Crystal structure of (4Z)-4-[(di-methyl-amino)-methyl-idene]-3,5-dioxo-2-phenyl-pyrazolidine-1-carbaldehyde.

In the title compound, C13H13N3O3, the pyrazolidine ring adopts a shallow envelope conformation, with the carbonyl C atom closest to the benzene ring as the flap [deviation of 0.126 (1) Å from the plane through the remaining atoms (r.m.s. deviation = 0.011 Å)]. The dihedral angle between the pyrazolidine ring (all atoms) and the benzene ring is 51.09 (4)°. An extremely short (2.08 Å) intra-molecular C-H⋯O contact is seen. In the crystal, mol-ecules are linked by C-H⋯O bonds, generating [010] chains. Extremely weak C-H⋯π inter-actions are also observed.

Related literature

For biological studies of azole compounds, see: Patel et al. (2012 ▸); Vijesh et al. (2011 ▸). For various medicinal and industrial applications of pyrrazole-containing compounds, see: Jin et al. (2011 ▸); Zhang et al. (2010 ▸); El-Sabbagh et al. (2009 ▸); Dekhane et al. (2011 ▸); Rostom et al. (2003 ▸); Zhou et al. (2010 ▸); Finkelstein & Strock (1997 ▸).

Experimental

Crystal data

C13H13N3O3

M = 259.26

Monoclinic,

a = 26.4235 (9) Å

b = 6.1033 (2) Å

c = 16.8611 (6) Å

β = 113.272 (1)°

V = 2497.96 (15) Å3

Z = 8

Cu Kα radiation

μ = 0.84 mm−1

T = 150 K

0.24 × 0.15 × 0.05 mm

Data collection

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer

Absorption correction: multi-scan (TWINABS; Sheldrick, 2009 ▸) T min = 0.82, T max = 0.96

26486 measured reflections

4565 independent reflections

3979 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.104

S = 1.04

4565 reflections

175 parameters

H-atom parameters constrained

Δρmax = 0.26 e Å−3

Δρmin = −0.20 e Å−3

Data collection: APEX2 (Bruker, 2014 ▸); cell refinement: SAINT (Bruker, 2014 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXT (Sheldrick, 2015a ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b ▸); 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/S2056989015010038/hb7425sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015010038/hb7425Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015010038/hb7425Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015010038/hb7425fig1.tif

The title mol­ecule with 50% probability ellipsoids.

Click here for additional data file.

b . DOI: 10.1107/S2056989015010038/hb7425fig2.tif

Packing viewed down the b axis. C—H⋯π inter­actions are shown by dotted lines.

CCDC reference: 1402532

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

C13H13N3O3	F(000) = 1088
Mr = 259.26	Dx = 1.379 Mg m−3
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54178 Å
a = 26.4235 (9) Å	Cell parameters from 9978 reflections
b = 6.1033 (2) Å	θ = 3.6–72.3°
c = 16.8611 (6) Å	µ = 0.84 mm−1
β = 113.272 (1)°	T = 150 K
V = 2497.96 (15) Å3	Rod, colourless
Z = 8	0.24 × 0.15 × 0.05 mm

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	4565 independent reflections
Radiation source: INCOATEC IµS micro–focus source	3979 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.021
Detector resolution: 10.4167 pixels mm-1	θmax = 72.3°, θmin = 3.6°
ω scans	h = −32→30
Absorption correction: multi-scan (TWINABS; Sheldrick, 2009)	k = −7→7
Tmin = 0.82, Tmax = 0.96	l = −20→20
26486 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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.104	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0577P)2 + 0.7347P] where P = (Fo2 + 2Fc2)/3
4565 reflections	(Δ/σ)max < 0.001
175 parameters	Δρmax = 0.26 e Å−3
0 restraints	Δρmin = −0.20 e Å−3

Experimental. Analysis of 3764 reflections having I/σ(I) > 12 and chosen fromthe full data set with CELL_NOW (Sheldrick, 2008) showedthe crystal to belong to the monoclinic system and to be twinnedby a 180° rotation about the c* axis. The raw data wereprocessed using the multi-component version of SAINT undercontrol of the two-component orientation file generated byCELL_NOW.

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 takeninto account individually in the estimation of e.s.d.'s in distances, anglesand torsion angles; correlations between e.s.d.'s in cell parameters are onlyused 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 andgoodness of fit S are based on F2, conventional R-factors R are basedon F, with F set to zero for negative F2. The threshold expression ofF2 > σ(F2) is used only for calculating R-factors(gt) etc. and isnot relevant to the choice of reflections for refinement. R-factors basedon 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 were placed incalculated positions (C—H = 0.95 - 0.98 Å) and included as ridingcontributions with isotropic displacement parameters 1.2 - 1.5 times thoseof the attached carbon atoms. The model was refined as a 2-component twin.

	x	y	z	Uiso*/Ueq
O1	0.43175 (4)	0.79022 (16)	0.28697 (7)	0.0296 (2)
O2	0.52891 (4)	0.15926 (16)	0.42906 (7)	0.0324 (3)
O3	0.37052 (4)	0.10698 (18)	0.39957 (6)	0.0316 (3)
N1	0.40831 (4)	0.46179 (18)	0.33205 (7)	0.0236 (3)
N2	0.43832 (4)	0.26978 (18)	0.36829 (7)	0.0239 (3)
N3	0.59876 (5)	0.64368 (19)	0.42207 (8)	0.0265 (3)
C1	0.44610 (5)	0.6170 (2)	0.32599 (8)	0.0233 (3)
C2	0.50109 (5)	0.5284 (2)	0.37179 (8)	0.0235 (3)
C3	0.49589 (5)	0.3060 (2)	0.39467 (8)	0.0242 (3)
C4	0.54556 (5)	0.6654 (2)	0.38045 (9)	0.0249 (3)
H4	0.5349	0.8001	0.3502	0.030*
C5	0.63539 (6)	0.8195 (3)	0.41755 (10)	0.0344 (3)
H5A	0.6133	0.9445	0.3861	0.052*
H5B	0.6580	0.7661	0.3874	0.052*
H5C	0.6594	0.8652	0.4761	0.052*
C6	0.62712 (6)	0.4598 (3)	0.47712 (10)	0.0344 (3)
H6A	0.6002	0.3471	0.4750	0.052*
H6B	0.6462	0.5109	0.5367	0.052*
H6C	0.6540	0.3978	0.4566	0.052*
C7	0.41757 (5)	0.1104 (2)	0.40511 (8)	0.0255 (3)
H7	0.4416	−0.0034	0.4367	0.031*
C8	0.35475 (5)	0.4373 (2)	0.26388 (8)	0.0235 (3)
C9	0.34078 (5)	0.2502 (2)	0.21315 (9)	0.0275 (3)
H9	0.3667	0.1349	0.2227	0.033*
C10	0.28831 (6)	0.2336 (3)	0.14813 (9)	0.0311 (3)
H10	0.2783	0.1062	0.1129	0.037*
C11	0.25040 (6)	0.4019 (3)	0.13433 (9)	0.0311 (3)
H11	0.2146	0.3899	0.0897	0.037*
C12	0.26490 (6)	0.5880 (2)	0.18593 (10)	0.0308 (3)
H12	0.2390	0.7031	0.1765	0.037*
C13	0.31717 (5)	0.6066 (2)	0.25127 (9)	0.0271 (3)
H13	0.3271	0.7333	0.2868	0.033*

	U11	U22	U33	U12	U13	U23
O1	0.0274 (5)	0.0239 (5)	0.0339 (5)	0.0033 (4)	0.0083 (4)	0.0053 (4)
O2	0.0221 (5)	0.0284 (5)	0.0409 (6)	0.0034 (4)	0.0063 (4)	0.0100 (4)
O3	0.0259 (5)	0.0404 (6)	0.0290 (5)	−0.0054 (4)	0.0115 (4)	0.0019 (4)
N1	0.0201 (5)	0.0227 (6)	0.0262 (6)	0.0027 (4)	0.0072 (4)	0.0031 (4)
N2	0.0190 (5)	0.0234 (6)	0.0267 (6)	0.0013 (4)	0.0062 (4)	0.0053 (4)
N3	0.0232 (5)	0.0306 (6)	0.0260 (6)	−0.0047 (4)	0.0099 (4)	−0.0026 (5)
C1	0.0241 (6)	0.0232 (6)	0.0227 (6)	0.0005 (5)	0.0093 (5)	−0.0009 (5)
C2	0.0211 (6)	0.0252 (7)	0.0233 (6)	0.0009 (5)	0.0077 (5)	0.0017 (5)
C3	0.0206 (6)	0.0268 (6)	0.0231 (6)	−0.0003 (5)	0.0063 (5)	0.0013 (5)
C4	0.0266 (6)	0.0250 (6)	0.0233 (6)	−0.0015 (5)	0.0102 (5)	−0.0005 (5)
C5	0.0296 (7)	0.0432 (8)	0.0314 (7)	−0.0132 (6)	0.0132 (6)	−0.0043 (7)
C6	0.0237 (6)	0.0348 (8)	0.0386 (8)	0.0007 (6)	0.0059 (6)	−0.0005 (6)
C7	0.0254 (6)	0.0271 (7)	0.0216 (6)	−0.0029 (5)	0.0066 (5)	0.0022 (5)
C8	0.0195 (6)	0.0289 (7)	0.0227 (6)	0.0010 (5)	0.0090 (5)	0.0033 (5)
C9	0.0247 (6)	0.0310 (7)	0.0258 (7)	0.0054 (5)	0.0089 (5)	0.0001 (5)
C10	0.0289 (7)	0.0344 (8)	0.0273 (7)	−0.0001 (6)	0.0082 (6)	−0.0029 (6)
C11	0.0212 (6)	0.0397 (8)	0.0281 (7)	0.0010 (6)	0.0053 (5)	0.0056 (6)
C12	0.0222 (6)	0.0319 (7)	0.0383 (8)	0.0060 (5)	0.0121 (6)	0.0072 (6)
C13	0.0240 (6)	0.0263 (7)	0.0326 (7)	0.0018 (5)	0.0128 (6)	0.0007 (5)

O1—C1	1.2234 (17)	C5—H5C	0.9800
O2—C3	1.2247 (17)	C6—H6A	0.9800
O3—C7	1.2096 (17)	C6—H6B	0.9800
N1—C1	1.4094 (17)	C6—H6C	0.9800
N1—N2	1.4116 (15)	C7—H7	0.9500
N1—C8	1.4356 (16)	C8—C9	1.387 (2)
N2—C7	1.3789 (17)	C8—C13	1.3898 (18)
N2—C3	1.4236 (16)	C9—C10	1.3903 (19)
N3—C4	1.3064 (17)	C9—H9	0.9500
N3—C6	1.4607 (19)	C10—C11	1.389 (2)
N3—C5	1.4669 (18)	C10—H10	0.9500
C1—C2	1.4538 (17)	C11—C12	1.389 (2)
C2—C4	1.4019 (18)	C11—H11	0.9500
C2—C3	1.4324 (19)	C12—C13	1.390 (2)
C4—H4	0.9500	C12—H12	0.9500
C5—H5A	0.9800	C13—H13	0.9500
C5—H5B	0.9800
C1—N1—N2	107.25 (10)	N3—C6—H6A	109.5
C1—N1—C8	120.96 (11)	N3—C6—H6B	109.5
N2—N1—C8	117.89 (10)	H6A—C6—H6B	109.5
C7—N2—N1	121.70 (11)	N3—C6—H6C	109.5
C7—N2—C3	122.33 (11)	H6A—C6—H6C	109.5
N1—N2—C3	110.76 (10)	H6B—C6—H6C	109.5
C4—N3—C6	126.32 (12)	O3—C7—N2	123.82 (13)
C4—N3—C5	119.34 (12)	O3—C7—H7	118.1
C6—N3—C5	114.31 (12)	N2—C7—H7	118.1
O1—C1—N1	122.81 (12)	C9—C8—C13	121.19 (12)
O1—C1—C2	129.76 (12)	C9—C8—N1	121.16 (11)
N1—C1—C2	107.42 (11)	C13—C8—N1	117.64 (12)
C4—C2—C3	134.64 (12)	C8—C9—C10	119.07 (13)
C4—C2—C1	117.00 (12)	C8—C9—H9	120.5
C3—C2—C1	108.28 (11)	C10—C9—H9	120.5
O2—C3—N2	120.52 (12)	C11—C10—C9	120.43 (14)
O2—C3—C2	133.97 (12)	C11—C10—H10	119.8
N2—C3—C2	105.51 (11)	C9—C10—H10	119.8
N3—C4—C2	132.47 (13)	C10—C11—C12	119.85 (13)
N3—C4—H4	113.8	C10—C11—H11	120.1
C2—C4—H4	113.8	C12—C11—H11	120.1
N3—C5—H5A	109.5	C11—C12—C13	120.33 (13)
N3—C5—H5B	109.5	C11—C12—H12	119.8
H5A—C5—H5B	109.5	C13—C12—H12	119.8
N3—C5—H5C	109.5	C8—C13—C12	119.12 (13)
H5A—C5—H5C	109.5	C8—C13—H13	120.4
H5B—C5—H5C	109.5	C12—C13—H13	120.4
C1—N1—N2—C7	161.44 (12)	C1—C2—C3—N2	−4.26 (14)
C8—N1—N2—C7	−57.85 (16)	C6—N3—C4—C2	−2.8 (2)
C1—N1—N2—C3	6.44 (14)	C5—N3—C4—C2	179.28 (14)
C8—N1—N2—C3	147.14 (11)	C3—C2—C4—N3	−9.4 (3)
N2—N1—C1—O1	170.26 (12)	C1—C2—C4—N3	174.34 (14)
C8—N1—C1—O1	31.01 (19)	N1—N2—C7—O3	10.0 (2)
N2—N1—C1—C2	−8.87 (14)	C3—N2—C7—O3	162.12 (13)
C8—N1—C1—C2	−148.12 (11)	C1—N1—C8—C9	111.30 (15)
O1—C1—C2—C4	6.4 (2)	N2—N1—C8—C9	−23.84 (17)
N1—C1—C2—C4	−174.52 (11)	C1—N1—C8—C13	−69.53 (16)
O1—C1—C2—C3	−170.80 (13)	N2—N1—C8—C13	155.33 (12)
N1—C1—C2—C3	8.25 (14)	C13—C8—C9—C10	0.6 (2)
C7—N2—C3—O2	24.0 (2)	N1—C8—C9—C10	179.72 (13)
N1—N2—C3—O2	178.78 (12)	C8—C9—C10—C11	−0.2 (2)
C7—N2—C3—C2	−156.09 (12)	C9—C10—C11—C12	−0.2 (2)
N1—N2—C3—C2	−1.27 (14)	C10—C11—C12—C13	0.0 (2)
C4—C2—C3—O2	−0.8 (3)	C9—C8—C13—C12	−0.7 (2)
C1—C2—C3—O2	175.68 (15)	N1—C8—C13—C12	−179.87 (12)
C4—C2—C3—N2	179.21 (14)	C11—C12—C13—C8	0.4 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···O2	0.98	2.08	3.016 (2)	160
C5—H5C···O3i	0.98	2.52	3.1803 (19)	124
C7—H7···O2ii	0.95	2.29	3.0663 (16)	139
C5—H5B···Cg1iii	0.98	2.98	3.8823 (18)	153

Table 1

Hydrogen-bond geometry (, )

Cg1 is the centroid of the C1/C2/C3/N1/N2 ring.

DHA	DH	HA	D A	DHA
C6H6AO2	0.98	2.08	3.016(2)	160
C5H5CO3i	0.98	2.52	3.1803(19)	124
C7H7O2ii	0.95	2.29	3.0663(16)	139
C5H5B Cg1iii	0.98	2.98	3.8823(18)	153

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