Crystal structure of ethyl 2-({[(4Z)-3,5-dioxo-1-phenyl-pyrazolidin-4-yl-idene]meth-yl}amino)-acetate.

The title compound, C14H15N3O4, is nearly planar, the dihedral angle between the planes of the phenyl and pyrazolidine rings being 1.13 (7) Å, and that between the plane of the pyrazolidine ring and the mean plane of the side chain [C-N-C-C(=O)-O; r.m.s. deviation = 0.024 Å] being 2.52 (7)°. This is due in large part to the presence of the intra-molecular N-H⋯O and C-H⋯O hydrogen bonds. In the crystal, pairwise N-H⋯O hydrogen bonds form inversion dimers, which are further associated into layers, lying very close to plane (-120), via pairwise C-H⋯O hydrogen bonds. The layers are then weakly connected through C-H⋯O hydrogen bonds, forming a three-dimensional structure.

Related literature

For the synthesis of compounds containing the pyrazolidinone nucleus and their biological activity, see: Ismail et al. (2012 ▶); Khodairy (2007 ▶); Khloya et al. (2013 ▶). For biologically active synthetic heterocyclic compounds containing the pyrazol-5(4H)-one core scaffold and displaying some inter­esting pharmaceutical properties, see: Uramaru et al. (2010 ▶) for analgesic; Thaker et al. (2011 ▶) and Chande et al. (2007 ▶) for anti­microbial; Mariappan et al. (2010 ▶) and Nishikimi et al. (2012 ▶) for anti-inflammatory; Chen et al. (2012 ▶) for cyto­toxicity.

Experimental

Crystal data

C14H15N3O4

M = 289.29

Triclinic,

a = 5.4984 (1) Å

b = 7.3585 (2) Å

c = 16.6265 (4) Å

α = 91.3290 (9)°

β = 97.325 (1)°

γ = 99.562 (1)°

V = 657.27 (3) Å3

Z = 2

Cu Kα radiation

μ = 0.91 mm−1

T = 100 K

0.27 × 0.09 × 0.04 mm

Data collection

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2013 ▶) T min = 0.91, T max = 0.96

5108 measured reflections

2450 independent reflections

2171 reflections with I > 2σ(I)

R int = 0.019

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.089

S = 1.02

2450 reflections

199 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.22 e Å−3

Δρmin = −0.19 e Å−3

Data collection: APEX2 (Bruker, 2013 ▶); cell refinement: SAINT (Bruker, 2013 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXT (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2012 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814016766/su2759sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814016766/su2759Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814016766/su2759Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S1600536814016766/su2759fig1.tif

The mol­ecular structure of the title mol­ecule, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

Click here for additional data file.

b . DOI: 10.1107/S1600536814016766/su2759fig2.tif

The crystal packing viewed along the b axis of the title compound. N—H⋯O and C—H⋯O hydrogen bonds are shown, respectively, as purple and black dotted lines (see Table 1 for details).

Click here for additional data file.

. DOI: 10.1107/S1600536814016766/su2759fig3.tif

The crystal packing of the title compound, showing the layer structure and the weak C—H⋯O inter­layer hydrogen bonds (black dotted lines; see Table 1 for details).

CCDC reference: 1015152

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

C14H15N3O4	Z = 2
Mr = 289.29	F(000) = 304
Triclinic, P1	Dx = 1.462 Mg m−3
a = 5.4984 (1) Å	Cu Kα radiation, λ = 1.54178 Å
b = 7.3585 (2) Å	Cell parameters from 3908 reflections
c = 16.6265 (4) Å	θ = 2.7–72.2°
α = 91.3290 (9)°	µ = 0.91 mm−1
β = 97.325 (1)°	T = 100 K
γ = 99.562 (1)°	Needle, yellow
V = 657.27 (3) Å3	0.27 × 0.09 × 0.04 mm

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	2450 independent reflections
Radiation source: INCOATEC IµS micro-focus source	2171 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.019
Detector resolution: 10.4167 pixels mm-1	θmax = 72.2°, θmin = 5.4°
ω scans	h = −6→6
Absorption correction: multi-scan (SADABS; Bruker, 2013)	k = −9→8
Tmin = 0.91, Tmax = 0.96	l = −20→20
5108 measured reflections

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)] = 0.033	Hydrogen site location: mixed
wR(F2) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0471P)2 + 0.2143P] where P = (Fo2 + 2Fc2)/3
2450 reflections	(Δ/σ)max < 0.001
199 parameters	Δρmax = 0.22 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. H-atoms attached to carbon were placed in calculated positions (C—H = 0.95 - 0.99 Å) and included as riding contributions with isotropic displacement parameters 1.2 - 1.5 times those of the attached carbon atoms. H-atoms attached to nitrogen were refined independently.

	x	y	z	Uiso*/Ueq
O1	0.81993 (17)	0.91924 (12)	0.58190 (5)	0.0208 (2)
O2	0.18424 (17)	0.56447 (13)	0.39606 (5)	0.0232 (2)
O3	0.56220 (17)	0.89351 (13)	0.80229 (5)	0.0238 (2)
O4	0.20347 (17)	0.77726 (12)	0.84951 (5)	0.0214 (2)
N1	0.7714 (2)	0.82957 (15)	0.44586 (6)	0.0193 (2)
N2	0.5788 (2)	0.73223 (15)	0.38878 (6)	0.0182 (2)
N3	0.3705 (2)	0.76426 (15)	0.64837 (6)	0.0185 (2)
C1	0.6132 (2)	0.71090 (16)	0.30668 (7)	0.0171 (3)
C2	0.8342 (2)	0.79219 (17)	0.27959 (7)	0.0187 (3)
H2	0.9640	0.8617	0.3167	0.022*
C3	0.8642 (3)	0.77134 (18)	0.19820 (8)	0.0221 (3)
H3	1.0142	0.8281	0.1799	0.026*
C4	0.6776 (3)	0.66856 (18)	0.14350 (8)	0.0224 (3)
H4	0.6992	0.6543	0.0881	0.027*
C5	0.4589 (3)	0.58691 (18)	0.17083 (8)	0.0224 (3)
H5	0.3308	0.5160	0.1336	0.027*
C6	0.4240 (2)	0.60707 (17)	0.25156 (7)	0.0203 (3)
H6	0.2729	0.5509	0.2693	0.024*
C7	0.3762 (2)	0.66257 (17)	0.42850 (7)	0.0177 (3)
C8	0.4474 (2)	0.72955 (16)	0.51201 (7)	0.0173 (3)
C9	0.6925 (2)	0.83530 (17)	0.51974 (7)	0.0175 (3)
C10	0.3003 (2)	0.69795 (17)	0.57301 (7)	0.0172 (3)
H10	0.1399	0.6246	0.5602	0.021*
C11	0.2115 (2)	0.73107 (18)	0.71157 (7)	0.0187 (3)
H11A	0.1573	0.5967	0.7154	0.022*
H11B	0.0614	0.7881	0.6980	0.022*
C12	0.3509 (2)	0.81183 (17)	0.79164 (7)	0.0188 (3)
C13	0.3112 (3)	0.84585 (19)	0.93050 (7)	0.0239 (3)
H13A	0.3525	0.9822	0.9326	0.029*
H13B	0.4654	0.7958	0.9472	0.029*
C14	0.1209 (3)	0.7838 (2)	0.98568 (8)	0.0326 (3)
H14A	−0.0333	0.8293	0.9670	0.049*
H14B	0.1841	0.8327	1.0411	0.049*
H14C	0.0877	0.6487	0.9850	0.049*
H1	0.896 (4)	0.907 (3)	0.4313 (10)	0.034 (5)*
H3A	0.525 (3)	0.834 (2)	0.6622 (10)	0.027 (4)*

	U11	U22	U33	U12	U13	U23
O1	0.0191 (5)	0.0237 (5)	0.0168 (4)	−0.0039 (4)	0.0017 (3)	−0.0013 (3)
O2	0.0169 (5)	0.0300 (5)	0.0190 (4)	−0.0062 (4)	0.0019 (3)	−0.0010 (4)
O3	0.0199 (5)	0.0270 (5)	0.0218 (4)	−0.0024 (4)	0.0014 (4)	−0.0012 (4)
O4	0.0214 (5)	0.0253 (5)	0.0158 (4)	−0.0016 (4)	0.0035 (3)	−0.0016 (3)
N1	0.0157 (6)	0.0226 (5)	0.0166 (5)	−0.0056 (4)	0.0023 (4)	−0.0017 (4)
N2	0.0154 (5)	0.0210 (5)	0.0158 (5)	−0.0029 (4)	0.0012 (4)	−0.0016 (4)
N3	0.0160 (6)	0.0208 (5)	0.0171 (5)	−0.0018 (4)	0.0028 (4)	0.0003 (4)
C1	0.0190 (6)	0.0162 (6)	0.0163 (6)	0.0036 (5)	0.0020 (5)	0.0012 (5)
C2	0.0182 (6)	0.0179 (6)	0.0193 (6)	0.0010 (5)	0.0023 (5)	0.0005 (5)
C3	0.0220 (7)	0.0228 (6)	0.0222 (6)	0.0034 (5)	0.0062 (5)	0.0028 (5)
C4	0.0275 (7)	0.0245 (7)	0.0161 (6)	0.0062 (6)	0.0037 (5)	0.0009 (5)
C5	0.0230 (7)	0.0236 (7)	0.0189 (6)	0.0022 (5)	−0.0005 (5)	−0.0009 (5)
C6	0.0181 (7)	0.0216 (6)	0.0197 (6)	0.0002 (5)	0.0018 (5)	0.0003 (5)
C7	0.0156 (6)	0.0179 (6)	0.0188 (6)	0.0005 (5)	0.0027 (5)	0.0017 (5)
C8	0.0168 (6)	0.0166 (6)	0.0174 (6)	0.0009 (5)	0.0011 (5)	0.0009 (5)
C9	0.0182 (6)	0.0164 (6)	0.0177 (6)	0.0016 (5)	0.0027 (5)	0.0010 (4)
C10	0.0149 (6)	0.0165 (6)	0.0189 (6)	0.0003 (5)	0.0009 (4)	0.0017 (4)
C11	0.0170 (6)	0.0212 (6)	0.0169 (6)	−0.0005 (5)	0.0036 (5)	0.0006 (5)
C12	0.0193 (7)	0.0177 (6)	0.0189 (6)	0.0022 (5)	0.0022 (5)	0.0015 (5)
C13	0.0270 (7)	0.0268 (7)	0.0157 (6)	0.0006 (6)	0.0008 (5)	−0.0021 (5)
C14	0.0382 (9)	0.0375 (8)	0.0204 (7)	−0.0017 (7)	0.0077 (6)	−0.0002 (6)

O1—C9	1.2580 (15)	C4—C5	1.388 (2)
O2—C7	1.2288 (16)	C4—H4	0.9500
O3—C12	1.2052 (17)	C5—C6	1.3879 (18)
O4—C12	1.3378 (16)	C5—H5	0.9500
O4—C13	1.4438 (14)	C6—H6	0.9500
N1—C9	1.3557 (16)	C7—C8	1.4455 (17)
N1—N2	1.4126 (14)	C8—C10	1.3764 (18)
N1—H1	0.88 (2)	C8—C9	1.4289 (18)
N2—C7	1.3975 (17)	C10—H10	0.9500
N2—C1	1.4105 (16)	C11—C12	1.5049 (16)
N3—C10	1.3201 (16)	C11—H11A	0.9900
N3—C11	1.4503 (16)	C11—H11B	0.9900
N3—H3A	0.914 (18)	C13—C14	1.500 (2)
C1—C2	1.3958 (19)	C13—H13A	0.9900
C1—C6	1.4023 (17)	C13—H13B	0.9900
C2—C3	1.3920 (18)	C14—H14A	0.9800
C2—H2	0.9500	C14—H14B	0.9800
C3—C4	1.3873 (18)	C14—H14C	0.9800
C3—H3	0.9500
C12—O4—C13	115.89 (10)	C10—C8—C9	126.25 (11)
C9—N1—N2	109.72 (10)	C10—C8—C7	125.21 (12)
C9—N1—H1	124.3 (11)	C9—C8—C7	108.54 (11)
N2—N1—H1	122.3 (11)	O1—C9—N1	124.26 (12)
C7—N2—C1	130.04 (10)	O1—C9—C8	128.51 (12)
C7—N2—N1	109.26 (10)	N1—C9—C8	107.22 (11)
C1—N2—N1	120.63 (10)	N3—C10—C8	123.39 (12)
C10—N3—C11	122.52 (11)	N3—C10—H10	118.3
C10—N3—H3A	119.8 (10)	C8—C10—H10	118.3
C11—N3—H3A	117.7 (10)	N3—C11—C12	109.81 (10)
C2—C1—C6	119.51 (11)	N3—C11—H11A	109.7
C2—C1—N2	120.64 (11)	C12—C11—H11A	109.7
C6—C1—N2	119.86 (11)	N3—C11—H11B	109.7
C3—C2—C1	119.92 (12)	C12—C11—H11B	109.7
C3—C2—H2	120.0	H11A—C11—H11B	108.2
C1—C2—H2	120.0	O3—C12—O4	125.26 (12)
C4—C3—C2	120.74 (12)	O3—C12—C11	125.64 (12)
C4—C3—H3	119.6	O4—C12—C11	109.10 (10)
C2—C3—H3	119.6	O4—C13—C14	106.97 (11)
C3—C4—C5	119.13 (12)	O4—C13—H13A	110.3
C3—C4—H4	120.4	C14—C13—H13A	110.3
C5—C4—H4	120.4	O4—C13—H13B	110.3
C4—C5—C6	121.15 (12)	C14—C13—H13B	110.3
C4—C5—H5	119.4	H13A—C13—H13B	108.6
C6—C5—H5	119.4	C13—C14—H14A	109.5
C5—C6—C1	119.55 (12)	C13—C14—H14B	109.5
C5—C6—H6	120.2	H14A—C14—H14B	109.5
C1—C6—H6	120.2	C13—C14—H14C	109.5
O2—C7—N2	124.92 (11)	H14A—C14—H14C	109.5
O2—C7—C8	129.97 (12)	H14B—C14—H14C	109.5
N2—C7—C8	105.10 (10)
C9—N1—N2—C7	−4.17 (14)	N2—C7—C8—C10	178.32 (11)
C9—N1—N2—C1	178.53 (10)	O2—C7—C8—C9	178.57 (13)
C7—N2—C1—C2	−179.41 (12)	N2—C7—C8—C9	−0.82 (13)
N1—N2—C1—C2	−2.73 (17)	N2—N1—C9—O1	−176.95 (11)
C7—N2—C1—C6	0.56 (19)	N2—N1—C9—C8	3.52 (13)
N1—N2—C1—C6	177.24 (11)	C10—C8—C9—O1	−0.3 (2)
C6—C1—C2—C3	0.66 (18)	C7—C8—C9—O1	178.83 (12)
N2—C1—C2—C3	−179.37 (11)	C10—C8—C9—N1	179.20 (12)
C1—C2—C3—C4	−0.74 (19)	C7—C8—C9—N1	−1.67 (14)
C2—C3—C4—C5	0.28 (19)	C11—N3—C10—C8	179.28 (12)
C3—C4—C5—C6	0.26 (19)	C9—C8—C10—N3	0.2 (2)
C4—C5—C6—C1	−0.33 (19)	C7—C8—C10—N3	−178.81 (11)
C2—C1—C6—C5	−0.13 (19)	C10—N3—C11—C12	175.64 (11)
N2—C1—C6—C5	179.90 (11)	C13—O4—C12—O3	0.30 (18)
C1—N2—C7—O2	0.5 (2)	C13—O4—C12—C11	179.81 (10)
N1—N2—C7—O2	−176.50 (12)	N3—C11—C12—O3	0.61 (18)
C1—N2—C7—C8	179.91 (11)	N3—C11—C12—O4	−178.90 (10)
N1—N2—C7—C8	2.93 (13)	C12—O4—C13—C14	−177.08 (11)
O2—C7—C8—C10	−2.3 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O1	0.914 (18)	2.250 (17)	2.9062 (14)	128.3 (13)
C6—H6···O2	0.95	2.23	2.8833 (16)	126
N1—H1···O1i	0.88 (2)	1.89 (2)	2.7573 (14)	170.7 (16)
C2—H2···O1i	0.95	2.36	3.2777 (15)	162
C10—H10···O2ii	0.95	2.28	3.1268 (16)	148
C11—H11A···O2ii	0.99	2.58	3.1498 (15)	117
C11—H11B···O1iii	0.99	2.51	3.3386 (15)	142

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O1	0.914 (18)	2.250 (17)	2.9062 (14)	128.3 (13)
C6—H6⋯O2	0.95	2.23	2.8833 (16)	126
N1—H1⋯O1i	0.88 (2)	1.89 (2)	2.7573 (14)	170.7 (16)
C2—H2⋯O1i	0.95	2.36	3.2777 (15)	162
C10—H10⋯O2ii	0.95	2.28	3.1268 (16)	148
C11—H11A⋯O2ii	0.99	2.58	3.1498 (15)	117
C11—H11B⋯O1iii	0.99	2.51	3.3386 (15)	142

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