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In the title compound, C13H17N3O3S·0.5H2O, the morpholine ring adopts a chair conformation. The conformation of the mol­ecule is stabilized by intra­molecular N—H...O and N—H...S hydrogen bonds. Inter­molecular N—H...O and O—H...O hydrogen bonds link the organic mol­ecules through the water mol­ecules to build up a channel running parallel to the c axis and containing the water mol­ecules.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807060515/dn2277sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807060515/dn2277Isup2.hkl
Contains datablock I

CCDC reference: 673078

Key indicators

  • Single-crystal X-ray study
  • T = 173 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.045
  • wR factor = 0.118
  • Data-to-parameter ratio = 13.8

checkCIF/PLATON results

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Alert level C PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ? PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 0.50 Ratio
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 2
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 3 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 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

Morpholine derivatives are an important type of fungicide (Badioli et al., 2001) and pharmaceutical drugs due to which they have attracted much attention in recent years in pharmaceuticals. The morpholine drugs are used in the reduction of blood sugar and control of lipid levels (Yoshioka, 1995) and insulin resistance (Fisher & Wyvratt,1990). Owing to their important pharmalogical activities and bioactivity, these compounds have received a great attention with respect to their syntheses and in the elucidation of their crystal structures.

The structure of (I) is shown in Fig 1. The morpholine ring exhibits a normal chair conformation. In the morpholine ring, the average Csp3—Nsp3, Csp3—Csp3 and Csp3—Osp3 bond distances [1.472 (2), 1.490 (2) and 1.4309 (2) Å], respectively, are in good agreement with earlier reports (Ramnathan et al.,1996). In the chair conformation, the four carbon atoms deviate only slightly from coplanarity. The dihedral angle between the carbonothioyl carbohydrazide unit and morpholine ring is 35.16 (2)°. Hydrazinic atoms H1 and H2 are trans to each other, as are the C(8)—S(1) and C(7)—O(2) groups [torsional angles, N2—N1—C7—O2 and N1—N2—C8—S1 = -6.31 (3)° and 5.8 (3)°, respectively]. In addition, the C—S and C—N bond distances are 1.683 (2) Å and 1.375 (2) Å respectively, which are intermediate between C—S (1.82 Å) and C=S (1.56 Å) (Wu et al., 2000) and C—N (1.450 Å) and C=N (1.250 Å) distances. The intermediate bond distances in compound (I) show extensive electron delocalization which provides stability to the molecule.

The conformation of the molecule is stabilized by an N—H···O and N—H···S intramolecular hydrogen bondings. Iintermolecular hydrogen bondings N—H···O [2.920 (2) Å] and O—H···O [2.759 (2) Å] links the molecules through the water to build up a channel running parallel to the c axis and containing the water molecules (Table 1, Fig. 2).

Related literature top

For related literature, see: Fisher & Wyvratt (1990); Yoshioka (1995); Ramnathan et al. (1996); Badioli et al. (2001). Wu et al. (2000).

Experimental top

Potassium[morpholine-4-carbodithioate] was synthesized by the reaction of CS2 (4.4 ml, 57.39 mmol) with morpholine (5 ml, 57.39 mmol) in MeOH (20 ml) in the presence of KOH (3.2 g, 57.39 mmol). The precipitated product (Yield 78%, 3.9 g, 31.15 mmol) was separated by filtration and reacted with choloroacetic acid (ClCH2COOH) (2.9 g, 31.15 mmol) neutralized with Na2CO3. The mixture was kept over night at room temperature and then made strongly acidic with conc. HCl to get the precipitate of (morpholine-4-carbothioyl sulfanyl) acetic acid (yield 69%, 2.7 g, 14.24 mmol). This was filtered off, washed with water and dried at room temperature.

The ester was recrystalized from CHCl3: MeOH mixture. 1H NMR (DMSO-d6, TMS): 10.62 (s, 1H, –COOH), 2.5 (s,2H, CH2), 3.35 (s, 3H, –OCH3), 7.90–7.18 (m, 4H, aromatic); 13C NMR (DMSO-d6, TMS): 205.41 (C=S), 121.22 (C1), 157.22 (C2), 112.50 (C3), 133.74 (C4), 120.54 (C5), 131.44 (C6), 169.65 (C7), 56.68 (C8), 36.53(C9).

The compound (I) was synthesized by reaction of the morpholine ester (2.7 g, 14.24 mmol) and o-methoxy benzoic acid hydrazide (2.4 g, 14.24 mmol). Both were dissolved separately in aqueous solution of NaOH, mixed together, kept for 2 h at room temperature and then acidified with dil. AcOH (20% v/v), whereupon a white precipitate formed. It was suction filtered, washed with water, dried at room temperature and crystalized from CHCl3: MeOH mixture (50: 50 v/v).

White color single crystals of (I) (m.p.413 K) suitable for X-ray analysis were obtained by slow evaporation of chloroform: methanolic solution over a period of 10 d. (yield 2.64 g, 66%). Analysis found (%) for C15H17N3O4S (608.208): C, 51.30; H, 5.97; N, 13.81; S, 10.51. Calculated (%): C, 51.35; H, 5.90; N, 13.99; S, 10.57.

1H NMR (DMSO-d6, TMS): 12.79, 11.63 (2H, –NH), 3.38 (3H, –OCH3), 2.50, 3.08 (8H, methylene, morpholine), 7.89–7.19 (m, 4H, aromatic). 13C NMR (DMSO-d6, TMS): 203.08 (C=S), 120.78 (C1), 157.06 (C2), 112.69 (C3), 133.88 (C4), 121.22 (C5), 130.01 (C6), 169.13 (C7), 56.05 (C13), 63.15 (C10,C11), 42.59 (C9,C12).

Refinement top

All H atoms were initially located in difference Fourier map. The were then placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances in the range 0.95–0.99 Å and with Uiso = 1.2 Ueq(C).

Computing details top

Data collection: Collect (Nonius, 1998); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom numbering scheme with displacement ellipsoid drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. Hydrogen bonds are shown as dashed lines.
[Figure 2] Fig. 2. Partial packing viewof (I), along c axis, showing hydrogen bonding interactions and the formation of channels.
[Figure 3] Fig. 3. Preparation of the title compound.
2-Methoxy-N'-(morpholin-4-ylcarbothioyl)benzohydrazide hemihydrate top
Crystal data top
C13H17N3O3S·0.5H2ODx = 1.374 Mg m3
Mr = 304.37Melting point: 413 K
Orthorhombic, PccnMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2acCell parameters from 1473 reflections
a = 13.4864 (2) Åθ = 1.0–27.5°
b = 24.6003 (6) ŵ = 0.24 mm1
c = 8.8726 (2) ÅT = 173 K
V = 2943.66 (11) Å3Chip, colourless
Z = 80.20 × 0.20 × 0.20 mm
F(000) = 1288
Data collection top
Nonius KappaCCD
diffractometer
2697 independent reflections
Radiation source: fine-focus sealed tube2080 reflections with I > 2σ(I)
Horizonally mounted graphite crystal monochromatorRint = 0.093
Detector resolution: 9 pixels mm-1θmax = 25.4°, θmin = 2.9°
ϕ scans and ω scans with κ offsetsh = 1616
Absorption correction: ψ scan
(North et al., 1968)
k = 2929
Tmin = 0.880, Tmax = 0.954l = 1010
35059 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.118H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.0622P)2 + 1.2085P]
where P = (Fo2 + 2Fc2)/3
2697 reflections(Δ/σ)max < 0.001
196 parametersΔρmax = 0.21 e Å3
2 restraintsΔρmin = 0.25 e Å3
Crystal data top
C13H17N3O3S·0.5H2OV = 2943.66 (11) Å3
Mr = 304.37Z = 8
Orthorhombic, PccnMo Kα radiation
a = 13.4864 (2) ŵ = 0.24 mm1
b = 24.6003 (6) ÅT = 173 K
c = 8.8726 (2) Å0.20 × 0.20 × 0.20 mm
Data collection top
Nonius KappaCCD
diffractometer
2697 independent reflections
Absorption correction: ψ scan
(North et al., 1968)
2080 reflections with I > 2σ(I)
Tmin = 0.880, Tmax = 0.954Rint = 0.093
35059 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0452 restraints
wR(F2) = 0.118H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.21 e Å3
2697 reflectionsΔρmin = 0.25 e Å3
196 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
S10.39345 (4)0.18214 (2)0.81529 (7)0.0347 (2)
O10.53195 (10)0.05419 (6)0.78451 (17)0.0300 (4)
O20.72871 (10)0.15538 (6)1.00899 (18)0.0331 (4)
O30.44448 (10)0.38946 (6)0.8740 (2)0.0369 (4)
N10.59668 (13)0.15023 (7)0.8537 (2)0.0295 (4)
H10.5474 (17)0.1302 (10)0.820 (3)0.035*
N20.58506 (13)0.20662 (7)0.8490 (2)0.0287 (4)
H20.6318 (13)0.2228 (9)0.801 (2)0.034*
N30.48296 (12)0.27922 (7)0.8073 (2)0.0324 (5)
C10.66929 (13)0.06691 (8)0.9476 (2)0.0216 (5)
C20.60297 (14)0.03135 (8)0.8743 (2)0.0219 (4)
C30.61164 (14)0.02433 (8)0.8933 (2)0.0252 (5)
H30.56620.04750.84770.030*
C40.68761 (15)0.04559 (9)0.9798 (2)0.0286 (5)
H40.69370.08310.99030.034*
C50.75466 (15)0.01163 (9)1.0509 (2)0.0281 (5)
H50.80610.02601.10800.034*
C60.74412 (14)0.04413 (8)1.0358 (2)0.0246 (5)
H60.78810.06701.08580.029*
C70.66677 (14)0.12779 (8)0.9407 (2)0.0229 (5)
C80.49040 (14)0.22514 (8)0.8232 (2)0.0251 (5)
C90.56444 (16)0.31790 (9)0.8275 (3)0.0336 (6)
H9A0.58430.33250.73040.040*
H9B0.62110.29960.87170.040*
C100.53137 (16)0.36312 (9)0.9283 (3)0.0381 (6)
H10A0.51840.34871.02810.046*
H10B0.58430.38960.93700.046*
C110.36544 (16)0.35094 (9)0.8625 (3)0.0363 (6)
H11A0.30620.36920.82660.044*
H11B0.35120.33620.96160.044*
C120.39068 (16)0.30563 (9)0.7580 (3)0.0383 (6)
H12A0.33720.27930.75680.046*
H12B0.39890.31970.65660.046*
C130.46377 (15)0.01932 (9)0.7067 (3)0.0311 (5)
H13A0.50000.00560.64440.047*
H13B0.42060.04090.64490.047*
H13C0.42510.00060.77880.047*
O40.75000.25000.6727 (3)0.0296 (5)
H4A0.7627 (18)0.2227 (7)0.618 (3)0.044*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0235 (3)0.0308 (3)0.0499 (4)0.0057 (2)0.0010 (3)0.0044 (3)
O10.0286 (8)0.0227 (8)0.0388 (9)0.0015 (6)0.0139 (7)0.0021 (7)
O20.0269 (8)0.0221 (8)0.0501 (10)0.0010 (6)0.0079 (7)0.0056 (7)
O30.0285 (8)0.0213 (8)0.0608 (11)0.0055 (6)0.0087 (7)0.0028 (8)
N10.0287 (10)0.0161 (9)0.0435 (12)0.0005 (7)0.0095 (9)0.0028 (8)
N20.0241 (9)0.0167 (9)0.0454 (12)0.0009 (7)0.0011 (8)0.0041 (8)
N30.0221 (10)0.0201 (10)0.0549 (13)0.0023 (7)0.0074 (8)0.0057 (9)
C10.0207 (10)0.0214 (11)0.0228 (11)0.0008 (8)0.0037 (8)0.0004 (9)
C20.0213 (10)0.0239 (11)0.0205 (11)0.0016 (8)0.0001 (8)0.0006 (9)
C30.0291 (11)0.0217 (11)0.0249 (12)0.0031 (8)0.0005 (9)0.0018 (9)
C40.0349 (12)0.0202 (11)0.0308 (12)0.0034 (9)0.0018 (10)0.0031 (9)
C50.0260 (11)0.0286 (12)0.0298 (12)0.0045 (9)0.0028 (9)0.0059 (10)
C60.0201 (10)0.0264 (12)0.0272 (11)0.0010 (8)0.0015 (8)0.0008 (9)
C70.0196 (10)0.0223 (11)0.0268 (11)0.0004 (8)0.0039 (8)0.0004 (9)
C80.0208 (11)0.0242 (12)0.0304 (12)0.0006 (8)0.0007 (9)0.0038 (9)
C90.0240 (12)0.0212 (12)0.0556 (16)0.0001 (8)0.0008 (10)0.0001 (11)
C100.0317 (12)0.0250 (12)0.0576 (17)0.0011 (9)0.0116 (11)0.0034 (11)
C110.0257 (11)0.0298 (13)0.0534 (16)0.0045 (9)0.0014 (11)0.0014 (11)
C120.0280 (13)0.0316 (13)0.0553 (17)0.0076 (9)0.0124 (11)0.0063 (12)
C130.0276 (11)0.0329 (12)0.0328 (13)0.0036 (9)0.0087 (9)0.0039 (10)
O40.0285 (11)0.0201 (11)0.0403 (14)0.0043 (9)0.0000.000
Geometric parameters (Å, º) top
S1—C81.683 (2)C4—C51.383 (3)
O1—C21.367 (2)C4—H40.9300
O1—C131.435 (2)C5—C61.386 (3)
O2—C71.235 (2)C5—H50.9300
O3—C101.423 (3)C6—H60.9300
O3—C111.430 (3)C9—C101.496 (3)
N1—C71.339 (3)C9—H9A0.9700
N1—N21.397 (2)C9—H9B0.9700
N1—H10.88 (2)C10—H10A0.9700
N2—C81.375 (3)C10—H10B0.9700
N2—H20.858 (10)C11—C121.490 (3)
N3—C81.342 (3)C11—H11A0.9700
N3—C91.464 (3)C11—H11B0.9700
N3—C121.471 (3)C12—H12A0.9700
C1—C61.395 (3)C12—H12B0.9700
C1—C21.410 (3)C13—H13A0.9600
C1—C71.499 (3)C13—H13B0.9600
C2—C31.385 (3)C13—H13C0.9600
C3—C41.383 (3)O4—H4A0.846 (10)
C3—H30.9300
C2—O1—C13118.93 (16)N3—C8—S1124.11 (15)
C10—O3—C11109.65 (16)N2—C8—S1121.33 (16)
C7—N1—N2120.40 (18)N3—C9—C10109.42 (18)
C7—N1—H1119.7 (16)N3—C9—H9A109.8
N2—N1—H1117.6 (16)C10—C9—H9A109.8
C8—N2—N1116.00 (16)N3—C9—H9B109.8
C8—N2—H2116.5 (17)C10—C9—H9B109.8
N1—N2—H2113.1 (16)H9A—C9—H9B108.2
C8—N3—C9125.13 (17)O3—C10—C9112.4 (2)
C8—N3—C12122.18 (17)O3—C10—H10A109.1
C9—N3—C12112.61 (17)C9—C10—H10A109.1
C6—C1—C2117.93 (18)O3—C10—H10B109.1
C6—C1—C7116.15 (18)C9—C10—H10B109.1
C2—C1—C7125.92 (18)H10A—C10—H10B107.8
O1—C2—C3122.46 (18)O3—C11—C12111.71 (19)
O1—C2—C1117.27 (17)O3—C11—H11A109.3
C3—C2—C1120.27 (18)C12—C11—H11A109.3
C4—C3—C2120.26 (19)O3—C11—H11B109.3
C4—C3—H3119.9C12—C11—H11B109.3
C2—C3—H3119.9H11A—C11—H11B107.9
C3—C4—C5120.6 (2)N3—C12—C11109.79 (19)
C3—C4—H4119.7N3—C12—H12A109.7
C5—C4—H4119.7C11—C12—H12A109.7
C4—C5—C6119.14 (19)N3—C12—H12B109.7
C4—C5—H5120.4C11—C12—H12B109.7
C6—C5—H5120.4H12A—C12—H12B108.2
C5—C6—C1121.75 (19)O1—C13—H13A109.5
C5—C6—H6119.1O1—C13—H13B109.5
C1—C6—H6119.1H13A—C13—H13B109.5
O2—C7—N1122.24 (19)O1—C13—H13C109.5
O2—C7—C1120.90 (18)H13A—C13—H13C109.5
N1—C7—C1116.83 (17)H13B—C13—H13C109.5
N3—C8—N2114.55 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.88 (2)1.91 (2)2.593 (2)134 (2)
N1—H1···S10.88 (2)2.44 (2)2.8714 (18)110.8 (19)
N2—H2···O40.86 (1)2.07 (1)2.921 (2)171 (2)
O4—H4A···O2i0.85 (1)1.92 (1)2.7590 (19)170 (2)
Symmetry code: (i) x+3/2, y, z1/2.

Experimental details

Crystal data
Chemical formulaC13H17N3O3S·0.5H2O
Mr304.37
Crystal system, space groupOrthorhombic, Pccn
Temperature (K)173
a, b, c (Å)13.4864 (2), 24.6003 (6), 8.8726 (2)
V3)2943.66 (11)
Z8
Radiation typeMo Kα
µ (mm1)0.24
Crystal size (mm)0.20 × 0.20 × 0.20
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.880, 0.954
No. of measured, independent and
observed [I > 2σ(I)] reflections
35059, 2697, 2080
Rint0.093
(sin θ/λ)max1)0.602
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.118, 1.05
No. of reflections2697
No. of parameters196
No. of restraints2
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.21, 0.25

Computer programs: Collect (Nonius, 1998), HKL SCALEPACK (Otwinowski & Minor 1997), HKL DENZO and SCALEPACK (Otwinowski & Minor 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.88 (2)1.91 (2)2.593 (2)134 (2)
N1—H1···S10.88 (2)2.44 (2)2.8714 (18)110.8 (19)
N2—H2···O40.858 (10)2.071 (11)2.921 (2)171 (2)
O4—H4A···O2i0.846 (10)1.921 (11)2.7590 (19)170 (2)
Symmetry code: (i) x+3/2, y, z1/2.
 

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