296	0.8091	0.051*
C20	0.9930 (2)	0.40511 (14)	0.73373 (9)	0.0402 (3)
H20	1.1001	0.3898	0.7538	0.048*
C21	0.90965 (19)	0.34405 (13)	0.67001 (9)	0.0350 (3)
C22	1.1419 (2)	0.25375 (17)	0.64403 (14)	0.0562 (5)
H22A	1.1802	0.3224	0.6253	0.084*
H22B	1.17	0.1909	0.6151	0.084*
H22C	1.1893	0.2443	0.6984	0.084*
N1	0.73260 (15)	0.13669 (10)	0.51526 (7)	0.0322 (3)
N2	0.65943 (15)	0.18347 (10)	0.57313 (7)	0.0331 (3)
O1	0.80755 (19)	−0.01451 (11)	0.45288 (8)	0.0575 (4)
O2	0.53946 (16)	0.16813 (11)	0.67456 (8)	0.0511 (3)
O3	0.7009 (2)	0.52090 (11)	0.48121 (10)	0.0660 (4)
O4	0.97523 (15)	0.25908 (12)	0.63425 (8)	0.0533 (4)

	U11	U22	U33	U12	U13	U23
C1	0.0434 (8)	0.0281 (7)	0.0371 (7)	−0.0015 (6)	0.0108 (6)	−0.0034 (5)
C2	0.0333 (7)	0.0295 (7)	0.0368 (7)	−0.0023 (5)	0.0038 (5)	0.0018 (5)
C3	0.0455 (9)	0.0316 (8)	0.0503 (9)	0.0000 (6)	0.0063 (7)	0.0012 (7)
C4	0.0474 (9)	0.0334 (8)	0.0614 (11)	−0.0041 (7)	0.0008 (8)	0.0097 (7)
C5	0.0398 (8)	0.0467 (10)	0.0576 (10)	−0.0079 (7)	0.0041 (7)	0.0190 (8)
C6	0.0393 (8)	0.0485 (10)	0.0479 (9)	−0.0041 (7)	0.0129 (7)	0.0096 (7)
C7	0.0293 (6)	0.0348 (7)	0.0378 (7)	−0.0027 (5)	0.0058 (5)	0.0040 (6)
C8	0.0335 (7)	0.0375 (8)	0.0365 (7)	−0.0027 (6)	0.0118 (5)	−0.0010 (6)
C9	0.0334 (7)	0.0283 (7)	0.0354 (7)	0.0020 (5)	0.0094 (5)	−0.0025 (5)
C10	0.0368 (7)	0.0303 (7)	0.0328 (6)	−0.0014 (6)	0.0075 (5)	0.0002 (5)
C11	0.0612 (11)	0.0334 (8)	0.0553 (10)	0.0031 (7)	0.0225 (8)	0.0080 (7)
C12	0.162 (3)	0.0495 (13)	0.105 (2)	0.0176 (16)	0.095 (2)	0.0275 (13)
C13	0.151 (3)	0.0484 (12)	0.118 (2)	0.0047 (15)	0.104 (2)	0.0130 (13)
C14	0.0528 (9)	0.0401 (8)	0.0422 (8)	−0.0032 (7)	0.0242 (7)	−0.0027 (7)
C15	0.0349 (7)	0.0310 (7)	0.0309 (6)	−0.0036 (5)	0.0087 (5)	−0.0010 (5)
C16	0.0368 (7)	0.0270 (6)	0.0323 (6)	0.0008 (5)	0.0107 (5)	−0.0015 (5)
C17	0.0401 (8)	0.0325 (7)	0.0451 (8)	0.0028 (6)	0.0161 (6)	−0.0045 (6)
C18	0.0539 (10)	0.0345 (8)	0.0467 (8)	0.0000 (7)	0.0210 (7)	−0.0113 (7)
C19	0.0536 (9)	0.0381 (8)	0.0366 (7)	−0.0072 (7)	0.0132 (7)	−0.0092 (6)
C20	0.0416 (8)	0.0416 (8)	0.0366 (7)	0.0011 (7)	0.0065 (6)	−0.0040 (6)
C21	0.0408 (8)	0.0312 (7)	0.0342 (7)	0.0049 (6)	0.0104 (6)	−0.0027 (5)
C22	0.0522 (10)	0.0382 (9)	0.0834 (14)	0.0091 (8)	0.0259 (10)	−0.0052 (9)
N1	0.0396 (6)	0.0275 (6)	0.0326 (6)	−0.0021 (5)	0.0145 (5)	−0.0036 (5)
N2	0.0398 (6)	0.0286 (6)	0.0346 (6)	−0.0010 (5)	0.0161 (5)	−0.0038 (5)
O1	0.0913 (10)	0.0349 (6)	0.0579 (8)	0.0002 (6)	0.0419 (7)	−0.0080 (6)
O2	0.0617 (8)	0.0472 (7)	0.0543 (7)	−0.0017 (6)	0.0349 (6)	−0.0038 (6)
O3	0.0920 (11)	0.0336 (7)	0.0801 (10)	0.0118 (7)	0.0353 (9)	0.0094 (6)
O4	0.0429 (6)	0.0565 (8)	0.0566 (7)	0.0165 (6)	0.0016 (5)	−0.0248 (6)

C1—O1	1.2168 (19)	C12—H12A	0.97
C1—N1	1.3794 (19)	C12—H12B	0.97
C1—C2	1.472 (2)	C13—C14	1.512 (3)
C2—C7	1.394 (2)	C13—H13A	0.97
C2—C3	1.401 (2)	C13—H13B	0.97
C3—C4	1.377 (2)	C14—C15	1.490 (2)
C3—H3	0.93	C14—H14A	0.97
C4—C5	1.387 (3)	C14—H14B	0.97
C4—H4	0.93	C15—N1	1.3977 (18)
C5—C6	1.384 (3)	C16—C17	1.386 (2)
C5—H5	0.93	C16—C21	1.396 (2)
C6—C7	1.396 (2)	C17—C18	1.386 (2)
C6—H6	0.93	C17—H17	0.93
C7—C8	1.483 (2)	C18—C19	1.379 (3)
C8—O2	1.2266 (18)	C18—H18	0.93
C8—N2	1.3526 (19)	C19—C20	1.382 (2)
C9—N2	1.4797 (19)	C19—H19	0.93
C9—C10	1.504 (2)	C20—C21	1.395 (2)
C9—C16	1.512 (2)	C20—H20	0.93
C9—H9	0.98	C21—O4	1.3684 (18)
C10—C15	1.344 (2)	C22—O4	1.406 (2)
C10—C11	1.448 (2)	C22—H22A	0.96
C11—O3	1.222 (2)	C22—H22B	0.96
C11—C12	1.507 (3)	C22—H22C	0.96
C12—C13	1.422 (4)	N1—N2	1.4143 (16)
O1—C1—N1	121.07 (14)	C14—C13—H13A	107.9
O1—C1—C2	124.22 (14)	C12—C13—H13B	107.9
N1—C1—C2	114.70 (13)	C14—C13—H13B	107.9
C7—C2—C3	119.78 (15)	H13A—C13—H13B	107.2
C7—C2—C1	121.59 (14)	C15—C14—C13	109.23 (15)
C3—C2—C1	118.63 (14)	C15—C14—H14A	109.8
C4—C3—C2	120.11 (17)	C13—C14—H14A	109.8
C4—C3—H3	119.9	C15—C14—H14B	109.8
C2—C3—H3	119.9	C13—C14—H14B	109.8
C3—C4—C5	120.23 (17)	H14A—C14—H14B	108.3
C3—C4—H4	119.9	C10—C15—N1	110.08 (12)
C5—C4—H4	119.9	C10—C15—C14	126.12 (14)
C6—C5—C4	120.21 (16)	N1—C15—C14	123.79 (13)
C6—C5—H5	119.9	C17—C16—C21	118.82 (14)
C4—C5—H5	119.9	C17—C16—C9	119.25 (13)
C5—C6—C7	120.20 (17)	C21—C16—C9	121.84 (12)
C5—C6—H6	119.9	C18—C17—C16	121.27 (15)
C7—C6—H6	119.9	C18—C17—H17	119.4
C2—C7—C6	119.45 (15)	C16—C17—H17	119.4
C2—C7—C8	121.20 (13)	C19—C18—C17	119.40 (14)
C6—C7—C8	119.34 (14)	C19—C18—H18	120.3
O2—C8—N2	120.73 (15)	C17—C18—H18	120.3
O2—C8—C7	124.31 (14)	C18—C19—C20	120.55 (15)
N2—C8—C7	114.96 (13)	C18—C19—H19	119.7
N2—C9—C10	100.10 (11)	C20—C19—H19	119.7
N2—C9—C16	114.01 (12)	C19—C20—C21	119.91 (15)
C10—C9—C16	113.99 (12)	C19—C20—H20	120
N2—C9—H9	109.5	C21—C20—H20	120
C10—C9—H9	109.5	O4—C21—C20	123.87 (14)
C16—C9—H9	109.5	O4—C21—C16	116.07 (13)
C15—C10—C11	122.13 (14)	C20—C21—C16	120.04 (14)
C15—C10—C9	111.54 (13)	O4—C22—H22A	109.5
C11—C10—C9	126.33 (14)	O4—C22—H22B	109.5
O3—C11—C10	122.89 (17)	H22A—C22—H22B	109.5
O3—C11—C12	122.94 (17)	O4—C22—H22C	109.5
C10—C11—C12	114.09 (16)	H22A—C22—H22C	109.5
C13—C12—C11	117.2 (2)	H22B—C22—H22C	109.5
C13—C12—H12A	108	C1—N1—C15	129.00 (12)
C11—C12—H12A	108	C1—N1—N2	123.30 (12)
C13—C12—H12B	108	C15—N1—N2	107.58 (11)
C11—C12—H12B	108	C8—N2—N1	124.21 (12)
H12A—C12—H12B	107.2	C8—N2—C9	125.25 (12)
C12—C13—C14	117.6 (2)	N1—N2—C9	110.53 (11)
C12—C13—H13A	107.9	C21—O4—C22	118.93 (14)
O1—C1—C2—C7	−178.79 (16)	N2—C9—C16—C17	−127.42 (14)
N1—C1—C2—C7	0.2 (2)	C10—C9—C16—C17	118.48 (15)
O1—C1—C2—C3	0.2 (2)	N2—C9—C16—C21	56.20 (18)
N1—C1—C2—C3	179.20 (14)	C10—C9—C16—C21	−57.90 (18)
C7—C2—C3—C4	−1.1 (2)	C21—C16—C17—C18	0.9 (2)
C1—C2—C3—C4	179.91 (15)	C9—C16—C17—C18	−175.63 (15)
C2—C3—C4—C5	0.3 (3)	C16—C17—C18—C19	−0.3 (3)
C3—C4—C5—C6	0.3 (3)	C17—C18—C19—C20	−0.5 (3)
C4—C5—C6—C7	−0.2 (3)	C18—C19—C20—C21	0.8 (3)
C3—C2—C7—C6	1.2 (2)	C19—C20—C21—O4	−178.87 (16)
C1—C2—C7—C6	−179.82 (14)	C19—C20—C21—C16	−0.2 (2)
C3—C2—C7—C8	−177.54 (14)	C17—C16—C21—O4	178.16 (14)
C1—C2—C7—C8	1.4 (2)	C9—C16—C21—O4	−5.4 (2)
C5—C6—C7—C2	−0.6 (2)	C17—C16—C21—C20	−0.6 (2)
C5—C6—C7—C8	178.20 (15)	C9—C16—C21—C20	175.82 (14)
C2—C7—C8—O2	177.83 (15)	O1—C1—N1—C15	1.5 (3)
C6—C7—C8—O2	−1.0 (2)	C2—C1—N1—C15	−177.53 (13)
C2—C7—C8—N2	−1.4 (2)	O1—C1—N1—N2	177.13 (15)
C6—C7—C8—N2	179.86 (14)	C2—C1—N1—N2	−1.9 (2)
N2—C9—C10—C15	−4.23 (16)	C10—C15—N1—C1	175.69 (15)
C16—C9—C10—C15	117.89 (14)	C14—C15—N1—C1	−5.3 (2)
N2—C9—C10—C11	175.59 (16)	C10—C15—N1—N2	−0.45 (16)
C16—C9—C10—C11	−62.3 (2)	C14—C15—N1—N2	178.51 (14)
C15—C10—C11—O3	178.88 (18)	O2—C8—N2—N1	−179.53 (14)
C9—C10—C11—O3	−0.9 (3)	C7—C8—N2—N1	−0.3 (2)
C15—C10—C11—C12	2.2 (3)	O2—C8—N2—C9	1.5 (2)
C9—C10—C11—C12	−177.6 (2)	C7—C8—N2—C9	−179.30 (13)
O3—C11—C12—C13	156.7 (3)	C1—N1—N2—C8	2.1 (2)
C10—C11—C12—C13	−26.6 (4)	C15—N1—N2—C8	178.49 (13)
C11—C12—C13—C14	45.2 (5)	C1—N1—N2—C9	−178.81 (13)
C12—C13—C14—C15	−35.9 (4)	C15—N1—N2—C9	−2.40 (15)
C11—C10—C15—N1	−176.72 (15)	C10—C9—N2—C8	−177.02 (14)
C9—C10—C15—N1	3.11 (17)	C16—C9—N2—C8	60.88 (19)
C11—C10—C15—C14	4.3 (3)	C10—C9—N2—N1	3.88 (14)
C9—C10—C15—C14	−175.83 (14)	C16—C9—N2—N1	−118.22 (13)
C13—C14—C15—C10	11.7 (3)	C20—C21—O4—C22	−20.5 (3)
C13—C14—C15—N1	−167.1 (2)	C16—C21—O4—C22	160.83 (16)

D—H···A	D—H	H···A	D···A	D—H···A
C22—H22B···O1i	0.96	2.43	3.379 (2)	168
C20—H20···Cg3ii	0.93	2.90	3.726 (2)	149

Table 1

Hydrogen-bond geometry (, )

Cg3 is the centroid of ring C2-C7.

DHA	DH	HA	D A	DHA
C22H22BO1i	0.96	2.43	3.379(2)	168
C20H20Cg3ii	0.93	2.90	3.726(2)	149

Symmetry codes: (i) ; (ii) .