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

In the title compound, the dihedral angle between the fused pyrazole and pyridine rings is 1.76 (7)°. The benzene and meth­oxy phenyl rings make dihedral angles of 44.8 (5) and 63.86 (5)°, respectively, with the pyrazolo­[3,4-b] pyridine moiety. An intra­molecular short S...O contact [3.215 (2) Å] is observed. The crystal packing features C—H...π inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.048
• wR factor = 0.168
• Data-to-parameter ratio = 18.2

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT910_ALERT_3_B Missing # of FCF Reflection(s) Below Theta(Min).         14 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=0.0480) and Goodness of Fit (GOOF) (S=1.064) of title compond were good enough for this structural assignment

Alert level C
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600         11 Report

Alert level G
PLAT063_ALERT_4_G Crystal Size Possibly too Large for Beam Size ..       0.75 mm
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600        832 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          1 Info

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

   0 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
   2 ALERT type 3 Indicator that the structure quality may be low
   2 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, 2015); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); 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 6-(4-methoxyphenyl)-1-methyl-4-methylsulfanyl-3-phenyl-1H-pyrazolo[3,4-b]pyridine-5-carboxylate

Crystal data

C24H23N3O3S	Z = 2
Mr = 433.51	F(000) = 456
Triclinic, P1	Dx = 1.294 Mg m^−3
a = 10.1911 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.7274 (6) Å	Cell parameters from 3586 reflections
c = 11.7692 (6) Å	θ = 3.8–29.1°
α = 98.550 (5)°	µ = 0.18 mm^−1
β = 105.632 (4)°	T = 298 K
γ = 111.015 (4)°	Block, colorless
V = 1112.75 (10) Å^3	0.75 × 0.44 × 0.42 mm

Data collection

Agilent Xcalibur, Eos diffractometer	5161 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3672 reflections with I > 2σ(I)
Detector resolution: 15.9821 pixels mm^-1	Rint = 0.026
ω scans	θmax = 29.2°, θmin = 3.8°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	h = −13→12
Tmin = 0.959, Tmax = 1.000	k = −13→14
13297 measured reflections	l = −15→15

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.168	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.1P)^2] where P = (Fo^2 + 2Fc^2)/3
5161 reflections	(Δ/σ)max < 0.001
284 parameters	Δρmax = 0.20 e Å^−3
0 restraints	Δρmin = −0.26 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	0.67085 (6)	0.56012 (6)	0.41095 (5)	0.0647 (2)
O2	0.38290 (15)	0.56954 (14)	0.22189 (15)	0.0618 (4)
N3	0.72006 (14)	0.40967 (14)	0.23884 (14)	0.0456 (4)
O3	−0.16778 (14)	0.10375 (17)	−0.27340 (14)	0.0716 (4)
O1	0.26375 (16)	0.36781 (15)	0.25921 (15)	0.0716 (4)
N2	0.74888 (15)	0.26571 (16)	0.08007 (15)	0.0507 (4)
N1	0.66463 (15)	0.17775 (16)	−0.03455 (15)	0.0524 (4)
C6	0.46748 (17)	0.39796 (17)	0.18528 (16)	0.0426 (4)
C18	0.25937 (17)	0.25136 (17)	−0.01408 (15)	0.0403 (4)
C5	0.41691 (17)	0.30623 (16)	0.07038 (15)	0.0397 (4)
C23	0.2031 (2)	0.33918 (19)	−0.06467 (18)	0.0509 (4)
H23	0.262169	0.434277	−0.040467	0.061*
C19	0.16737 (17)	0.11066 (18)	−0.05037 (16)	0.0450 (4)
H19	0.203616	0.050794	−0.017572	0.054*
C4	0.52914 (18)	0.17844 (18)	−0.06206 (17)	0.0440 (4)
C3	0.52331 (17)	0.26645 (16)	0.03830 (16)	0.0403 (4)
C12	0.41458 (18)	0.09398 (18)	−0.18366 (16)	0.0443 (4)
C21	−0.02998 (18)	0.1451 (2)	−0.18636 (17)	0.0507 (4)
C20	0.02258 (18)	0.05683 (19)	−0.13439 (16)	0.0491 (4)
H20	−0.038626	−0.037581	−0.155630	0.059*
C7	0.61907 (18)	0.44751 (18)	0.26597 (17)	0.0451 (4)
C17	0.3250 (2)	0.1467 (2)	−0.25396 (17)	0.0518 (4)
H17	0.335347	0.236158	−0.223765	0.062*
C22	0.0606 (2)	0.2860 (2)	−0.15032 (19)	0.0575 (5)
H22	0.024819	0.345484	−0.184333	0.069*
C1	0.9027 (2)	0.2863 (3)	0.1384 (2)	0.0737 (6)
H1A	0.954270	0.370449	0.204079	0.110*
H1B	0.952102	0.292919	0.079218	0.110*
H1C	0.903503	0.209297	0.170462	0.110*
C2	0.66831 (17)	0.32140 (18)	0.12734 (17)	0.0435 (4)
C16	0.2213 (2)	0.0669 (2)	−0.36804 (19)	0.0632 (5)
H16	0.161631	0.102596	−0.414423	0.076*
C13	0.3980 (2)	−0.0386 (2)	−0.23167 (19)	0.0583 (5)
H13	0.458611	−0.074552	−0.186802	0.070*
C9	0.35959 (19)	0.44074 (19)	0.22766 (17)	0.0477 (4)
C10	0.2937 (3)	0.6327 (2)	0.2651 (3)	0.0740 (7)
H10A	0.202428	0.560492	0.264182	0.089*
H10B	0.265806	0.685559	0.210502	0.089*
C15	0.2054 (3)	−0.0656 (2)	−0.4137 (2)	0.0716 (6)
H15	0.135537	−0.119091	−0.490858	0.086*
C8	0.8584 (2)	0.5829 (3)	0.4825 (2)	0.0821 (7)
H8A	0.859059	0.495191	0.489817	0.123*
H8B	0.900377	0.646868	0.562541	0.123*
H8C	0.917043	0.619009	0.433710	0.123*
C11	0.3801 (3)	0.7253 (3)	0.3911 (3)	0.0868 (8)
H11A	0.402829	0.671847	0.445827	0.130*
H11B	0.321725	0.769022	0.416900	0.130*
H11C	0.471812	0.795051	0.392304	0.130*
C24	−0.2684 (2)	−0.0390 (3)	−0.3089 (3)	0.0881 (8)
H24A	−0.228284	−0.093559	−0.348676	0.132*
H24B	−0.363754	−0.052474	−0.364364	0.132*
H24C	−0.280979	−0.067455	−0.237465	0.132*
C14	0.2926 (3)	−0.1182 (2)	−0.3453 (2)	0.0756 (7)
H14	0.280866	−0.208232	−0.375564	0.091*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0602 (3)	0.0687 (4)	0.0507 (3)	0.0333 (3)	−0.0005 (2)	−0.0037 (3)
O2	0.0566 (7)	0.0531 (8)	0.0840 (11)	0.0294 (6)	0.0309 (7)	0.0137 (7)
N3	0.0379 (7)	0.0429 (8)	0.0482 (9)	0.0157 (6)	0.0063 (6)	0.0105 (7)
O3	0.0436 (7)	0.0890 (11)	0.0611 (10)	0.0256 (7)	−0.0054 (7)	0.0109 (8)
O1	0.0659 (9)	0.0703 (10)	0.0955 (12)	0.0307 (7)	0.0459 (9)	0.0313 (9)
N2	0.0348 (7)	0.0594 (9)	0.0538 (10)	0.0211 (6)	0.0110 (7)	0.0093 (8)
N1	0.0436 (8)	0.0610 (10)	0.0527 (10)	0.0239 (7)	0.0166 (7)	0.0112 (8)
C6	0.0380 (8)	0.0409 (9)	0.0459 (10)	0.0173 (7)	0.0096 (7)	0.0109 (8)
C18	0.0347 (8)	0.0456 (9)	0.0397 (9)	0.0177 (7)	0.0101 (7)	0.0123 (7)
C5	0.0366 (8)	0.0395 (8)	0.0419 (9)	0.0163 (6)	0.0099 (7)	0.0144 (7)
C23	0.0478 (9)	0.0459 (10)	0.0541 (11)	0.0218 (8)	0.0078 (8)	0.0129 (8)
C19	0.0405 (9)	0.0471 (9)	0.0474 (10)	0.0181 (7)	0.0137 (8)	0.0167 (8)
C4	0.0400 (8)	0.0466 (9)	0.0459 (10)	0.0178 (7)	0.0155 (7)	0.0141 (8)
C3	0.0359 (8)	0.0391 (8)	0.0440 (10)	0.0155 (6)	0.0101 (7)	0.0137 (7)
C12	0.0414 (8)	0.0489 (10)	0.0404 (10)	0.0150 (7)	0.0174 (7)	0.0098 (8)
C21	0.0370 (9)	0.0682 (12)	0.0419 (10)	0.0220 (8)	0.0081 (8)	0.0120 (9)
C20	0.0388 (9)	0.0520 (10)	0.0486 (11)	0.0124 (7)	0.0131 (8)	0.0130 (8)
C7	0.0411 (8)	0.0406 (9)	0.0452 (10)	0.0154 (7)	0.0059 (7)	0.0097 (7)
C17	0.0512 (10)	0.0547 (11)	0.0459 (11)	0.0210 (8)	0.0145 (8)	0.0111 (9)
C22	0.0532 (10)	0.0623 (12)	0.0574 (12)	0.0329 (9)	0.0073 (9)	0.0182 (10)
C1	0.0404 (10)	0.0916 (16)	0.0792 (16)	0.0328 (10)	0.0088 (10)	0.0052 (13)
C2	0.0370 (8)	0.0442 (9)	0.0484 (10)	0.0180 (7)	0.0112 (7)	0.0149 (8)
C16	0.0566 (11)	0.0755 (14)	0.0472 (12)	0.0219 (10)	0.0108 (9)	0.0167 (11)
C13	0.0737 (12)	0.0529 (11)	0.0523 (12)	0.0292 (9)	0.0241 (10)	0.0152 (9)
C9	0.0413 (9)	0.0508 (10)	0.0460 (10)	0.0199 (7)	0.0098 (8)	0.0077 (8)
C10	0.0638 (13)	0.0697 (14)	0.1010 (19)	0.0400 (11)	0.0353 (13)	0.0147 (13)
C15	0.0773 (14)	0.0637 (14)	0.0447 (12)	0.0073 (11)	0.0135 (11)	0.0049 (10)
C8	0.0566 (12)	0.0955 (18)	0.0603 (15)	0.0251 (12)	−0.0075 (11)	−0.0043 (13)
C11	0.1061 (19)	0.0984 (19)	0.0812 (19)	0.0613 (16)	0.0479 (16)	0.0204 (16)
C24	0.0442 (11)	0.1039 (19)	0.0718 (17)	0.0056 (11)	−0.0057 (11)	0.0133 (15)
C14	0.1098 (18)	0.0521 (12)	0.0520 (13)	0.0261 (12)	0.0237 (13)	0.0066 (10)

Geometric parameters (Å, º)

S1—C7	1.7590 (19)	C12—C17	1.392 (3)
S1—C8	1.777 (2)	C21—C22	1.383 (3)
O2—C9	1.331 (2)	C21—C20	1.385 (3)
O2—C10	1.460 (2)	C20—H20	0.9300
N3—C7	1.328 (2)	C17—C16	1.378 (3)
N3—C2	1.340 (2)	C17—H17	0.9300
O3—C21	1.364 (2)	C22—H22	0.9300
O3—C24	1.423 (3)	C1—H1A	0.9600
O1—O1	0.000 (4)	C1—H1B	0.9600
O1—C9	1.199 (2)	C1—H1C	0.9600
N2—C2	1.356 (2)	C16—C15	1.377 (3)
N2—N1	1.365 (2)	C16—H16	0.9300
N2—C1	1.450 (2)	C13—C14	1.378 (3)
N1—C4	1.334 (2)	C13—H13	0.9300
C6—C5	1.388 (2)	C10—C11	1.481 (3)
C6—C7	1.429 (2)	C10—H10A	0.9700
C6—C9	1.503 (2)	C10—H10B	0.9700
C18—C19	1.385 (2)	C15—C14	1.366 (4)
C18—C23	1.393 (2)	C15—H15	0.9300
C18—C5	1.483 (2)	C8—H8A	0.9600
C5—C3	1.416 (2)	C8—H8B	0.9600
C23—C22	1.377 (3)	C8—H8C	0.9600
C23—H23	0.9300	C11—H11A	0.9600
C19—C20	1.386 (2)	C11—H11B	0.9600
C19—H19	0.9300	C11—H11C	0.9600
C4—C3	1.427 (2)	C24—H24A	0.9600
C4—C12	1.479 (2)	C24—H24B	0.9600
C3—C2	1.409 (2)	C24—H24C	0.9600
C12—C13	1.381 (3)	C14—H14	0.9300
C7—S1—C8	102.08 (11)	H1A—C1—H1B	109.5
C9—O2—C10	118.64 (16)	N2—C1—H1C	109.5
C7—N3—C2	114.13 (14)	H1A—C1—H1C	109.5
C21—O3—C24	117.99 (17)	H1B—C1—H1C	109.5
C2—N2—N1	111.38 (13)	N3—C2—N2	125.09 (15)
C2—N2—C1	127.81 (17)	N3—C2—C3	128.10 (15)
N1—N2—C1	120.77 (16)	N2—C2—C3	106.80 (15)
C4—N1—N2	106.91 (14)	C15—C16—C17	120.3 (2)
C5—C6—C7	120.93 (15)	C15—C16—H16	119.9
C5—C6—C9	119.54 (14)	C17—C16—H16	119.9
C7—C6—C9	119.47 (16)	C14—C13—C12	120.77 (19)
C19—C18—C23	118.28 (15)	C14—C13—H13	119.6
C19—C18—C5	120.91 (14)	C12—C13—H13	119.6
C23—C18—C5	120.70 (15)	O1—C9—O2	124.91 (16)
C6—C5—C3	116.49 (14)	O1—C9—O2	124.91 (16)
C6—C5—C18	121.92 (14)	O1—C9—C6	124.73 (17)
C3—C5—C18	121.59 (15)	O1—C9—C6	124.73 (17)
C22—C23—C18	120.38 (17)	O2—C9—C6	110.33 (15)
C22—C23—H23	119.8	O2—C10—C11	110.43 (19)
C18—C23—H23	119.8	O2—C10—H10A	109.6
C18—C19—C20	121.62 (15)	C11—C10—H10A	109.6
C18—C19—H19	119.2	O2—C10—H10B	109.6
C20—C19—H19	119.2	C11—C10—H10B	109.6
N1—C4—C3	110.06 (15)	H10A—C10—H10B	108.1
N1—C4—C12	118.69 (16)	C14—C15—C16	119.8 (2)
C3—C4—C12	131.25 (14)	C14—C15—H15	120.1
C2—C3—C5	116.67 (15)	C16—C15—H15	120.1
C2—C3—C4	104.82 (14)	S1—C8—H8A	109.5
C5—C3—C4	138.47 (15)	S1—C8—H8B	109.5
C13—C12—C17	118.49 (17)	H8A—C8—H8B	109.5
C13—C12—C4	120.04 (16)	S1—C8—H8C	109.5
C17—C12—C4	121.44 (16)	H8A—C8—H8C	109.5
O3—C21—C22	115.77 (17)	H8B—C8—H8C	109.5
O3—C21—C20	124.66 (17)	C10—C11—H11A	109.5
C22—C21—C20	119.56 (16)	C10—C11—H11B	109.5
C21—C20—C19	119.30 (17)	H11A—C11—H11B	109.5
C21—C20—H20	120.4	C10—C11—H11C	109.5
C19—C20—H20	120.4	H11A—C11—H11C	109.5
N3—C7—C6	123.66 (17)	H11B—C11—H11C	109.5
N3—C7—S1	118.89 (13)	O3—C24—H24A	109.5
C6—C7—S1	117.42 (13)	O3—C24—H24B	109.5
C16—C17—C12	120.30 (19)	H24A—C24—H24B	109.5
C16—C17—H17	119.9	O3—C24—H24C	109.5
C12—C17—H17	119.9	H24A—C24—H24C	109.5
C23—C22—C21	120.80 (17)	H24B—C24—H24C	109.5
C23—C22—H22	119.6	C15—C14—C13	120.3 (2)
C21—C22—H22	119.6	C15—C14—H14	119.8
N2—C1—H1A	109.5	C13—C14—H14	119.8
N2—C1—H1B	109.5
C2—N2—N1—C4	0.92 (19)	C5—C6—C7—S1	−178.50 (13)
C1—N2—N1—C4	178.78 (17)	C9—C6—C7—S1	−1.3 (2)
C7—C6—C5—C3	−0.5 (2)	C8—S1—C7—N3	−2.36 (18)
C9—C6—C5—C3	−177.72 (15)	C8—S1—C7—C6	175.47 (15)
C7—C6—C5—C18	178.87 (14)	C13—C12—C17—C16	0.8 (3)
C9—C6—C5—C18	1.6 (2)	C4—C12—C17—C16	178.66 (16)
C19—C18—C5—C6	−117.54 (18)	C18—C23—C22—C21	0.9 (3)
C23—C18—C5—C6	66.4 (2)	O3—C21—C22—C23	−178.79 (18)
C19—C18—C5—C3	61.8 (2)	C20—C21—C22—C23	0.9 (3)
C23—C18—C5—C3	−114.30 (19)	C7—N3—C2—N2	−178.44 (16)
C19—C18—C23—C22	−1.3 (3)	C7—N3—C2—C3	0.3 (2)
C5—C18—C23—C22	174.93 (17)	N1—N2—C2—N3	178.93 (15)
C23—C18—C19—C20	−0.2 (3)	C1—N2—C2—N3	1.3 (3)
C5—C18—C19—C20	−176.43 (16)	N1—N2—C2—C3	0.00 (19)
N2—N1—C4—C3	−1.47 (18)	C1—N2—C2—C3	−177.67 (18)
N2—N1—C4—C12	178.47 (14)	C5—C3—C2—N3	−1.5 (3)
C6—C5—C3—C2	1.5 (2)	C4—C3—C2—N3	−179.75 (16)
C18—C5—C3—C2	−177.89 (14)	C5—C3—C2—N2	177.41 (14)
C6—C5—C3—C4	178.94 (18)	C4—C3—C2—N2	−0.86 (17)
C18—C5—C3—C4	−0.4 (3)	C12—C17—C16—C15	−0.2 (3)
N1—C4—C3—C2	1.46 (18)	C17—C12—C13—C14	−1.6 (3)
C12—C4—C3—C2	−178.47 (17)	C4—C12—C13—C14	−179.45 (18)
N1—C4—C3—C5	−176.19 (19)	O1—O1—C9—O2	0.00 (13)
C12—C4—C3—C5	3.9 (3)	O1—O1—C9—C6	0.00 (9)
N1—C4—C12—C13	42.4 (2)	C10—O2—C9—O1	4.7 (3)
C3—C4—C12—C13	−137.69 (19)	C10—O2—C9—O1	4.7 (3)
N1—C4—C12—C17	−135.43 (18)	C10—O2—C9—C6	−177.05 (17)
C3—C4—C12—C17	44.5 (3)	C5—C6—C9—O1	73.3 (2)
C24—O3—C21—C22	−176.7 (2)	C7—C6—C9—O1	−104.0 (2)
C24—O3—C21—C20	3.6 (3)	C5—C6—C9—O1	73.3 (2)
O3—C21—C20—C19	177.29 (17)	C7—C6—C9—O1	−104.0 (2)
C22—C21—C20—C19	−2.4 (3)	C5—C6—C9—O2	−104.97 (18)
C18—C19—C20—C21	2.1 (3)	C7—C6—C9—O2	77.8 (2)
C2—N3—C7—C6	0.9 (2)	C9—O2—C10—C11	99.1 (2)
C2—N3—C7—S1	178.58 (12)	C17—C16—C15—C14	0.3 (3)
C5—C6—C7—N3	−0.8 (3)	C16—C15—C14—C13	−1.0 (4)
C9—C6—C7—N3	176.44 (16)	C12—C13—C14—C15	1.7 (3)

Hydrogen-bond geometry (Å, º)

Cg1 and Cg2 are the centroids of the N1/N2/C2–C4 and the N3/C2/C3/C5–C7 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···Cg1^i	0.93	2.85	3.455 (2)	124
C23—H23···Cg2^ii	0.93	3.02	3.738 (2)	136

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