Crystal structure analysis of ethyl 3-(4-chloro­phen­yl)-1,6-dimethyl-4-methyl­sulfanyl-1H-pyrazolo[3,4-b]pyridine-5-carboxyl­ate

In the title compound, the dihedral angle between the fused pyrazole and pyridine rings is 3.81 (9)°. The benzene ring forms dihedral angles of 35.08 (10) and 36.26 (9)° with the pyrazole and pyridine rings, respectively. In the crystal, weak C—H...O hydrogen bonds connect mol­ecules along [100].

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.049
• wR factor = 0.161
• Data-to-parameter ratio = 18.9

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT910_ALERT_3_B Missing # of FCF Reflection(s) Below Theta(Min).         12 Note

Author Response: The unit cell of title compound is reasonable large and these low angle reflections are probably missing due to the beamstop. However the values obtained from R-factor (R=0.0487) and Goodness of Fit (GOOF) (S=1.104) of title compond were good enough for this structural assignment

Alert level C
PLAT715_ALERT_1_C D-H     Unknown or Inconsistent Label ..........          . Check
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      2.411 Check
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600          5 Report
PLAT918_ALERT_3_C Reflection(s) with I(obs) much Smaller I(calc) .          1 Check

Alert level G
PLAT063_ALERT_4_G Crystal Size Possibly too Large for Beam Size ..       0.65 mm
PLAT128_ALERT_4_G Alternate Setting for Input Space Group  P21/a        P21/c Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600        552 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          6 Info

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 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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Computing details

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), PLATON (Spek, 2020) and Mercury (Macrae et al., 2020); software used to prepare material for publication: ORTEP-3 for Windows (Farrugia, 2012), PLATON (Spek, 2020) and Mercury (Macrae et al., 2020).

Ethyl 3-(4-chlorophenyl)-1,6-dimethyl-4-methylsulfanyl-1H-pyrazolo[3,4-b]pyridine-5-carboxylate

Crystal data

C18H18ClN3O2S	F(000) = 784
Mr = 375.86	Dx = 1.354 Mg m^−3
Monoclinic, P21/a	Mo Kα radiation, λ = 0.71073 Å
a = 8.9995 (5) Å	Cell parameters from 4472 reflections
b = 16.7778 (11) Å	θ = 3.9–29.0°
c = 12.3595 (8) Å	µ = 0.34 mm^−1
β = 98.892 (6)°	T = 298 K
V = 1843.8 (2) Å^3	Block, colourless
Z = 4	0.65 × 0.6 × 0.24 mm

Data collection

Agilent Xcalibur Eos diffractometer	4340 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3323 reflections with I > 2σ(I)
Detector resolution: 15.9821 pixels mm^-1	Rint = 0.027
ω scans	θmax = 29.0°, θmin = 3.9°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	h = −11→12
Tmin = 0.857, Tmax = 1.000	k = −22→22
13882 measured reflections	l = −15→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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.161	H-atom parameters constrained
S = 1.10	w = 1/[σ^2(Fo^2) + (0.1P)^2] where P = (Fo^2 + 2Fc^2)/3
4340 reflections	(Δ/σ)max = 0.006
230 parameters	Δρmax = 0.30 e Å^−3
0 restraints	Δρmin = −0.41 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
S1	0.38706 (5)	−0.06089 (3)	0.65888 (4)	0.04572 (19)
Cl1	−0.26383 (7)	0.13979 (4)	0.63284 (7)	0.0751 (3)
O1	0.77428 (16)	−0.12709 (8)	0.67467 (12)	0.0460 (4)
N1	0.73909 (16)	0.02099 (9)	0.95211 (12)	0.0363 (4)
N2	0.57052 (18)	0.12776 (9)	0.97183 (14)	0.0404 (4)
O2	0.62392 (19)	−0.20707 (9)	0.75585 (14)	0.0599 (4)
N3	0.42863 (18)	0.15124 (10)	0.92994 (14)	0.0409 (4)
C9	0.6093 (2)	0.06010 (10)	0.92252 (14)	0.0335 (4)
C7	0.37469 (19)	0.09887 (11)	0.85219 (15)	0.0347 (4)
C14	0.75435 (19)	−0.04529 (11)	0.89531 (15)	0.0340 (4)
C3	0.1239 (2)	0.04255 (12)	0.77078 (17)	0.0421 (5)
H3	0.161730	−0.008533	0.785668	0.051*
C8	0.48642 (19)	0.03902 (11)	0.84112 (14)	0.0323 (4)
C15	0.8936 (2)	−0.09402 (12)	0.93020 (17)	0.0430 (5)
H15A	0.968939	−0.061386	0.972304	0.064*
H15B	0.930807	−0.113697	0.866557	0.064*
H15C	0.869892	−0.138103	0.974026	0.064*
C6	0.21737 (19)	0.10825 (11)	0.79948 (15)	0.0345 (4)
C12	0.51150 (19)	−0.02733 (11)	0.77555 (14)	0.0329 (4)
C2	−0.0231 (2)	0.05183 (12)	0.72086 (17)	0.0435 (5)
H2	−0.083292	0.007504	0.701057	0.052*
C5	0.0072 (2)	0.19448 (12)	0.73163 (18)	0.0463 (5)
H5	−0.032853	0.245383	0.719599	0.056*
C13	0.64421 (19)	−0.06941 (10)	0.80566 (14)	0.0322 (4)
C4	0.1552 (2)	0.18420 (12)	0.78090 (17)	0.0410 (4)
H4	0.214097	0.228738	0.801982	0.049*
C10	0.6609 (3)	0.17282 (13)	1.05805 (19)	0.0525 (5)
H10A	0.723443	0.137017	1.105641	0.079*
H10B	0.596079	0.201357	1.099350	0.079*
H10C	0.722908	0.209945	1.026288	0.079*
C16	0.6758 (2)	−0.14269 (11)	0.74373 (15)	0.0372 (4)
C1	−0.0800 (2)	0.12802 (13)	0.70063 (17)	0.0439 (5)
C11	0.3529 (3)	0.02945 (16)	0.57990 (18)	0.0586 (6)
H11A	0.303494	0.067547	0.620089	0.088*
H11B	0.290191	0.017846	0.511611	0.088*
H11C	0.446915	0.051040	0.565940	0.088*
C17	0.8220 (3)	−0.19386 (15)	0.6139 (2)	0.0620 (7)
H17A	0.741429	−0.209688	0.556464	0.074*
H17B	0.847277	−0.238963	0.662333	0.074*
C18	0.9549 (3)	−0.16898 (19)	0.5657 (2)	0.0784 (9)
H18A	0.928634	−0.124659	0.517341	0.118*
H18B	0.988342	−0.212571	0.525243	0.118*
H18C	1.034070	−0.153518	0.623018	0.118*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0408 (3)	0.0500 (3)	0.0424 (3)	0.0014 (2)	−0.0061 (2)	−0.0113 (2)
Cl1	0.0410 (3)	0.0734 (5)	0.1034 (6)	0.0093 (3)	−0.0123 (3)	−0.0214 (4)
O1	0.0491 (8)	0.0400 (8)	0.0522 (8)	0.0015 (6)	0.0179 (7)	−0.0078 (6)
N1	0.0350 (8)	0.0336 (8)	0.0387 (8)	−0.0032 (6)	0.0005 (6)	−0.0019 (7)
N2	0.0426 (9)	0.0337 (9)	0.0426 (9)	−0.0007 (6)	−0.0009 (7)	−0.0074 (7)
O2	0.0696 (10)	0.0392 (9)	0.0749 (11)	−0.0140 (7)	0.0236 (8)	−0.0115 (8)
N3	0.0411 (9)	0.0371 (9)	0.0436 (9)	0.0035 (7)	0.0040 (7)	−0.0016 (7)
C9	0.0356 (9)	0.0319 (9)	0.0327 (9)	−0.0041 (7)	0.0042 (7)	−0.0007 (7)
C7	0.0375 (9)	0.0305 (9)	0.0368 (9)	0.0014 (7)	0.0084 (7)	0.0017 (7)
C14	0.0308 (8)	0.0332 (9)	0.0370 (9)	−0.0045 (7)	0.0027 (7)	0.0027 (8)
C3	0.0426 (10)	0.0332 (10)	0.0522 (12)	0.0002 (8)	0.0122 (9)	0.0019 (9)
C8	0.0312 (8)	0.0317 (9)	0.0339 (9)	−0.0015 (7)	0.0048 (7)	0.0008 (7)
C15	0.0360 (9)	0.0422 (11)	0.0476 (11)	0.0032 (8)	−0.0030 (8)	−0.0006 (9)
C6	0.0323 (8)	0.0373 (10)	0.0357 (9)	0.0010 (7)	0.0105 (7)	0.0015 (8)
C12	0.0306 (8)	0.0361 (9)	0.0319 (9)	−0.0044 (7)	0.0049 (7)	0.0006 (7)
C2	0.0375 (10)	0.0416 (11)	0.0531 (12)	−0.0053 (8)	0.0122 (8)	−0.0061 (9)
C5	0.0408 (10)	0.0391 (11)	0.0590 (13)	0.0088 (8)	0.0075 (9)	−0.0040 (10)
C13	0.0320 (8)	0.0312 (9)	0.0334 (9)	−0.0030 (7)	0.0050 (7)	−0.0004 (7)
C4	0.0376 (9)	0.0355 (10)	0.0511 (11)	−0.0009 (8)	0.0101 (8)	−0.0049 (9)
C10	0.0624 (13)	0.0420 (12)	0.0490 (12)	−0.0044 (10)	−0.0044 (10)	−0.0149 (10)
C16	0.0333 (9)	0.0364 (10)	0.0405 (10)	0.0003 (7)	0.0015 (7)	−0.0031 (8)
C1	0.0349 (10)	0.0494 (12)	0.0487 (11)	0.0037 (8)	0.0098 (8)	−0.0067 (9)
C11	0.0595 (13)	0.0778 (17)	0.0367 (10)	0.0189 (12)	0.0022 (9)	0.0032 (11)
C17	0.0615 (14)	0.0577 (15)	0.0692 (15)	0.0088 (11)	0.0179 (12)	−0.0218 (12)
C18	0.0790 (19)	0.092 (2)	0.0719 (17)	0.0399 (16)	0.0366 (15)	0.0135 (16)

Geometric parameters (Å, º)

S1—C12	1.7752 (18)	C15—H15C	0.9600
S1—C11	1.803 (3)	C6—C4	1.396 (3)
Cl1—C1	1.746 (2)	C12—C13	1.388 (2)
O1—C16	1.347 (2)	C2—C1	1.385 (3)
O1—C17	1.450 (2)	C2—H2	0.9300
N1—C14	1.333 (2)	C5—C1	1.383 (3)
N1—C9	1.340 (2)	C5—C4	1.387 (3)
N2—C9	1.359 (2)	C5—H5	0.9300
N2—N3	1.360 (2)	C13—C16	1.499 (2)
N2—C10	1.449 (2)	C4—H4	0.9300
O2—C16	1.195 (2)	C10—H10A	0.9600
N3—C7	1.337 (2)	C10—H10B	0.9600
C9—C8	1.420 (2)	C10—H10C	0.9600
C7—C8	1.442 (2)	C11—H11A	0.9600
C7—C6	1.473 (2)	C11—H11B	0.9600
C14—C13	1.426 (2)	C11—H11C	0.9600
C14—C15	1.502 (3)	C17—C18	1.476 (3)
C3—C2	1.380 (3)	C17—H17A	0.9700
C3—C6	1.399 (3)	C17—H17B	0.9700
C3—H3	0.9300	C18—H18A	0.9600
C8—C12	1.415 (2)	C18—H18B	0.9600
C15—H15A	0.9600	C18—H18C	0.9600
C15—H15B	0.9600
C12—S1—C11	101.91 (10)	C1—C5—H5	120.4
C16—O1—C17	117.03 (16)	C4—C5—H5	120.4
C14—N1—C9	114.90 (15)	C12—C13—C14	122.00 (17)
C9—N2—N3	111.25 (15)	C12—C13—C16	120.27 (16)
C9—N2—C10	127.70 (17)	C14—C13—C16	117.74 (16)
N3—N2—C10	121.05 (16)	C5—C4—C6	121.27 (18)
C7—N3—N2	107.38 (15)	C5—C4—H4	119.4
N1—C9—N2	124.05 (17)	C6—C4—H4	119.4
N1—C9—C8	128.45 (16)	N2—C10—H10A	109.5
N2—C9—C8	107.43 (16)	N2—C10—H10B	109.5
N3—C7—C8	110.17 (16)	H10A—C10—H10B	109.5
N3—C7—C6	117.73 (15)	N2—C10—H10C	109.5
C8—C7—C6	131.99 (16)	H10A—C10—H10C	109.5
N1—C14—C13	121.99 (16)	H10B—C10—H10C	109.5
N1—C14—C15	116.87 (16)	O2—C16—O1	124.26 (18)
C13—C14—C15	121.14 (17)	O2—C16—C13	124.64 (17)
C2—C3—C6	121.48 (19)	O1—C16—C13	111.07 (15)
C2—C3—H3	119.3	C5—C1—C2	121.04 (19)
C6—C3—H3	119.3	C5—C1—Cl1	119.79 (16)
C12—C8—C9	115.20 (15)	C2—C1—Cl1	119.16 (16)
C12—C8—C7	140.99 (16)	S1—C11—H11A	109.5
C9—C8—C7	103.74 (15)	S1—C11—H11B	109.5
C14—C15—H15A	109.5	H11A—C11—H11B	109.5
C14—C15—H15B	109.5	S1—C11—H11C	109.5
H15A—C15—H15B	109.5	H11A—C11—H11C	109.5
C14—C15—H15C	109.5	H11B—C11—H11C	109.5
H15A—C15—H15C	109.5	O1—C17—C18	108.3 (2)
H15B—C15—H15C	109.5	O1—C17—H17A	110.0
C4—C6—C3	117.87 (17)	C18—C17—H17A	110.0
C4—C6—C7	120.25 (17)	O1—C17—H17B	110.0
C3—C6—C7	121.83 (17)	C18—C17—H17B	110.0
C13—C12—C8	116.96 (16)	H17A—C17—H17B	108.4
C13—C12—S1	117.71 (14)	C17—C18—H18A	109.5
C8—C12—S1	125.32 (13)	C17—C18—H18B	109.5
C3—C2—C1	119.14 (19)	H18A—C18—H18B	109.5
C3—C2—H2	120.4	C17—C18—H18C	109.5
C1—C2—H2	120.4	H18A—C18—H18C	109.5
C1—C5—C4	119.13 (19)	H18B—C18—H18C	109.5
C9—N2—N3—C7	−0.4 (2)	C9—C8—C12—S1	−173.01 (13)
C10—N2—N3—C7	179.58 (18)	C7—C8—C12—S1	3.2 (3)
C14—N1—C9—N2	178.40 (16)	C11—S1—C12—C13	−128.93 (15)
C14—N1—C9—C8	1.6 (3)	C11—S1—C12—C8	51.29 (17)
N3—N2—C9—N1	−175.78 (16)	C6—C3—C2—C1	−1.2 (3)
C10—N2—C9—N1	4.2 (3)	C8—C12—C13—C14	−2.9 (3)
N3—N2—C9—C8	1.6 (2)	S1—C12—C13—C14	177.35 (13)
C10—N2—C9—C8	−178.42 (19)	C8—C12—C13—C16	177.08 (15)
N2—N3—C7—C8	−0.9 (2)	S1—C12—C13—C16	−2.7 (2)
N2—N3—C7—C6	175.72 (15)	N1—C14—C13—C12	−3.1 (3)
C9—N1—C14—C13	3.7 (2)	C15—C14—C13—C12	176.81 (16)
C9—N1—C14—C15	−176.20 (16)	N1—C14—C13—C16	177.00 (15)
N1—C9—C8—C12	−7.2 (3)	C15—C14—C13—C16	−3.1 (3)
N2—C9—C8—C12	175.55 (15)	C1—C5—C4—C6	0.1 (3)
N1—C9—C8—C7	175.22 (17)	C3—C6—C4—C5	−2.5 (3)
N2—C9—C8—C7	−2.00 (19)	C7—C6—C4—C5	−179.85 (17)
N3—C7—C8—C12	−174.7 (2)	C17—O1—C16—O2	−1.7 (3)
C6—C7—C8—C12	9.4 (4)	C17—O1—C16—C13	176.52 (18)
N3—C7—C8—C9	1.81 (19)	C12—C13—C16—O2	−79.4 (3)
C6—C7—C8—C9	−174.18 (18)	C14—C13—C16—O2	100.5 (2)
C2—C3—C6—C4	3.1 (3)	C12—C13—C16—O1	102.39 (19)
C2—C3—C6—C7	−179.64 (17)	C14—C13—C16—O1	−77.7 (2)
N3—C7—C6—C4	35.3 (2)	C4—C5—C1—C2	1.8 (3)
C8—C7—C6—C4	−148.98 (19)	C4—C5—C1—Cl1	−177.07 (15)
N3—C7—C6—C3	−141.96 (19)	C3—C2—C1—C5	−1.3 (3)
C8—C7—C6—C3	33.8 (3)	C3—C2—C1—Cl1	177.61 (15)
C9—C8—C12—C13	7.2 (2)	C16—O1—C17—C18	−166.05 (19)
C7—C8—C12—C13	−176.6 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1^i	0.93	2.59	3.513 (2)	170

Symmetry code: (i) x−1, y, z.