Ethyl 4-(3-chloro­phen­yl)-3,6-dihydr­oxy-6-methyl-2-(2-pyrid­yl)-4,5,6,7-tetra­hydro­indazole-5-carboxyl­ate

Amirthaganesan, S.; Aridoss, G.; D.Gayathri; Park, K.S.; Jeong, Y.T.

doi:10.1107/S1600536810009360

organic compounds

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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page o861

doi:10.1107/S1600536810009360

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Ethyl 4-(3-chlorophenyl)-3,6-dihydroxy-6-methyl-2-(2-pyridyl)-4,5,6,7-tetrahydroindazole-5-carboxylate

S. Amirthaganesan,^a G. Aridoss,^a D.Gayathri,^b Keun Soo Park ^a and Yeon Tae Jeong ^a ^*

^aDivision of Image Science and Information Engineering, Pukyong National University, Busan 608-739, Republic of Korea, and ^bInstitute of Structural Biology and Biophysics-2: Molecular Biophysics, Research Centre Jülich, D-52425 Jülich, Germany
^*Correspondence e-mail: ytjeong@pknu.ac.kr

(Received 10 March 2010; accepted 12 March 2010; online 17 March 2010)

In the title compound, C₂₂H₂₂ClN₃O₄, the cyclohexane ring adopts a twisted half-chair conformation. The molecule is stabilized by an intramolecular O—H⋯N interaction, generating an S(6) motif. The crystal packing is stabilized by intermolecular O—H⋯N and C—H⋯O interactions.

Related literature

For the synthesis and stereochemistry investigations through NMR of N(2)-pyridyl tetrahydroindazoles, see: Amirthaganesan et al. (2008 ). For the biological activity of tetrahydroindazoles, see: Connolly et al. (1997 ). For ring conformational analysis, see: Cremer & Pople (1975 ); Nardelli (1983 ).

Experimental

Crystal data

C₂₂H₂₂ClN₃O₄
M_r = 427.88
Triclinic, $[P \overline 1]$
a = 8.585 (5) Å
b = 9.053 (3) Å
c = 14.884 (3) Å
α = 94.68 (2)°
β = 90.19 (2)°
γ = 115.66 (3)°
V = 1038.3 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 293 K
0.30 × 0.22 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.937, T_max = 0.958
4446 measured reflections
3647 independent reflections
3025 reflections with I > 2σ(I)
R_int = 0.010

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.092
S = 1.04
3647 reflections
274 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4⋯N3	0.82	1.90	2.604 (3)	143
O3—H3⋯N1ⁱ	0.82	2.10	2.920 (2)	176
C11—H11⋯O3ⁱⁱ	0.93	2.58	3.418 (3)	151
C16—H16C⋯O4ⁱⁱⁱ	0.96	2.57	3.397 (3)	144
Symmetry codes: (i) -x, -y, -z+1; (ii) x+1, y, z; (iii) x-1, y-1, z.

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810009360/ng2744sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810009360/ng2744Isup2.hkl

checkCIF report

Comment top

In azole family, tetrahydroindazoles (cycloalkane derivatives of pyrazoles) are having much importance for their effective biological potencies (Connolly et al., 1997). Our current research work is focused on the stereospecific synthesis of 1(H) and various N-substituted tetrahydroindazoles by taking cyclic β keto esters as an effective synthons, and exploring their stereochemistry. Recently, we have described complete structural elucidation and conformation of a series of N(2)-pyridyl tetrahydroindazoles (Amirthaganesan et al., 2008). One and two dimensional NMR investigations strongly proved that all the compounds obtained as a single isomer where cyclohexane ring adopts slightly distorted chair conformation and pyridyl moiety favored at N(2) position in the azole ring. We report here the X-ray crystal structure of the title compound.

The sum of the bond angles at N2 (359.9 (3)°) indicates the sp² hybridization. Atoms O4 and Cl1 lie in the plane of the rings to which they are attached with the deviation of 0.002 (2) and -0.004 (1) Å, respectively. The pyridine (or pyridyl) ring, attached at N(2) position of the pyrazole ring, is parallel to the pyrazole ring with the dihedral angle of 8.0 (1)°. The dihedral angle between the phenyl ring and the pyridine (or pyridyl) ring is 64.2 (1)°. Torsion angle (3.9 (3)°) around O1—C13—O2—C14 indicates the planarity of the moiety. The cyclohexane ring adopts twisted half-chair conformation in solid state, with the puckering parameters (Cremer & Pople, 1975) and the smallest displacement asymmetry parameters (Nardelli, 1983) being q₂ = 0.373 (2) Å, q₃ = -0.346 (2) Å; Q_T = 0.509 (2)Å and θ = 132.8 (2)°.

The molecule is stabilized by strong O—H···N intramolecular interaction, wherein, atom O4 acts as donor to N3 generating S(6) motif. The crystal packing is stabilized by O—H···N and C—H···O intermolecular interactions. Atoms C11 and C16 act as donors to O3 and O4, respectively, each generating chain of C(8), which in turn generates R₄⁴(28) graph set along ab plane. Atom O3 acts as donor to N1 at (-x,-y,-z+1) generating a centrosymmetric dimer of R₂²(12) graph set.

Related literature top

For the synthesis and stereochemistry investigations through NMR of N(2)-pyridyl tetrahydroindazoles, see: Amirthaganesan et al. (2008). For the biological activity of tetrahydroindazoles, see: Connolly et al. (1997). For ring conformational analysis, see: Cremer & Pople (1975); Nardelli (1983).

Experimental top

A mixture of r-2,c(4)-bis(ethoxycarbonyl)-c(5)-hydroxy-t(5)-methyl-t(3)- (p-chlorophenyl)cyclohexanone (1 mmol) and 2-hydrazinopyridine (1.2 mmol) in toluene with the addition of catalytic amount of acetic acid were refluxed for about 6 h. After completion of the reaction, the solvent was evaporated under vacuum and the resultant residue was recrystallized from ethanol.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of title compound, showing 30% probability displacement ellipsoids.
	Fig. 2. The molecular packing of (I). For clarity, hydrogen atoms which are not involved in hydrogen bonding are omitted.

Ethyl 4-(3-chlorophenyl)-3,6-dihydroxy-6-methyl-2-(2-pyridyl)-4,5,6,7- tetrahydroindazole-5-carboxylate top

Crystal data top

C₂₂H₂₂ClN₃O₄	Z = 2
M_r = 427.88	F(000) = 448
Triclinic, P1	D_x = 1.369 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.585 (5) Å	Cell parameters from 1965 reflections
b = 9.053 (3) Å	θ = 2.5–25.0°
c = 14.884 (3) Å	µ = 0.22 mm⁻¹
α = 94.68 (2)°	T = 293 K
β = 90.19 (2)°	Prism, colourless
γ = 115.66 (3)°	0.30 × 0.22 × 0.20 mm
V = 1038.3 (7) Å³

Data collection top

Bruker Kappa APEXII CCD diffractometer	3647 independent reflections
Radiation source: fine-focus sealed tube	3025 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.010
ω and ϕ scan	θ_max = 25.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −1→10
T_min = 0.937, T_max = 0.958	k = −10→10
4446 measured reflections	l = −17→17

Refinement top

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)] = 0.033	H-atom parameters constrained
wR(F²) = 0.092	w = 1/[σ²(F_o²) + (0.0426P)² + 0.3338P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
3647 reflections	Δρ_max = 0.24 e Å⁻³
274 parameters	Δρ_min = −0.30 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0065 (15)

Crystal data top

C₂₂H₂₂ClN₃O₄	γ = 115.66 (3)°
M_r = 427.88	V = 1038.3 (7) Å³
Triclinic, P1	Z = 2
a = 8.585 (5) Å	Mo Kα radiation
b = 9.053 (3) Å	µ = 0.22 mm⁻¹
c = 14.884 (3) Å	T = 293 K
α = 94.68 (2)°	0.30 × 0.22 × 0.20 mm
β = 90.19 (2)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	3647 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	3025 reflections with I > 2σ(I)
T_min = 0.937, T_max = 0.958	R_int = 0.010
4446 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.092	H-atom parameters constrained
S = 1.04	Δρ_max = 0.24 e Å⁻³
3647 reflections	Δρ_min = −0.30 e Å⁻³
274 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.23589 (18)	0.01801 (18)	0.72716 (10)	0.0366 (3)
H1	0.2978	−0.0511	0.7220	0.044*
C2	0.07219 (19)	−0.06547 (18)	0.66275 (10)	0.0375 (3)
C3	0.12780 (19)	−0.09587 (18)	0.56754 (10)	0.0396 (4)
H3A	0.1634	−0.1841	0.5665	0.048*
H3B	0.0304	−0.1297	0.5248	0.048*
C4	0.27363 (19)	0.05594 (18)	0.54012 (10)	0.0361 (3)
C5	0.38310 (19)	0.18470 (18)	0.60252 (10)	0.0369 (3)
C6	0.36178 (19)	0.19180 (18)	0.70250 (10)	0.0356 (3)
H6	0.3088	0.2666	0.7180	0.043*
C7	0.53145 (18)	0.25391 (18)	0.75799 (10)	0.0351 (3)
C8	0.5566 (2)	0.3545 (2)	0.83731 (10)	0.0414 (4)
H8	0.4731	0.3891	0.8551	0.050*
C9	0.7067 (2)	0.4029 (2)	0.88964 (10)	0.0447 (4)
C10	0.8331 (2)	0.3542 (2)	0.86565 (11)	0.0469 (4)
H10	0.9332	0.3878	0.9019	0.056*
C11	0.8082 (2)	0.2543 (2)	0.78656 (11)	0.0469 (4)
H11	0.8920	0.2196	0.7693	0.056*
C12	0.6592 (2)	0.2054 (2)	0.73290 (11)	0.0417 (4)
H12	0.6445	0.1393	0.6794	0.050*
C13	0.1873 (2)	0.0274 (2)	0.82426 (11)	0.0427 (4)
C14	0.1681 (4)	−0.0911 (3)	0.96324 (14)	0.0803 (7)
H14A	0.1570	−0.1955	0.9816	0.096*
H14B	0.0556	−0.0903	0.9672	0.096*
C15	0.2938 (3)	0.0447 (3)	1.02645 (15)	0.0851 (7)
H15A	0.4060	0.0462	1.0219	0.128*
H15B	0.2568	0.0276	1.0871	0.128*
H15C	0.2997	0.1479	1.0111	0.128*
C16	−0.0561 (2)	−0.2271 (2)	0.69547 (12)	0.0507 (4)
H16A	−0.0970	−0.2058	0.7528	0.076*
H16B	−0.0002	−0.2976	0.7018	0.076*
H16C	−0.1521	−0.2799	0.6525	0.076*
C17	0.5006 (2)	0.29568 (19)	0.55071 (10)	0.0413 (4)
C18	0.5488 (2)	0.30146 (19)	0.38582 (11)	0.0402 (4)
C19	0.4867 (2)	0.2333 (2)	0.29936 (11)	0.0466 (4)
H19	0.3820	0.1401	0.2887	0.056*
C20	0.5862 (3)	0.3088 (2)	0.22937 (12)	0.0575 (5)
H20	0.5490	0.2663	0.1701	0.069*
C21	0.7400 (3)	0.4464 (3)	0.24685 (13)	0.0605 (5)
H21	0.8084	0.4975	0.2000	0.073*
C22	0.7904 (2)	0.5064 (2)	0.33443 (13)	0.0584 (5)
H22	0.8939	0.6006	0.3462	0.070*
N1	0.31575 (16)	0.08157 (15)	0.45512 (8)	0.0394 (3)
N2	0.45910 (16)	0.23300 (15)	0.46190 (8)	0.0408 (3)
N3	0.69768 (19)	0.43596 (18)	0.40430 (10)	0.0510 (4)
O1	0.12768 (17)	0.11693 (18)	0.85661 (8)	0.0608 (4)
O2	0.21903 (18)	−0.07785 (16)	0.87015 (8)	0.0602 (3)
O3	−0.00213 (13)	0.04846 (13)	0.66127 (7)	0.0443 (3)
H3	−0.0884	0.0092	0.6272	0.066*
O4	0.63299 (16)	0.44010 (14)	0.57502 (8)	0.0589 (3)
H4	0.6822	0.4810	0.5300	0.088*
Cl1	0.73648 (7)	0.52862 (8)	0.98989 (3)	0.0772 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0313 (7)	0.0407 (8)	0.0381 (8)	0.0167 (7)	−0.0041 (6)	−0.0003 (6)
C2	0.0317 (7)	0.0382 (8)	0.0398 (8)	0.0136 (6)	−0.0052 (6)	−0.0027 (6)
C3	0.0354 (8)	0.0369 (8)	0.0406 (8)	0.0118 (7)	−0.0072 (6)	−0.0052 (6)
C4	0.0328 (7)	0.0377 (8)	0.0358 (8)	0.0147 (6)	−0.0055 (6)	−0.0031 (6)
C5	0.0352 (8)	0.0366 (8)	0.0348 (8)	0.0128 (6)	−0.0085 (6)	−0.0031 (6)
C6	0.0326 (7)	0.0380 (8)	0.0347 (8)	0.0153 (6)	−0.0073 (6)	−0.0039 (6)
C7	0.0314 (7)	0.0369 (8)	0.0327 (7)	0.0113 (6)	−0.0038 (6)	0.0006 (6)
C8	0.0338 (8)	0.0494 (9)	0.0390 (8)	0.0178 (7)	−0.0043 (6)	−0.0045 (7)
C9	0.0370 (8)	0.0543 (10)	0.0334 (8)	0.0126 (7)	−0.0061 (6)	−0.0048 (7)
C10	0.0304 (8)	0.0625 (11)	0.0408 (9)	0.0138 (8)	−0.0064 (6)	0.0052 (8)
C11	0.0347 (8)	0.0575 (10)	0.0494 (10)	0.0211 (8)	0.0011 (7)	0.0042 (8)
C12	0.0388 (8)	0.0449 (9)	0.0388 (8)	0.0171 (7)	−0.0017 (6)	−0.0036 (7)
C13	0.0309 (8)	0.0504 (9)	0.0407 (9)	0.0125 (7)	−0.0048 (6)	0.0017 (7)
C14	0.1040 (18)	0.0827 (15)	0.0467 (11)	0.0304 (14)	0.0103 (11)	0.0233 (11)
C15	0.0936 (17)	0.114 (2)	0.0490 (12)	0.0472 (16)	−0.0075 (11)	0.0030 (12)
C16	0.0395 (9)	0.0468 (9)	0.0552 (10)	0.0094 (8)	−0.0018 (8)	0.0015 (8)
C17	0.0393 (8)	0.0374 (8)	0.0394 (8)	0.0106 (7)	−0.0094 (7)	−0.0029 (6)
C18	0.0387 (8)	0.0418 (8)	0.0432 (9)	0.0201 (7)	−0.0002 (7)	0.0050 (7)
C19	0.0447 (9)	0.0489 (9)	0.0447 (9)	0.0197 (8)	−0.0006 (7)	0.0004 (7)
C20	0.0642 (12)	0.0695 (12)	0.0421 (10)	0.0326 (10)	0.0043 (8)	0.0030 (9)
C21	0.0576 (11)	0.0710 (13)	0.0536 (11)	0.0264 (10)	0.0143 (9)	0.0183 (10)
C22	0.0458 (10)	0.0565 (11)	0.0648 (12)	0.0127 (9)	0.0058 (9)	0.0166 (9)
N1	0.0339 (7)	0.0389 (7)	0.0380 (7)	0.0102 (6)	−0.0048 (5)	−0.0038 (5)
N2	0.0373 (7)	0.0400 (7)	0.0364 (7)	0.0093 (6)	−0.0040 (5)	0.0005 (5)
N3	0.0447 (8)	0.0494 (8)	0.0506 (8)	0.0123 (7)	−0.0010 (6)	0.0075 (7)
O1	0.0593 (8)	0.0877 (10)	0.0464 (7)	0.0437 (8)	0.0021 (6)	−0.0024 (6)
O2	0.0762 (9)	0.0632 (8)	0.0440 (7)	0.0315 (7)	0.0015 (6)	0.0137 (6)
O3	0.0353 (6)	0.0488 (6)	0.0494 (6)	0.0210 (5)	−0.0127 (5)	−0.0083 (5)
O4	0.0561 (7)	0.0446 (7)	0.0471 (7)	−0.0039 (6)	−0.0076 (6)	−0.0020 (5)
Cl1	0.0581 (3)	0.1098 (5)	0.0520 (3)	0.0334 (3)	−0.0211 (2)	−0.0374 (3)

Geometric parameters (Å, º) top

C1—C13	1.512 (2)	C13—O2	1.333 (2)
C1—C6	1.550 (2)	C14—O2	1.453 (2)
C1—C2	1.555 (2)	C14—C15	1.489 (3)
C1—H1	0.9800	C14—H14A	0.9700
C2—O3	1.4300 (19)	C14—H14B	0.9700
C2—C16	1.521 (2)	C15—H15A	0.9600
C2—C3	1.538 (2)	C15—H15B	0.9600
C3—C4	1.492 (2)	C15—H15C	0.9600
C3—H3A	0.9700	C16—H16A	0.9600
C3—H3B	0.9700	C16—H16B	0.9600
C4—N1	1.328 (2)	C16—H16C	0.9600
C4—C5	1.405 (2)	C17—O4	1.3287 (19)
C5—C17	1.369 (2)	C17—N2	1.377 (2)
C5—C6	1.500 (2)	C18—N3	1.337 (2)
C6—C7	1.525 (2)	C18—C19	1.379 (2)
C6—H6	0.9800	C18—N2	1.402 (2)
C7—C8	1.387 (2)	C19—C20	1.378 (3)
C7—C12	1.389 (2)	C19—H19	0.9300
C8—C9	1.381 (2)	C20—C21	1.372 (3)
C8—H8	0.9300	C20—H20	0.9300
C9—C10	1.375 (2)	C21—C22	1.363 (3)
C9—Cl1	1.7482 (17)	C21—H21	0.9300
C10—C11	1.381 (2)	C22—N3	1.340 (2)
C10—H10	0.9300	C22—H22	0.9300
C11—C12	1.384 (2)	N1—N2	1.3854 (19)
C11—H11	0.9300	O3—H3	0.8200
C12—H12	0.9300	O4—H4	0.8200
C13—O1	1.204 (2)

C13—C1—C6	109.76 (12)	O1—C13—O2	123.97 (16)
C13—C1—C2	111.12 (12)	O1—C13—C1	125.16 (15)
C6—C1—C2	113.02 (12)	O2—C13—C1	110.87 (14)
C13—C1—H1	107.6	O2—C14—C15	112.8 (2)
C6—C1—H1	107.6	O2—C14—H14A	109.0
C2—C1—H1	107.6	C15—C14—H14A	109.0
O3—C2—C16	110.78 (13)	O2—C14—H14B	109.0
O3—C2—C3	109.40 (13)	C15—C14—H14B	109.0
C16—C2—C3	110.15 (13)	H14A—C14—H14B	107.8
O3—C2—C1	106.58 (12)	C14—C15—H15A	109.5
C16—C2—C1	111.06 (13)	C14—C15—H15B	109.5
C3—C2—C1	108.78 (12)	H15A—C15—H15B	109.5
C4—C3—C2	110.91 (12)	C14—C15—H15C	109.5
C4—C3—H3A	109.5	H15A—C15—H15C	109.5
C2—C3—H3A	109.5	H15B—C15—H15C	109.5
C4—C3—H3B	109.5	C2—C16—H16A	109.5
C2—C3—H3B	109.5	C2—C16—H16B	109.5
H3A—C3—H3B	108.0	H16A—C16—H16B	109.5
N1—C4—C5	113.24 (14)	C2—C16—H16C	109.5
N1—C4—C3	123.79 (13)	H16A—C16—H16C	109.5
C5—C4—C3	122.95 (14)	H16B—C16—H16C	109.5
C17—C5—C4	104.49 (13)	O4—C17—C5	130.01 (14)
C17—C5—C6	130.71 (13)	O4—C17—N2	122.42 (15)
C4—C5—C6	124.75 (14)	C5—C17—N2	107.56 (13)
C5—C6—C7	113.80 (13)	N3—C18—C19	123.45 (16)
C5—C6—C1	108.64 (12)	N3—C18—N2	114.62 (14)
C7—C6—C1	110.03 (12)	C19—C18—N2	121.93 (15)
C5—C6—H6	108.1	C20—C19—C18	117.28 (17)
C7—C6—H6	108.1	C20—C19—H19	121.4
C1—C6—H6	108.1	C18—C19—H19	121.4
C8—C7—C12	118.85 (14)	C21—C20—C19	120.22 (18)
C8—C7—C6	119.86 (13)	C21—C20—H20	119.9
C12—C7—C6	121.22 (13)	C19—C20—H20	119.9
C9—C8—C7	119.45 (15)	C22—C21—C20	118.54 (18)
C9—C8—H8	120.3	C22—C21—H21	120.7
C7—C8—H8	120.3	C20—C21—H21	120.7
C10—C9—C8	122.03 (15)	N3—C22—C21	122.97 (18)
C10—C9—Cl1	118.91 (12)	N3—C22—H22	118.5
C8—C9—Cl1	119.06 (13)	C21—C22—H22	118.5
C9—C10—C11	118.52 (15)	C4—N1—N2	103.89 (12)
C9—C10—H10	120.7	C17—N2—N1	110.81 (13)
C11—C10—H10	120.7	C17—N2—C18	127.39 (13)
C10—C11—C12	120.31 (15)	N1—N2—C18	121.72 (13)
C10—C11—H11	119.8	C18—N3—C22	117.54 (16)
C12—C11—H11	119.8	C13—O2—C14	117.31 (16)
C11—C12—C7	120.83 (15)	C2—O3—H3	109.5
C11—C12—H12	119.6	C17—O4—H4	109.5
C7—C12—H12	119.6

C13—C1—C2—O3	70.80 (16)	C10—C11—C12—C7	−0.9 (3)
C6—C1—C2—O3	−53.11 (16)	C8—C7—C12—C11	1.0 (2)
C13—C1—C2—C16	−49.95 (17)	C6—C7—C12—C11	−176.00 (15)
C6—C1—C2—C16	−173.86 (13)	C6—C1—C13—O1	54.3 (2)
C13—C1—C2—C3	−171.33 (13)	C2—C1—C13—O1	−71.5 (2)
C6—C1—C2—C3	64.75 (16)	C6—C1—C13—O2	−125.83 (14)
O3—C2—C3—C4	66.92 (16)	C2—C1—C13—O2	108.41 (15)
C16—C2—C3—C4	−171.08 (13)	C4—C5—C17—O4	179.84 (17)
C1—C2—C3—C4	−49.14 (17)	C6—C5—C17—O4	2.2 (3)
C2—C3—C4—N1	−160.33 (14)	C4—C5—C17—N2	0.32 (17)
C2—C3—C4—C5	21.3 (2)	C6—C5—C17—N2	−177.30 (15)
N1—C4—C5—C17	−0.35 (18)	N3—C18—C19—C20	0.6 (3)
C3—C4—C5—C17	178.15 (14)	N2—C18—C19—C20	−179.03 (15)
N1—C4—C5—C6	177.45 (14)	C18—C19—C20—C21	−0.2 (3)
C3—C4—C5—C6	−4.0 (2)	C19—C20—C21—C22	−0.5 (3)
C17—C5—C6—C7	−44.3 (2)	C20—C21—C22—N3	0.9 (3)
C4—C5—C6—C7	138.48 (15)	C5—C4—N1—N2	0.23 (17)
C17—C5—C6—C1	−167.28 (16)	C3—C4—N1—N2	−178.26 (13)
C4—C5—C6—C1	15.5 (2)	O4—C17—N2—N1	−179.77 (14)
C13—C1—C6—C5	−170.09 (12)	C5—C17—N2—N1	−0.21 (18)
C2—C1—C6—C5	−45.43 (16)	O4—C17—N2—C18	3.5 (3)
C13—C1—C6—C7	64.71 (16)	C5—C17—N2—C18	−176.92 (14)
C2—C1—C6—C7	−170.63 (12)	C4—N1—N2—C17	−0.01 (16)
C5—C6—C7—C8	142.41 (15)	C4—N1—N2—C18	176.92 (13)
C1—C6—C7—C8	−95.41 (17)	N3—C18—N2—C17	5.5 (2)
C5—C6—C7—C12	−40.7 (2)	C19—C18—N2—C17	−174.84 (15)
C1—C6—C7—C12	81.54 (17)	N3—C18—N2—N1	−170.91 (13)
C12—C7—C8—C9	−0.5 (2)	C19—C18—N2—N1	8.8 (2)
C6—C7—C8—C9	176.50 (15)	C19—C18—N3—C22	−0.3 (3)
C7—C8—C9—C10	−0.1 (3)	N2—C18—N3—C22	179.38 (15)
C7—C8—C9—Cl1	−179.58 (12)	C21—C22—N3—C18	−0.5 (3)
C8—C9—C10—C11	0.2 (3)	O1—C13—O2—C14	3.9 (3)
Cl1—C9—C10—C11	179.72 (13)	C1—C13—O2—C14	−175.97 (16)
C9—C10—C11—C12	0.3 (3)	C15—C14—O2—C13	−79.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···N3	0.82	1.90	2.604 (3)	143
O3—H3···N1ⁱ	0.82	2.10	2.920 (2)	176
C11—H11···O3ⁱⁱ	0.93	2.58	3.418 (3)	151
C16—H16C···O4ⁱⁱⁱ	0.96	2.57	3.397 (3)	144

Symmetry codes: (i) −x, −y, −z+1; (ii) x+1, y, z; (iii) x−1, y−1, z.

Experimental details

Crystal data
Chemical formula	C₂₂H₂₂ClN₃O₄
M_r	427.88
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	8.585 (5), 9.053 (3), 14.884 (3)
α, β, γ (°)	94.68 (2), 90.19 (2), 115.66 (3)
V (Å³)	1038.3 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.22
Crystal size (mm)	0.30 × 0.22 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.937, 0.958
No. of measured, independent and observed [I > 2σ(I)] reflections	4446, 3647, 3025
R_int	0.010
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.092, 1.04
No. of reflections	3647
No. of parameters	274
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.30

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SIR92 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···N3	0.82	1.90	2.604 (3)	143.4
O3—H3···N1ⁱ	0.82	2.10	2.920 (2)	176
C11—H11···O3ⁱⁱ	0.93	2.58	3.418 (3)	150.7
C16—H16C···O4ⁱⁱⁱ	0.96	2.57	3.397 (3)	144

Symmetry codes: (i) −x, −y, −z+1; (ii) x+1, y, z; (iii) x−1, y−1, z.

Acknowledgements

This study was supported financially by Pukyong National University under the 2009 Post-Doc Program.

References

Altomare, A., Burla, M. C., Camalli, M., Carrozzini, B., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Rizzi, R. (1999). J. Appl. Cryst. 32, 339–340. Web of Science CrossRef CAS IUCr Journals Google Scholar
Amirthaganesan, S., Aridoss, G., Park, Y. H., Kim, J. S., Son, S. M. & Jeong, Y. T. (2008). Heterocycles, 75, 537–554. CAS Google Scholar
Bruker (2004). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Connolly, P., Wetter, S., Beers, K., Hamel, S., Haynes-Johnson, D., Kiddoe, M., Kraft, P., Lai, M., Campen, C., Palmer, S. & Phillips, A. (1997). Bioorg. Med. Chem. Lett. 7, 2551–2556. CrossRef CAS Web of Science Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Nardelli, M. (1983). Acta Cryst. C39, 1141–1142. CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 66| Part 4| April 2010| Page o861

doi:10.1107/S1600536810009360

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Ethyl 4-(3-chloro­phen­yl)-3,6-dihydr­­oxy-6-methyl-2-(2-pyrid­yl)-4,5,6,7-tetra­hydro­indazole-5-carboxyl­ate

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Experimental

Crystal data

Data collection

Refinement

Supporting information

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References

organic compounds

Ethyl 4-(3-chlorophenyl)-3,6-dihydroxy-6-methyl-2-(2-pyridyl)-4,5,6,7-tetrahydroindazole-5-carboxylate