Ethyl 4,6-dimethyl-3-oxo-2-phenyl-3,7-di­hydro-2H-pyrazolo­[3,4-b]pyridine-5-carboxyl­ate monohydrate

In the title compound, C₁₇H₁₇N₃O₃·H₂O, the dihedral angle between the 4,6-dimethyl-pyrazolo­[3,4-b]pyridine-3-one unit [maximum deviation = 0.048 (2) Å] and the phenyl ring is 5.1 (1)°. The structure is characterized by disorder of the carboxyl­ate O atoms, which are split into two parts with a major component of 0.898 (4). In the crystal, the organic mol­ecules and lattice water mol­ecules are linked via O—H...O, O—H...N and N—H...O hydrogen bonds. The mol­ecules are also linked by C—H...π and weak offset π–π stacking inter­actions, forming sheets parallel to (001).

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• Disorder in main residue
• R factor = 0.056
• wR factor = 0.166
• Data-to-parameter ratio = 12.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT241_ALERT_2_C High   'MainMol' Ueq as Compared to Neighbors of        C16 Check
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds ...............    0.00467 Ang.
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      8.045 Check
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.595          2 Report
PLAT978_ALERT_2_C Number C-C Bonds with Positive Residual Density           0 Note

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          4 Note
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          1 Report
PLAT171_ALERT_4_G The CIF-Embedded .res File Contains EADP Records          2 Report
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          2 Report
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT230_ALERT_2_G Hirshfeld Test Diff for    O3A    --  C15     ..       34.0 s.u.
PLAT301_ALERT_3_G Main Residue  Disorder ............ Percentage =          9 Note
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          2 Note
PLAT933_ALERT_2_G Number of OMIT records in Embedded RES .........          1 Note
PLAT961_ALERT_5_G Dataset Contains no Negative Intensities .......     Please Check

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   5 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  11 ALERT level G = General information/check it is not something unexpected

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

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Computing details

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg et al., 2012); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Ethyl 4,6-dimethyl-3-oxo-2-phenyl-3,7-dihydro-2H-pyrazolo[3,4-b]pyridine-5-carboxylate monohydrate

Crystal data

C17H17N3O3·H2O	F(000) = 696
Mr = 329.35	Dx = 1.336 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.5321 (15) Å	Cell parameters from 2879 reflections
b = 18.794 (3) Å	θ = 2.1–25.0°
c = 9.0491 (12) Å	µ = 0.10 mm^−1
β = 113.903 (5)°	T = 293 K
V = 1637.6 (4) Å^3	Block, orange
Z = 4	0.32 × 0.24 × 0.15 mm

Data collection

Bruker DUO APEXII CCD diffractometer	1709 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.056
Absorption correction: multi-scan (SADABS; Bruker, 2009)	θmax = 25.0°, θmin = 2.1°
Tmin = 0.696, Tmax = 0.746	h = −12→11
15373 measured reflections	k = −22→22
2879 independent reflections	l = −10→10

Refinement

Refinement on F^2	2 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.056	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.166	w = 1/[σ^2(Fo^2) + (0.0837P)^2 + 0.5493P] where P = (Fo^2 + 2Fc^2)/3
S = 0.96	(Δ/σ)max < 0.001
2879 reflections	Δρmax = 0.26 e Å^−3
235 parameters	Δρmin = −0.24 e Å^−3

Special details

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.2341 (2)	−0.04229 (12)	0.5100 (2)	0.0593 (6)
O2	−0.1524 (3)	0.14716 (15)	0.0298 (4)	0.0671 (8)	0.898 (4)
O3	−0.0117 (3)	0.21966 (17)	−0.0281 (4)	0.1033 (12)	0.898 (4)
O2A	−0.1029 (19)	0.1830 (15)	0.092 (3)	0.0671 (8)	0.102 (4)
O3A	−0.121 (2)	0.1625 (14)	−0.133 (2)	0.1033 (12)	0.102 (4)
N1	0.3718 (2)	−0.06247 (12)	0.3654 (3)	0.0446 (6)
N2	0.3789 (2)	−0.04097 (13)	0.2189 (3)	0.0453 (6)
C1	0.2639 (3)	−0.03131 (16)	0.3926 (3)	0.0451 (7)
C2	0.1975 (3)	0.01464 (15)	0.2528 (3)	0.0419 (7)
C3	0.0919 (3)	0.06363 (15)	0.2102 (3)	0.0455 (7)
C4	0.0624 (3)	0.10151 (16)	0.0640 (3)	0.0476 (7)
C5	0.1344 (3)	0.08678 (16)	−0.0323 (3)	0.0481 (7)
C6	0.2745 (3)	0.00291 (14)	0.1589 (3)	0.0408 (7)
C7	0.4740 (3)	−0.11041 (15)	0.4645 (3)	0.0443 (7)
C15	−0.0376 (4)	0.1618 (2)	0.0152 (4)	0.0646 (9)
N3	0.2371 (2)	0.03840 (12)	0.0153 (3)	0.0458 (6)
H3N	0.2801	0.0295	−0.0456	0.055*
C8	0.5713 (3)	−0.13804 (16)	0.4129 (4)	0.0508 (8)
H8	0.5677	−0.1259	0.3117	0.061*
C9	0.6732 (3)	−0.18347 (16)	0.5113 (4)	0.0556 (8)
H9	0.7381	−0.2015	0.4758	0.067*
C10	0.6803 (3)	−0.20245 (17)	0.6610 (4)	0.0616 (9)
H10	0.7498	−0.2328	0.7271	0.074*
C11	0.5833 (4)	−0.17590 (17)	0.7113 (4)	0.0634 (9)
H11	0.5869	−0.1889	0.8121	0.076*
C12	0.4808 (3)	−0.13044 (16)	0.6156 (4)	0.0562 (8)
H12	0.4158	−0.1130	0.6518	0.067*
C13	0.0193 (3)	0.07762 (19)	0.3210 (4)	0.0654 (10)
H13A	0.0138	0.1280	0.3351	0.098*
H13B	0.0706	0.0558	0.4241	0.098*
H13C	−0.0727	0.0580	0.2744	0.098*
C14	0.1036 (4)	0.12011 (18)	−0.1943 (4)	0.0657 (9)
H14A	0.1171	0.1706	−0.1817	0.099*
H14B	0.0092	0.1103	−0.2659	0.099*
H14C	0.1650	0.1007	−0.2386	0.099*
C16	−0.2515 (4)	0.2055 (2)	0.0019 (6)	0.0954 (14)
H16A	−0.2026	0.2497	0.0444	0.115*
H16B	−0.3065	0.2115	−0.1130	0.115*
C17	−0.3398 (5)	0.1878 (2)	0.0831 (6)	0.1029 (15)
H17A	−0.4087	0.2242	0.0629	0.154*
H17B	−0.2849	0.1842	0.1972	0.154*
H17C	−0.3847	0.1431	0.0432	0.154*
O4	0.3690 (3)	0.00542 (15)	0.8210 (3)	0.0673 (7)
H1W	0.443 (5)	0.023 (3)	0.819 (6)	0.131 (19)*
H2W	0.317 (4)	−0.010 (2)	0.720 (6)	0.114 (16)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0515 (13)	0.0909 (16)	0.0426 (11)	0.0058 (12)	0.0263 (10)	0.0118 (11)
O2	0.0455 (16)	0.0638 (18)	0.092 (2)	0.0074 (14)	0.0281 (15)	0.0040 (15)
O3	0.088 (2)	0.078 (2)	0.167 (3)	0.0230 (17)	0.076 (2)	0.048 (2)
O2A	0.0455 (16)	0.0638 (18)	0.092 (2)	0.0074 (14)	0.0281 (15)	0.0040 (15)
O3A	0.088 (2)	0.078 (2)	0.167 (3)	0.0230 (17)	0.076 (2)	0.048 (2)
N1	0.0414 (14)	0.0569 (15)	0.0391 (13)	0.0032 (12)	0.0202 (11)	0.0044 (11)
N2	0.0426 (14)	0.0588 (15)	0.0386 (13)	0.0019 (13)	0.0208 (12)	0.0017 (11)
C1	0.0382 (16)	0.0599 (18)	0.0377 (15)	−0.0039 (14)	0.0160 (14)	−0.0036 (14)
C2	0.0345 (16)	0.0557 (17)	0.0366 (14)	−0.0047 (14)	0.0155 (13)	−0.0040 (13)
C3	0.0386 (17)	0.0561 (17)	0.0436 (16)	−0.0014 (14)	0.0183 (14)	−0.0029 (14)
C4	0.0374 (17)	0.0568 (18)	0.0478 (17)	−0.0009 (15)	0.0164 (14)	−0.0026 (14)
C5	0.0372 (17)	0.0579 (18)	0.0460 (16)	−0.0027 (15)	0.0136 (14)	0.0017 (14)
C6	0.0392 (16)	0.0506 (17)	0.0333 (14)	−0.0037 (14)	0.0154 (13)	−0.0025 (13)
C7	0.0437 (17)	0.0467 (16)	0.0410 (16)	−0.0011 (14)	0.0156 (14)	−0.0019 (13)
C15	0.052 (2)	0.078 (3)	0.064 (2)	0.011 (2)	0.0243 (18)	0.0137 (19)
N3	0.0430 (14)	0.0613 (15)	0.0387 (13)	0.0014 (13)	0.0221 (11)	0.0008 (12)
C8	0.0470 (18)	0.0544 (18)	0.0496 (18)	−0.0001 (15)	0.0183 (15)	−0.0016 (15)
C9	0.0482 (19)	0.0523 (18)	0.065 (2)	0.0031 (16)	0.0216 (17)	−0.0080 (16)
C10	0.062 (2)	0.0532 (19)	0.062 (2)	0.0086 (17)	0.0168 (18)	0.0018 (16)
C11	0.079 (2)	0.057 (2)	0.0509 (19)	0.0140 (19)	0.0230 (18)	0.0108 (16)
C12	0.067 (2)	0.0563 (19)	0.0494 (17)	0.0076 (17)	0.0274 (17)	0.0025 (15)
C13	0.054 (2)	0.092 (3)	0.0580 (19)	0.0108 (18)	0.0308 (17)	0.0053 (18)
C14	0.066 (2)	0.077 (2)	0.056 (2)	0.0057 (18)	0.0266 (18)	0.0152 (17)
C16	0.070 (3)	0.102 (3)	0.125 (3)	0.042 (2)	0.051 (3)	0.037 (3)
C17	0.107 (3)	0.113 (3)	0.112 (3)	0.046 (3)	0.068 (3)	0.021 (3)
O4	0.0592 (16)	0.102 (2)	0.0534 (15)	−0.0104 (14)	0.0353 (13)	−0.0105 (13)

Geometric parameters (Å, º)

O1—C1	1.241 (3)	C8—C9	1.378 (4)
O2—C15	1.299 (4)	C8—H8	0.9300
O2—C16	1.464 (4)	C9—C10	1.373 (4)
O3—C15	1.223 (4)	C9—H9	0.9300
O2A—C15	1.23 (2)	C10—C11	1.370 (4)
O2A—C16	1.504 (16)	C10—H10	0.9300
O3A—C15	1.272 (18)	C11—C12	1.374 (4)
N1—C1	1.386 (4)	C11—H11	0.9300
N1—C7	1.412 (4)	C12—H12	0.9300
N1—N2	1.417 (3)	C13—H13A	0.9600
N2—C6	1.303 (3)	C13—H13B	0.9600
C1—C2	1.455 (4)	C13—H13C	0.9600
C2—C3	1.373 (4)	C14—H14A	0.9600
C2—C6	1.411 (4)	C14—H14B	0.9600
C3—C4	1.421 (4)	C14—H14C	0.9600
C3—C13	1.511 (4)	C16—C17	1.439 (5)
C4—C5	1.396 (4)	C16—H16A	0.9700
C4—C15	1.487 (4)	C16—H16B	0.9700
C5—N3	1.343 (4)	C17—H17A	0.9600
C5—C14	1.503 (4)	C17—H17B	0.9600
C6—N3	1.368 (3)	C17—H17C	0.9600
C7—C8	1.387 (4)	O4—H1W	0.86 (5)
C7—C12	1.392 (4)	O4—H2W	0.90 (5)
N3—H3N	0.8600
C15—O2—C16	116.8 (3)	C10—C9—C8	121.0 (3)
C15—O2A—C16	118.7 (19)	C10—C9—H9	119.5
C1—N1—C7	128.7 (2)	C8—C9—H9	119.5
C1—N1—N2	113.8 (2)	C11—C10—C9	118.9 (3)
C7—N1—N2	117.4 (2)	C11—C10—H10	120.6
C6—N2—N1	102.4 (2)	C9—C10—H10	120.6
O1—C1—N1	126.3 (3)	C10—C11—C12	121.2 (3)
O1—C1—C2	130.1 (3)	C10—C11—H11	119.4
N1—C1—C2	103.7 (2)	C12—C11—H11	119.4
C3—C2—C6	122.2 (2)	C11—C12—C7	120.1 (3)
C3—C2—C1	133.8 (2)	C11—C12—H12	119.9
C6—C2—C1	103.9 (2)	C7—C12—H12	119.9
C2—C3—C4	116.4 (2)	C3—C13—H13A	109.5
C2—C3—C13	120.0 (3)	C3—C13—H13B	109.5
C4—C3—C13	123.5 (3)	H13A—C13—H13B	109.5
C5—C4—C3	120.9 (3)	C3—C13—H13C	109.5
C5—C4—C15	117.7 (3)	H13A—C13—H13C	109.5
C3—C4—C15	121.3 (3)	H13B—C13—H13C	109.5
N3—C5—C4	120.3 (2)	C5—C14—H14A	109.5
N3—C5—C14	115.0 (3)	C5—C14—H14B	109.5
C4—C5—C14	124.7 (3)	H14A—C14—H14B	109.5
N2—C6—N3	125.0 (2)	C5—C14—H14C	109.5
N2—C6—C2	116.2 (2)	H14A—C14—H14C	109.5
N3—C6—C2	118.7 (3)	H14B—C14—H14C	109.5
C8—C7—C12	118.6 (3)	C17—C16—O2	107.5 (3)
C8—C7—N1	120.2 (2)	C17—C16—O2A	113.7 (11)
C12—C7—N1	121.3 (3)	C17—C16—H16A	110.2
O2A—C15—O3A	107.0 (15)	O2—C16—H16A	110.2
O3—C15—O2	124.0 (3)	C17—C16—H16B	110.2
O3—C15—C4	123.4 (3)	O2—C16—H16B	110.2
O2A—C15—C4	124.8 (11)	H16A—C16—H16B	108.5
O3A—C15—C4	115.0 (13)	C16—C17—H17A	109.5
O2—C15—C4	112.6 (3)	C16—C17—H17B	109.5
C5—N3—C6	121.3 (2)	H17A—C17—H17B	109.5
C5—N3—H3N	119.3	C16—C17—H17C	109.5
C6—N3—H3N	119.3	H17A—C17—H17C	109.5
C9—C8—C7	120.2 (3)	H17B—C17—H17C	109.5
C9—C8—H8	119.9	H1W—O4—H2W	107 (4)
C7—C8—H8	119.9

Hydrogen-bond geometry (Å, º)

Cg3 is the centroid of the C7–C12 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···O4^i	0.86	1.86	2.718 (3)	177
O4—H1W···N2^ii	0.86 (5)	2.07 (5)	2.899 (3)	164 (5)
O4—H2W···O1	0.90 (5)	1.84 (5)	2.739 (3)	172 (4)
C17—H17A···Cg3^iii	0.96	2.79	3.717 (4)	163

Symmetry codes: (i) x, y, z−1; (ii) −x+1, −y, −z+1; (iii) −x, y+1/2, −z+1/2.