Crystal structure of (4Z)-4-{[(2-chloro-phen-yl)amino](furan-2-yl)methyl-idene}-3-methyl-1-phenyl-4,5-di-hydro-1H-pyrazol-5-one.

In the title compound, C21H16ClN3O2, the pyrazolone ring and the O=C-C=C-N mean plane [maximum deviation = 0.022 (2) Å] are nearly coplanar, making a dihedral angle 4.56 (8)°, while the phenyl and pyrazole rings subtend a dihedral angle of 19.75 (8)°. The compound is in the enamine-keto form and its structure is stabilized by an intra-molecular N-H⋯O hydrogen bond. In the crystal, mol-ecules are linked via C-H⋯N hydrogen bonds, forming chains along [010]. Between the chains there are π-π inter-actions [inter-centroid distances = 3.3902 (9) and 3.5956 (11) Å], linking the chains to form sheets parallel to (10-1).

Related literature

For details of the synthesis of 4-heterocyclic acylpyrazolones, see: Jensen (1959 ▸); Dong et al. (1983 ▸). For applications of 4-pyrazolo­nes, see: Casas et al. (2007 ▸). For the anti­bacterial activity of pyrazolone derivatives, see: Li et al. (2000 ▸); Zhang et al. (2008 ▸); Raman et al. (2001 ▸). For related structures, see: Zhang et al. (2007 ▸); Li et al. (2009 ▸).

Experimental

Crystal data

C21H16ClN3O2

M = 377.82

Monoclinic,

a = 17.1008 (16) Å

b = 12.4737 (12) Å

c = 17.9070 (17) Å

β = 111.276 (2)°

V = 3559.4 (6) Å3

Z = 8

Mo Kα radiation

μ = 0.24 mm−1

T = 295 K

0.28 × 0.25 × 0.21 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

11255 measured reflections

4048 independent reflections

3245 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.095

S = 1.01

4048 reflections

245 parameters

H-atom parameters constrained

Δρmax = 0.30 e Å−3

Δρmin = −0.33 e Å−3

Data collection: APEX2 (Bruker, 2007 ▸); cell refinement: SAINT (Bruker, 2007 ▸); 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 ▸ and PLATON (Spek, 2009 ▸); software used to prepare material for publication: WinGX publication routines (Farrugia, 2012 ▸) and PLATON.

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015002698/su5081sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015002698/su5081Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015002698/su5081Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015002698/su5081fig1.tif

The mol­ecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at 30% probability level.

Click here for additional data file.

b . DOI: 10.1107/S2056989015002698/su5081fig2.tif

A perspective view along the b axis of the crystal packing of the title compound. The hydrogen bonds are shown as dashed lines (see Table 1 for details; H atoms not involved in hydrogen bonding have been omitted for clarity).

CCDC reference: 1048268

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

C21H16ClN3O2	F(000) = 1568
Mr = 377.82	Dx = 1.410 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3518 reflections
a = 17.1008 (16) Å	θ = 2.6–27.3°
b = 12.4737 (12) Å	µ = 0.24 mm−1
c = 17.9070 (17) Å	T = 295 K
β = 111.276 (2)°	Block, yellow
V = 3559.4 (6) Å3	0.28 × 0.25 × 0.21 mm
Z = 8

Bruker APEXII CCD area-detector diffractometer	3245 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.025
Graphite monochromator	θmax = 27.4°, θmin = 2.1°
phi and ω scans	h = −22→22
11255 measured reflections	k = −16→16
4048 independent reflections	l = −11→23

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.095	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.0422P)2 + 2.6702P] where P = (Fo2 + 2Fc2)/3
4048 reflections	(Δ/σ)max = 0.001
245 parameters	Δρmax = 0.30 e Å−3
0 restraints	Δρmin = −0.33 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	0.44525 (8)	0.57307 (12)	0.57260 (8)	0.0224 (3)
C2	0.40060 (9)	0.51564 (12)	0.50340 (8)	0.0243 (3)
H2	0.4079	0.4420	0.5014	0.029*
C3	0.34516 (9)	0.56928 (13)	0.43753 (9)	0.0293 (3)
H3	0.3152	0.5311	0.3914	0.035*
C4	0.33398 (10)	0.67869 (14)	0.43979 (10)	0.0350 (4)
H4	0.2970	0.7142	0.3953	0.042*
C5	0.37828 (10)	0.73525 (13)	0.50892 (10)	0.0356 (4)
H5	0.3707	0.8089	0.5107	0.043*
C6	0.43372 (9)	0.68315 (12)	0.57541 (10)	0.0288 (3)
H6	0.4631	0.7216	0.6216	0.035*
C7	0.51617 (9)	0.41344 (12)	0.65574 (8)	0.0226 (3)
C8	0.59225 (8)	0.40755 (12)	0.72738 (8)	0.0226 (3)
C9	0.61904 (9)	0.51729 (12)	0.74541 (8)	0.0231 (3)
C10	0.69450 (9)	0.56344 (13)	0.80961 (9)	0.0288 (3)
H10A	0.7004	0.6375	0.7980	0.043*
H10B	0.7437	0.5246	0.8116	0.043*
H10C	0.6878	0.5578	0.8604	0.043*
C11	0.62715 (9)	0.31029 (12)	0.75986 (8)	0.0234 (3)
C12	0.70547 (9)	0.30187 (12)	0.82951 (9)	0.0243 (3)
C13	0.73360 (9)	0.34085 (13)	0.90500 (9)	0.0291 (3)
H13	0.7052	0.3870	0.9271	0.035*
C14	0.81512 (10)	0.29751 (14)	0.94399 (9)	0.0312 (3)
H14	0.8505	0.3098	0.9966	0.037*
C15	0.83107 (9)	0.23514 (13)	0.88992 (9)	0.0287 (3)
H15	0.8805	0.1970	0.8997	0.034*
C16	0.60305 (9)	0.11363 (12)	0.75154 (9)	0.0268 (3)
C17	0.62669 (10)	0.09001 (14)	0.83295 (10)	0.0337 (4)
H17	0.6358	0.1454	0.8699	0.040*
C18	0.63667 (10)	−0.01516 (15)	0.85909 (11)	0.0409 (4)
H18	0.6530	−0.0300	0.9135	0.049*
C19	0.62263 (10)	−0.09799 (15)	0.80517 (13)	0.0435 (5)
H19	0.6304	−0.1685	0.8233	0.052*
C20	0.59700 (10)	−0.07661 (14)	0.72421 (12)	0.0390 (4)
H20	0.5864	−0.1326	0.6876	0.047*
C21	0.58720 (9)	0.02863 (13)	0.69779 (10)	0.0302 (3)
Cl1	0.55346 (3)	0.05471 (4)	0.59572 (3)	0.04238 (13)
N1	0.50433 (7)	0.52104 (10)	0.63947 (7)	0.0226 (3)
N2	0.56763 (7)	0.58347 (10)	0.69457 (7)	0.0244 (3)
N3	0.59039 (8)	0.21931 (10)	0.72231 (7)	0.0271 (3)
H3A	0.5546	0.2271	0.6744	0.033*
O1	0.47138 (6)	0.33913 (8)	0.61635 (6)	0.0261 (2)
O2	0.76468 (6)	0.23556 (8)	0.81867 (6)	0.0259 (2)

	U11	U22	U33	U12	U13	U23
C1	0.0186 (6)	0.0280 (7)	0.0231 (7)	0.0013 (5)	0.0104 (6)	0.0028 (6)
C2	0.0228 (7)	0.0272 (7)	0.0240 (7)	0.0006 (6)	0.0099 (6)	0.0010 (6)
C3	0.0247 (7)	0.0381 (9)	0.0241 (7)	0.0017 (6)	0.0079 (6)	0.0027 (6)
C4	0.0301 (8)	0.0403 (9)	0.0315 (8)	0.0086 (7)	0.0074 (7)	0.0095 (7)
C5	0.0354 (8)	0.0282 (8)	0.0421 (10)	0.0082 (7)	0.0127 (7)	0.0045 (7)
C6	0.0271 (7)	0.0281 (8)	0.0304 (8)	0.0012 (6)	0.0094 (6)	−0.0023 (6)
C7	0.0227 (7)	0.0265 (7)	0.0201 (7)	0.0000 (6)	0.0097 (6)	0.0009 (6)
C8	0.0215 (7)	0.0286 (7)	0.0179 (7)	−0.0010 (6)	0.0074 (5)	−0.0005 (5)
C9	0.0213 (6)	0.0289 (7)	0.0211 (7)	−0.0009 (6)	0.0102 (6)	−0.0023 (6)
C10	0.0258 (7)	0.0336 (8)	0.0243 (7)	−0.0040 (6)	0.0058 (6)	−0.0039 (6)
C11	0.0243 (7)	0.0295 (7)	0.0178 (7)	−0.0003 (6)	0.0092 (6)	−0.0005 (6)
C12	0.0237 (7)	0.0277 (7)	0.0226 (7)	0.0024 (6)	0.0099 (6)	0.0016 (6)
C13	0.0288 (7)	0.0367 (9)	0.0224 (7)	0.0039 (6)	0.0101 (6)	−0.0009 (6)
C14	0.0265 (7)	0.0437 (9)	0.0208 (7)	0.0012 (7)	0.0054 (6)	0.0031 (6)
C15	0.0210 (7)	0.0352 (8)	0.0278 (8)	0.0036 (6)	0.0062 (6)	0.0067 (6)
C16	0.0207 (7)	0.0283 (8)	0.0306 (8)	0.0015 (6)	0.0084 (6)	0.0035 (6)
C17	0.0293 (8)	0.0387 (9)	0.0292 (8)	−0.0028 (7)	0.0059 (7)	0.0058 (7)
C18	0.0289 (8)	0.0452 (10)	0.0430 (10)	−0.0031 (7)	0.0064 (7)	0.0176 (8)
C19	0.0271 (8)	0.0351 (9)	0.0668 (13)	0.0025 (7)	0.0151 (8)	0.0189 (9)
C20	0.0288 (8)	0.0295 (9)	0.0619 (12)	−0.0015 (7)	0.0203 (8)	−0.0023 (8)
C21	0.0240 (7)	0.0322 (8)	0.0355 (8)	−0.0012 (6)	0.0122 (6)	−0.0005 (7)
Cl1	0.0543 (3)	0.0414 (2)	0.0326 (2)	−0.0103 (2)	0.01723 (19)	−0.01043 (18)
N1	0.0204 (6)	0.0253 (6)	0.0206 (6)	−0.0018 (5)	0.0057 (5)	−0.0014 (5)
N2	0.0216 (6)	0.0279 (6)	0.0229 (6)	−0.0032 (5)	0.0071 (5)	−0.0039 (5)
N3	0.0291 (6)	0.0281 (7)	0.0196 (6)	0.0012 (5)	0.0034 (5)	0.0014 (5)
O1	0.0252 (5)	0.0264 (5)	0.0232 (5)	−0.0031 (4)	0.0045 (4)	−0.0001 (4)
O2	0.0243 (5)	0.0291 (5)	0.0250 (5)	0.0030 (4)	0.0097 (4)	0.0003 (4)

C1—C6	1.391 (2)	C11—C12	1.466 (2)
C1—C2	1.395 (2)	C12—C13	1.350 (2)
C1—N1	1.4135 (18)	C12—O2	1.3746 (17)
C2—C3	1.388 (2)	C13—C14	1.420 (2)
C2—H2	0.9300	C13—H13	0.9300
C3—C4	1.381 (2)	C14—C15	1.345 (2)
C3—H3	0.9300	C14—H14	0.9300
C4—C5	1.387 (2)	C15—O2	1.3659 (18)
C4—H4	0.9300	C15—H15	0.9300
C5—C6	1.385 (2)	C16—C21	1.391 (2)
C5—H5	0.9300	C16—C17	1.396 (2)
C6—H6	0.9300	C16—N3	1.4058 (19)
C7—O1	1.2456 (17)	C17—C18	1.382 (2)
C7—N1	1.3727 (19)	C17—H17	0.9300
C7—C8	1.4602 (19)	C18—C19	1.375 (3)
C8—C11	1.384 (2)	C18—H18	0.9300
C8—C9	1.442 (2)	C19—C20	1.380 (3)
C9—N2	1.3047 (19)	C19—H19	0.9300
C9—C10	1.497 (2)	C20—C21	1.385 (2)
C10—H10A	0.9600	C20—H20	0.9300
C10—H10B	0.9600	C21—Cl1	1.7362 (17)
C10—H10C	0.9600	N1—N2	1.4060 (16)
C11—N3	1.3522 (19)	N3—H3A	0.8600
C6—C1—C2	120.02 (13)	C13—C12—C11	135.20 (14)
C6—C1—N1	119.33 (13)	O2—C12—C11	114.55 (12)
C2—C1—N1	120.62 (13)	C12—C13—C14	106.54 (14)
C3—C2—C1	119.50 (14)	C12—C13—H13	126.7
C3—C2—H2	120.3	C14—C13—H13	126.7
C1—C2—H2	120.3	C15—C14—C13	106.59 (14)
C4—C3—C2	120.72 (15)	C15—C14—H14	126.7
C4—C3—H3	119.6	C13—C14—H14	126.7
C2—C3—H3	119.6	C14—C15—O2	110.69 (13)
C3—C4—C5	119.49 (15)	C14—C15—H15	124.7
C3—C4—H4	120.3	O2—C15—H15	124.7
C5—C4—H4	120.3	C21—C16—C17	118.14 (15)
C6—C5—C4	120.68 (15)	C21—C16—N3	119.48 (14)
C6—C5—H5	119.7	C17—C16—N3	122.27 (14)
C4—C5—H5	119.7	C18—C17—C16	120.49 (17)
C5—C6—C1	119.59 (15)	C18—C17—H17	119.8
C5—C6—H6	120.2	C16—C17—H17	119.8
C1—C6—H6	120.2	C19—C18—C17	120.45 (17)
O1—C7—N1	126.47 (13)	C19—C18—H18	119.8
O1—C7—C8	128.96 (13)	C17—C18—H18	119.8
N1—C7—C8	104.56 (12)	C18—C19—C20	120.05 (16)
C11—C8—C9	133.20 (13)	C18—C19—H19	120.0
C11—C8—C7	121.62 (13)	C20—C19—H19	120.0
C9—C8—C7	104.97 (12)	C19—C20—C21	119.67 (17)
N2—C9—C8	111.44 (13)	C19—C20—H20	120.2
N2—C9—C10	117.86 (13)	C21—C20—H20	120.2
C8—C9—C10	130.69 (13)	C20—C21—C16	121.15 (16)
C9—C10—H10A	109.5	C20—C21—Cl1	119.34 (14)
C9—C10—H10B	109.5	C16—C21—Cl1	119.51 (12)
H10A—C10—H10B	109.5	C7—N1—N2	112.08 (11)
C9—C10—H10C	109.5	C7—N1—C1	129.33 (12)
H10A—C10—H10C	109.5	N2—N1—C1	118.15 (12)
H10B—C10—H10C	109.5	C9—N2—N1	106.94 (12)
N3—C11—C8	118.36 (13)	C11—N3—C16	128.37 (13)
N3—C11—C12	118.65 (13)	C11—N3—H3A	115.8
C8—C11—C12	122.83 (13)	C16—N3—H3A	115.8
C13—C12—O2	110.18 (13)	C15—O2—C12	106.00 (11)
C6—C1—C2—C3	0.3 (2)	N3—C16—C17—C18	178.52 (14)
N1—C1—C2—C3	−177.69 (12)	C16—C17—C18—C19	−0.6 (2)
C1—C2—C3—C4	0.2 (2)	C17—C18—C19—C20	−1.1 (3)
C2—C3—C4—C5	−0.5 (2)	C18—C19—C20—C21	1.3 (2)
C3—C4—C5—C6	0.2 (2)	C19—C20—C21—C16	0.2 (2)
C4—C5—C6—C1	0.3 (2)	C19—C20—C21—Cl1	−179.07 (12)
C2—C1—C6—C5	−0.6 (2)	C17—C16—C21—C20	−1.9 (2)
N1—C1—C6—C5	177.51 (13)	N3—C16—C21—C20	−178.43 (14)
O1—C7—C8—C11	2.7 (2)	C17—C16—C21—Cl1	177.36 (11)
N1—C7—C8—C11	−176.44 (12)	N3—C16—C21—Cl1	0.88 (19)
O1—C7—C8—C9	178.06 (14)	O1—C7—N1—N2	−178.37 (12)
N1—C7—C8—C9	−1.11 (14)	C8—C7—N1—N2	0.82 (15)
C11—C8—C9—N2	175.64 (15)	O1—C7—N1—C1	−6.2 (2)
C7—C8—C9—N2	1.09 (16)	C8—C7—N1—C1	173.00 (12)
C11—C8—C9—C10	−2.8 (3)	C6—C1—N1—C7	167.80 (14)
C7—C8—C9—C10	−177.36 (14)	C2—C1—N1—C7	−14.1 (2)
C9—C8—C11—N3	−171.97 (14)	C6—C1—N1—N2	−20.42 (18)
C7—C8—C11—N3	1.8 (2)	C2—C1—N1—N2	157.62 (12)
C9—C8—C11—C12	3.4 (2)	C8—C9—N2—N1	−0.60 (15)
C7—C8—C11—C12	177.17 (12)	C10—C9—N2—N1	178.07 (11)
N3—C11—C12—C13	−129.37 (19)	C7—N1—N2—C9	−0.17 (15)
C8—C11—C12—C13	55.3 (2)	C1—N1—N2—C9	−173.31 (11)
N3—C11—C12—O2	47.33 (18)	C8—C11—N3—C16	−165.70 (14)
C8—C11—C12—O2	−127.98 (14)	C12—C11—N3—C16	18.8 (2)
O2—C12—C13—C14	0.34 (18)	C21—C16—N3—C11	−154.71 (15)
C11—C12—C13—C14	177.15 (16)	C17—C16—N3—C11	29.0 (2)
C12—C13—C14—C15	−0.11 (19)	C14—C15—O2—C12	0.37 (17)
C13—C14—C15—O2	−0.17 (18)	C13—C12—O2—C15	−0.44 (16)
C21—C16—C17—C18	2.1 (2)	C11—C12—O2—C15	−177.97 (12)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O1	0.86	2.00	2.678 (2)	135
C15—H15···N2i	0.93	2.59	3.282 (2)	131

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N3H3AO1	0.86	2.00	2.678(2)	135
C15H15N2i	0.93	2.59	3.282(2)	131

Symmetry code: (i) .