Tert-butyl 3-oxo-2,3,4,5,6,7-hexa-hydro-1H-pyrazolo[4,3-c]pyridine-5-carboxyl-ate.

In the title compound, C(11)H(17)N(3)O(3), the pyrazole ring is approximately planar, with a maximum deviation of 0.005 (2) Å, and forms a dihedral angle of 5.69 (13)° with the plane through the six atoms of the piperidine ring. In the crystal, pairs of inter-molecular N-H⋯O hydrogen bonds form dimers with neighbouring mol-ecules, generating R(2) (2)(8) ring motifs. These dimers are further linked into two-dimensional arrays parallel to the bc plane by inter-molecular N-H⋯O and C-H⋯O hydrogen bonds.

Related literature

For the biological activity of pyrazolone derivatives, see: Al-Haiza et al. (2001 ▶); Brogden, (1986 ▶); Coersmeier et al. (1986 ▶); Gursoy et al. (2000 ▶). For myocardial ischemia, see: Wu et al. (2002 ▶). For brain ischemia, see: Watanabe et al. (1984 ▶); Kawai et al. (1997 ▶). For new compounds with the pyrazolone unit, see: Al-Haiza et al. (2001 ▶). For a related structure, see: Shahani et al. (2009 ▶). For ring conformations, see: Cremer & Pople (1975 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For bond-length data, see: Allen et al. (1987 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C11H17N3O3

M = 239.28

Monoclinic,

a = 18.6250 (12) Å

b = 6.0893 (5) Å

c = 10.7414 (7) Å

β = 104.100 (4)°

V = 1181.51 (15) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 100 K

0.97 × 0.35 × 0.14 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.910, T max = 0.986

13101 measured reflections

2690 independent reflections

2136 reflections with I > 2σ(I)

R int = 0.035

Refinement

R[F 2 > 2σ(F 2)] = 0.054

wR(F 2) = 0.172

S = 1.24

2690 reflections

222 parameters

All H-atom parameters refined

Δρmax = 0.39 e Å−3

Δρmin = −0.31 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809053021/ng2705sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809053021/ng2705Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C11H17N3O3	F(000) = 512
Mr = 239.28	Dx = 1.345 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7287 reflections
a = 18.6250 (12) Å	θ = 2.3–33.5°
b = 6.0893 (5) Å	µ = 0.10 mm−1
c = 10.7414 (7) Å	T = 100 K
β = 104.100 (4)°	Plate, colourless
V = 1181.51 (15) Å3	0.97 × 0.35 × 0.14 mm
Z = 4

Bruker SMART APEXII CCD area-detector diffractometer	2690 independent reflections
Radiation source: fine-focus sealed tube	2136 reflections with I > 2σ(I)
graphite	Rint = 0.035
φ and ω scans	θmax = 27.5°, θmin = 1.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −24→24
Tmin = 0.910, Tmax = 0.986	k = −7→7
13101 measured reflections	l = −13→13

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.172	All H-atom parameters refined
S = 1.24	w = 1/[σ2(Fo2) + (0.0688P)2 + 1.2823P] where P = (Fo2 + 2Fc2)/3
2690 reflections	(Δ/σ)max < 0.001
222 parameters	Δρmax = 0.39 e Å−3
0 restraints	Δρmin = −0.31 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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	0.30793 (9)	0.5995 (3)	0.33483 (16)	0.0205 (4)
O2	0.04609 (9)	0.9437 (3)	0.36561 (15)	0.0205 (4)
O3	0.34752 (9)	0.2971 (3)	0.45801 (16)	0.0231 (4)
N1	0.07659 (11)	0.5955 (4)	0.62882 (18)	0.0191 (4)
N2	0.04170 (11)	0.7682 (4)	0.55702 (19)	0.0186 (4)
N3	0.23023 (11)	0.4313 (3)	0.43120 (19)	0.0191 (4)
C1	0.20586 (14)	0.2460 (4)	0.4972 (2)	0.0215 (5)
C2	0.17706 (14)	0.3233 (4)	0.6127 (2)	0.0225 (5)
C3	0.12708 (12)	0.5145 (4)	0.5701 (2)	0.0185 (5)
C4	0.06920 (12)	0.7945 (4)	0.4514 (2)	0.0167 (5)
C5	0.12428 (12)	0.6319 (4)	0.4598 (2)	0.0172 (5)
C6	0.17364 (13)	0.5912 (4)	0.3715 (2)	0.0190 (5)
C7	0.30029 (12)	0.4308 (4)	0.4123 (2)	0.0180 (5)
C8	0.38126 (12)	0.6603 (4)	0.3140 (2)	0.0186 (5)
C9	0.43236 (15)	0.7313 (5)	0.4403 (3)	0.0258 (6)
C10	0.36107 (14)	0.8534 (5)	0.2231 (3)	0.0249 (6)
C11	0.41358 (14)	0.4723 (5)	0.2519 (2)	0.0215 (5)
H1A	0.2501 (16)	0.144 (5)	0.527 (3)	0.027 (7)*
H1B	0.1645 (16)	0.173 (5)	0.437 (3)	0.025 (7)*
H2A	0.1514 (16)	0.203 (6)	0.639 (3)	0.032 (8)*
H2B	0.2187 (16)	0.364 (5)	0.682 (3)	0.026 (7)*
H6A	0.1980 (15)	0.727 (5)	0.353 (3)	0.023 (7)*
H6B	0.1445 (14)	0.539 (5)	0.286 (3)	0.021 (7)*
H9A	0.4124 (16)	0.854 (5)	0.476 (3)	0.026 (8)*
H9B	0.4808 (16)	0.779 (5)	0.428 (3)	0.026 (7)*
H9C	0.4426 (16)	0.611 (6)	0.504 (3)	0.035 (9)*
H10A	0.4080 (17)	0.909 (5)	0.201 (3)	0.035 (8)*
H10B	0.3254 (17)	0.809 (5)	0.139 (3)	0.033 (8)*
H10C	0.3394 (19)	0.970 (6)	0.264 (3)	0.049 (10)*
H11A	0.4596 (16)	0.530 (5)	0.227 (3)	0.031 (8)*
H11B	0.4299 (15)	0.344 (5)	0.313 (3)	0.027 (7)*
H11C	0.3819 (18)	0.421 (6)	0.172 (3)	0.042 (9)*
H1N1	0.0676 (18)	0.566 (6)	0.714 (3)	0.043 (9)*
H1N2	0.0081 (18)	0.852 (6)	0.589 (3)	0.046 (10)*

	U11	U22	U33	U12	U13	U23
O1	0.0230 (8)	0.0192 (9)	0.0230 (8)	0.0028 (7)	0.0124 (6)	0.0066 (7)
O2	0.0288 (8)	0.0201 (9)	0.0164 (8)	0.0054 (7)	0.0128 (6)	0.0019 (7)
O3	0.0267 (8)	0.0206 (10)	0.0245 (9)	0.0053 (7)	0.0109 (7)	0.0061 (8)
N1	0.0267 (10)	0.0186 (11)	0.0152 (9)	−0.0001 (8)	0.0111 (7)	0.0008 (8)
N2	0.0246 (9)	0.0184 (11)	0.0160 (9)	0.0018 (8)	0.0110 (7)	0.0002 (8)
N3	0.0250 (10)	0.0148 (11)	0.0210 (10)	0.0028 (8)	0.0121 (8)	0.0043 (9)
C1	0.0285 (12)	0.0144 (12)	0.0253 (12)	0.0000 (10)	0.0138 (10)	0.0016 (11)
C2	0.0299 (12)	0.0177 (13)	0.0237 (12)	0.0001 (10)	0.0134 (10)	0.0069 (11)
C3	0.0235 (11)	0.0153 (12)	0.0192 (11)	−0.0036 (9)	0.0103 (9)	−0.0027 (10)
C4	0.0212 (10)	0.0163 (12)	0.0153 (10)	−0.0027 (9)	0.0099 (8)	−0.0018 (9)
C5	0.0224 (10)	0.0151 (12)	0.0164 (10)	−0.0015 (9)	0.0094 (8)	−0.0019 (9)
C6	0.0259 (11)	0.0182 (13)	0.0166 (11)	0.0041 (10)	0.0121 (9)	0.0014 (10)
C7	0.0244 (11)	0.0150 (12)	0.0167 (10)	0.0001 (10)	0.0089 (8)	−0.0012 (10)
C8	0.0222 (11)	0.0162 (12)	0.0213 (11)	−0.0014 (9)	0.0127 (9)	0.0010 (10)
C9	0.0327 (13)	0.0248 (15)	0.0224 (13)	−0.0028 (11)	0.0115 (10)	−0.0041 (12)
C10	0.0298 (12)	0.0237 (14)	0.0250 (13)	0.0024 (11)	0.0140 (10)	0.0053 (11)
C11	0.0265 (12)	0.0208 (13)	0.0198 (12)	0.0023 (10)	0.0106 (9)	−0.0032 (11)

O1—C7	1.351 (3)	C3—C5	1.374 (3)
O1—C8	1.484 (3)	C4—C5	1.413 (3)
O2—C4	1.290 (3)	C5—C6	1.494 (3)
O3—C7	1.212 (3)	C6—H6A	0.98 (3)
N1—C3	1.347 (3)	C6—H6B	1.00 (3)
N1—N2	1.371 (3)	C8—C10	1.516 (4)
N1—H1N1	0.99 (3)	C8—C9	1.518 (4)
N2—C4	1.364 (3)	C8—C11	1.521 (3)
N2—H1N2	0.94 (4)	C9—H9A	0.96 (3)
N3—C7	1.369 (3)	C9—H9B	0.99 (3)
N3—C1	1.462 (3)	C9—H9C	0.99 (3)
N3—C6	1.463 (3)	C10—H10A	1.02 (3)
C1—C2	1.540 (3)	C10—H10B	1.02 (3)
C1—H1A	1.02 (3)	C10—H10C	0.97 (4)
C1—H1B	0.98 (3)	C11—H11A	1.02 (3)
C2—C3	1.491 (4)	C11—H11B	1.02 (3)
C2—H2A	0.95 (3)	C11—H11C	0.97 (3)
C2—H2B	0.97 (3)
C7—O1—C8	121.42 (18)	N3—C6—H6A	109.1 (16)
C3—N1—N2	107.86 (19)	C5—C6—H6A	111.8 (17)
C3—N1—H1N1	132 (2)	N3—C6—H6B	111.4 (16)
N2—N1—H1N1	120 (2)	C5—C6—H6B	110.9 (15)
C4—N2—N1	109.62 (19)	H6A—C6—H6B	105 (2)
C4—N2—H1N2	132 (2)	O3—C7—O1	125.9 (2)
N1—N2—H1N2	118 (2)	O3—C7—N3	124.4 (2)
C7—N3—C1	119.4 (2)	O1—C7—N3	109.70 (19)
C7—N3—C6	123.2 (2)	O1—C8—C10	101.39 (18)
C1—N3—C6	116.77 (19)	O1—C8—C9	109.63 (18)
N3—C1—C2	111.4 (2)	C10—C8—C9	111.0 (2)
N3—C1—H1A	107.4 (17)	O1—C8—C11	110.8 (2)
C2—C1—H1A	110.2 (16)	C10—C8—C11	111.3 (2)
N3—C1—H1B	108.7 (17)	C9—C8—C11	112.2 (2)
C2—C1—H1B	107.2 (16)	C8—C9—H9A	111.1 (17)
H1A—C1—H1B	112 (2)	C8—C9—H9B	110.9 (16)
C3—C2—C1	107.8 (2)	H9A—C9—H9B	106 (2)
C3—C2—H2A	111.7 (19)	C8—C9—H9C	112.3 (19)
C1—C2—H2A	107.4 (19)	H9A—C9—H9C	110 (2)
C3—C2—H2B	111.2 (19)	H9B—C9—H9C	106 (2)
C1—C2—H2B	108.9 (17)	C8—C10—H10A	108.3 (18)
H2A—C2—H2B	110 (3)	C8—C10—H10B	111.7 (19)
N1—C3—C5	109.2 (2)	H10A—C10—H10B	107 (2)
N1—C3—C2	126.6 (2)	C8—C10—H10C	110 (2)
C5—C3—C2	124.1 (2)	H10A—C10—H10C	110 (3)
O2—C4—N2	123.3 (2)	H10B—C10—H10C	110 (3)
O2—C4—C5	130.5 (2)	C8—C11—H11A	107.7 (18)
N2—C4—C5	106.2 (2)	C8—C11—H11B	112.6 (17)
C3—C5—C4	107.13 (19)	H11A—C11—H11B	107 (2)
C3—C5—C6	124.1 (2)	C8—C11—H11C	114 (2)
C4—C5—C6	128.7 (2)	H11A—C11—H11C	105 (3)
N3—C6—C5	108.74 (19)	H11B—C11—H11C	110 (3)
C3—N1—N2—C4	1.0 (3)	O2—C4—C5—C6	2.0 (4)
C7—N3—C1—C2	125.7 (2)	N2—C4—C5—C6	−177.9 (2)
C6—N3—C1—C2	−63.6 (3)	C7—N3—C6—C5	−148.5 (2)
N3—C1—C2—C3	45.8 (3)	C1—N3—C6—C5	41.2 (3)
N2—N1—C3—C5	−0.9 (3)	C3—C5—C6—N3	−7.8 (3)
N2—N1—C3—C2	−178.8 (2)	C4—C5—C6—N3	170.1 (2)
C1—C2—C3—N1	162.0 (2)	C8—O1—C7—O3	−10.1 (4)
C1—C2—C3—C5	−15.7 (3)	C8—O1—C7—N3	170.38 (19)
N1—N2—C4—O2	179.3 (2)	C1—N3—C7—O3	−8.0 (4)
N1—N2—C4—C5	−0.8 (3)	C6—N3—C7—O3	−178.1 (2)
N1—C3—C5—C4	0.4 (3)	C1—N3—C7—O1	171.5 (2)
C2—C3—C5—C4	178.4 (2)	C6—N3—C7—O1	1.4 (3)
N1—C3—C5—C6	178.6 (2)	C7—O1—C8—C10	−179.8 (2)
C2—C3—C5—C6	−3.4 (4)	C7—O1—C8—C9	−62.4 (3)
O2—C4—C5—C3	−179.8 (2)	C7—O1—C8—C11	61.9 (3)
N2—C4—C5—C3	0.3 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O2i	0.99 (3)	1.77 (3)	2.748 (3)	171 (3)
N2—H1N2···O2ii	0.94 (3)	1.75 (4)	2.665 (3)	167 (3)
C1—H1B···O2iii	0.98 (3)	2.57 (3)	3.492 (3)	157 (3)
C11—H11C···O3iv	0.97 (3)	2.60 (3)	3.504 (3)	156 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O2i	0.99 (3)	1.77 (3)	2.748 (3)	171 (3)
N2—H1N2⋯O2ii	0.94 (3)	1.75 (4)	2.665 (3)	167 (3)
C1—H1B⋯O2iii	0.98 (3)	2.57 (3)	3.492 (3)	157 (3)
C11—H11C⋯O3iv	0.97 (3)	2.60 (3)	3.504 (3)	156 (3)

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