tert-Butyl 3-amino-2-methyl-6,7-dihydro-2H-pyrazolo[4,3-c]pyridine-5(4H)-carboxyl-ate.

In the mol-ecule of the title compound, C(12)H(20)N(4)O(2), the dihydro-piperidine ring assumes a half-chair conformation. In the crystal, cllassical N-H⋯O and N-H⋯N inter-molecular hydrogen bonds link mol-ecules into double chains along the a axis.

Related literature

For the synthesis and properties of related kinase inhibitors, see: Fancelli et al. (2005 ▶); Gadekar et al. (1968 ▶).

Experimental

Crystal data

C12H20N4O2

M = 252.32

Triclinic,

a = 6.3151 (13) Å

b = 9.3615 (19) Å

c = 11.215 (2) Å

α = 85.837 (4)°

β = 86.794 (4)°

γ = 87.733 (4)°

V = 659.8 (2) Å3

Z = 2

Mo Kα radiation

μ = 0.09 mm−1

T = 293 K

0.30 × 0.26 × 0.16 mm

Data collection

Rigaku, SCXmini diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.972, T max = 0.985

6859 measured reflections

3008 independent reflections

1737 reflections with I > 2σ(I)

R int = 0.052

Refinement

R[F 2 > 2σ(F 2)] = 0.064

wR(F 2) = 0.170

S = 1.01

3008 reflections

167 parameters

H-atom parameters constrained

Δρmax = 0.28 e Å−3

Δρmin = −0.36 e Å−3

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL/PC (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL/PC.

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536810013218/rz2434sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810013218/rz2434Isup2.hkl

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

C12H20N4O2	Z = 2
Mr = 252.32	F(000) = 272
Triclinic, P1	Dx = 1.270 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.3151 (13) Å	Cell parameters from 5123 reflections
b = 9.3615 (19) Å	θ = 3.2–27.5°
c = 11.215 (2) Å	µ = 0.09 mm−1
α = 85.837 (4)°	T = 293 K
β = 86.794 (4)°	Block, colourless
γ = 87.733 (4)°	0.30 × 0.26 × 0.16 mm
V = 659.8 (2) Å3

Rigaku, SCXmini diffractometer	3008 independent reflections
Radiation source: fine-focus sealed tube	1737 reflections with I > 2σ(I)
graphite	Rint = 0.052
Detector resolution: 13.6612 pixels mm-1	θmax = 27.5°, θmin = 3.2°
ω scans	h = −8→8
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −12→12
Tmin = 0.972, Tmax = 0.985	l = −14→14
6859 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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.170	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.081P)2] where P = (Fo2 + 2Fc2)/3
3008 reflections	(Δ/σ)max < 0.001
167 parameters	Δρmax = 0.28 e Å−3
0 restraints	Δρmin = −0.36 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.3109 (4)	0.0363 (3)	0.6957 (2)	0.0386 (6)
H1A	0.2825	−0.0408	0.6462	0.046*
H1B	0.3436	−0.0061	0.7744	0.046*
C2	0.5027 (4)	0.1173 (3)	0.6406 (2)	0.0398 (6)
H2A	0.5619	0.1713	0.7007	0.048*
H2B	0.6113	0.0498	0.6125	0.048*
C3	0.4344 (4)	0.2180 (2)	0.5375 (2)	0.0331 (6)
C4	0.2211 (4)	0.2453 (3)	0.5144 (2)	0.0329 (5)
C5	0.0400 (4)	0.1836 (3)	0.59148 (19)	0.0385 (6)
H5A	−0.0710	0.2567	0.6030	0.046*
H5B	−0.0191	0.1057	0.5531	0.046*
C6	0.2214 (4)	0.3437 (3)	0.4173 (2)	0.0346 (6)
C7	0.5130 (4)	0.4687 (3)	0.2914 (2)	0.0479 (7)
H7A	0.3984	0.5194	0.2522	0.072*
H7B	0.5974	0.4162	0.2344	0.072*
H7C	0.5997	0.5358	0.3251	0.072*
C8	0.0740 (4)	0.2085 (3)	0.8027 (2)	0.0327 (5)
C9	0.1596 (4)	0.2266 (3)	1.0122 (2)	0.0371 (6)
C10	0.2487 (5)	0.3756 (3)	0.9930 (3)	0.0561 (8)
H10A	0.3934	0.3684	0.9622	0.084*
H10B	0.2431	0.4197	1.0679	0.084*
H10C	0.1660	0.4329	0.9369	0.084*
C11	−0.0678 (4)	0.2267 (3)	1.0624 (2)	0.0486 (7)
H11A	−0.1532	0.2919	1.0136	0.073*
H11B	−0.0739	0.2563	1.1427	0.073*
H11C	−0.1206	0.1319	1.0627	0.073*
C12	0.2991 (5)	0.1310 (3)	1.0927 (2)	0.0564 (8)
H12A	0.2457	0.0360	1.1008	0.085*
H12B	0.2984	0.1687	1.1701	0.085*
H12C	0.4416	0.1279	1.0580	0.085*
N1	0.1203 (3)	0.1310 (2)	0.70667 (17)	0.0353 (5)
N2	0.5648 (3)	0.2928 (2)	0.46032 (17)	0.0388 (5)
N3	0.4281 (3)	0.3700 (2)	0.38587 (17)	0.0386 (5)
N4	0.0539 (3)	0.4037 (2)	0.35407 (19)	0.0507 (6)
H4A	0.0781	0.4606	0.2915	0.061*
H4B	−0.0744	0.3840	0.3773	0.061*
O1	0.1814 (3)	0.15709 (17)	0.89818 (14)	0.0398 (4)
O2	−0.0535 (3)	0.31087 (19)	0.80320 (15)	0.0480 (5)

	U11	U22	U33	U12	U13	U23
C1	0.0362 (14)	0.0381 (14)	0.0400 (14)	0.0063 (11)	0.0030 (11)	−0.0011 (11)
C2	0.0327 (14)	0.0447 (15)	0.0402 (14)	0.0078 (11)	0.0001 (11)	0.0032 (12)
C3	0.0273 (12)	0.0387 (14)	0.0327 (12)	0.0038 (10)	−0.0009 (10)	−0.0015 (11)
C4	0.0268 (12)	0.0436 (14)	0.0285 (12)	0.0024 (10)	−0.0019 (9)	−0.0044 (10)
C5	0.0308 (13)	0.0529 (16)	0.0319 (13)	−0.0022 (11)	−0.0021 (10)	−0.0040 (12)
C6	0.0296 (13)	0.0445 (14)	0.0299 (12)	0.0033 (11)	−0.0042 (10)	−0.0053 (11)
C7	0.0437 (16)	0.0557 (17)	0.0420 (15)	−0.0021 (13)	0.0000 (12)	0.0110 (13)
C8	0.0271 (12)	0.0374 (13)	0.0323 (12)	−0.0002 (11)	0.0005 (10)	0.0037 (11)
C9	0.0413 (15)	0.0385 (14)	0.0312 (13)	−0.0011 (11)	−0.0013 (10)	−0.0018 (11)
C10	0.0587 (19)	0.0517 (18)	0.0591 (18)	−0.0151 (14)	−0.0054 (14)	−0.0026 (14)
C11	0.0493 (17)	0.0514 (17)	0.0440 (15)	−0.0054 (13)	0.0103 (13)	−0.0028 (13)
C12	0.065 (2)	0.0602 (19)	0.0440 (16)	0.0080 (15)	−0.0120 (14)	0.0000 (14)
N1	0.0302 (11)	0.0431 (12)	0.0317 (10)	0.0020 (9)	0.0024 (8)	−0.0015 (9)
N2	0.0274 (11)	0.0496 (13)	0.0376 (11)	0.0047 (9)	−0.0007 (9)	0.0052 (10)
N3	0.0292 (11)	0.0487 (13)	0.0360 (11)	0.0037 (9)	−0.0020 (9)	0.0067 (10)
N4	0.0365 (13)	0.0750 (17)	0.0386 (12)	0.0059 (11)	−0.0059 (10)	0.0092 (11)
O1	0.0475 (11)	0.0406 (10)	0.0307 (9)	0.0096 (8)	−0.0045 (7)	−0.0031 (7)
O2	0.0519 (12)	0.0496 (11)	0.0403 (10)	0.0201 (9)	−0.0040 (8)	0.0006 (8)

C1—N1	1.471 (3)	C8—O2	1.227 (3)
C1—C2	1.532 (3)	C8—O1	1.349 (3)
C1—H1A	0.9700	C8—N1	1.354 (3)
C1—H1B	0.9700	C9—O1	1.474 (3)
C2—C3	1.509 (3)	C9—C11	1.513 (3)
C2—H2A	0.9700	C9—C12	1.516 (3)
C2—H2B	0.9700	C9—C10	1.521 (3)
C3—N2	1.340 (3)	C10—H10A	0.9600
C3—C4	1.396 (3)	C10—H10B	0.9600
C4—C6	1.375 (3)	C10—H10C	0.9600
C4—C5	1.502 (3)	C11—H11A	0.9600
C5—N1	1.460 (3)	C11—H11B	0.9600
C5—H5A	0.9700	C11—H11C	0.9600
C5—H5B	0.9700	C12—H12A	0.9600
C6—N3	1.360 (3)	C12—H12B	0.9600
C6—N4	1.384 (3)	C12—H12C	0.9600
C7—N3	1.448 (3)	N2—N3	1.382 (3)
C7—H7A	0.9600	N4—H4A	0.8600
C7—H7B	0.9600	N4—H4B	0.8600
C7—H7C	0.9600
N1—C1—C2	111.82 (19)	O1—C9—C11	111.03 (19)
N1—C1—H1A	109.3	O1—C9—C12	102.7 (2)
C2—C1—H1A	109.3	C11—C9—C12	110.1 (2)
N1—C1—H1B	109.3	O1—C9—C10	108.8 (2)
C2—C1—H1B	109.3	C11—C9—C10	113.5 (2)
H1A—C1—H1B	107.9	C12—C9—C10	110.2 (2)
C3—C2—C1	109.5 (2)	C9—C10—H10A	109.5
C3—C2—H2A	109.8	C9—C10—H10B	109.5
C1—C2—H2A	109.8	H10A—C10—H10B	109.5
C3—C2—H2B	109.8	C9—C10—H10C	109.5
C1—C2—H2B	109.8	H10A—C10—H10C	109.5
H2A—C2—H2B	108.2	H10B—C10—H10C	109.5
N2—C3—C4	112.4 (2)	C9—C11—H11A	109.5
N2—C3—C2	125.5 (2)	C9—C11—H11B	109.5
C4—C3—C2	122.1 (2)	H11A—C11—H11B	109.5
C6—C4—C3	105.4 (2)	C9—C11—H11C	109.5
C6—C4—C5	130.6 (2)	H11A—C11—H11C	109.5
C3—C4—C5	123.8 (2)	H11B—C11—H11C	109.5
N1—C5—C4	108.28 (18)	C9—C12—H12A	109.5
N1—C5—H5A	110.0	C9—C12—H12B	109.5
C4—C5—H5A	110.0	H12A—C12—H12B	109.5
N1—C5—H5B	110.0	C9—C12—H12C	109.5
C4—C5—H5B	110.0	H12A—C12—H12C	109.5
H5A—C5—H5B	108.4	H12B—C12—H12C	109.5
N3—C6—C4	106.7 (2)	C8—N1—C5	118.53 (19)
N3—C6—N4	123.2 (2)	C8—N1—C1	122.99 (19)
C4—C6—N4	129.9 (2)	C5—N1—C1	113.39 (19)
N3—C7—H7A	109.5	C3—N2—N3	103.51 (18)
N3—C7—H7B	109.5	C6—N3—N2	111.98 (19)
H7A—C7—H7B	109.5	C6—N3—C7	128.4 (2)
N3—C7—H7C	109.5	N2—N3—C7	119.56 (19)
H7A—C7—H7C	109.5	C6—N4—H4A	120.0
H7B—C7—H7C	109.5	C6—N4—H4B	120.0
O2—C8—O1	124.3 (2)	H4A—N4—H4B	120.0
O2—C8—N1	124.0 (2)	C8—O1—C9	121.18 (18)
O1—C8—N1	111.59 (19)
N1—C1—C2—C3	−42.3 (3)	C4—C5—N1—C8	104.8 (2)
C1—C2—C3—N2	−171.7 (2)	C4—C5—N1—C1	−50.8 (3)
C1—C2—C3—C4	9.9 (3)	C2—C1—N1—C8	−86.9 (3)
N2—C3—C4—C6	−0.3 (3)	C2—C1—N1—C5	67.4 (2)
C2—C3—C4—C6	178.3 (2)	C4—C3—N2—N3	0.0 (3)
N2—C3—C4—C5	−175.9 (2)	C2—C3—N2—N3	−178.6 (2)
C2—C3—C4—C5	2.8 (4)	C4—C6—N3—N2	−0.7 (3)
C6—C4—C5—N1	−157.6 (2)	N4—C6—N3—N2	−177.5 (2)
C3—C4—C5—N1	16.7 (3)	C4—C6—N3—C7	−178.1 (2)
C3—C4—C6—N3	0.6 (3)	N4—C6—N3—C7	5.1 (4)
C5—C4—C6—N3	175.7 (2)	C3—N2—N3—C6	0.4 (2)
C3—C4—C6—N4	177.1 (2)	C3—N2—N3—C7	178.1 (2)
C5—C4—C6—N4	−7.8 (4)	O2—C8—O1—C9	−2.9 (3)
O2—C8—N1—C5	9.7 (3)	N1—C8—O1—C9	178.62 (19)
O1—C8—N1—C5	−171.83 (18)	C11—C9—O1—C8	60.3 (3)
O2—C8—N1—C1	162.8 (2)	C12—C9—O1—C8	177.9 (2)
O1—C8—N1—C1	−18.7 (3)	C10—C9—O1—C8	−65.3 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···O2i	0.86	2.32	3.093 (3)	149
N4—H4B···N2ii	0.86	2.57	3.420 (3)	172

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4A⋯O2i	0.86	2.32	3.093 (3)	149
N4—H4B⋯N2ii	0.86	2.57	3.420 (3)	172

Symmetry codes: (i) ; (ii) .