4-(2,4-Dinitro­phenyl­sulfanyl)­morpholine

In the title compound, C₁₀H₁₁N₃O₅S, the 2,4-dinitro­phenyl fragment is connected by an S atom to the morpholine ring, which is in a chair conformation. The ortho- and para-nitro groups are slightly twisted out of the plane of the benzene ring. The mol­ecules are linked into C(7) and C(10) chains by two inter­molecular C—H...O hydrogen bonds.

S1. Comment

Sulfenamides are important compounds with versatile industrial applications. Bond polarization in sulfenamide derivatives, resulting from the difference in electronegativity between S and N, activates the S—N bond for attack by both nucleophiles and electrophiles and appears to be the factor primarily responsible for the chemistry of these compounds. The title compound, (I), is the result of the condensation reaction of 2,4-dinitrophenylsulfanylphalimide and morpholine. Its structure is decribed here as part of our work involving the study of the synthesis and structural characterization of divalent-sulfur compounds (Brito et al., 2004, 2005, 2006). A search of the Cambridge Structural Database (CSD, Version 5.27; Allen, 2002) for the morpholine fragment with an S^II—X substituent (where X is alkyl, aryl or any adequate group) yielded only one example, viz 1,3-bis(2-methylphenyl)-2-(4-morpholino)isothiurea (CSD refcode TEHDAL; Sudha et al., 1996).

A view of the molecular structure of (I) is given in Fig. 1, and selected geometric parameters are listed in Table 1. The morpholine ring has a chair conformation [puckering amplitude Q_T = 0.573 (3) Å, θ = 180.0 (3)° and ϕ = 210 (25)° (Cremer & Pople, 1975)], with atoms N1 and O1 displaced by −0.659 (2) and 0.658 (2) Å, respectively, from the best plane through atoms C1, C2, C3 and C4 [maximum deviation ±0.0003 Å]. A survey of structures with morpholine rings shows wide variability, with the sum of the angles at the N atom ranging from 336 to 359° (Wong-Ng et al., 1982). In the present case, the sum of the angles at N1 is 336.7 (2)°.

The morpholine ring in (I) is oriented in such a way that the N1 lone pair can accept an intramolecular hydrogen bond from the C10—H10 group. To achieve this favourable intramolecular interaction, the N1—S1—C5—C10 torsion angle has a value of −4.5 (2)°, while the best planes of the 2,4-dinitrophenyl and morpholino groups are almost perpendicular to one another [dihedral angle 101.4 (2)°]. The average Csp³—Nsp³, Csp³—Csp³ and Csp³—Osp³ bond distances [1.474 (4), 1.449 (5) and 1.420 (4) Å, respectively] are comparable with the literature values (Allen et al., 1987).

The phenyl ring is slightly deformed, with atom C5 displaced out of the mean ring plane by 0.0095 (15) Å. The nitro groups in the ortho and para positions are rotated by 3.5 (4) and 6.1 (5)° from the aromatic ring, respectively. The C—S distance is shorter than the value of 1.777 (6) Å found in 4-[(dimethylamino)thio]-1,3-dinitrobenzene (Aupers et al.,1999) but longer than the value of 1.735 (4) Å found in 2-(2,4-dinitrophenylthioamino)-2,3,4,5-tetraphenyl-2H-pyrrole benzene solvate (Atkinson et al., 1985). The S—N distance is shorter than the normal S—N single-bond length (1.74 Å; Reference?), but is normal for this type of structure, many of which have S—N single bonds in the range 1.63–1.68 Å as a result of the π character of the S—N bond (Reference?).

The crystal structure of (I) is built up by an intramolecular C—H.·N hydrogen bond and two weak intermolecular C—H.·O hydrogen bonds. The intramolecular C10—H10···N interaction forms a five-membered closed S1/N1/C10/C5/H10 ring (Fig. 2). The molecules are linked into chains by two intermolecular C—H···O hydrogen bonds. Atoms C3 and C9 in the molecule at (x,y,z) acts as hydrogen-bond donors via atoms H3B and H9 to sulfenamide atoms O5 and O3 in the molecules at (x − 1,-y + 1/2,z + 1/2) and (x + 1,-y + 1/2, z + 1/2), so generating by translation two C(10) and C(7) (Bernstein et al., 1995) chains running parallel to the [100] direction (Fig. 3, Table 2). Such interactions involving the nitro O atoms are generally the dominant feature of the crystal structures of compounds containing nitroarenethiolate (O₂NC₆H₄SX) fragments (Kucsman et al., 1984; Aupers et al., 1999; Low et al., 2000; Glidewell et al., 2000), as well as those of simple nitrobenzenes (Boonstra, 1963; Trotter & Williston, 1966; Choi & Abel, 1972; Herbstein & Kapon, 1990; Boese et al., 1992; Sekine et al., 1994).

S2. Experimental

All reactions were carried out under an atmosphere of purified nitrogen. Solvents used were dried and distilled prior to use. 2,4-Dinitrophenylsulfenyl chloride and phthalimide were purchased from Aldrich. The precursor compound, C₁₄H₇N₃O₆S, was prepared according to the method of Wunderly (1972). A solution of 2,4-dinitrophenyl chloride (2.487 g, 0.008 mol) in dry methanol (80 ml) was added dropwise to a stirred solution of phthalimide (1.176 g, 0.008 mol) and triethylamine (1.49 ml, 0.008 mol) in dimethylformamide (5 ml) under a nitrogen atmosphere. Stirring was continued for 30 min at 298 K. Cold destilled water (100 ml) was added and stirring was continued for a further 30 min. The yellow precipitate which formed was filtered off, washed with pentane and dried at room temperature. The title compound, C₁₀H₁₁N₃O₅S, (I), was prepared according to the method of Harpp & Back (1971). Orange crystals of (I) suitable for X-ray studies were obtained by slow evaporation of a solution of the product in diethyl ether.

S3. Refinement

H atoms were positioned geometrically and refined using a riding model, with U_iso(H) = 1.2U_eq(C) (C_aromatic—H = 0.93 Å and C_methylene—H = 0.97 Å). The material was difficult to obtain in a suitable crystalline form and the best available specimen was lost late in the data collection, resulting in 97% completeness after merging equivalents.

Computing details

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; 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) and PLATON (Spek, 2003); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. A view of the molecule of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A view of the hydrogen-bonding interactions in (I). H atoms not involved in these contacts have been omitted for clarity. [Symmetry codes: (i) x − 1, −y + 1/2, z + 1/2; (ii) x + 1, −y + 1/2, z + 1/2.]
	Fig. 3. A stereoview of part of the crystal structure of (I), showing the formation of two C(7) and C(10) chains along [100]. For the sake of clarity, H atoms not involved in the motif shown have been omitted.

4-(2,4-Dinitrophenylsulfanyl)morpholine

Crystal data

C10H11N3O5S	F(000) = 592
Mr = 285.28	Dx = 1.521 Mg m^−3
Monoclinic, P21/c	Melting point: 196.4 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 6.4280 (2) Å	Cell parameters from 6390 reflections
b = 16.0850 (7) Å	θ = 2.1–27.9°
c = 12.1500 (6) Å	µ = 0.28 mm^−1
β = 97.4900 (16)°	T = 298 K
V = 1245.52 (9) Å^3	Prism, orange
Z = 4	0.40 × 0.25 × 0.18 mm

Data collection

Nonius KappaCCD area-detector diffractometer	2901 independent reflections
Radiation source: fine-focus sealed tube	2311 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.086
ϕ scans, and ω scans with κ offsets	θmax = 27.9°, θmin = 2.1°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −8→7
Tmin = 0.915, Tmax = 0.950	k = −21→19
7918 measured reflections	l = −16→12

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.069	w = 1/[σ^2(Fo^2) + (0.1026P)^2 + 0.3584P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.206	(Δ/σ)max < 0.001
S = 1.12	Δρmax = 0.37 e Å^−3
2901 reflections	Δρmin = −0.37 e Å^−3
172 parameters

Special details

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.

Mean-plane data from final SHELXL refinement run: Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

−3.3714(0.0264)x + 10.5066(0.0237)y + 7.4096(0.0391)z = 5.9233(0.0055) * 0.0000 (0.0000) O2 * 0.0000 (0.0000) N2 * 0.0000 (0.0000) O3 Rms deviation of fitted atoms = 0.0000

−3.3269(0.0051)x + 11.1616(0.0103)y + 6.8502(0.0094)z = 5.8081(0.0041) A ngle to previous plane (with approximate e.s.d.) = 3.52(0.41) * −0.0095 (0.0015) C5 * 0.0036 (0.0015) C6 * 0.0056 (0.0015) C7 * −0.0089 (0.0016) C8 * 0.0025 (0.0017) C9 * 0.0067 (0.0017) C10 − 0.0424 (0.0035) N3 0.0218 (0.0035) N2 − 0.0910 (0.0030) S1 Rms deviation of fitted atoms = 0.0067

−2.8459(0.0250)x + 11.0671(0.0527)y + 7.6275(0.0228)z = 6.2840(0.0200) A ngle to previous plane (with approximate e.s.d.) = 6.06(0.45) * 0.0000 (0.0000) O5 * 0.0000 (0.0000) N3 * 0.0000 (0.0000) O4 Rms deviation of fitted atoms = 0.0000

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 (Ų)

	x	y	z	Uiso*/Ueq
S1	−0.28752 (10)	0.07516 (5)	0.57249 (6)	0.0556 (3)
O1	−0.1272 (4)	−0.06892 (13)	0.8830 (2)	0.0744 (7)
O2	−0.4449 (4)	0.14649 (19)	0.3893 (2)	0.0884 (8)
O3	−0.3347 (4)	0.24689 (18)	0.2970 (2)	0.0899 (8)
O4	0.5261 (3)	0.32752 (16)	0.5449 (2)	0.0762 (7)
O5	0.3200 (4)	0.37217 (15)	0.40325 (19)	0.0720 (6)
N1	−0.1800 (3)	0.03842 (14)	0.69808 (18)	0.0514 (6)
N2	−0.3142 (3)	0.19874 (16)	0.37465 (19)	0.0554 (6)
N3	0.3595 (3)	0.32676 (15)	0.4839 (2)	0.0526 (6)
C1	0.0267 (5)	−0.0637 (2)	0.8098 (3)	0.0702 (9)
H1A	0.0982	−0.1167	0.8082	0.084*
H1B	0.13	−0.0221	0.8368	0.084*
C2	−0.0696 (5)	−0.04138 (18)	0.6945 (3)	0.0597 (7)
H2A	0.0388	−0.0369	0.6463	0.072*
H2B	−0.1674	−0.0843	0.6652	0.072*
C3	−0.3366 (5)	0.03413 (18)	0.7767 (3)	0.0617 (8)
H3A	−0.4447	−0.0059	0.7506	0.074*
H3B	−0.4025	0.088	0.7817	0.074*
C4	−0.2309 (6)	0.0090 (2)	0.8872 (3)	0.0729 (9)
H4A	−0.1293	0.0511	0.9147	0.088*
H4B	−0.334	0.0052	0.9386	0.088*
C5	−0.1028 (3)	0.15150 (14)	0.54972 (19)	0.0397 (5)
C6	−0.1267 (3)	0.20323 (15)	0.45573 (18)	0.0407 (5)
C7	0.0213 (3)	0.26079 (15)	0.43413 (19)	0.0414 (5)
H7	0.0006	0.2942	0.3712	0.05*
C8	0.2000 (3)	0.26718 (15)	0.50838 (19)	0.0401 (5)
C9	0.2318 (3)	0.21931 (17)	0.60350 (19)	0.0449 (6)
H9	0.3536	0.2255	0.6533	0.054*
C10	0.0820 (4)	0.16247 (15)	0.62395 (19)	0.0437 (5)
H10	0.1032	0.1306	0.6883	0.052*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0488 (4)	0.0610 (5)	0.0569 (5)	−0.0164 (3)	0.0064 (3)	−0.0080 (3)
O1	0.0940 (16)	0.0520 (12)	0.0837 (16)	0.0128 (11)	0.0368 (13)	0.0186 (11)
O2	0.0587 (13)	0.120 (2)	0.0787 (16)	−0.0279 (13)	−0.0213 (11)	−0.0049 (14)
O3	0.0905 (16)	0.0885 (18)	0.0759 (15)	0.0047 (13)	−0.0444 (12)	0.0135 (13)
O4	0.0486 (11)	0.0835 (15)	0.0938 (17)	−0.0204 (10)	−0.0008 (10)	0.0052 (13)
O5	0.0788 (14)	0.0718 (14)	0.0684 (14)	−0.0115 (11)	0.0206 (11)	0.0174 (11)
N1	0.0563 (12)	0.0447 (12)	0.0570 (13)	−0.0007 (9)	0.0222 (10)	−0.0008 (10)
N2	0.0457 (11)	0.0656 (15)	0.0499 (13)	0.0062 (10)	−0.0121 (9)	−0.0143 (11)
N3	0.0501 (12)	0.0501 (12)	0.0595 (14)	−0.0057 (9)	0.0139 (10)	−0.0034 (11)
C1	0.0680 (18)	0.0626 (19)	0.083 (2)	0.0130 (14)	0.0207 (16)	0.0092 (16)
C2	0.0597 (15)	0.0498 (15)	0.0739 (19)	0.0046 (12)	0.0250 (14)	−0.0088 (13)
C3	0.0713 (17)	0.0479 (15)	0.0730 (19)	0.0042 (13)	0.0360 (15)	0.0003 (13)
C4	0.100 (2)	0.0549 (17)	0.071 (2)	0.0143 (16)	0.0378 (18)	0.0082 (15)
C5	0.0372 (11)	0.0427 (12)	0.0390 (12)	−0.0014 (8)	0.0042 (8)	−0.0099 (9)
C6	0.0371 (11)	0.0456 (12)	0.0368 (11)	0.0056 (9)	−0.0042 (8)	−0.0090 (10)
C7	0.0472 (12)	0.0418 (12)	0.0342 (11)	0.0073 (9)	0.0015 (9)	−0.0006 (9)
C8	0.0389 (11)	0.0404 (12)	0.0409 (12)	−0.0017 (9)	0.0053 (9)	−0.0036 (9)
C9	0.0391 (11)	0.0511 (13)	0.0413 (12)	−0.0029 (9)	−0.0068 (9)	−0.0019 (10)
C10	0.0468 (12)	0.0465 (13)	0.0351 (11)	−0.0032 (10)	−0.0040 (9)	0.0009 (10)

Geometric parameters (Å, º)

S1—N1	1.697 (2)	C2—H2B	0.97
S1—C5	1.755 (2)	C3—C4	1.481 (5)
O1—C1	1.417 (4)	C3—H3A	0.97
O1—C4	1.423 (4)	C3—H3B	0.97
O2—N2	1.218 (3)	C4—H4A	0.97
O3—N2	1.214 (3)	C4—H4B	0.97
O4—N3	1.220 (3)	C5—C6	1.405 (3)
O5—N3	1.222 (3)	C5—C10	1.406 (3)
N1—C2	1.470 (4)	C6—C7	1.377 (3)
N1—C3	1.477 (3)	C7—C8	1.369 (3)
N2—C6	1.456 (3)	C7—H7	0.93
N3—C8	1.462 (3)	C8—C9	1.382 (3)
C1—C2	1.500 (5)	C9—C10	1.374 (3)
C1—H1A	0.97	C9—H9	0.93
C1—H1B	0.97	C10—H10	0.93
C2—H2A	0.97
N1—S1—C5	100.41 (11)	C4—C3—H3B	109.8
C1—O1—C4	109.8 (2)	H3A—C3—H3B	108.3
C2—N1—C3	110.5 (2)	O1—C4—C3	111.7 (3)
C2—N1—S1	114.76 (19)	O1—C4—H4A	109.3
C3—N1—S1	111.44 (19)	C3—C4—H4A	109.3
O3—N2—O2	123.1 (2)	O1—C4—H4B	109.3
O3—N2—C6	119.4 (2)	C3—C4—H4B	109.3
O2—N2—C6	117.5 (2)	H4A—C4—H4B	107.9
O4—N3—O5	123.7 (2)	C6—C5—C10	116.2 (2)
O4—N3—C8	117.8 (2)	C6—C5—S1	122.54 (17)
O5—N3—C8	118.5 (2)	C10—C5—S1	121.28 (19)
O1—C1—C2	111.3 (3)	C7—C6—C5	123.2 (2)
O1—C1—H1A	109.4	C7—C6—N2	115.9 (2)
C2—C1—H1A	109.4	C5—C6—N2	120.9 (2)
O1—C1—H1B	109.4	C8—C7—C6	117.8 (2)
C2—C1—H1B	109.4	C8—C7—H7	121.1
H1A—C1—H1B	108	C6—C7—H7	121.1
N1—C2—C1	108.9 (2)	C7—C8—C9	122.0 (2)
N1—C2—H2A	109.9	C7—C8—N3	117.8 (2)
C1—C2—H2A	109.9	C9—C8—N3	120.3 (2)
N1—C2—H2B	109.9	C10—C9—C8	119.4 (2)
C1—C2—H2B	109.9	C10—C9—H9	120.3
H2A—C2—H2B	108.3	C8—C9—H9	120.3
N1—C3—C4	109.2 (3)	C9—C10—C5	121.4 (2)
N1—C3—H3A	109.8	C9—C10—H10	119.3
C4—C3—H3A	109.8	C5—C10—H10	119.3
N1—C3—H3B	109.8
C5—S1—N1—C2	−102.4 (2)	O2—N2—C6—C7	177.5 (2)
C5—S1—N1—C3	131.02 (18)	O3—N2—C6—C5	176.6 (2)
C4—O1—C1—C2	−59.9 (4)	O2—N2—C6—C5	−2.7 (3)
C3—N1—C2—C1	−56.0 (3)	C5—C6—C7—C8	0.2 (3)
S1—N1—C2—C1	176.94 (19)	N2—C6—C7—C8	179.9 (2)
O1—C1—C2—N1	58.2 (3)	C6—C7—C8—C9	−1.4 (3)
C2—N1—C3—C4	56.1 (3)	C6—C7—C8—N3	178.42 (19)
S1—N1—C3—C4	−175.0 (2)	O4—N3—C8—C7	−173.9 (2)
C1—O1—C4—C3	60.1 (4)	O5—N3—C8—C7	5.3 (3)
N1—C3—C4—O1	−58.0 (4)	O4—N3—C8—C9	5.9 (4)
N1—S1—C5—C6	−177.40 (18)	O5—N3—C8—C9	−174.9 (2)
N1—S1—C5—C10	4.5 (2)	C7—C8—C9—C10	1.1 (4)
C10—C5—C6—C7	1.2 (3)	N3—C8—C9—C10	−178.7 (2)
S1—C5—C6—C7	−176.94 (17)	C8—C9—C10—C5	0.4 (4)
C10—C5—C6—N2	−178.5 (2)	C6—C5—C10—C9	−1.5 (3)
S1—C5—C6—N2	3.3 (3)	S1—C5—C10—C9	176.68 (19)
O3—N2—C6—C7	−3.2 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3B···O5^i	0.97	2.54	3.224 (4)	127
C9—H9···O3^ii	0.93	2.52	3.446 (4)	174
C10—H10···N1	0.93	2.36	2.833 (3)	111

Symmetry codes: (i) x−1, −y+1/2, z+1/2; (ii) x+1, −y+1/2, z+1/2.