6,7-Dihydro-6-meth­yl-3-(methyl­sulfanyl)-1-(p-tolyl)­pyrano[4,3-c]pyrazol-4(1H)-one

The title compound, C₁₅H₁₆N₂O₂S, which is a potentially new bioactive mol­ecule containing pyrazole and pyrone ring systems, was synthesized by the reaction of 1-p-tolyl­hydrazine and 3-[bis­(methyl­thio)methyl­ene]dihydro-6-meth­yl-3H-pyran-2,4-dione in ethanol.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.038
• wR factor = 0.110
• Data-to-parameter ratio = 16.4

checkCIF/PLATON results

No syntax errors found



Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.736     0.970
            Tmin' and Tmax expected:      0.943     0.970
            RR' =      0.780
            Please check that your absorption correction is appropriate.
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.78
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K

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

   2 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
   2 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL.

6,7-dihydro-6-methyl-3-(methylthio)-1-p-tolylpyrano[4,3-c]pyrazol-4(1H)-one

Crystal data

C15H16N2O2S	F(000) = 608
Mr = 288.36	Dx = 1.290 Mg m^−3
Monoclinic, P21/c	Melting point: 429 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 10.662 (2) Å	Cell parameters from 2931 reflections
b = 18.315 (4) Å	θ = 2.2–26.1°
c = 7.6831 (15) Å	µ = 0.22 mm^−1
β = 98.377 (3)°	T = 293 K
V = 1484.3 (5) Å^3	Prism, colourless
Z = 4	0.26 × 0.24 × 0.14 mm

Data collection

Bruker SMART CCD area-detector diffractometer	3015 independent reflections
Radiation source: fine-focus sealed tube	2130 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
Detector resolution: 0 pixels mm^-1	θmax = 26.3°, θmin = 1.9°
φ and ω scans	h = −11→13
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −20→22
Tmin = 0.736, Tmax = 0.970	l = −9→9
8492 measured reflections

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.110	H-atom parameters constrained
S = 0.98	w = 1/[σ^2(Fo^2) + (0.065P)^2 + 0.0755P] where P = (Fo^2 + 2Fc^2)/3
3015 reflections	(Δ/σ)max = 0.005
184 parameters	Δρmax = 0.21 e Å^−3
0 restraints	Δρmin = −0.19 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
S1	−0.27249 (4)	0.21988 (3)	0.42790 (7)	0.05044 (18)
O1	−0.02034 (12)	0.02459 (7)	0.69617 (18)	0.0475 (3)
O2	−0.20616 (12)	0.05048 (8)	0.5402 (2)	0.0569 (4)
N1	0.08140 (13)	0.23491 (8)	0.6109 (2)	0.0407 (4)
N2	−0.03258 (14)	0.26575 (8)	0.5344 (2)	0.0433 (4)
C1	0.1660 (2)	−0.01265 (11)	0.8814 (3)	0.0578 (6)
H1A	0.1137	−0.0465	0.9336	0.087*
H1B	0.2353	0.0025	0.9678	0.087*
H1C	0.1984	−0.0358	0.7850	0.087*
C2	0.08833 (17)	0.05302 (10)	0.8150 (3)	0.0459 (5)
H2	0.0568	0.0761	0.9153	0.055*
C3	0.16283 (17)	0.10946 (10)	0.7286 (3)	0.0437 (5)
H3A	0.2242	0.1333	0.8159	0.052*
H3B	0.2078	0.0865	0.6420	0.052*
C4	0.06990 (16)	0.16341 (10)	0.6426 (2)	0.0392 (4)
C5	−0.05433 (16)	0.14515 (10)	0.5857 (2)	0.0400 (4)
C6	−0.10203 (17)	0.07221 (10)	0.6034 (3)	0.0432 (4)
C7	−0.11344 (16)	0.21054 (10)	0.5194 (2)	0.0406 (4)
C8	−0.28529 (19)	0.31695 (12)	0.4096 (3)	0.0559 (5)
H8A	−0.2689	0.3384	0.5247	0.084*
H8B	−0.3692	0.3298	0.3553	0.084*
H8C	−0.2246	0.3348	0.3391	0.084*
C9	0.18827 (16)	0.28174 (10)	0.6533 (2)	0.0371 (4)
C10	0.30694 (17)	0.26044 (11)	0.6192 (3)	0.0443 (5)
H10	0.3185	0.2148	0.5708	0.053*
C11	0.40781 (17)	0.30769 (11)	0.6581 (3)	0.0490 (5)
H11	0.4878	0.2931	0.6371	0.059*
C12	0.39302 (18)	0.37628 (11)	0.7275 (3)	0.0484 (5)
C13	0.27320 (17)	0.39607 (10)	0.7613 (3)	0.0450 (5)
H13	0.2614	0.4417	0.8093	0.054*
C14	0.17121 (16)	0.34935 (10)	0.7250 (2)	0.0399 (4)
H14	0.0916	0.3634	0.7488	0.048*
C15	0.5019 (2)	0.42989 (14)	0.7625 (4)	0.0791 (8)
H15A	0.5449	0.4232	0.8801	0.119*
H15B	0.4696	0.4788	0.7495	0.119*
H15C	0.5600	0.4217	0.6802	0.119*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0386 (3)	0.0513 (3)	0.0576 (3)	−0.0055 (2)	−0.0055 (2)	0.0000 (2)
O1	0.0476 (7)	0.0374 (8)	0.0564 (9)	−0.0052 (6)	0.0041 (6)	−0.0005 (6)
O2	0.0462 (8)	0.0501 (9)	0.0715 (10)	−0.0136 (6)	−0.0008 (7)	0.0004 (7)
N1	0.0336 (8)	0.0400 (10)	0.0475 (9)	−0.0039 (6)	0.0029 (7)	0.0008 (7)
N2	0.0351 (8)	0.0448 (9)	0.0481 (9)	−0.0030 (7)	−0.0001 (7)	0.0037 (7)
C1	0.0614 (13)	0.0494 (13)	0.0618 (14)	0.0055 (10)	0.0063 (11)	0.0067 (10)
C2	0.0465 (11)	0.0451 (12)	0.0459 (11)	0.0011 (9)	0.0058 (9)	−0.0026 (9)
C3	0.0402 (10)	0.0426 (11)	0.0475 (11)	−0.0009 (8)	0.0040 (8)	−0.0026 (8)
C4	0.0395 (10)	0.0375 (11)	0.0412 (10)	−0.0025 (8)	0.0076 (8)	−0.0029 (8)
C5	0.0381 (9)	0.0411 (11)	0.0407 (10)	−0.0047 (8)	0.0057 (8)	−0.0035 (8)
C6	0.0442 (11)	0.0417 (11)	0.0447 (11)	−0.0038 (9)	0.0102 (8)	−0.0051 (9)
C7	0.0364 (9)	0.0444 (11)	0.0405 (10)	−0.0040 (8)	0.0040 (8)	−0.0003 (8)
C8	0.0485 (12)	0.0553 (14)	0.0632 (14)	0.0034 (10)	0.0051 (10)	0.0039 (11)
C9	0.0357 (9)	0.0387 (10)	0.0361 (10)	−0.0047 (8)	0.0021 (7)	0.0025 (8)
C10	0.0425 (10)	0.0404 (11)	0.0505 (12)	−0.0007 (8)	0.0083 (9)	−0.0053 (9)
C11	0.0321 (10)	0.0523 (12)	0.0623 (13)	0.0001 (8)	0.0056 (9)	−0.0002 (10)
C12	0.0392 (10)	0.0430 (12)	0.0596 (13)	−0.0048 (9)	−0.0044 (9)	0.0050 (9)
C13	0.0487 (11)	0.0343 (10)	0.0499 (12)	0.0004 (8)	−0.0002 (9)	−0.0012 (8)
C14	0.0365 (9)	0.0409 (11)	0.0422 (10)	0.0024 (8)	0.0053 (8)	0.0038 (8)
C15	0.0501 (13)	0.0565 (15)	0.125 (2)	−0.0139 (11)	−0.0067 (14)	−0.0054 (14)

Geometric parameters (Å, º)

S1—C7	1.7470 (18)	C5—C7	1.413 (3)
S1—C8	1.787 (2)	C5—C6	1.443 (3)
O1—C6	1.359 (2)	C8—H8A	0.9600
O1—C2	1.463 (2)	C8—H8B	0.9600
O2—C6	1.212 (2)	C8—H8C	0.9600
N1—C4	1.341 (2)	C9—C14	1.378 (3)
N1—N2	1.390 (2)	C9—C10	1.385 (3)
N1—C9	1.425 (2)	C10—C11	1.379 (3)
N2—C7	1.323 (2)	C10—H10	0.9300
C1—C2	1.506 (3)	C11—C12	1.383 (3)
C1—H1A	0.9600	C11—H11	0.9300
C1—H1B	0.9600	C12—C13	1.388 (3)
C1—H1C	0.9600	C12—C15	1.514 (3)
C2—C3	1.515 (3)	C13—C14	1.380 (2)
C2—H2	0.9800	C13—H13	0.9300
C3—C4	1.485 (2)	C14—H14	0.9300
C3—H3A	0.9700	C15—H15A	0.9600
C3—H3B	0.9700	C15—H15B	0.9600
C4—C5	1.374 (2)	C15—H15C	0.9600
C7—S1—C8	100.81 (9)	N2—C7—C5	111.45 (16)
C6—O1—C2	119.20 (14)	N2—C7—S1	122.84 (14)
C4—N1—N2	112.09 (14)	C5—C7—S1	125.71 (14)
C4—N1—C9	129.59 (15)	S1—C8—H8A	109.5
N2—N1—C9	118.20 (14)	S1—C8—H8B	109.5
C7—N2—N1	104.16 (14)	H8A—C8—H8B	109.5
C2—C1—H1A	109.5	S1—C8—H8C	109.5
C2—C1—H1B	109.5	H8A—C8—H8C	109.5
H1A—C1—H1B	109.5	H8B—C8—H8C	109.5
C2—C1—H1C	109.5	C14—C9—C10	120.40 (16)
H1A—C1—H1C	109.5	C14—C9—N1	118.98 (16)
H1B—C1—H1C	109.5	C10—C9—N1	120.60 (16)
O1—C2—C1	105.85 (16)	C11—C10—C9	119.18 (18)
O1—C2—C3	112.80 (15)	C11—C10—H10	120.4
C1—C2—C3	113.33 (16)	C9—C10—H10	120.4
O1—C2—H2	108.2	C10—C11—C12	121.64 (18)
C1—C2—H2	108.2	C10—C11—H11	119.2
C3—C2—H2	108.2	C12—C11—H11	119.2
C4—C3—C2	106.91 (15)	C11—C12—C13	117.97 (17)
C4—C3—H3A	110.3	C11—C12—C15	122.03 (19)
C2—C3—H3A	110.3	C13—C12—C15	119.98 (19)
C4—C3—H3B	110.3	C14—C13—C12	121.33 (18)
C2—C3—H3B	110.3	C14—C13—H13	119.3
H3A—C3—H3B	108.6	C12—C13—H13	119.3
N1—C4—C5	106.82 (16)	C9—C14—C13	119.46 (17)
N1—C4—C3	131.16 (16)	C9—C14—H14	120.3
C5—C4—C3	121.96 (17)	C13—C14—H14	120.3
C4—C5—C7	105.48 (16)	C12—C15—H15A	109.5
C4—C5—C6	122.14 (17)	C12—C15—H15B	109.5
C7—C5—C6	132.36 (16)	H15A—C15—H15B	109.5
O2—C6—O1	118.62 (17)	C12—C15—H15C	109.5
O2—C6—C5	125.51 (18)	H15A—C15—H15C	109.5
O1—C6—C5	115.85 (16)	H15B—C15—H15C	109.5
C4—N1—N2—C7	−0.5 (2)	N1—N2—C7—C5	0.5 (2)
C9—N1—N2—C7	−176.89 (16)	N1—N2—C7—S1	−179.42 (13)
C6—O1—C2—C1	−174.21 (16)	C4—C5—C7—N2	−0.3 (2)
C6—O1—C2—C3	−49.7 (2)	C6—C5—C7—N2	177.86 (19)
O1—C2—C3—C4	49.7 (2)	C4—C5—C7—S1	179.58 (14)
C1—C2—C3—C4	169.99 (17)	C6—C5—C7—S1	−2.3 (3)
N2—N1—C4—C5	0.3 (2)	C8—S1—C7—N2	−9.51 (19)
C9—N1—C4—C5	176.19 (17)	C8—S1—C7—C5	170.62 (17)
N2—N1—C4—C3	−176.83 (19)	C4—N1—C9—C14	−134.8 (2)
C9—N1—C4—C3	−0.9 (3)	N2—N1—C9—C14	40.8 (2)
C2—C3—C4—N1	149.8 (2)	C4—N1—C9—C10	46.7 (3)
C2—C3—C4—C5	−27.0 (2)	N2—N1—C9—C10	−137.64 (19)
N1—C4—C5—C7	0.0 (2)	C14—C9—C10—C11	0.0 (3)
C3—C4—C5—C7	177.44 (17)	N1—C9—C10—C11	178.50 (17)
N1—C4—C5—C6	−178.41 (17)	C9—C10—C11—C12	−1.1 (3)
C3—C4—C5—C6	−0.9 (3)	C10—C11—C12—C13	1.4 (3)
C2—O1—C6—O2	−162.12 (17)	C10—C11—C12—C15	−177.1 (2)
C2—O1—C6—C5	19.3 (2)	C11—C12—C13—C14	−0.8 (3)
C4—C5—C6—O2	−171.81 (19)	C15—C12—C13—C14	177.7 (2)
C7—C5—C6—O2	10.3 (3)	C10—C9—C14—C13	0.6 (3)
C4—C5—C6—O1	6.7 (3)	N1—C9—C14—C13	−177.89 (16)
C7—C5—C6—O1	−171.25 (19)	C12—C13—C14—C9	−0.2 (3)