Crystal structure of ethyl N-(1,5-dimethyl-3-oxo-2-phenyl-2,3-di-hydro-1H-pyrazol-4-yl)carbamate.

In the title compound, C14H17N3O3, the dihedral angle between the benzene ring and the five-membered di-hydro-pyrazole ring is 52.26 (9)°. The ethyl ester group is approximately planar (r.m.s. deviation 0.0568 Å) and subtends an angle 67.73 (8)° to the pyrazole ring. In the crystal, molecules are linked by pairs of N-H⋯O hydrogen bonds, forming inversion dimers with an R 2 (2)(10) ring motif. Weaker C-H⋯O contacts link these dimers into a three-dimensional network of mol-ecules stacked along the a-axis direction. Offset π-π stacking inter-actions between the benzene rings [centroid-to-centroid distance = 3.8832 (12) Å] further stabilize the crystal packing.

Related literature

For related structures see: Li et al. (2013 ▸).

Experimental

Crystal data

C14H17N3O3

M = 275.30

Monoclinic,

a = 8.2100 (4) Å

b = 11.4137 (6) Å

c = 15.1594 (8) Å

β = 93.403 (3)°

V = 1418.03 (13) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 296 K

0.38 × 0.34 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▸) T min = 0.968, T max = 0.983

11712 measured reflections

3098 independent reflections

2368 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.127

S = 1.06

3098 reflections

185 parameters

H-atom parameters constrained

Δρmax = 0.19 e Å−3

Δρmin = −0.17 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: SHELXL2014/6 (Sheldrick, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸) and PLATON (Spek, 2009 ▸); software used to prepare material for publication: WinGX (Farrugia, 2012 ▸) and PLATON.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015006106/sj5447sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015006106/sj5447Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015006106/sj5447Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015006106/sj5447fig1.tif

View of the asymmetric unit of title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as small circles of arbitrary radii.

Click here for additional data file.

a . DOI: 10.1107/S2056989015006106/sj5447fig2.tif

The crystal packing of (I), viewed along the a axis, with hydrogen bonds shown as dashed lines.

CCDC reference: 1056157

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

C14H17N3O3	F(000) = 584
Mr = 275.30	Dx = 1.290 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.2100 (4) Å	Cell parameters from 2368 reflections
b = 11.4137 (6) Å	θ = 2.2–27.0°
c = 15.1594 (8) Å	µ = 0.09 mm−1
β = 93.403 (3)°	T = 296 K
V = 1418.03 (13) Å3	Plate, light yellow
Z = 4	0.38 × 0.34 × 0.20 mm

Bruker Kappa APEXII CCD diffractometer	3098 independent reflections
Radiation source: fine-focus sealed tube	2368 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
Detector resolution: 7.80 pixels mm-1	θmax = 27.0°, θmin = 2.2°
ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −14→13
Tmin = 0.968, Tmax = 0.983	l = −19→19
11712 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.043	H-atom parameters constrained
wR(F2) = 0.127	w = 1/[σ2(Fo2) + (0.0592P)2 + 0.2848P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max < 0.001
3098 reflections	Δρmax = 0.19 e Å−3
185 parameters	Δρmin = −0.17 e Å−3
0 restraints	Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.027 (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
O1	0.54493 (13)	0.33953 (9)	0.54004 (6)	0.0503 (3)
O2	0.13321 (16)	0.32771 (12)	0.33957 (11)	0.0819 (5)
O3	0.09391 (13)	0.51504 (10)	0.38192 (8)	0.0617 (3)
N1	0.65770 (15)	0.23072 (11)	0.42996 (8)	0.0458 (3)
N2	0.62265 (16)	0.21412 (12)	0.33892 (8)	0.0510 (3)
N3	0.34531 (15)	0.44615 (11)	0.38501 (8)	0.0480 (3)
H3A	0.3728	0.5172	0.3977	0.058*
C1	0.72550 (18)	0.13738 (13)	0.48290 (10)	0.0472 (4)
C2	0.8305 (2)	0.16528 (17)	0.55395 (11)	0.0592 (4)
H2	0.8595	0.2428	0.5653	0.071*
C3	0.8922 (3)	0.0764 (2)	0.60812 (14)	0.0791 (6)
H3	0.9628	0.0945	0.6565	0.095*
C4	0.8508 (3)	−0.0376 (2)	0.59139 (18)	0.0851 (7)
H4	0.8924	−0.0967	0.6285	0.102*
C5	0.7481 (3)	−0.06516 (17)	0.52008 (19)	0.0841 (7)
H5	0.7216	−0.1431	0.5085	0.101*
C6	0.6830 (2)	0.02230 (15)	0.46480 (14)	0.0639 (5)
H6	0.6122	0.0038	0.4166	0.077*
C7	0.55368 (17)	0.31534 (12)	0.46080 (9)	0.0406 (3)
C8	0.46691 (17)	0.35940 (13)	0.38352 (9)	0.0430 (3)
C9	0.51590 (19)	0.30017 (14)	0.31216 (10)	0.0487 (4)
C10	0.4694 (3)	0.3221 (2)	0.21696 (12)	0.0755 (6)
H10A	0.4626	0.2489	0.1858	0.113*
H10B	0.5502	0.3709	0.1921	0.113*
H10C	0.3654	0.3607	0.2117	0.113*
C11	0.7583 (2)	0.17664 (16)	0.28711 (12)	0.0621 (5)
H11A	0.7971	0.1016	0.3078	0.093*
H11B	0.8452	0.2329	0.2937	0.093*
H11C	0.7217	0.1709	0.2259	0.093*
C12	0.1866 (2)	0.42031 (14)	0.36699 (11)	0.0528 (4)
C13	−0.0815 (2)	0.4956 (2)	0.37242 (17)	0.0818 (6)
H13A	−0.1108	0.4609	0.3152	0.098*
H13B	−0.1145	0.4424	0.4179	0.098*
C14	−0.1628 (3)	0.6069 (3)	0.3803 (2)	0.1237 (11)
H14A	−0.2786	0.5946	0.3798	0.186*
H14B	−0.1381	0.6563	0.3316	0.186*
H14C	−0.1259	0.6438	0.4348	0.186*

	U11	U22	U33	U12	U13	U23
O1	0.0619 (7)	0.0475 (6)	0.0425 (6)	0.0067 (5)	0.0099 (5)	−0.0044 (4)
O2	0.0552 (7)	0.0589 (9)	0.1307 (13)	−0.0026 (6)	−0.0010 (8)	−0.0187 (8)
O3	0.0453 (6)	0.0558 (7)	0.0849 (8)	0.0115 (5)	0.0113 (6)	0.0010 (6)
N1	0.0493 (7)	0.0440 (7)	0.0445 (7)	0.0090 (6)	0.0050 (5)	−0.0052 (5)
N2	0.0517 (7)	0.0558 (8)	0.0458 (7)	0.0106 (6)	0.0067 (6)	−0.0112 (6)
N3	0.0459 (7)	0.0395 (7)	0.0586 (8)	0.0054 (5)	0.0037 (6)	−0.0030 (5)
C1	0.0421 (7)	0.0439 (8)	0.0568 (9)	0.0089 (6)	0.0134 (6)	0.0019 (7)
C2	0.0558 (9)	0.0613 (11)	0.0607 (10)	0.0102 (8)	0.0043 (8)	0.0035 (8)
C3	0.0691 (12)	0.0960 (17)	0.0724 (12)	0.0247 (12)	0.0054 (10)	0.0187 (11)
C4	0.0744 (14)	0.0786 (15)	0.1049 (17)	0.0307 (12)	0.0268 (13)	0.0369 (13)
C5	0.0725 (13)	0.0453 (11)	0.138 (2)	0.0119 (10)	0.0371 (14)	0.0176 (12)
C6	0.0542 (10)	0.0488 (10)	0.0901 (13)	0.0032 (8)	0.0156 (9)	−0.0036 (9)
C7	0.0411 (7)	0.0350 (7)	0.0464 (8)	−0.0002 (6)	0.0086 (6)	−0.0038 (6)
C8	0.0423 (7)	0.0396 (8)	0.0476 (8)	0.0030 (6)	0.0067 (6)	−0.0019 (6)
C9	0.0472 (8)	0.0521 (9)	0.0470 (8)	0.0031 (7)	0.0029 (6)	−0.0056 (6)
C10	0.0805 (13)	0.0979 (16)	0.0474 (10)	0.0178 (11)	−0.0019 (9)	−0.0074 (9)
C11	0.0611 (10)	0.0664 (11)	0.0605 (10)	0.0110 (9)	0.0174 (8)	−0.0146 (8)
C12	0.0487 (8)	0.0479 (9)	0.0622 (10)	0.0056 (7)	0.0067 (7)	0.0021 (7)
C13	0.0470 (10)	0.0869 (15)	0.1121 (17)	0.0083 (10)	0.0091 (10)	0.0007 (13)
C14	0.0581 (13)	0.105 (2)	0.211 (3)	0.0252 (14)	0.0337 (17)	0.016 (2)

O1—C7	1.2387 (17)	C4—H4	0.9300
O2—C12	1.208 (2)	C5—C6	1.390 (3)
O3—C12	1.3489 (19)	C5—H5	0.9300
O3—C13	1.456 (2)	C6—H6	0.9300
N1—C7	1.3886 (18)	C7—C8	1.426 (2)
N1—N2	1.4057 (17)	C8—C9	1.357 (2)
N1—C1	1.4269 (19)	C9—C10	1.492 (2)
N2—C9	1.362 (2)	C10—H10A	0.9600
N2—C11	1.4645 (19)	C10—H10B	0.9600
N3—C12	1.348 (2)	C10—H10C	0.9600
N3—C8	1.4072 (18)	C11—H11A	0.9600
N3—H3A	0.8600	C11—H11B	0.9600
C1—C2	1.376 (2)	C11—H11C	0.9600
C1—C6	1.383 (2)	C13—C14	1.443 (3)
C2—C3	1.382 (3)	C13—H13A	0.9700
C2—H2	0.9300	C13—H13B	0.9700
C3—C4	1.365 (3)	C14—H14A	0.9600
C3—H3	0.9300	C14—H14B	0.9600
C4—C5	1.367 (4)	C14—H14C	0.9600
C12—O3—C13	115.20 (15)	C9—C8—C7	108.79 (13)
C7—N1—N2	109.28 (11)	N3—C8—C7	123.72 (12)
C7—N1—C1	123.86 (12)	C8—C9—N2	109.74 (13)
N2—N1—C1	120.12 (12)	C8—C9—C10	128.08 (15)
C9—N2—N1	106.61 (11)	N2—C9—C10	122.17 (14)
C9—N2—C11	123.19 (14)	C9—C10—H10A	109.5
N1—N2—C11	116.61 (13)	C9—C10—H10B	109.5
C12—N3—C8	121.39 (13)	H10A—C10—H10B	109.5
C12—N3—H3A	119.3	C9—C10—H10C	109.5
C8—N3—H3A	119.3	H10A—C10—H10C	109.5
C2—C1—C6	120.94 (16)	H10B—C10—H10C	109.5
C2—C1—N1	118.21 (15)	N2—C11—H11A	109.5
C6—C1—N1	120.81 (15)	N2—C11—H11B	109.5
C1—C2—C3	119.05 (19)	H11A—C11—H11B	109.5
C1—C2—H2	120.5	N2—C11—H11C	109.5
C3—C2—H2	120.5	H11A—C11—H11C	109.5
C4—C3—C2	120.7 (2)	H11B—C11—H11C	109.5
C4—C3—H3	119.6	O2—C12—N3	125.98 (15)
C2—C3—H3	119.6	O2—C12—O3	124.21 (15)
C3—C4—C5	120.1 (2)	N3—C12—O3	109.79 (14)
C3—C4—H4	120.0	C14—C13—O3	108.53 (19)
C5—C4—H4	120.0	C14—C13—H13A	110.0
C4—C5—C6	120.6 (2)	O3—C13—H13A	110.0
C4—C5—H5	119.7	C14—C13—H13B	110.0
C6—C5—H5	119.7	O3—C13—H13B	110.0
C1—C6—C5	118.6 (2)	H13A—C13—H13B	108.4
C1—C6—H6	120.7	C13—C14—H14A	109.5
C5—C6—H6	120.7	C13—C14—H14B	109.5
O1—C7—N1	123.62 (13)	H14A—C14—H14B	109.5
O1—C7—C8	131.54 (13)	C13—C14—H14C	109.5
N1—C7—C8	104.82 (12)	H14A—C14—H14C	109.5
C9—C8—N3	127.41 (14)	H14B—C14—H14C	109.5
C7—N1—N2—C9	9.01 (16)	C12—N3—C8—C9	67.6 (2)
C1—N1—N2—C9	161.31 (13)	C12—N3—C8—C7	−108.89 (18)
C7—N1—N2—C11	151.05 (14)	O1—C7—C8—C9	−177.01 (16)
C1—N1—N2—C11	−56.66 (19)	N1—C7—C8—C9	1.68 (16)
C7—N1—C1—C2	−64.2 (2)	O1—C7—C8—N3	0.0 (3)
N2—N1—C1—C2	147.71 (14)	N1—C7—C8—N3	178.73 (13)
C7—N1—C1—C6	113.91 (17)	N3—C8—C9—N2	−172.97 (14)
N2—N1—C1—C6	−34.2 (2)	C7—C8—C9—N2	3.95 (18)
C6—C1—C2—C3	−0.7 (2)	N3—C8—C9—C10	8.5 (3)
N1—C1—C2—C3	177.40 (15)	C7—C8—C9—C10	−174.57 (18)
C1—C2—C3—C4	0.4 (3)	N1—N2—C9—C8	−7.90 (17)
C2—C3—C4—C5	0.5 (3)	C11—N2—C9—C8	−146.82 (15)
C3—C4—C5—C6	−1.0 (3)	N1—N2—C9—C10	170.73 (16)
C2—C1—C6—C5	0.2 (2)	C11—N2—C9—C10	31.8 (3)
N1—C1—C6—C5	−177.87 (15)	C8—N3—C12—O2	−8.1 (3)
C4—C5—C6—C1	0.7 (3)	C8—N3—C12—O3	173.51 (13)
N2—N1—C7—O1	172.30 (14)	C13—O3—C12—O2	6.8 (3)
C1—N1—C7—O1	21.3 (2)	C13—O3—C12—N3	−174.78 (15)
N2—N1—C7—C8	−6.52 (16)	C12—O3—C13—C14	−173.5 (2)
C1—N1—C7—C8	−157.55 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O1i	0.86	1.99	2.8223 (17)	164
C10—H10A···O1ii	0.96	2.56	3.343 (2)	139
C11—H11B···O2iii	0.96	2.66	3.576 (2)	161

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N3H3AO1i	0.86	1.99	2.8223(17)	164
C10H10AO1ii	0.96	2.56	3.343(2)	139
C11H11BO2iii	0.96	2.66	3.576(2)	161

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