5-[3-(2,5-Dimethoxy­phen­yl)prop-2-enyl­idene]-1,3-diethyl-2-thioxohexa­hydro­pyrimidine-4,6-dione

Asiri, A.M.; Khan, S.A.; Ng, S.W.

doi:10.1107/S1600536809026099

organic compounds

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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o1820

doi:10.1107/S1600536809026099

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5-[3-(2,5-Dimethoxyphenyl)prop-2-enylidene]-1,3-diethyl-2-thioxohexahydropyrimidine-4,6-dione

Abdullah Mohamed Asiri,^a Salman A. Khan ^a and Seik Weng Ng ^b ^*

^aChemistry Department, Faculty of Science, King Abdul Aziz University, Jeddah, Saudi Arabia, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 4 July 2009; accepted 5 July 2009; online 11 July 2009)

1,3-Diethyl-2-thiobarbituric acid reacts with 2,5-dimethoxybenzaldehyde to form the title Knoevenagel product, C₁₉H₂₂N₂O₄S. In the compound, the two six-membered rings at either end of the three-membered –CHCHCH– chain are nearly coplanar with this fragment (r.m.s. deviation of the two six-membered rings and the three chain atoms = 0.08 Å).

Related literature

For the reaction of 1,3-diethyl-2-thiobarbituric acid with aromatic aldehydes to form the Knoevenagel and Michael products, see: Adamson et al. (1999 ).

Experimental

Crystal data

C₁₉H₂₂N₂O₄S
M_r = 374.45
Monoclinic, P 2₁ /n
a = 10.0519 (2) Å
b = 15.5942 (3) Å
c = 11.5920 (2) Å
β = 90.813 (1)°
V = 1816.88 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 140 K
0.35 × 0.25 × 0.15 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.932, T_max = 0.970
12384 measured reflections
4124 independent reflections
3351 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.119
S = 1.02
4124 reflections
239 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809026099/xu2548sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809026099/xu2548Isup2.hkl

checkCIF report

Related literature top

For the reaction of 1,3-diethyl-2-thiobarbituric acid with aromatic aldehydes to form the Knoevenagel and Michael products, see: Adamson et al. (1999).

Experimental top

1,3-Diethyl-2-thiobarbituric acid (1 g, 0.005 mol) and 2,5-dimethoxybenzaldehyde (0.83 g, 0.005 mol) were heated in ethanol (15 ml) for 3 h; several drops of pyridine were added. The progress of reaction was monitored by TLC. The solid that seperated from the cool mixture was collected and recrystallized from a methanol-chloroform mixture in 50% yield; m.p. 454 K.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C₁₉H₂₂N₂O₄S at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

5-[3-(2,5-Dimethoxyphenyl)prop-2-enylidene]-1,3-diethyl-2- thioxohexahydropyrimidine-4,6-dione top

Crystal data top

C₁₉H₂₂N₂O₄S	F(000) = 792
M_r = 374.45	D_x = 1.369 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4985 reflections
a = 10.0519 (2) Å	θ = 2.2–28.3°
b = 15.5942 (3) Å	µ = 0.21 mm⁻¹
c = 11.5920 (2) Å	T = 140 K
β = 90.813 (1)°	Irregular, gold–green
V = 1816.88 (6) Å³	0.35 × 0.25 × 0.15 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	4124 independent reflections
Radiation source: fine-focus sealed tube	3351 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ω scans	θ_max = 27.5°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→13
T_min = 0.932, T_max = 0.970	k = −20→19
12384 measured reflections	l = −15→15

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.119	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0635P)² + 0.8319P] where P = (F_o² + 2F_c²)/3
4124 reflections	(Δ/σ)_max = 0.001
239 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₁₉H₂₂N₂O₄S	V = 1816.88 (6) Å³
M_r = 374.45	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.0519 (2) Å	µ = 0.21 mm⁻¹
b = 15.5942 (3) Å	T = 140 K
c = 11.5920 (2) Å	0.35 × 0.25 × 0.15 mm
β = 90.813 (1)°

Data collection top

Bruker SMART APEX diffractometer	4124 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3351 reflections with I > 2σ(I)
T_min = 0.932, T_max = 0.970	R_int = 0.021
12384 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.119	H-atom parameters constrained
S = 1.02	Δρ_max = 0.38 e Å⁻³
4124 reflections	Δρ_min = −0.31 e Å⁻³
239 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.45514 (5)	0.17006 (3)	0.48043 (5)	0.04028 (15)
O1	0.65557 (12)	0.44794 (7)	0.58487 (12)	0.0369 (3)
O2	0.88016 (13)	0.19441 (7)	0.68934 (12)	0.0368 (3)
O3	1.30863 (11)	0.51465 (7)	0.76778 (11)	0.0323 (3)
O4	1.02427 (13)	0.79694 (8)	0.61792 (13)	0.0412 (3)
N1	0.57177 (12)	0.31723 (8)	0.53660 (11)	0.0229 (3)
N2	0.67570 (13)	0.19089 (8)	0.60462 (11)	0.0238 (3)
C1	0.67099 (15)	0.37060 (9)	0.58438 (13)	0.0242 (3)
C2	0.78972 (15)	0.32772 (9)	0.63022 (13)	0.0229 (3)
C3	0.78870 (16)	0.23434 (9)	0.64445 (13)	0.0250 (3)
C4	0.57229 (15)	0.22878 (10)	0.54306 (14)	0.0248 (3)
C5	0.45950 (15)	0.36105 (10)	0.47751 (14)	0.0265 (3)
H5A	0.4319	0.3274	0.4088	0.032*
H5B	0.4890	0.4182	0.4508	0.032*
C6	0.34165 (17)	0.37168 (11)	0.55619 (16)	0.0341 (4)
H6A	0.2705	0.4026	0.5152	0.051*
H6B	0.3690	0.4042	0.6249	0.051*
H6C	0.3092	0.3151	0.5794	0.051*
C7	0.67507 (17)	0.09673 (10)	0.62395 (15)	0.0303 (4)
H7A	0.5820	0.0766	0.6301	0.036*
H7B	0.7216	0.0837	0.6977	0.036*
C8	0.7422 (2)	0.04915 (11)	0.52713 (19)	0.0415 (4)
H8A	0.7466	−0.0121	0.5458	0.062*
H8B	0.8325	0.0715	0.5175	0.062*
H8C	0.6911	0.0572	0.4553	0.062*
C9	0.90368 (16)	0.36954 (10)	0.66047 (13)	0.0250 (3)
H9	0.9718	0.3342	0.6923	0.030*
C10	0.93689 (16)	0.45823 (10)	0.65184 (13)	0.0254 (3)
H10	0.8741	0.4981	0.6216	0.031*
C11	1.05873 (16)	0.48485 (10)	0.68724 (14)	0.0258 (3)
H11	1.1170	0.4415	0.7155	0.031*
C12	1.11166 (16)	0.57152 (10)	0.68749 (13)	0.0246 (3)
C13	1.24183 (16)	0.58518 (10)	0.72991 (13)	0.0252 (3)
C14	1.29543 (16)	0.66804 (10)	0.73119 (14)	0.0275 (3)
H14	1.3836	0.6774	0.7589	0.033*
C15	1.21964 (17)	0.73610 (10)	0.69203 (15)	0.0294 (4)
H15	1.2566	0.7922	0.6926	0.035*
C16	1.08972 (17)	0.72399 (10)	0.65159 (14)	0.0288 (3)
C17	1.03685 (16)	0.64216 (10)	0.64830 (14)	0.0262 (3)
H17	0.9490	0.6336	0.6192	0.031*
C18	1.44150 (17)	0.52479 (11)	0.81125 (16)	0.0328 (4)
H18A	1.4763	0.4690	0.8361	0.049*
H18B	1.4415	0.5643	0.8770	0.049*
H18C	1.4978	0.5481	0.7504	0.049*
C19	0.89413 (19)	0.78713 (12)	0.56997 (19)	0.0415 (4)
H19A	0.8576	0.8436	0.5503	0.062*
H19B	0.8368	0.7592	0.6264	0.062*
H19C	0.8983	0.7518	0.5002	0.062*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0323 (2)	0.0271 (2)	0.0610 (3)	−0.00414 (17)	−0.0128 (2)	−0.0060 (2)
O1	0.0306 (6)	0.0158 (5)	0.0640 (8)	0.0014 (5)	−0.0106 (6)	0.0012 (5)
O2	0.0364 (7)	0.0202 (5)	0.0534 (8)	0.0041 (5)	−0.0167 (6)	0.0012 (5)
O3	0.0260 (6)	0.0242 (6)	0.0465 (7)	−0.0029 (5)	−0.0060 (5)	−0.0024 (5)
O4	0.0380 (7)	0.0223 (6)	0.0629 (9)	−0.0045 (5)	−0.0123 (6)	0.0066 (6)
N1	0.0214 (6)	0.0185 (6)	0.0287 (6)	−0.0005 (5)	−0.0028 (5)	0.0002 (5)
N2	0.0250 (7)	0.0158 (6)	0.0307 (7)	−0.0010 (5)	−0.0004 (5)	0.0005 (5)
C1	0.0230 (8)	0.0185 (7)	0.0312 (8)	−0.0009 (6)	−0.0002 (6)	0.0016 (6)
C2	0.0249 (8)	0.0167 (7)	0.0270 (7)	0.0005 (6)	−0.0025 (6)	−0.0014 (5)
C3	0.0274 (8)	0.0186 (7)	0.0288 (8)	0.0006 (6)	−0.0017 (6)	−0.0006 (6)
C4	0.0244 (8)	0.0200 (7)	0.0300 (8)	−0.0015 (6)	0.0008 (6)	−0.0011 (6)
C5	0.0242 (8)	0.0241 (7)	0.0309 (8)	0.0020 (6)	−0.0053 (6)	0.0034 (6)
C6	0.0285 (9)	0.0318 (9)	0.0419 (10)	0.0039 (7)	−0.0002 (7)	−0.0008 (7)
C7	0.0322 (9)	0.0160 (7)	0.0427 (9)	−0.0018 (6)	0.0037 (7)	0.0029 (6)
C8	0.0402 (10)	0.0252 (8)	0.0594 (12)	0.0003 (7)	0.0068 (9)	−0.0097 (8)
C9	0.0255 (8)	0.0202 (7)	0.0293 (8)	0.0011 (6)	−0.0020 (6)	−0.0024 (6)
C10	0.0262 (8)	0.0202 (7)	0.0299 (8)	−0.0005 (6)	−0.0010 (6)	−0.0021 (6)
C11	0.0270 (8)	0.0207 (7)	0.0298 (8)	−0.0001 (6)	0.0009 (6)	−0.0033 (6)
C12	0.0260 (8)	0.0220 (7)	0.0260 (7)	−0.0039 (6)	0.0029 (6)	−0.0045 (6)
C13	0.0254 (8)	0.0228 (7)	0.0275 (8)	−0.0009 (6)	0.0030 (6)	−0.0036 (6)
C14	0.0254 (8)	0.0271 (8)	0.0300 (8)	−0.0066 (6)	0.0018 (6)	−0.0054 (6)
C15	0.0313 (9)	0.0226 (7)	0.0345 (8)	−0.0091 (6)	0.0034 (7)	−0.0039 (6)
C16	0.0328 (9)	0.0224 (7)	0.0314 (8)	−0.0021 (6)	0.0013 (7)	0.0000 (6)
C17	0.0251 (8)	0.0230 (7)	0.0305 (8)	−0.0038 (6)	−0.0003 (6)	−0.0008 (6)
C18	0.0264 (8)	0.0320 (9)	0.0398 (9)	−0.0031 (7)	−0.0051 (7)	0.0009 (7)
C19	0.0365 (10)	0.0292 (9)	0.0587 (12)	−0.0017 (7)	−0.0097 (9)	0.0094 (8)

Geometric parameters (Å, º) top

S1—C4	1.6516 (16)	C8—H8A	0.9800
O1—C1	1.2160 (19)	C8—H8B	0.9800
O2—C3	1.2207 (19)	C8—H8C	0.9800
O3—C13	1.3582 (19)	C9—C10	1.427 (2)
O3—C18	1.430 (2)	C9—H9	0.9500
O4—C16	1.368 (2)	C10—C11	1.351 (2)
O4—C19	1.422 (2)	C10—H10	0.9500
N1—C4	1.3815 (19)	C11—C12	1.453 (2)
N1—C1	1.4065 (19)	C11—H11	0.9500
N1—C5	1.4791 (19)	C12—C17	1.405 (2)
N2—C4	1.385 (2)	C12—C13	1.407 (2)
N2—C3	1.396 (2)	C13—C14	1.400 (2)
N2—C7	1.4852 (19)	C14—C15	1.379 (2)
C1—C2	1.461 (2)	C14—H14	0.9500
C2—C9	1.360 (2)	C15—C16	1.394 (2)
C2—C3	1.465 (2)	C15—H15	0.9500
C5—C6	1.514 (2)	C16—C17	1.383 (2)
C5—H5A	0.9900	C17—H17	0.9500
C5—H5B	0.9900	C18—H18A	0.9800
C6—H6A	0.9800	C18—H18B	0.9800
C6—H6B	0.9800	C18—H18C	0.9800
C6—H6C	0.9800	C19—H19A	0.9800
C7—C8	1.512 (2)	C19—H19B	0.9800
C7—H7A	0.9900	C19—H19C	0.9800
C7—H7B	0.9900

C13—O3—C18	118.65 (12)	H8A—C8—H8C	109.5
C16—O4—C19	117.25 (14)	H8B—C8—H8C	109.5
C4—N1—C1	124.56 (13)	C2—C9—C10	130.09 (15)
C4—N1—C5	119.26 (13)	C2—C9—H9	115.0
C1—N1—C5	116.18 (12)	C10—C9—H9	115.0
C4—N2—C3	124.38 (13)	C11—C10—C9	119.24 (15)
C4—N2—C7	119.65 (13)	C11—C10—H10	120.4
C3—N2—C7	115.81 (13)	C9—C10—H10	120.4
O1—C1—N1	119.92 (14)	C10—C11—C12	128.08 (15)
O1—C1—C2	123.75 (14)	C10—C11—H11	116.0
N1—C1—C2	116.32 (13)	C12—C11—H11	116.0
C9—C2—C1	123.71 (14)	C17—C12—C13	119.00 (14)
C9—C2—C3	117.04 (14)	C17—C12—C11	122.30 (15)
C1—C2—C3	119.24 (13)	C13—C12—C11	118.70 (14)
O2—C3—N2	119.86 (14)	O3—C13—C14	123.75 (15)
O2—C3—C2	123.26 (14)	O3—C13—C12	116.31 (13)
N2—C3—C2	116.89 (13)	C14—C13—C12	119.94 (15)
N1—C4—N2	117.14 (13)	C15—C14—C13	119.73 (15)
N1—C4—S1	121.84 (12)	C15—C14—H14	120.1
N2—C4—S1	121.01 (11)	C13—C14—H14	120.1
N1—C5—C6	111.71 (13)	C14—C15—C16	121.12 (14)
N1—C5—H5A	109.3	C14—C15—H15	119.4
C6—C5—H5A	109.3	C16—C15—H15	119.4
N1—C5—H5B	109.3	O4—C16—C17	125.20 (16)
C6—C5—H5B	109.3	O4—C16—C15	115.32 (14)
H5A—C5—H5B	107.9	C17—C16—C15	119.48 (15)
C5—C6—H6A	109.5	C16—C17—C12	120.71 (15)
C5—C6—H6B	109.5	C16—C17—H17	119.6
H6A—C6—H6B	109.5	C12—C17—H17	119.6
C5—C6—H6C	109.5	O3—C18—H18A	109.5
H6A—C6—H6C	109.5	O3—C18—H18B	109.5
H6B—C6—H6C	109.5	H18A—C18—H18B	109.5
N2—C7—C8	111.72 (14)	O3—C18—H18C	109.5
N2—C7—H7A	109.3	H18A—C18—H18C	109.5
C8—C7—H7A	109.3	H18B—C18—H18C	109.5
N2—C7—H7B	109.3	O4—C19—H19A	109.5
C8—C7—H7B	109.3	O4—C19—H19B	109.5
H7A—C7—H7B	107.9	H19A—C19—H19B	109.5
C7—C8—H8A	109.5	O4—C19—H19C	109.5
C7—C8—H8B	109.5	H19A—C19—H19C	109.5
H8A—C8—H8B	109.5	H19B—C19—H19C	109.5
C7—C8—H8C	109.5

C4—N1—C1—O1	−172.42 (15)	C4—N2—C7—C8	88.82 (18)
C5—N1—C1—O1	6.6 (2)	C3—N2—C7—C8	−86.77 (18)
C4—N1—C1—C2	8.2 (2)	C1—C2—C9—C10	−2.7 (3)
C5—N1—C1—C2	−172.73 (13)	C3—C2—C9—C10	176.85 (15)
O1—C1—C2—C9	−11.3 (3)	C2—C9—C10—C11	−179.44 (16)
N1—C1—C2—C9	167.98 (14)	C9—C10—C11—C12	−179.07 (15)
O1—C1—C2—C3	169.12 (15)	C10—C11—C12—C17	0.0 (3)
N1—C1—C2—C3	−11.6 (2)	C10—C11—C12—C13	179.19 (15)
C4—N2—C3—O2	−173.69 (15)	C18—O3—C13—C14	−0.2 (2)
C7—N2—C3—O2	1.7 (2)	C18—O3—C13—C12	179.70 (14)
C4—N2—C3—C2	6.8 (2)	C17—C12—C13—O3	179.26 (13)
C7—N2—C3—C2	−177.84 (13)	C11—C12—C13—O3	0.1 (2)
C9—C2—C3—O2	5.6 (2)	C17—C12—C13—C14	−0.8 (2)
C1—C2—C3—O2	−174.83 (15)	C11—C12—C13—C14	−179.99 (14)
C9—C2—C3—N2	−174.93 (14)	O3—C13—C14—C15	−179.33 (14)
C1—C2—C3—N2	4.7 (2)	C12—C13—C14—C15	0.7 (2)
C1—N1—C4—N2	2.4 (2)	C13—C14—C15—C16	0.4 (2)
C5—N1—C4—N2	−176.56 (13)	C19—O4—C16—C17	−3.6 (3)
C1—N1—C4—S1	−177.59 (12)	C19—O4—C16—C15	176.54 (16)
C5—N1—C4—S1	3.42 (19)	C14—C15—C16—O4	178.46 (15)
C3—N2—C4—N1	−10.5 (2)	C14—C15—C16—C17	−1.4 (2)
C7—N2—C4—N1	174.31 (13)	O4—C16—C17—C12	−178.52 (15)
C3—N2—C4—S1	169.52 (12)	C15—C16—C17—C12	1.3 (2)
C7—N2—C4—S1	−5.67 (19)	C13—C12—C17—C16	−0.2 (2)
C4—N1—C5—C6	82.80 (17)	C11—C12—C17—C16	178.91 (15)
C1—N1—C5—C6	−96.28 (16)

Experimental details

Crystal data
Chemical formula	C₁₉H₂₂N₂O₄S
M_r	374.45
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	140
a, b, c (Å)	10.0519 (2), 15.5942 (3), 11.5920 (2)
β (°)	90.813 (1)
V (Å³)	1816.88 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.21
Crystal size (mm)	0.35 × 0.25 × 0.15

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.932, 0.970
No. of measured, independent and observed [I > 2σ(I)] reflections	12384, 4124, 3351
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.119, 1.02
No. of reflections	4124
No. of parameters	239
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.31

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

Acknowledgements

We thank King Abdul Aziz University and the University of Malaya for supporting this study.

References

Adamson, J., Coe, B. J., Grassam, H. L., Jeffery, J. C., Coles, S. J. & Hursthouse, M. B. (1999). J. Chem. Soc. Perkin Trans. 1, pp. 2483–2488. Web of Science CSD CrossRef Google Scholar
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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2009). publCIF. In preparation. Google Scholar

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