2,7-Dimethyl-1,3-thia­zolo[4,5-d]pyridazin-4(5H)-one

Al-Youbi, A.O.; Asiri, A.M.; Faidallah, H.M.; Ng, S.W.

doi:10.1107/S1600536811034192

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page o2467

doi:10.1107/S1600536811034192

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2,7-Dimethyl-1,3-thiazolo[4,5-d]pyridazin-4(5H)-one

Abdulrahman O. Al-Youbi,^a Abdullah M. Asiri,^a Hassan M. Faidallah ^a and Seik Weng Ng ^b,^a ^*

^aChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203, Jeddah, Saudi Arabia, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 6 August 2011; accepted 20 August 2011; online 27 August 2011)

The nine-membered fused-ring system of the title pyridazine derivative, C₇H₇N₃OS, is almost planar (r.m.s. deviation 0.012 Å). In the crystal, the amino H atom forms a hydrogen bond to the ketonic O atom of a neighboring molecule to generate a centrosymmetric dimer.

Related literature

For a related structure, see: Abdel-Aziz et al. (2010 ). For the biological activity of the class of pyridazines, see: Faid-Allah et al. (2011 ); Makki & Faid-Allah (1996 ).

Experimental

Crystal data

C₇H₇N₃OS
M_r = 181.22
Triclinic, $[P \overline 1]$
a = 6.9262 (4) Å
b = 7.0540 (4) Å
c = 8.8079 (6) Å
α = 71.002 (6)°
β = 75.845 (5)°
γ = 85.570 (5)°
V = 394.54 (4) Å³
Z = 2
Cu Kα radiation
μ = 3.26 mm⁻¹
T = 100 K
0.30 × 0.25 × 0.20 mm

Data collection

Agilent Technologies SuperNova Dual diffractometer with Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ) T_min = 0.442, T_max = 0.562
2363 measured reflections
1539 independent reflections
1523 reflections with I > 2σ(I)
R_int = 0.012

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.080
S = 1.05
1539 reflections
115 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1ⁱ	0.88 (2)	1.97 (2)	2.845 (2)	173 (2)
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811034192/xu5288sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811034192/xu5288Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811034192/xu5288Isup3.cml

checkCIF report

Comment top

We have reported the synthesis of some pyridazines, which exhibit biological activity (Faid-Allah et al., 2011; Makki & Faid-Allah, 1996). There are few crystal structure reports of such systems; recently, we reported the crystal structure of 3-methyl-2-(4-methyl)-2H-pyrazolo[3,4-d]pyridazin-5-ium thiocyanate, a salt (Abdel-Aziz et al., 2010). The nine-membered fused-ring system of C₇H₇N₃OS (Scheme I) is planar (Fig. 1). The amino group forms a hydrogen bond to the ketonic O atom of a neigboring molecule to form a dimer (Table 1).

Related literature top

For a related structure, see: Abdel-Aziz et al. (2010). For the biological activity of the class of pyridazines, see: Faid-Allah et al. (2011); Makki & Faid-Allah (1996).

Experimental top

A solution of ethyl 5-acetyl-3-methylisoxazole-4-carboxylate (2.10 g, 10 mmol) in ethanol (25 ml) was refluxed with hydrazine hydrate (0.50 g, 10 mmol) for 2 h. The pyridazine which separated after concentration of the reaction mixture was filtered off, washed with ethanol and recrystallized from the same solvent to give colorless prisms in 90% yield, mp 527 K.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); 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, 2010).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C₇H₇N₃OS at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

2,7-Dimethyl-1,3-thiazolo[4,5-d]pyridazin-4(5H)-one top

Crystal data top

C₇H₇N₃OS	Z = 2
M_r = 181.22	F(000) = 188
Triclinic, P1	D_x = 1.525 Mg m⁻³
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54184 Å
a = 6.9262 (4) Å	Cell parameters from 1965 reflections
b = 7.0540 (4) Å	θ = 6.6–74.2°
c = 8.8079 (6) Å	µ = 3.26 mm⁻¹
α = 71.002 (6)°	T = 100 K
β = 75.845 (5)°	Prism, colorless
γ = 85.570 (5)°	0.30 × 0.25 × 0.20 mm
V = 394.54 (4) Å³

Data collection top

Agilent Technologies SuperNova Dual diffractometer with Atlas detector	1539 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	1523 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.012
Detector resolution: 10.4041 pixels mm^-1	θ_max = 74.4°, θ_min = 6.6°
ω scan	h = −8→7
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −8→4
T_min = 0.442, T_max = 0.562	l = −10→10
2363 measured reflections

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.080	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0494P)² + 0.260P] where P = (F_o² + 2F_c²)/3
1539 reflections	(Δ/σ)_max = 0.001
115 parameters	Δρ_max = 0.41 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₇H₇N₃OS	γ = 85.570 (5)°
M_r = 181.22	V = 394.54 (4) Å³
Triclinic, P1	Z = 2
a = 6.9262 (4) Å	Cu Kα radiation
b = 7.0540 (4) Å	µ = 3.26 mm⁻¹
c = 8.8079 (6) Å	T = 100 K
α = 71.002 (6)°	0.30 × 0.25 × 0.20 mm
β = 75.845 (5)°

Data collection top

Agilent Technologies SuperNova Dual diffractometer with Atlas detector	1539 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	1523 reflections with I > 2σ(I)
T_min = 0.442, T_max = 0.562	R_int = 0.012
2363 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.080	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.41 e Å⁻³
1539 reflections	Δρ_min = −0.30 e Å⁻³
115 parameters

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

	x	y	z	U_iso*/U_eq
S1	1.29210 (5)	0.13257 (5)	0.50269 (4)	0.01037 (14)
O1	0.59921 (15)	0.34439 (15)	0.67118 (13)	0.0136 (2)
N1	0.97795 (18)	0.13725 (17)	0.73210 (15)	0.0114 (3)
N2	0.74300 (18)	0.42456 (18)	0.39677 (15)	0.0112 (3)
H2	0.636 (3)	0.490 (3)	0.371 (3)	0.027 (5)*
N3	0.88967 (18)	0.43408 (18)	0.25907 (15)	0.0121 (3)
C1	1.2623 (2)	−0.0391 (2)	0.84407 (19)	0.0157 (3)
H1A	1.1669	−0.0660	0.9512	0.024*
H1B	1.3732	0.0410	0.8415	0.024*
H1C	1.3131	−0.1663	0.8277	0.024*
C2	1.1611 (2)	0.0736 (2)	0.70979 (18)	0.0118 (3)
C3	0.9338 (2)	0.2388 (2)	0.58191 (17)	0.0103 (3)
C4	0.7459 (2)	0.3356 (2)	0.56003 (18)	0.0107 (3)
C5	1.0839 (2)	0.2502 (2)	0.44375 (18)	0.0101 (3)
C6	1.0596 (2)	0.3495 (2)	0.27985 (18)	0.0111 (3)
C7	1.2245 (2)	0.3608 (2)	0.13145 (18)	0.0167 (3)
H7A	1.1756	0.4244	0.0312	0.025*
H7B	1.2713	0.2252	0.1345	0.025*
H7C	1.3346	0.4401	0.1314	0.025*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0081 (2)	0.0092 (2)	0.0123 (2)	0.00189 (13)	−0.00196 (13)	−0.00205 (14)
O1	0.0089 (5)	0.0137 (5)	0.0156 (5)	0.0007 (4)	0.0001 (4)	−0.0034 (4)
N1	0.0113 (6)	0.0082 (6)	0.0136 (6)	−0.0004 (4)	−0.0028 (5)	−0.0019 (5)
N2	0.0081 (6)	0.0104 (6)	0.0140 (6)	0.0020 (5)	−0.0022 (5)	−0.0032 (5)
N3	0.0120 (6)	0.0103 (6)	0.0130 (6)	0.0000 (5)	−0.0018 (5)	−0.0029 (5)
C1	0.0147 (7)	0.0150 (7)	0.0155 (7)	0.0025 (6)	−0.0051 (6)	−0.0015 (6)
C2	0.0124 (7)	0.0076 (6)	0.0142 (7)	−0.0016 (5)	−0.0020 (5)	−0.0021 (5)
C3	0.0103 (7)	0.0057 (6)	0.0137 (7)	−0.0016 (5)	−0.0019 (5)	−0.0016 (5)
C4	0.0103 (7)	0.0057 (6)	0.0157 (7)	−0.0021 (5)	−0.0030 (5)	−0.0025 (5)
C5	0.0095 (6)	0.0060 (6)	0.0151 (7)	0.0002 (5)	−0.0034 (5)	−0.0034 (5)
C6	0.0122 (7)	0.0078 (6)	0.0127 (7)	−0.0011 (5)	−0.0026 (5)	−0.0022 (5)
C7	0.0151 (7)	0.0191 (8)	0.0127 (7)	0.0022 (6)	−0.0017 (6)	−0.0022 (6)

Geometric parameters (Å, º) top

S1—C5	1.7141 (14)	C1—H1A	0.9800
S1—C2	1.7546 (15)	C1—H1B	0.9800
O1—C4	1.2404 (18)	C1—H1C	0.9800
N1—C2	1.3025 (19)	C3—C5	1.378 (2)
N1—C3	1.3797 (18)	C3—C4	1.4480 (19)
N2—N3	1.3647 (17)	C5—C6	1.430 (2)
N2—C4	1.3736 (19)	C6—C7	1.4953 (19)
N2—H2	0.88 (2)	C7—H7A	0.9800
N3—C6	1.3037 (19)	C7—H7B	0.9800
C1—C2	1.493 (2)	C7—H7C	0.9800

C5—S1—C2	89.25 (7)	N1—C3—C4	125.15 (13)
C2—N1—C3	110.07 (12)	O1—C4—N2	120.86 (13)
N3—N2—C4	129.17 (12)	O1—C4—C3	126.43 (13)
N3—N2—H2	111.4 (14)	N2—C4—C3	112.70 (12)
C4—N2—H2	119.3 (14)	C3—C5—C6	122.57 (13)
C6—N3—N2	117.76 (12)	C3—C5—S1	109.49 (11)
C2—C1—H1A	109.5	C6—C5—S1	127.94 (11)
C2—C1—H1B	109.5	N3—C6—C5	119.21 (13)
H1A—C1—H1B	109.5	N3—C6—C7	119.01 (13)
C2—C1—H1C	109.5	C5—C6—C7	121.77 (13)
H1A—C1—H1C	109.5	C6—C7—H7A	109.5
H1B—C1—H1C	109.5	C6—C7—H7B	109.5
N1—C2—C1	125.25 (13)	H7A—C7—H7B	109.5
N1—C2—S1	114.91 (11)	C6—C7—H7C	109.5
C1—C2—S1	119.83 (11)	H7A—C7—H7C	109.5
C5—C3—N1	116.28 (12)	H7B—C7—H7C	109.5
C5—C3—C4	118.56 (13)

C4—N2—N3—C6	−0.4 (2)	N1—C3—C5—C6	179.58 (12)
C3—N1—C2—C1	178.83 (13)	C4—C3—C5—C6	−1.6 (2)
C3—N1—C2—S1	−0.33 (15)	N1—C3—C5—S1	−0.99 (16)
C5—S1—C2—N1	−0.18 (11)	C4—C3—C5—S1	177.81 (10)
C5—S1—C2—C1	−179.39 (12)	C2—S1—C5—C3	0.63 (10)
C2—N1—C3—C5	0.86 (17)	C2—S1—C5—C6	−179.99 (13)
C2—N1—C3—C4	−177.85 (12)	N2—N3—C6—C5	0.55 (19)
N3—N2—C4—O1	178.56 (12)	N2—N3—C6—C7	−178.84 (12)
N3—N2—C4—C3	−0.7 (2)	C3—C5—C6—N3	0.5 (2)
C5—C3—C4—O1	−177.59 (13)	S1—C5—C6—N3	−178.85 (10)
N1—C3—C4—O1	1.1 (2)	C3—C5—C6—C7	179.84 (13)
C5—C3—C4—N2	1.63 (18)	S1—C5—C6—C7	0.5 (2)
N1—C3—C4—N2	−179.69 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1ⁱ	0.88 (2)	1.97 (2)	2.845 (2)	173 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₇H₇N₃OS
M_r	181.22
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	6.9262 (4), 7.0540 (4), 8.8079 (6)
α, β, γ (°)	71.002 (6), 75.845 (5), 85.570 (5)
V (Å³)	394.54 (4)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	3.26
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Agilent Technologies SuperNova Dual diffractometer with Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2010)
T_min, T_max	0.442, 0.562
No. of measured, independent and observed [I > 2σ(I)] reflections	2363, 1539, 1523
R_int	0.012
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.080, 1.05
No. of reflections	1539
No. of parameters	115
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.30

Computer programs: CrysAlis PRO (Agilent, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1ⁱ	0.88 (2)	1.97 (2)	2.845 (2)	173 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

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

References

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