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Acta Cryst. (2009). E65, o2435    [ doi:10.1107/S1600536809035405 ]

4-(2-Chloroethyl)morpholinium picrate

R. Kant, S. Kohli, L. Sarmal, B. Narayana and S. Samshuddin

Abstract top

The title compound, C6H13ClNO+·C6H2N3O7-, was synthesized from picric acid and 4-(2-chloroethyl)morpholine. The crystal structure is stabilized by C-H...O and N-H...O hydrogen-bond interactions.

Comment top

The metal derivatives of picric acid are also known as medicines in homeopathy (Maurya et al., 1999). Silver picrate is a good antimicrobial agent. Zinc picrate is used in Bright's disease, headache, exhaustion, facial paralysis, nymphomania, paralysis, seminal emissions, spiral weakness, loss of memory and energy.

Ammonium picrate is a remedy for malarial fever and neuralgia, whooping cough, pain in the occiput and mastoid regions (Boericke, 1982).

N-substituted morpholines were used as anti-malarials (Lutz et al., 1947) and 4-methyl-4-(2-phenylethyl)-morpholinium iodide have shown marked hypertension in dogs at a dose of 5 mg./kg (Hazard et al., 1948). Morpholine derivatives are also used as agricultural fungicides in cereals and are known as ergosterol biosynthesis inhibitors (Raymond et al., 1999).

A search of the Cambridge Structural Database (Version 5.26; Allen, 2002) reveals that there are 90 known structures that contain the morpholinium cation. Of these there are 24 that have an N-ethyl chain, or longer, including the structure of 4-(2-fluoroethyl) morpholinium chloride (Briggs et al., 2004).

The title compound, [C6 H13Cl N O]+ [C6 H2N3 O7]-, was synthesized from picric acid and 4-(2-chloroethyl)morpholine.All geometrical parameters are in their usual ranges. The crystal structure is stabilized by C—H···O and N—H···O hydrogen interactions.

Related literature top

For the homeopathic uses of the metal derivatives of picric acid, see: Maurya et al. (1999). For the medical applications of ammonium picrate, see: Boericke (1982) and of morpholine derivatives, see: Lutz et al. (1947); Hazard et al. (1948); Raymond et al. (1999).For a related structure, see: Briggs et al. (2004). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

Picric acid (2.29 g, 0.01 mol) was dissolved in water. 4-(2-chloroethyl) morpholine (1.49 g 0.01 mol) was dissolved in 25 ml of ethanol. The two solutions were mixed and 5 ml of 5 M HCl was added to this mixture and stirred for few minutes,filtered, dried and yellow crystals of 4-(2-Chloroethyl)morpholinium picrate were obtained by slow evaporation in ethanol. (m.p. 394 K). Analytical data: Found (Cald): C %: 36.89(37.96); H%: 4.22 (4.25); N%:14.67(14.75).

Refinement top

All hydrogen atoms were located from the difference Fourier map and refined isotropically with distance restraints 0.830–0.982 Å.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2007); cell refinement: CrysAlis PRO (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows(Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. View of (I) (50% probability displacement ellipsoids).
[Figure 2] Fig. 2. Depiction of C—H···O and N—H···O interactions in the title compound(I)
4-(2-Chloroethyl)morpholinium picrate top
Crystal data top
C6H13ClNO+·C6H2N3O7−Z = 2
Mr = 378.72F(000) = 392
Triclinic, P1Dx = 1.611 Mg m−3
a = 8.2063 (4) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.3075 (5) ÅCell parameters from 3665 reflections
c = 10.2896 (6) Åθ = 3.3–32.3°
α = 93.954 (5)°µ = 0.30 mm−1
β = 95.284 (5)°T = 293 K
γ = 90.376 (4)°Rectangular, yellow
V = 780.65 (7) Å30.30 × 0.24 × 0.18 mm
Data collection top
Oxford Diffraction Xcalibur
diffractometer		Rint = 0.016
ω–2θ scansθmax = 32.3°, θmin = 3.3°
8478 measured reflectionsh = −12→12
4960 independent reflectionsk = −8→13
3665 reflections with I > 2σ(I)l = −14→15
Refinement top
Refinement on F20 restraints
Least-squares matrix: full0 constraints
R[F2 > 2σ(F2)] = 0.058H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.179 w = 1/[σ2(Fo2) + (0.0877P)2 + 0.2886P]
where P = (Fo2 + 2Fc2)/3
S = 1.12(Δ/σ)max < 0.001
4960 reflectionsΔρmax = 0.85 e Å−3
286 parametersΔρmin = −0.60 e Å−3
Crystal data top
C6H13ClNO+·C6H2N3O7−γ = 90.376 (4)°
Mr = 378.72V = 780.65 (7) Å3
Triclinic, P1Z = 2
a = 8.2063 (4) ÅMo Kα radiation
b = 9.3075 (5) ŵ = 0.30 mm−1
c = 10.2896 (6) ÅT = 293 K
α = 93.954 (5)°0.30 × 0.24 × 0.18 mm
β = 95.284 (5)°
Data collection top
Oxford Diffraction Xcalibur
diffractometer		3665 reflections with I > 2σ(I)
8478 measured reflectionsRint = 0.016
4960 independent reflectionsθmax = 32.3°
Refinement top
R[F2 > 2σ(F2)] = 0.058H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.179Δρmax = 0.85 e Å−3
S = 1.12Δρmin = −0.60 e Å−3
4960 reflectionsAbsolute structure: ?
286 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
H8B−0.178 (3)−0.150 (3)0.786 (2)0.035 (6)*
H9B−0.286 (3)0.146 (3)0.883 (3)0.041 (6)*
H40.386 (3)0.587 (2)0.610 (2)0.033 (6)*
H9A−0.401 (3)0.024 (3)0.793 (2)0.036 (6)*
H10A−0.331 (3)0.311 (3)0.731 (2)0.039 (6)*
H20.299 (3)0.541 (3)0.972 (3)0.042 (7)*
H11A−0.135 (3)−0.023 (3)0.548 (2)0.040 (6)*
H12A−0.241 (3)0.215 (3)0.532 (3)0.049 (7)*
H8A−0.102 (3)−0.044 (2)0.887 (3)0.033 (6)*
H11B−0.300 (3)−0.076 (3)0.597 (2)0.037 (6)*
H7B0.087 (4)−0.208 (3)0.791 (3)0.058 (8)*
H12B−0.355 (4)0.101 (3)0.435 (3)0.055 (8)*
H7A0.069 (3)−0.121 (3)0.678 (3)0.052 (7)*
H10B−0.504 (4)0.259 (3)0.757 (3)0.052 (7)*
H4'−0.106 (3)0.125 (3)0.743 (2)0.037 (6)*
Cl0.22010 (6)0.00390 (7)0.83918 (7)0.0572 (2)
N4−0.18045 (17)0.05189 (15)0.73274 (15)0.0277 (3)
C8−0.1068 (2)−0.0703 (2)0.8042 (2)0.0333 (4)
C9−0.3282 (2)0.1067 (2)0.7962 (2)0.0343 (4)
O8−0.4535 (2)0.1794 (2)0.58892 (18)0.0535 (4)
C11−0.2318 (2)0.0085 (2)0.5915 (2)0.0365 (4)
C10−0.4054 (3)0.2269 (2)0.7217 (3)0.0469 (5)
C70.0592 (2)−0.1150 (2)0.7678 (2)0.0405 (4)
C12−0.3138 (3)0.1338 (3)0.5261 (2)0.0465 (5)
C50.2198 (2)0.43814 (18)0.62764 (19)0.0308 (3)
N20.47503 (19)0.70058 (17)0.84556 (19)0.0374 (4)
C20.2800 (2)0.51646 (19)0.8933 (2)0.0325 (4)
O10.0317 (2)0.25764 (19)0.67334 (16)0.0543 (5)
C40.3325 (2)0.54510 (18)0.6696 (2)0.0318 (4)
C30.3613 (2)0.58362 (18)0.80201 (19)0.0310 (4)
C10.1667 (2)0.40844 (18)0.85050 (19)0.0311 (4)
C60.1275 (2)0.35914 (19)0.71437 (19)0.0330 (4)
N30.0845 (2)0.34768 (17)0.95407 (18)0.0384 (4)
N10.1924 (2)0.40692 (18)0.48624 (17)0.0389 (4)
O50.5335 (2)0.76658 (17)0.76105 (19)0.0541 (4)
O2−0.0347 (2)0.2682 (2)0.92512 (19)0.0603 (5)
O40.5057 (2)0.73018 (19)0.96342 (19)0.0542 (4)
O30.1342 (2)0.3801 (2)1.06775 (18)0.0568 (5)
O70.0693 (3)0.3444 (3)0.4397 (2)0.0808 (7)
O60.2896 (3)0.4530 (3)0.4174 (2)0.0902 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl0.0304 (2)0.0661 (4)0.0743 (5)−0.0029 (2)0.0023 (2)0.0011 (3)
N40.0240 (6)0.0286 (6)0.0314 (7)−0.0047 (5)0.0033 (5)0.0069 (5)
C80.0287 (8)0.0346 (9)0.0378 (10)−0.0009 (7)0.0032 (7)0.0116 (7)
C90.0269 (8)0.0356 (9)0.0411 (10)−0.0010 (6)0.0065 (7)0.0041 (7)
O80.0401 (8)0.0624 (10)0.0567 (11)0.0076 (7)−0.0100 (7)0.0140 (8)
C110.0333 (9)0.0426 (10)0.0330 (9)−0.0036 (7)0.0009 (7)0.0027 (7)
C100.0431 (11)0.0402 (10)0.0573 (14)0.0088 (9)0.0011 (10)0.0067 (9)
C70.0340 (9)0.0425 (10)0.0449 (12)0.0056 (8)0.0033 (8)0.0012 (9)
C120.0446 (11)0.0585 (13)0.0362 (11)−0.0044 (10)−0.0058 (9)0.0152 (9)
C50.0287 (7)0.0271 (7)0.0367 (9)−0.0030 (6)0.0012 (6)0.0057 (6)
N20.0289 (7)0.0288 (7)0.0537 (11)−0.0048 (6)0.0011 (7)0.0009 (7)
C20.0306 (8)0.0285 (8)0.0382 (10)−0.0009 (6)0.0009 (7)0.0042 (7)
O10.0577 (10)0.0596 (10)0.0445 (9)−0.0371 (8)−0.0041 (7)0.0103 (7)
C40.0265 (7)0.0258 (7)0.0442 (10)−0.0024 (6)0.0056 (7)0.0089 (7)
C30.0261 (7)0.0242 (7)0.0425 (10)−0.0044 (6)0.0011 (7)0.0036 (7)
C10.0293 (8)0.0284 (7)0.0366 (9)−0.0038 (6)0.0041 (7)0.0083 (7)
C60.0282 (8)0.0305 (8)0.0409 (10)−0.0069 (6)0.0002 (7)0.0103 (7)
N30.0397 (8)0.0313 (7)0.0467 (10)−0.0014 (6)0.0122 (7)0.0101 (7)
N10.0435 (9)0.0361 (8)0.0369 (9)−0.0018 (7)0.0037 (7)0.0020 (7)
O50.0504 (9)0.0417 (8)0.0711 (12)−0.0223 (7)0.0093 (8)0.0074 (8)
O20.0626 (11)0.0575 (10)0.0627 (11)−0.0316 (8)0.0238 (9)−0.0016 (8)
O40.0494 (9)0.0505 (9)0.0590 (11)−0.0126 (7)−0.0051 (8)−0.0080 (8)
O30.0639 (11)0.0647 (11)0.0439 (9)−0.0126 (9)0.0067 (8)0.0163 (8)
O70.0923 (16)0.1001 (17)0.0461 (11)−0.0532 (14)−0.0013 (10)−0.0075 (10)
O60.0833 (15)0.142 (2)0.0462 (11)−0.0453 (16)0.0161 (10)0.0066 (13)
Geometric parameters (Å, °) top
Cl—C71.788 (2)C12—H12A0.96 (3)
N4—C81.497 (2)C12—H12B0.99 (3)
N4—C111.503 (2)C5—C41.374 (2)
N4—C91.504 (2)C5—C61.455 (2)
N4—H4'0.91 (2)C5—N11.460 (3)
C8—C71.500 (3)N2—O41.228 (3)
C8—H8B0.94 (2)N2—O51.229 (2)
C8—H8A0.87 (3)N2—C31.449 (2)
C9—C101.510 (3)C2—C31.382 (3)
C9—H9B0.98 (3)C2—C11.386 (2)
C9—H9A0.97 (2)C2—H20.83 (3)
O8—C121.420 (3)O1—C61.250 (2)
O8—C101.426 (3)C4—C31.383 (3)
C11—C121.517 (3)C4—H40.89 (2)
C11—H11A0.98 (3)C1—C61.450 (3)
C11—H11B0.97 (2)C1—N31.456 (2)
C10—H10A0.98 (3)N3—O31.220 (2)
C10—H10B0.96 (3)N3—O21.225 (2)
C7—H7B0.93 (3)N1—O71.206 (3)
C7—H7A0.94 (3)N1—O61.210 (3)
C8—N4—C11112.20 (15)Cl—C7—H7A105.7 (17)
C8—N4—C9110.07 (14)H7B—C7—H7A103 (3)
C11—N4—C9108.38 (14)O8—C12—C11111.16 (18)
C8—N4—H4'106.9 (15)O8—C12—H12A106.5 (17)
C11—N4—H4'113.0 (15)C11—C12—H12A110.6 (16)
C9—N4—H4'106.1 (15)O8—C12—H12B106.1 (17)
N4—C8—C7115.12 (16)C11—C12—H12B108.8 (16)
N4—C8—H8B107.4 (14)H12A—C12—H12B113 (2)
C7—C8—H8B108.0 (14)C4—C5—C6124.17 (18)
N4—C8—H8A106.8 (16)C4—C5—N1116.02 (16)
C7—C8—H8A110.2 (15)C6—C5—N1119.80 (15)
H8B—C8—H8A109 (2)O4—N2—O5123.60 (17)
N4—C9—C10110.06 (17)O4—N2—C3118.95 (17)
N4—C9—H9B105.2 (15)O5—N2—C3117.44 (18)
C10—C9—H9B108.9 (15)C3—C2—C1118.96 (18)
N4—C9—H9A105.1 (14)C3—C2—H2120.0 (18)
C10—C9—H9A111.6 (14)C1—C2—H2121.0 (18)
H9B—C9—H9A116 (2)C5—C4—C3119.30 (16)
C12—O8—C10109.70 (17)C5—C4—H4118.7 (15)
N4—C11—C12109.86 (17)C3—C4—H4122.0 (15)
N4—C11—H11A109.0 (14)C2—C3—C4121.53 (16)
C12—C11—H11A111.4 (14)C2—C3—N2119.26 (17)
N4—C11—H11B102.7 (14)C4—C3—N2119.18 (16)
C12—C11—H11B116.2 (14)C2—C1—C6124.15 (16)
H11A—C11—H11B107 (2)C2—C1—N3114.57 (17)
O8—C10—C9111.16 (18)C6—C1—N3121.27 (15)
O8—C10—H10A113.2 (15)O1—C6—C1125.59 (17)
C9—C10—H10A109.7 (14)O1—C6—C5122.46 (18)
O8—C10—H10B105.5 (17)C1—C6—C5111.90 (15)
C9—C10—H10B111.4 (17)O3—N3—O2121.69 (18)
H10A—C10—H10B106 (2)O3—N3—C1118.95 (17)
C8—C7—Cl113.24 (15)O2—N3—C1119.35 (18)
C8—C7—H7B113.2 (19)O7—N1—O6121.2 (2)
Cl—C7—H7B107.2 (18)O7—N1—C5119.83 (18)
C8—C7—H7A114.0 (18)O6—N1—C5118.78 (18)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N4—H4'···O10.91 (3)1.89 (3)2.718 (2)151.2 (19)
N4—H4'···O20.91 (3)2.25 (2)2.896 (2)127.6 (17)
C2—H2···O30.83 (3)2.34 (3)2.637 (3)102 (2)
C2—H2···O40.83 (2)2.45 (2)2.723 (3)101 (2)
C4—H4···O60.90 (3)2.34 (3)2.667 (3)101.7 (15)
C7—H7A···O7i0.93 (3)2.54 (3)3.026 (3)113 (2)
C8—H8B···O5ii0.94 (3)2.47 (2)3.290 (2)146 (2)
C9—H9A···O5ii0.97 (3)2.45 (3)3.341 (2)154 (2)
C9—H9B···O20.97 (3)2.34 (3)2.985 (3)123 (2)
C12—H12A···O10.96 (3)2.57 (2)3.254 (3)129 (2)
Symmetry codes: (i) −x, −y, −z+1; (ii) x−1, y−1, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N4—H4'···O10.91 (3)1.89 (3)2.718 (2)151.2 (19)
N4—H4'···O20.91 (3)2.25 (2)2.896 (2)127.6 (17)
C2—H2···O30.83 (3)2.34 (3)2.637 (3)102 (2)
C2—H2···O40.83 (2)2.45 (2)2.723 (3)101 (2)
C4—H4···O60.90 (3)2.34 (3)2.667 (3)101.7 (15)
C7—H7A···O7i0.93 (3)2.54 (3)3.026 (3)113 (2)
C8—H8B···O5ii0.94 (3)2.47 (2)3.290 (2)146 (2)
C9—H9A···O5ii0.97 (3)2.45 (3)3.341 (2)154 (2)
C9—H9B···O20.97 (3)2.34 (3)2.985 (3)123 (2)
C12—H12A···O10.96 (3)2.57 (2)3.254 (3)129 (2)
Symmetry codes: (i) −x, −y, −z+1; (ii) x−1, y−1, z.
Acknowledgements top

The authors are grateful to the Department of Science and Technology of the Government of India for funding under SR/S2/CMP-47/2003 research project.

references
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