3-Hy­droxy-1-[(morpholin-4-yl)meth­yl]pyridazin-6(1H)-one

Santhi, P.R.; Selvanathan, G.; Poongothai, G.; Srinivasan, T.; Velmurugan, D.

doi:10.1107/S1600536813010477

organic compounds

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Volume 69| Part 5| May 2013| Page o778

https://doi.org/10.1107/S1600536813010477

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3-Hydroxy-1-[(morpholin-4-yl)methyl]pyridazin-6(1H)-one

P. R. Santhi,^a G. Selvanathan,^a G. Poongothai,^b T. Srinivasan ^c and D. Velmurugan ^c ^*

^aDepartment of Chemistry, AVC College (Autonomous), Mannampandal 609 305, Tamilnadu, India, ^bDepartment of Chemistry, Government Arts College for Men (Autonomous), Nandanam, Chennai-35, Tamilnadu, India, and ^cCentre of Advanced Study in Crystallography and Biophysics, University of Madras, Guindy Campus, Chennai 600 025, India
^*Correspondence e-mail: shirai2011@gmail.com

(Received 20 March 2013; accepted 17 April 2013; online 20 April 2013)

In the title compound, C₉H₁₃N₃O₃, the morpholine ring adopts a chair conformation and its mean plane makes a dihedral angle of 68.00 (11)° with the pyridazine ring. The carbonyl O atom deviates from the plane of the pyridazine ring by 0.0482 (12) Å. An intramolecular C—H⋯O hydrogen bond occurs. In the crystal, molecules are linked by O—H⋯O and C—H⋯O hydrogen bonds, forming chains along [1-10].

Related literature

For the biological activity of morpholine derivatives, see: Lan et al. (2010 ); Raparti et al. (2009 ). For a related structure, see: Wang et al. (2012 ).

Experimental

Crystal data

C₉H₁₃N₃O₃
M_r = 211.22
Triclinic, $[P \overline 1]$
a = 5.2110 (3) Å
b = 5.4165 (4) Å
c = 18.4544 (12) Å
α = 87.232 (2)°
β = 83.993 (6)°
γ = 80.862 (4)°
V = 511.18 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker SMART APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.969, T_max = 0.979
8839 measured reflections
2530 independent reflections
1679 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.158
S = 1.07
2530 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2ⁱ	0.82	1.77	2.5777 (16)	167
C2—H2⋯O1ⁱⁱ	0.93	2.55	3.478 (2)	175
C5—H5A⋯O2	0.97	2.44	2.772 (2)	100
Symmetry codes: (i) x-1, y+1, z; (ii) -x, -y+1, -z.

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: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536813010477/pv2627sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813010477/pv2627Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536813010477/pv2627Isup3.cml

checkCIF report

Comment top

Morpholine derivatives possess anticancer and antimicrobial activities (Lan et al., 2010; Raparti et al., 2009). In the title compound (Fig. 1), the morpholine ring (N3/O3/C6-C9) adopts a chair conformation. The morpholine ring makes a dihedral angle of 68.00 (11)° with the pyridazin ring (N1/N2/C1-C4). The hydroxyl oxygen atom O1 attached with the pyridazin ring deviates by 0.0242 (13)Å. The oxygen atom O2 attached with the pyridazin ring deviates by 0.0482 (12)Å. The packing of the crystal is stabilised by intermolcular O—H···O hydrogen bonds and weak intramolecular C—H···O hydrogen bonds (Fig. 2 & Table 1).

Related literature top

For the biological activity of morpholine derivatives, see: Lan et al. (2010); Raparti et al. (2009). For a related structure, see: Wang et al. (2012).

Experimental top

The new Mannich base morpholino methyl maleic hydrazide(MMMH) was synthesised by introducing morpholino methyl moiety in place of active hydrogen atom attached to nitrogen of maleic hydrazide through Mannich reaction. An equimolar mixture of maleic hydrazide (11.20 g), formaldehyde (3.00 g) and morpholine (8.7 g) was dissolved in 400 ml of ethanol and refluxed for about 5 hours. The formation of the product MMMH and the completion of the reaction was identified by the formation of a clear solution. The resulting solution was concentrated to 200 ml by distillation under reduced pressure. The concentrate on cooling yielded a colourless crystalline solid, the crude product (20.6g) that was first washed with ethanol and then ether and dried in vacuum oven. The compound MMMH was dissolved in hot ethanol and the homogeneous solution was allowed to evaporate slowly. After two weeks the colourless crystalline solid separated out which was washed with minimum amount of ethanol and then dried in a vaccum oven; a crystal was chosen for X-ray diffraction studies from this sample.

Structure description top

For the biological activity of morpholine derivatives, see: Lan et al. (2010); Raparti et al. (2009). For a related structure, see: Wang et al. (2012).

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: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids drawn at the 30% probability level. H atoms are presented as small spheres of arbitrary radius.
	Fig. 2. The crystal packing of the title compound viewed down a axis. H-atoms not involved in H-bonds have been excluded for clarity.

3-Hydroxy-1-[(morpholin-4-yl)methyl]pyridazin-6(1H)-one top

Crystal data top

C₉H₁₃N₃O₃	Z = 2
M_r = 211.22	F(000) = 224
Triclinic, P1	D_x = 1.372 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.2110 (3) Å	Cell parameters from 2530 reflections
b = 5.4165 (4) Å	θ = 1.1–28.4°
c = 18.4544 (12) Å	µ = 0.11 mm⁻¹
α = 87.232 (2)°	T = 293 K
β = 83.993 (6)°	Block, colourless
γ = 80.862 (4)°	0.30 × 0.25 × 0.20 mm
V = 511.18 (6) Å³

Data collection top

Bruker SMART APEXII area-detector diffractometer	2530 independent reflections
Radiation source: fine-focus sealed tube	1679 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ω and φ scans	θ_max = 28.4°, θ_min = 1.1°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −6→6
T_min = 0.969, T_max = 0.979	k = −7→7
8839 measured reflections	l = −24→24

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.158	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0734P)² + 0.1237P] where P = (F_o² + 2F_c²)/3
2530 reflections	(Δ/σ)_max < 0.001
136 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₉H₁₃N₃O₃	γ = 80.862 (4)°
M_r = 211.22	V = 511.18 (6) Å³
Triclinic, P1	Z = 2
a = 5.2110 (3) Å	Mo Kα radiation
b = 5.4165 (4) Å	µ = 0.11 mm⁻¹
c = 18.4544 (12) Å	T = 293 K
α = 87.232 (2)°	0.30 × 0.25 × 0.20 mm
β = 83.993 (6)°

Data collection top

Bruker SMART APEXII area-detector diffractometer	2530 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	1679 reflections with I > 2σ(I)
T_min = 0.969, T_max = 0.979	R_int = 0.027
8839 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.158	H-atom parameters constrained
S = 1.07	Δρ_max = 0.31 e Å⁻³
2530 reflections	Δρ_min = −0.23 e Å⁻³
136 parameters

Special details top

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.

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 > 2sigma(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 (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.2321 (3)	0.5749 (3)	0.10380 (9)	0.0350 (4)
C2	0.3128 (3)	0.3529 (3)	0.06412 (9)	0.0393 (4)
H2	0.2234	0.3183	0.0257	0.047*
C3	0.5197 (3)	0.1956 (3)	0.08329 (9)	0.0397 (4)
H3	0.5754	0.0493	0.0580	0.048*
C4	0.6579 (3)	0.2491 (3)	0.14265 (9)	0.0341 (4)
C5	0.6847 (3)	0.5467 (3)	0.23871 (9)	0.0382 (4)
H5A	0.8698	0.4820	0.2316	0.046*
H5B	0.6670	0.7278	0.2356	0.046*
C6	0.6498 (5)	0.2102 (4)	0.32915 (12)	0.0650 (6)
H6A	0.8343	0.1520	0.3166	0.078*
H6B	0.5510	0.1163	0.3018	0.078*
C7	0.5809 (7)	0.1687 (6)	0.40974 (14)	0.0896 (9)
H7A	0.6172	−0.0086	0.4221	0.108*
H7B	0.6888	0.2541	0.4367	0.108*
C8	0.2589 (6)	0.5165 (7)	0.41244 (14)	0.0896 (9)
H8A	0.3627	0.6065	0.4394	0.107*
H8B	0.0761	0.5767	0.4269	0.107*
C9	0.3172 (4)	0.5693 (5)	0.33187 (11)	0.0609 (6)
H9A	0.2066	0.4883	0.3046	0.073*
H9B	0.2821	0.7480	0.3214	0.073*
N1	0.3486 (3)	0.6309 (2)	0.15815 (7)	0.0350 (3)
N2	0.5574 (2)	0.4640 (2)	0.17747 (7)	0.0326 (3)
N3	0.5895 (3)	0.4751 (3)	0.31060 (8)	0.0430 (4)
O1	0.0275 (2)	0.7323 (2)	0.08280 (7)	0.0511 (4)
H1	−0.0028	0.8530	0.1092	0.077*
O2	0.8565 (2)	0.1128 (2)	0.16258 (7)	0.0484 (4)
O3	0.3137 (5)	0.2588 (5)	0.43038 (10)	0.1016 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0322 (8)	0.0339 (8)	0.0352 (8)	0.0063 (6)	−0.0032 (6)	−0.0019 (6)
C2	0.0397 (9)	0.0387 (9)	0.0382 (9)	0.0042 (7)	−0.0095 (7)	−0.0088 (7)
C3	0.0432 (10)	0.0327 (9)	0.0403 (9)	0.0070 (7)	−0.0066 (7)	−0.0111 (7)
C4	0.0337 (8)	0.0291 (8)	0.0366 (8)	0.0037 (6)	−0.0019 (6)	−0.0027 (6)
C5	0.0377 (9)	0.0374 (9)	0.0411 (9)	−0.0050 (7)	−0.0100 (7)	−0.0064 (7)
C6	0.0911 (17)	0.0508 (13)	0.0530 (12)	−0.0103 (12)	−0.0110 (11)	0.0064 (10)
C7	0.132 (3)	0.0806 (19)	0.0567 (15)	−0.0218 (18)	−0.0130 (16)	0.0188 (13)
C8	0.0836 (19)	0.125 (3)	0.0571 (15)	−0.0191 (18)	0.0134 (13)	−0.0112 (16)
C9	0.0515 (12)	0.0807 (16)	0.0503 (12)	−0.0107 (11)	0.0010 (9)	−0.0100 (11)
N1	0.0349 (7)	0.0299 (7)	0.0373 (7)	0.0065 (5)	−0.0063 (6)	−0.0043 (5)
N2	0.0314 (7)	0.0292 (7)	0.0353 (7)	0.0039 (5)	−0.0066 (5)	−0.0042 (5)
N3	0.0480 (9)	0.0448 (9)	0.0375 (8)	−0.0066 (7)	−0.0093 (6)	−0.0049 (6)
O1	0.0495 (8)	0.0477 (8)	0.0504 (8)	0.0227 (6)	−0.0192 (6)	−0.0131 (6)
O2	0.0417 (7)	0.0458 (7)	0.0523 (8)	0.0175 (6)	−0.0137 (6)	−0.0091 (6)
O3	0.1169 (18)	0.1262 (19)	0.0662 (12)	−0.0507 (15)	0.0097 (11)	0.0167 (12)

Geometric parameters (Å, º) top

C1—N1	1.297 (2)	C6—H6A	0.9700
C1—O1	1.3341 (18)	C6—H6B	0.9700
C1—C2	1.421 (2)	C7—O3	1.419 (4)
C2—C3	1.331 (2)	C7—H7A	0.9700
C2—H2	0.9300	C7—H7B	0.9700
C3—C4	1.437 (2)	C8—O3	1.410 (4)
C3—H3	0.9300	C8—C9	1.509 (3)
C4—O2	1.2497 (18)	C8—H8A	0.9700
C4—N2	1.360 (2)	C8—H8B	0.9700
C5—N3	1.425 (2)	C9—N3	1.449 (3)
C5—N2	1.4892 (19)	C9—H9A	0.9700
C5—H5A	0.9700	C9—H9B	0.9700
C5—H5B	0.9700	N1—N2	1.3660 (17)
C6—N3	1.452 (3)	O1—H1	0.8200
C6—C7	1.508 (3)

N1—C1—O1	119.33 (14)	C6—C7—H7A	109.4
N1—C1—C2	123.26 (14)	O3—C7—H7B	109.4
O1—C1—C2	117.41 (14)	C6—C7—H7B	109.4
C3—C2—C1	118.37 (15)	H7A—C7—H7B	108.0
C3—C2—H2	120.8	O3—C8—C9	111.8 (2)
C1—C2—H2	120.8	O3—C8—H8A	109.3
C2—C3—C4	120.80 (14)	C9—C8—H8A	109.3
C2—C3—H3	119.6	O3—C8—H8B	109.3
C4—C3—H3	119.6	C9—C8—H8B	109.3
O2—C4—N2	120.60 (14)	H8A—C8—H8B	107.9
O2—C4—C3	124.21 (14)	N3—C9—C8	108.85 (19)
N2—C4—C3	115.19 (13)	N3—C9—H9A	109.9
N3—C5—N2	116.93 (13)	C8—C9—H9A	109.9
N3—C5—H5A	108.1	N3—C9—H9B	109.9
N2—C5—H5A	108.1	C8—C9—H9B	109.9
N3—C5—H5B	108.1	H9A—C9—H9B	108.3
N2—C5—H5B	108.1	C1—N1—N2	117.12 (12)
H5A—C5—H5B	107.3	C4—N2—N1	125.20 (13)
N3—C6—C7	109.2 (2)	C4—N2—C5	121.09 (13)
N3—C6—H6A	109.8	N1—N2—C5	113.57 (12)
C7—C6—H6A	109.8	C5—N3—C9	115.28 (15)
N3—C6—H6B	109.8	C5—N3—C6	115.05 (15)
C7—C6—H6B	109.8	C9—N3—C6	110.95 (18)
H6A—C6—H6B	108.3	C1—O1—H1	109.5
O3—C7—C6	111.4 (2)	C8—O3—C7	109.8 (2)
O3—C7—H7A	109.4

N1—C1—C2—C3	−0.6 (3)	C1—N1—N2—C4	2.5 (2)
O1—C1—C2—C3	178.72 (16)	C1—N1—N2—C5	178.12 (14)
C1—C2—C3—C4	0.0 (3)	N3—C5—N2—C4	−94.05 (18)
C2—C3—C4—O2	−178.44 (17)	N3—C5—N2—N1	90.12 (17)
C2—C3—C4—N2	1.7 (2)	N2—C5—N3—C9	−61.2 (2)
N3—C6—C7—O3	57.7 (3)	N2—C5—N3—C6	69.9 (2)
O3—C8—C9—N3	−58.1 (3)	C8—C9—N3—C5	−170.26 (19)
O1—C1—N1—N2	−179.85 (14)	C8—C9—N3—C6	56.7 (2)
C2—C1—N1—N2	−0.5 (2)	C7—C6—N3—C5	170.00 (19)
O2—C4—N2—N1	177.10 (14)	C7—C6—N3—C9	−56.9 (3)
C3—C4—N2—N1	−3.0 (2)	C9—C8—O3—C7	59.2 (3)
O2—C4—N2—C5	1.8 (2)	C6—C7—O3—C8	−58.9 (3)
C3—C4—N2—C5	−178.32 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.82	1.77	2.5777 (16)	167
C2—H2···O1ⁱⁱ	0.93	2.55	3.478 (2)	175
C5—H5A···O2	0.97	2.44	2.772 (2)	100

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

Experimental details

Crystal data
Chemical formula	C₉H₁₃N₃O₃
M_r	211.22
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	5.2110 (3), 5.4165 (4), 18.4544 (12)
α, β, γ (°)	87.232 (2), 83.993 (6), 80.862 (4)
V (Å³)	511.18 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Bruker SMART APEXII area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.969, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	8839, 2530, 1679
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.158, 1.07
No. of reflections	2530
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.23

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.82	1.77	2.5777 (16)	167
C2—H2···O1ⁱⁱ	0.93	2.55	3.478 (2)	175
C5—H5A···O2	0.97	2.44	2.772 (2)	100

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

Acknowledgements

The authors thank the TBI X-ray facility, CAS in Crystallography and Biophysics, University of Madras, India, for the data collection. TS thanks the DST for an Inspire fellowship. The UGC (SAP–CAS) is acknowleged for departmental facilities.

References

Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Lan, P., Chen, W. N., Xiao, G. K., Sun, P. H. & Chen, W. M. (2010). Bioorg. Med. Chem. Lett. 20, 6764–6772. Web of Science CrossRef CAS PubMed Google Scholar
Raparti, V., Chitre, T., Bothara, K., Kumar, V., Dangre, S., Khachane, C., Gore, S. & Deshmane, B. (2009). Eur. J. Med. Chem. 44, 3954–3960. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, L.-J., Li, W.-W., Yang, S.-Y. & Yang, L. (2012). Acta Cryst. E68, o1235. CSD CrossRef IUCr Journals Google Scholar