Ethyl 3,6-dihy­droxy-6-methyl-4-phenyl-4,5,6,7-tetra­hydro-1H-indazole-5-carboxyl­ate monohydrate

In the title compound, C₁₇H₂₀N₂O₄·H₂O, the cyclo­hexene ring adopts a half-chair conformation while the indazole ring is essentially planar [maximum deviation = 0.0192 (12) Å]. In the crystal, pairs of inter­molecular O—H...N hydrogen bonds link the mol­ecules into dimers lying about inversion centers and intra­molecular O—H...O hydrogen bonds result in six-membered rings. The dimers are further connected by N—H...O and O—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.077
• wR factor = 0.198
• Data-to-parameter ratio = 12.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.97
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds (x 1000) Ang ..          5
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          1
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.595         89

Alert level G
PLAT793_ALERT_4_G The Model has Chirality at C4      (Verify) ....          R
PLAT793_ALERT_4_G The Model has Chirality at C5      (Verify) ....          S
PLAT793_ALERT_4_G The Model has Chirality at C6      (Verify) ....          R

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

In the field of heterocyclic compounds, azoles are important due to their wide range of applications (Genin et al., 2000). In the microbial evaluation of organic compounds for the development of current research in drug discovery and medicinal chemistry we have prepared the title compound and determined its crystal structure which has been presented in this article.

In the title compound (Fig. 1), the cyclohexene ring adopts a half-chair conformation, C6 lies 0.685 (3) Å out of the plane formed by the rest of the ring atoms. The indazole ring (N1/N2/C3/C3A/C7A) is essentially planar with maximum deviation from the ring plane being 0.0192 (12) Å for C7A. In the crystal structure, intermolecular hydrogen bonds O1—H1B···N2 result in centrosymmetric dimers lying about inversion centers. Intramolecular hydrogen bonds O4—H4A···O3 result in six-membered rings. The dimers are further packed and stabilized by N—H···O and O—H···O hydrogen bonds (Table 1 and Fig. 2).

The molecular dimensions in the title compound are in close agreement with the corresponding molecular dimensions of a closely related compoud (Hema et al., 2006).

Related literature

For general background to azoles, see: Genin et al. (2000). For a related structure, see: Hema et al. (2006).

S2. Experimental

(rac)-Diethyl-4-hydroxy-4-methyl-6-oxo-2-phenyl-1,3-dicarboxylate (20 mmol) and hydroxylamine hydrochloride (20 mmol) were dissolved in 20 ml e thanol. The mixture was stirred at 345–350 K for 10 h. After cooling to a room temperature colorless crystals were obtained which were filtered and washed with ethanol. The crystals were dissolved in ethanol (50 ml) and recrystallized to yield colourless block-shaped crystals of the title compound suitable for X-ray crystallographic analysis..

S3. Refinement

The hydrogen atoms of the water of hydration and amino group were localized from difference-Fourier maps and included in the refinement with isotropic displacement parameters. The rest of the hydrogen atoms were placed in calculated positions with and refined in the riding model at O—H = 0.82 and C—H = 0.93-0.98 Å with isotropic displacement parameters U_iso(H) = 1.2 or 1.5U_eq(parent atoms).

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of the title compound, with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.
	Fig. 2. The hydrogen-bonded (dashed lines) packing in the title compound; H-atoms not involved in hydrogen bonding have been excluded for clarity.

Ethyl 3,6-dihydroxy-6-methyl-4-phenyl-4,5,6,7-tetrahydro-1H-indazole-5- carboxylate monohydrate

Crystal data

C17H20N2O4·H2O	Z = 2
Mr = 334.37	F(000) = 356
Triclinic, P1	Dx = 1.315 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.9964 (15) Å	Cell parameters from 909 reflections
b = 8.8647 (19) Å	θ = 2.5–30.6°
c = 15.124 (4) Å	µ = 0.10 mm^−1
α = 99.363 (6)°	T = 296 K
β = 95.281 (6)°	Prism, colourless
γ = 112.271 (4)°	0.20 × 0.20 × 0.20 mm
V = 844.2 (3) Å^3

Data collection

Bruker APEXII CCD diffractometer	2889 independent reflections
Radiation source: fine-focus sealed tube	2327 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.065
ϕ and ω scans	θmax = 25.0°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −8→8
Tmin = 0.981, Tmax = 0.981	k = −10→10
6332 measured reflections	l = −17→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.077	Hydrogen site location: difference Fourier map
wR(F^2) = 0.198	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0611P)^2 + 0.4352P] where P = (Fo^2 + 2Fc^2)/3
2889 reflections	(Δ/σ)max < 0.001
231 parameters	Δρmax = 0.27 e Å^−3
0 restraints	Δρmin = −0.37 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.9685 (3)	1.3998 (2)	0.37394 (14)	0.0463 (5)
H1B	0.9998	1.4897	0.4089	0.069*
O2	0.7109 (3)	0.6179 (2)	0.15151 (15)	0.0544 (6)
O3	0.4935 (3)	0.7477 (2)	0.14842 (13)	0.0421 (5)
O4	0.3968 (2)	0.8009 (2)	0.33029 (13)	0.0363 (5)
H4A	0.3737	0.7989	0.2759	0.054*
O5	0.0528 (4)	0.5446 (3)	0.2177 (2)	0.0637 (7)
H5B	0.009 (6)	0.485 (6)	0.264 (3)	0.081 (13)*
H5C	−0.051 (6)	0.563 (5)	0.198 (3)	0.068 (11)*
N1	0.8141 (3)	1.1503 (2)	0.52847 (16)	0.0340 (5)
N2	0.8884 (3)	1.3042 (2)	0.50553 (16)	0.0373 (6)
C3	0.8995 (4)	1.2791 (3)	0.41766 (18)	0.0326 (6)
C3A	0.8266 (3)	1.1038 (3)	0.38069 (17)	0.0302 (6)
C4	0.7975 (3)	1.0105 (3)	0.28485 (17)	0.0306 (6)
H4B	0.6826	1.0230	0.2490	0.037*
C5	0.7311 (3)	0.8213 (3)	0.28392 (18)	0.0312 (6)
H5A	0.8575	0.8062	0.3058	0.037*
C6	0.5710 (3)	0.7581 (3)	0.34881 (18)	0.0316 (6)
C7	0.6747 (4)	0.8481 (3)	0.44704 (18)	0.0325 (6)
H7A	0.5710	0.8228	0.4869	0.039*
H7B	0.7819	0.8107	0.4667	0.039*
C7A	0.7705 (3)	1.0317 (3)	0.45193 (17)	0.0307 (6)
C8	0.9887 (4)	1.0726 (3)	0.23964 (18)	0.0327 (6)
C9	1.1870 (4)	1.1056 (3)	0.2856 (2)	0.0430 (7)
H9A	1.2015	1.0902	0.3449	0.052*
C10	1.3610 (5)	1.1603 (3)	0.2451 (3)	0.0546 (9)
H10A	1.4921	1.1823	0.2771	0.066*
C11	1.3422 (5)	1.1827 (4)	0.1572 (3)	0.0635 (10)
H11A	1.4600	1.2185	0.1294	0.076*
C12	1.1468 (6)	1.1516 (4)	0.1104 (3)	0.0690 (10)
H12A	1.1332	1.1688	0.0515	0.083*
C13	0.9724 (5)	1.0950 (4)	0.1516 (2)	0.0519 (8)
H13A	0.8412	1.0715	0.1193	0.062*
C14	0.6486 (4)	0.7183 (3)	0.18762 (19)	0.0350 (6)
C15	0.3862 (5)	0.6480 (4)	0.0578 (2)	0.0511 (8)
H15A	0.3097	0.5325	0.0606	0.061*
H15B	0.4869	0.6527	0.0172	0.061*
C16	0.2398 (6)	0.7190 (5)	0.0244 (3)	0.0693 (10)
H16A	0.1663	0.6560	−0.0352	0.104*
H16B	0.3173	0.8331	0.0217	0.104*
H16C	0.1409	0.7137	0.0650	0.104*
C17	0.4995 (4)	0.5701 (3)	0.3400 (2)	0.0432 (7)
H17A	0.4114	0.5349	0.3842	0.065*
H17B	0.6197	0.5438	0.3502	0.065*
H17C	0.4224	0.5133	0.2800	0.065*
H1A	0.760 (4)	1.143 (3)	0.582 (2)	0.034 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0653 (12)	0.0205 (8)	0.0410 (13)	0.0057 (8)	0.0101 (9)	0.0015 (8)
O2	0.0622 (12)	0.0460 (11)	0.0529 (15)	0.0319 (10)	−0.0016 (10)	−0.0141 (10)
O3	0.0449 (10)	0.0372 (9)	0.0360 (12)	0.0172 (8)	−0.0059 (8)	−0.0085 (8)
O4	0.0331 (9)	0.0360 (9)	0.0361 (11)	0.0138 (7)	0.0014 (7)	0.0008 (8)
O5	0.0449 (12)	0.0594 (14)	0.075 (2)	0.0095 (10)	−0.0053 (12)	0.0196 (13)
N1	0.0382 (11)	0.0261 (10)	0.0290 (14)	0.0056 (8)	0.0054 (9)	0.0006 (9)
N2	0.0442 (12)	0.0233 (10)	0.0366 (15)	0.0075 (8)	0.0055 (9)	0.0015 (9)
C3	0.0356 (12)	0.0247 (11)	0.0302 (15)	0.0065 (9)	0.0043 (10)	0.0011 (10)
C3A	0.0316 (11)	0.0210 (11)	0.0312 (15)	0.0065 (8)	0.0028 (9)	−0.0015 (10)
C4	0.0349 (12)	0.0222 (11)	0.0304 (15)	0.0095 (9)	0.0001 (10)	0.0020 (9)
C5	0.0313 (11)	0.0212 (11)	0.0361 (16)	0.0089 (9)	0.0009 (10)	−0.0002 (10)
C6	0.0315 (11)	0.0227 (11)	0.0352 (16)	0.0079 (9)	0.0020 (10)	0.0012 (10)
C7	0.0339 (12)	0.0258 (11)	0.0337 (16)	0.0085 (9)	0.0037 (10)	0.0053 (10)
C7A	0.0291 (11)	0.0249 (11)	0.0316 (15)	0.0082 (9)	−0.0002 (9)	−0.0020 (10)
C8	0.0404 (13)	0.0190 (10)	0.0341 (16)	0.0097 (9)	0.0057 (10)	−0.0003 (10)
C9	0.0459 (15)	0.0370 (13)	0.0455 (19)	0.0168 (11)	0.0067 (12)	0.0072 (12)
C10	0.0438 (15)	0.0390 (15)	0.081 (3)	0.0164 (12)	0.0190 (15)	0.0091 (15)
C11	0.063 (2)	0.0436 (16)	0.080 (3)	0.0124 (14)	0.0382 (19)	0.0118 (17)
C12	0.087 (3)	0.062 (2)	0.048 (2)	0.0133 (18)	0.0266 (18)	0.0183 (17)
C13	0.0565 (17)	0.0467 (16)	0.044 (2)	0.0117 (13)	0.0081 (14)	0.0102 (14)
C14	0.0347 (12)	0.0235 (11)	0.0412 (17)	0.0080 (9)	0.0060 (11)	0.0015 (10)
C15	0.0574 (17)	0.0436 (15)	0.0371 (19)	0.0143 (13)	−0.0075 (13)	−0.0090 (13)
C16	0.074 (2)	0.070 (2)	0.053 (2)	0.0300 (18)	−0.0157 (17)	−0.0018 (17)
C17	0.0453 (14)	0.0245 (12)	0.051 (2)	0.0060 (10)	0.0055 (12)	0.0053 (11)

Geometric parameters (Å, º)

O1—C3	1.308 (3)	C7—C7A	1.493 (3)
O1—H1B	0.8200	C7—H7A	0.9700
O2—C14	1.209 (3)	C7—H7B	0.9700
O3—C14	1.321 (3)	C8—C13	1.379 (4)
O3—C15	1.462 (3)	C8—C9	1.394 (4)
O4—C6	1.425 (3)	C9—C10	1.371 (4)
O4—H4A	0.8200	C9—H9A	0.9300
O5—H5B	0.95 (5)	C10—C11	1.378 (5)
O5—H5C	0.85 (4)	C10—H10A	0.9300
N1—C7A	1.354 (3)	C11—C12	1.385 (6)
N1—N2	1.379 (3)	C11—H11A	0.9300
N1—H1A	0.92 (3)	C12—C13	1.381 (5)
N2—C3	1.326 (4)	C12—H12A	0.9300
C3—C3A	1.432 (3)	C13—H13A	0.9300
C3A—C7A	1.355 (4)	C15—C16	1.482 (5)
C3A—C4	1.502 (3)	C15—H15A	0.9700
C4—C8	1.514 (3)	C15—H15B	0.9700
C4—C5	1.558 (3)	C16—H16A	0.9600
C4—H4B	0.9800	C16—H16B	0.9600
C5—C14	1.517 (3)	C16—H16C	0.9600
C5—C6	1.561 (4)	C17—H17A	0.9600
C5—H5A	0.9800	C17—H17B	0.9600
C6—C17	1.526 (3)	C17—H17C	0.9600
C6—C7	1.532 (3)
C3—O1—H1B	109.5	C3A—C7A—C7	125.0 (2)
C14—O3—C15	117.9 (2)	C13—C8—C9	117.9 (3)
C6—O4—H4A	109.5	C13—C8—C4	121.4 (2)
H5B—O5—H5C	105 (4)	C9—C8—C4	120.6 (2)
C7A—N1—N2	108.2 (2)	C10—C9—C8	121.2 (3)
C7A—N1—H1A	130.0 (17)	C10—C9—H9A	119.4
N2—N1—H1A	117.5 (17)	C8—C9—H9A	119.4
C3—N2—N1	107.5 (2)	C9—C10—C11	120.2 (3)
O1—C3—N2	123.5 (2)	C9—C10—H10A	119.9
O1—C3—C3A	126.8 (2)	C11—C10—H10A	119.9
N2—C3—C3A	109.6 (2)	C10—C11—C12	119.6 (3)
C7A—C3A—C3	104.3 (2)	C10—C11—H11A	120.2
C7A—C3A—C4	124.9 (2)	C12—C11—H11A	120.2
C3—C3A—C4	130.6 (2)	C13—C12—C11	119.6 (4)
C3A—C4—C8	114.11 (18)	C13—C12—H12A	120.2
C3A—C4—C5	109.1 (2)	C11—C12—H12A	120.2
C8—C4—C5	109.85 (19)	C8—C13—C12	121.4 (3)
C3A—C4—H4B	107.8	C8—C13—H13A	119.3
C8—C4—H4B	107.8	C12—C13—H13A	119.3
C5—C4—H4B	107.8	O2—C14—O3	123.6 (2)
C14—C5—C4	110.5 (2)	O2—C14—C5	125.0 (2)
C14—C5—C6	111.47 (18)	O3—C14—C5	111.4 (2)
C4—C5—C6	112.80 (19)	O3—C15—C16	107.3 (2)
C14—C5—H5A	107.2	O3—C15—H15A	110.3
C4—C5—H5A	107.2	C16—C15—H15A	110.3
C6—C5—H5A	107.2	O3—C15—H15B	110.3
O4—C6—C17	111.01 (18)	C16—C15—H15B	110.3
O4—C6—C7	106.04 (18)	H15A—C15—H15B	108.5
C17—C6—C7	109.6 (2)	C15—C16—H16A	109.5
O4—C6—C5	110.4 (2)	C15—C16—H16B	109.5
C17—C6—C5	110.5 (2)	H16A—C16—H16B	109.5
C7—C6—C5	109.18 (18)	C15—C16—H16C	109.5
C7A—C7—C6	109.0 (2)	H16A—C16—H16C	109.5
C7A—C7—H7A	109.9	H16B—C16—H16C	109.5
C6—C7—H7A	109.9	C6—C17—H17A	109.5
C7A—C7—H7B	109.9	C6—C17—H17B	109.5
C6—C7—H7B	109.9	H17A—C17—H17B	109.5
H7A—C7—H7B	108.3	C6—C17—H17C	109.5
N1—C7A—C3A	110.2 (2)	H17A—C17—H17C	109.5
N1—C7A—C7	124.8 (2)	H17B—C17—H17C	109.5
C7A—N1—N2—C3	−3.1 (3)	C3—C3A—C7A—N1	−3.0 (3)
N1—N2—C3—O1	−178.5 (2)	C4—C3A—C7A—N1	−178.8 (2)
N1—N2—C3—C3A	1.2 (3)	C3—C3A—C7A—C7	177.1 (2)
O1—C3—C3A—C7A	−179.2 (2)	C4—C3A—C7A—C7	1.3 (4)
N2—C3—C3A—C7A	1.1 (3)	C6—C7—C7A—N1	157.6 (2)
O1—C3—C3A—C4	−3.8 (4)	C6—C7—C7A—C3A	−22.5 (3)
N2—C3—C3A—C4	176.5 (2)	C3A—C4—C8—C13	−135.7 (2)
C7A—C3A—C4—C8	−133.3 (2)	C5—C4—C8—C13	101.3 (3)
C3—C3A—C4—C8	52.1 (3)	C3A—C4—C8—C9	45.6 (3)
C7A—C3A—C4—C5	−10.0 (3)	C5—C4—C8—C9	−77.3 (3)
C3—C3A—C4—C5	175.4 (2)	C13—C8—C9—C10	0.7 (4)
C3A—C4—C5—C14	165.98 (18)	C4—C8—C9—C10	179.3 (2)
C8—C4—C5—C14	−68.2 (2)	C8—C9—C10—C11	−0.4 (4)
C3A—C4—C5—C6	40.4 (2)	C9—C10—C11—C12	0.8 (5)
C8—C4—C5—C6	166.2 (2)	C10—C11—C12—C13	−1.4 (5)
C14—C5—C6—O4	−72.4 (2)	C9—C8—C13—C12	−1.3 (4)
C4—C5—C6—O4	52.7 (2)	C4—C8—C13—C12	−180.0 (3)
C14—C5—C6—C17	50.8 (3)	C11—C12—C13—C8	1.7 (5)
C4—C5—C6—C17	175.87 (19)	C15—O3—C14—O2	2.6 (4)
C14—C5—C6—C7	171.44 (19)	C15—O3—C14—C5	−175.3 (2)
C4—C5—C6—C7	−63.5 (2)	C4—C5—C14—O2	126.8 (3)
O4—C6—C7—C7A	−68.0 (2)	C6—C5—C14—O2	−106.9 (3)
C17—C6—C7—C7A	172.1 (2)	C4—C5—C14—O3	−55.4 (3)
C5—C6—C7—C7A	50.9 (2)	C6—C5—C14—O3	70.9 (3)
N2—N1—C7A—C3A	3.9 (3)	C14—O3—C15—C16	−172.8 (3)
N2—N1—C7A—C7	−176.2 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1B···N2	0.82	1.89	2.705 (2)	171
O4—H4A···O3	0.82	2.22	2.897 (2)	141
N1—H1A···O4	0.93 (3)	1.94	2.778 (3)	155
O5—H5B···O1	0.95 (5)	2.01	2.874 (2)	165
O5—H5C···O2	0.84 (4)	1.97	2.844 (3)	179