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The central N atom of C18H12N4O8S is essentially planar, lying 0.071 (2) Å out of the plane defined by the three S atoms. N-S distances are 1.712 (2) and 1.721 (2) Å to S-Ar, and 1.681 (2) Å to SO2-Ar. The nitro group on the phenyl ring carrying the SO2 group lies out of plane, with C-C-N-O- torsion angle 69.8 (3)°, while the other two nitro groups are near coplanarity, with torsion angle magnitudes 10.4 (3) and 14.0 (3)°.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199016121/qb0136sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270199016121/qb0136Isup2.hkl
Contains datablock I

CCDC reference: 140866

Comment top

The aim of the study was to synthesize O,N-bis(2-nitrobenzenesulfonyl)hydroxylamine, which could deliver its protected amino group to various nucleophiles via electrophilic amination. This is important in the synthesis of α-hyrazino acids for the synthesis of hydrazino peptides. When N,N-diisopropylethylamine, (DIEA) was used as a base in the reaction, the main product was the title compound. When collidine was used in place of DIEA, the desired product was obtained without formation of the title compound·We thus believe that the DIEA is acting as a reducing agent in the formation of the title compound.

The central N atom is essentially planar, lying 0.071 (2) Å out of the plane defined by the three S atoms. Tris(thiophenyl)amine (Carruthers et al., 1981) also has a near planar central N atom. N—S distances to thiol S are 1.712 (2) and 1.721 (2) Å, while the N1—S1 distance is shorter, 1.681 (2) Å. The nitro group on phenyl ring C1 through C6 lies out of plane, with C3—C2—N2—O3 torsion angle 69.8 (3)°. The other two nitro groups are nearer coplanarity with their respective phenyl rings, with torsion angles O6—N3—C8—C7 10.4 (3) and O8—N4—C14—C13 − 14.0 (3)°.

Short intermolecular contacts exist between nitro groups of inversion-related molecules. O6 has distances of 2.772 (2) Å to O6i and 2.827 (2) Å to N3i [symmetry code: (i) 1 − x, 1 − y, 2 − z], as well as a distance of 2.785 (2) Å to O7ii [symmetry code: (ii) 1 − x, 1 − y, 1 − z]. An N3···O7ii contact of distance 2.848 (2) Å also exists.

Experimental top

Under an argon atmosphere, 2-nitrobenzenesulfonyl chloride (2.5 equivalents, 19.94 g, 0.09 mol) was added slowly to a stirred solution of DIEA (3 equivalents, 18.81 ml, 0.108 mol) and hydroxylamine hydrochloride (1 equivalents, 2.5 g, 0.036 mol) in dry acetonitrile (72 ml). The reaction mixture was stirred overnight at room temperature. The solvent was evaporated in vacuo. The residue was diluted with dichloromethane, extracted with 5% NaOH, dried over MgSO4, and evaporated in vacuo. Solvent removal left a pale yellow semi-solid, which was dissolved in hot toluene and kept in a freezer overnight. The resulting pale-yellow crystals were filtered and washed with cold toluene. The yield was 22%.

Refinement top

H atoms were located in difference maps. For refinement, they were placed in calculated positions with C—H distance 0.95 Å and Biso = 1.3Beq for the bonded C atom, and thereafter treated as riding.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf-Nonius, 1994); data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SIR (Burla et al., 1989); program(s) used to refine structure: LSFM in MolEN (Fair, 1990); software used to prepare material for publication: CIFGEN in MolEN (Fair, 1990).

2-nitro-N,N-bis(2-nitrophenylthio)benzenesulfonamide top
Crystal data top
C18H12N4O8S3F(000) = 1040
Mr = 508.51Dx = 1.619 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 25 reflections
a = 7.670 (3) Åθ = 10.5–18.1°
b = 19.766 (5) ŵ = 0.41 mm1
c = 13.759 (3) ÅT = 100 K
β = 90.63 (3)°Prism, yellow
V = 2085.8 (11) Å30.50 × 0.33 × 0.32 mm
Z = 4
Data collection top
Enraf-Nonius CAD-4 (with Oxford Cryostream)
diffractometer
3426 reflections with I > 3σ(I)
Radiation source: sealed tubeRint = 0.018
Graphite monochromatorθmax = 27.5°, θmin = 2.5°
θ/2θ scansh = 09
Absorption correction: ψ scan
(North et al., 1968)
k = 250
Tmin = 0.835, Tmax = 0.882l = 1717
5118 measured reflections3 standard reflections every 60 min
4775 independent reflections intensity decay: 2.9%
Refinement top
Refinement on F20 restraints
Least-squares matrix: full0 constraints
R[F2 > 2σ(F2)] = 0.038H-atom parameters constrained
wR(F2) = 0.040w = 4Fo2/[σ2(Fo2) + 0.0004Fo4]
S = 1.32(Δ/σ)max = 0.001
4775 reflectionsΔρmax = 0.62 e Å3
298 parametersΔρmin = 0.37 e Å3
Crystal data top
C18H12N4O8S3V = 2085.8 (11) Å3
Mr = 508.51Z = 4
Monoclinic, P21/nMo Kα radiation
a = 7.670 (3) ŵ = 0.41 mm1
b = 19.766 (5) ÅT = 100 K
c = 13.759 (3) Å0.50 × 0.33 × 0.32 mm
β = 90.63 (3)°
Data collection top
Enraf-Nonius CAD-4 (with Oxford Cryostream)
diffractometer
3426 reflections with I > 3σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.018
Tmin = 0.835, Tmax = 0.8823 standard reflections every 60 min
5118 measured reflections intensity decay: 2.9%
4775 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.040H-atom parameters constrained
S = 1.32Δρmax = 0.62 e Å3
4775 reflectionsΔρmin = 0.37 e Å3
298 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.66531 (7)0.29449 (3)0.70051 (4)0.0180 (2)
S20.54977 (7)0.42605 (3)0.77802 (4)0.0186 (2)
S30.64999 (7)0.40948 (3)0.56947 (4)0.0179 (2)
O10.8301 (2)0.28243 (8)0.6572 (1)0.0227 (8)
O20.6404 (2)0.28076 (8)0.8010 (1)0.0238 (8)
O30.2660 (2)0.20796 (9)0.8248 (1)0.0316 (9)
O40.2594 (2)0.31341 (8)0.7824 (1)0.0289 (9)
O50.5973 (2)0.60058 (8)0.9551 (1)0.0304 (9)
O60.4663 (2)0.51013 (8)0.9019 (1)0.0235 (8)
O70.5594 (2)0.41081 (9)0.2652 (1)0.0303 (9)
O80.7003 (2)0.44192 (8)0.3954 (1)0.0258 (8)
N10.6122 (2)0.37610 (9)0.6828 (1)0.0182 (9)
N20.2878 (2)0.2537 (1)0.7662 (1)0.0223 (9)
N30.5973 (2)0.5461 (1)0.9129 (1)0.0220 (9)
N40.5683 (2)0.41973 (9)0.3533 (1)0.0223 (9)
C10.5069 (3)0.2514 (1)0.6309 (1)0.016 (1)
C20.3425 (3)0.2349 (1)0.6668 (1)0.018 (1)
C30.2195 (3)0.2024 (1)0.6098 (2)0.020 (1)
C40.2586 (3)0.1880 (1)0.5139 (2)0.022 (1)
C50.4208 (3)0.2040 (1)0.4770 (1)0.020 (1)
C60.5455 (3)0.2349 (1)0.5354 (2)0.018 (1)
C70.7515 (3)0.4648 (1)0.8101 (1)0.018 (1)
C80.7571 (3)0.5207 (1)0.8719 (2)0.019 (1)
C90.9113 (3)0.5543 (1)0.8951 (2)0.025 (1)
C101.0635 (3)0.5324 (1)0.8561 (2)0.030 (1)
C111.0631 (3)0.4767 (1)0.7954 (2)0.028 (1)
C120.9106 (3)0.4431 (1)0.7724 (2)0.023 (1)
C130.4407 (3)0.4006 (1)0.5136 (2)0.017 (1)
C140.4195 (3)0.4045 (1)0.4126 (2)0.018 (1)
C150.2593 (3)0.3944 (1)0.3671 (2)0.026 (1)
C160.1151 (3)0.3814 (1)0.4217 (2)0.029 (1)
C170.1320 (3)0.3778 (1)0.5217 (2)0.027 (1)
C180.2921 (3)0.3873 (1)0.5671 (2)0.022 (1)
H30.10980.19000.63590.0267*
H40.17360.16710.47320.0289*
H50.44660.19370.41130.0268*
H60.65750.24470.51020.0236*
H90.91040.59210.93770.0331*
H101.16960.55520.87050.0421*
H111.16990.46120.76900.0401*
H120.91370.40480.73060.0302*
H150.24980.39650.29830.0340*
H160.00450.37500.39130.0389*
H170.03220.36870.55990.0362*
H180.30050.38460.63590.0283*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0167 (2)0.0188 (2)0.0185 (2)0.0015 (2)0.0045 (2)0.0007 (2)
S20.0147 (2)0.0239 (3)0.0185 (2)0.0020 (2)0.0013 (2)0.0044 (2)
S30.0159 (2)0.0199 (2)0.0180 (2)0.0027 (2)0.0013 (2)0.0002 (2)
O10.0159 (7)0.0239 (8)0.0306 (8)0.0008 (7)0.0033 (6)0.0014 (7)
O20.0278 (8)0.0264 (8)0.0183 (7)0.0038 (7)0.0073 (6)0.0027 (7)
O30.047 (1)0.0309 (9)0.0215 (8)0.0100 (8)0.0045 (8)0.0072 (7)
O40.0391 (9)0.0244 (8)0.0252 (8)0.0015 (8)0.0065 (7)0.0051 (7)
O50.0319 (9)0.0255 (8)0.0345 (9)0.0042 (7)0.0008 (7)0.0117 (8)
O60.0182 (7)0.0338 (9)0.0212 (7)0.0012 (7)0.0005 (6)0.0033 (7)
O70.0366 (9)0.044 (1)0.0174 (7)0.0080 (9)0.0003 (7)0.0038 (8)
O80.0223 (8)0.0288 (8)0.0267 (8)0.0049 (7)0.0011 (7)0.0049 (7)
N10.0209 (9)0.0185 (9)0.0156 (8)0.0006 (8)0.0018 (7)0.0002 (7)
N20.0206 (9)0.031 (1)0.0174 (9)0.0035 (9)0.0006 (7)0.0006 (8)
N30.0211 (9)0.027 (1)0.0189 (9)0.0028 (8)0.0044 (7)0.0007 (8)
N40.027 (1)0.0201 (9)0.0204 (9)0.0052 (8)0.0006 (8)0.0040 (8)
C10.018 (1)0.0127 (9)0.018 (1)0.0006 (8)0.0054 (8)0.0021 (8)
C20.023 (1)0.016 (1)0.0148 (9)0.0012 (9)0.0016 (8)0.0017 (9)
C30.020 (1)0.019 (1)0.023 (1)0.0029 (9)0.0028 (9)0.0029 (9)
C40.023 (1)0.021 (1)0.022 (1)0.0046 (9)0.0077 (9)0.0004 (9)
C50.028 (1)0.019 (1)0.0144 (9)0.001 (1)0.0017 (9)0.0013 (9)
C60.018 (1)0.015 (1)0.020 (1)0.0011 (9)0.0002 (9)0.0022 (9)
C70.015 (1)0.019 (1)0.018 (1)0.0029 (9)0.0040 (8)0.0019 (9)
C80.017 (1)0.020 (1)0.019 (1)0.0026 (9)0.0011 (8)0.0025 (9)
C90.024 (1)0.020 (1)0.033 (1)0.001 (1)0.006 (1)0.006 (1)
C100.019 (1)0.029 (1)0.049 (1)0.005 (1)0.006 (1)0.008 (1)
C110.015 (1)0.033 (1)0.045 (1)0.001 (1)0.002 (1)0.008 (1)
C120.020 (1)0.022 (1)0.027 (1)0.001 (1)0.0006 (9)0.007 (1)
C130.019 (1)0.014 (1)0.019 (1)0.0010 (9)0.0036 (8)0.0002 (9)
C140.020 (1)0.014 (1)0.021 (1)0.0028 (9)0.0013 (9)0.0013 (9)
C150.031 (1)0.025 (1)0.022 (1)0.002 (1)0.007 (1)0.003 (1)
C160.020 (1)0.033 (1)0.036 (1)0.001 (1)0.012 (1)0.004 (1)
C170.017 (1)0.033 (1)0.033 (1)0.002 (1)0.001 (1)0.005 (1)
C180.020 (1)0.025 (1)0.019 (1)0.003 (1)0.0005 (9)0.0018 (9)
Geometric parameters (Å, º) top
S1—O11.423 (2)C5—C61.384 (3)
S1—O21.424 (2)C5—H50.95
S1—N11.681 (2)C6—H60.95
S1—C11.758 (2)C7—C81.395 (3)
S2—N11.712 (2)C7—C121.399 (3)
S2—C71.777 (2)C8—C91.391 (3)
S3—N11.721 (2)C9—C101.361 (3)
S3—C131.781 (2)C9—H90.95
O3—N21.224 (2)C10—C111.382 (4)
O4—N21.220 (3)C10—H100.95
O5—N31.224 (2)C11—C121.378 (3)
O6—N31.239 (2)C11—H110.95
O7—N41.225 (2)C12—H120.95
O8—N41.241 (2)C13—C141.399 (3)
N2—C21.482 (3)C13—C181.389 (3)
N3—C81.445 (3)C14—C151.387 (3)
N4—C141.443 (3)C15—C161.369 (3)
C1—C21.397 (3)C15—H150.95
C1—C61.389 (3)C16—C171.382 (3)
C2—C31.380 (3)C16—H160.95
C3—C41.386 (3)C17—C181.384 (3)
C3—H30.95C17—H170.95
C4—C51.386 (3)C18—H180.95
C4—H40.95
O1—S1—O2120.26 (9)C5—C6—H6120.0
O1—S1—N1108.37 (9)S2—C7—C8120.9 (2)
O1—S1—C1107.6 (1)S2—C7—C12122.4 (2)
O2—S1—N1106.76 (9)C8—C7—C12116.6 (2)
O2—S1—C1109.7 (1)N3—C8—C7119.6 (2)
N1—S1—C1102.74 (9)N3—C8—C9117.8 (2)
N1—S2—C7100.85 (9)C7—C8—C9122.6 (2)
N1—S3—C13101.14 (9)C8—C9—C10119.2 (2)
S1—N1—S2120.8 (1)C8—C9—H9120.4
S1—N1—S3117.1 (1)C10—C9—H9120.4
S2—N1—S3121.6 (1)C9—C10—C11119.7 (2)
O3—N2—O4124.6 (2)C9—C10—H10120.1
O3—N2—C2117.7 (2)C11—C10—H10120.1
O4—N2—C2117.6 (2)C10—C11—C12121.3 (2)
O5—N3—O6124.0 (2)C10—C11—H11119.4
O5—N3—C8119.7 (2)C12—C11—H11119.4
O6—N3—C8116.3 (2)C7—C12—C11120.5 (2)
O7—N4—O8123.3 (2)C7—C12—H12119.7
O7—N4—C14119.6 (2)C11—C12—H12119.7
O8—N4—C14117.1 (2)S3—C13—C14121.2 (2)
S1—C1—C2122.8 (2)S3—C13—C18122.1 (2)
S1—C1—C6118.4 (2)C14—C13—C18116.7 (2)
C2—C1—C6118.8 (2)N4—C14—C13119.3 (2)
N2—C2—C1122.2 (2)N4—C14—C15118.5 (2)
N2—C2—C3116.3 (2)C13—C14—C15122.2 (2)
C1—C2—C3121.5 (2)C14—C15—C16119.7 (2)
C2—C3—C4118.9 (2)C14—C15—H15120.1
C2—C3—H3120.6C16—C15—H15120.1
C4—C3—H3120.6C15—C16—C17119.3 (2)
C3—C4—C5120.4 (2)C15—C16—H16120.4
C3—C4—H4119.8C17—C16—H16120.4
C5—C4—H4119.8C16—C17—C18121.0 (2)
C4—C5—C6120.4 (2)C16—C17—H17119.5
C4—C5—H5119.8C18—C17—H17119.5
C6—C5—H5119.8C13—C18—C17121.1 (2)
C1—C6—C5120.0 (2)C13—C18—H18119.5
C1—C6—H6120.0C17—C18—H18119.5
O1—S1—N1—S2128.9 (1)S1—C1—C2—C3178.6 (2)
O1—S1—N1—S342.9 (1)C6—C1—C2—N2177.0 (2)
O2—S1—N1—S21.9 (1)C6—C1—C2—C30.4 (3)
O2—S1—N1—S3173.8 (1)S1—C1—C6—C5176.8 (2)
C1—S1—N1—S2117.4 (1)C2—C1—C6—C51.5 (3)
C1—S1—N1—S370.8 (1)N2—C2—C3—C4175.3 (2)
O1—S1—C1—C2160.1 (2)C1—C2—C3—C42.3 (3)
O1—S1—C1—C621.7 (2)C2—C3—C4—C52.2 (3)
O2—S1—C1—C227.6 (2)C3—C4—C5—C60.4 (3)
O2—S1—C1—C6154.2 (2)C4—C5—C6—C11.5 (3)
N1—S1—C1—C285.6 (2)S2—C7—C8—N32.1 (3)
N1—S1—C1—C692.6 (2)S2—C7—C8—C9176.9 (2)
C7—S2—N1—S194.9 (1)C12—C7—C8—N3179.6 (2)
C7—S2—N1—S376.6 (1)C12—C7—C8—C90.6 (3)
N1—S2—C7—C8166.4 (2)S2—C7—C12—C11176.7 (2)
N1—S2—C7—C1210.9 (2)C8—C7—C12—C110.7 (3)
C13—S3—N1—S196.3 (1)N3—C8—C9—C10178.8 (2)
C13—S3—N1—S291.9 (1)C7—C8—C9—C100.3 (3)
N1—S3—C13—C14162.7 (2)C8—C9—C10—C110.9 (4)
N1—S3—C13—C1814.9 (2)C9—C10—C11—C120.8 (4)
O3—N2—C2—C1112.6 (2)C10—C11—C12—C70.1 (4)
O3—N2—C2—C369.8 (3)S3—C13—C14—N43.6 (3)
O4—N2—C2—C170.9 (3)S3—C13—C14—C15176.7 (2)
O4—N2—C2—C3106.6 (2)C18—C13—C14—N4178.6 (2)
O5—N3—C8—C7169.2 (2)C18—C13—C14—C151.0 (3)
O5—N3—C8—C99.8 (3)S3—C13—C18—C17177.3 (2)
O6—N3—C8—C710.4 (3)C14—C13—C18—C170.5 (3)
O6—N3—C8—C9170.6 (2)N4—C14—C15—C16178.5 (2)
O7—N4—C14—C13166.4 (2)C13—C14—C15—C161.2 (3)
O7—N4—C14—C1514.0 (3)C14—C15—C16—C170.7 (4)
O8—N4—C14—C1314.0 (3)C15—C16—C17—C180.1 (4)
O8—N4—C14—C15165.7 (2)C16—C17—C18—C130.0 (5)
S1—C1—C2—N21.2 (3)

Experimental details

Crystal data
Chemical formulaC18H12N4O8S3
Mr508.51
Crystal system, space groupMonoclinic, P21/n
Temperature (K)100
a, b, c (Å)7.670 (3), 19.766 (5), 13.759 (3)
β (°) 90.63 (3)
V3)2085.8 (11)
Z4
Radiation typeMo Kα
µ (mm1)0.41
Crystal size (mm)0.50 × 0.33 × 0.32
Data collection
DiffractometerEnraf-Nonius CAD-4 (with Oxford Cryostream)
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.835, 0.882
No. of measured, independent and
observed [I > 3σ(I)] reflections
5118, 4775, 3426
Rint0.018
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.040, 1.32
No. of reflections4775
No. of parameters298
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.62, 0.37

Computer programs: CAD-4 EXPRESS (Enraf-Nonius, 1994), SIR (Burla et al., 1989), LSFM in MolEN (Fair, 1990), CIFGEN in MolEN (Fair, 1990).

 

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