Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103000842/ga1005sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103000842/ga1005Isup2.hkl |
CCDC reference: 208037
Bromine (0.83 g, 0.26 ml, 5 mmol) was added dropwise into a stirred suspension of sodium 1,1-dioxo-3-methyl-2-thiolenyl-4-nitronate (0.5 g, 2.5 mmol) in dry ether (15 ml) at room temperature. The sodium 1,1-dioxo-3-methyl-2-thiolenyl-4-nitronate dissolved and colourless crystals were formed. After 1.5 h, the crystals of NaBr were filtered off and the mother liquor was concentrated by evaporation in a Petri dish. A colourless oil (0.63 g) was formed, which was crystallized from methanol. A colourless deposit formed and this was washed with methanol and dried. This preparation produced both the title compound, 2-bromo-3-methyl-4-nitro-2-thiolene 1,1-dioxide, (I), and 2,4-dibromo-3-methyl-4-nitro-2-thiolene 1,1-dioxide. Fractional recrystallization from chloroform yielded 0.25 g (39%) of (I) (m.p. 433–434 K Please clarify − 373 K given in data tables) and 0.24 g (29%) of 2,4-dibromo-3-methyl-4-nitro-2-thiolene 1,1-dioxide (m.p. 372–373 K). Elemental analysis of (I), found: C 23.49 and 23.44, H 2.53 and 2.51, N 5.49 and 5.51%; calculated for C5H6BrNO4S: C 23.40, H 2.34, N 5.47%. Please clarify the origin of two values `found' for each element. Two samples? If so, which was used here?
H atoms were treated as riding, with C—H distances in the range 0.96–0.98 Å. Is this added text OK?
Data collection: COLLECT (Nonius, 1998); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and ATOMS (Dowty, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
C5H6BrNO4S | F(000) = 504 |
Mr = 256.08 | Dx = 2.00 Mg m−3 |
Monoclinic, P121/c1 | Melting point: 373 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 5.0733 (10) Å | Cell parameters from 3563 reflections |
b = 18.465 (4) Å | θ = 1.0–27.5° |
c = 10.029 (2) Å | µ = 5.05 mm−1 |
β = 115.12 (3)° | T = 185 K |
V = 850.6 (3) Å3 | Rod, colourless |
Z = 4 | 0.31 × 0.24 × 0.11 mm |
Nonius KappaCCD area-detector diffractometer | 1603 reflections with I > 2σ(I) |
ϕ and ω scans to fill Ewald sphere | Rint = 0.040 |
Absorption correction: multi-scan (HKL2002; Otwinowski & Minor, 1997) | θmax = 27.4°, θmin = 2.5° |
Tmin = 0.287, Tmax = 0.574 | h = −6→6 |
7018 measured reflections | k = −23→23 |
1933 independent reflections | l = −12→12 |
Refinement on F2 | H-atom parameters constrained |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.029P)2 + 0.7325P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.031 | (Δ/σ)max < 0.001 |
wR(F2) = 0.073 | Δρmax = 0.34 e Å−3 |
S = 1.07 | Δρmin = −0.53 e Å−3 |
1933 reflections | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
111 parameters | Extinction coefficient: 0.0029 (9) |
0 restraints |
C5H6BrNO4S | V = 850.6 (3) Å3 |
Mr = 256.08 | Z = 4 |
Monoclinic, P121/c1 | Mo Kα radiation |
a = 5.0733 (10) Å | µ = 5.05 mm−1 |
b = 18.465 (4) Å | T = 185 K |
c = 10.029 (2) Å | 0.31 × 0.24 × 0.11 mm |
β = 115.12 (3)° |
Nonius KappaCCD area-detector diffractometer | 1933 independent reflections |
Absorption correction: multi-scan (HKL2002; Otwinowski & Minor, 1997) | 1603 reflections with I > 2σ(I) |
Tmin = 0.287, Tmax = 0.574 | Rint = 0.040 |
7018 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.073 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.34 e Å−3 |
1933 reflections | Δρmin = −0.53 e Å−3 |
111 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C6 | 0.6424 (7) | 0.46883 (16) | 0.2305 (3) | 0.0324 (6) | |
H6A | 0.5203 | 0.4893 | 0.1364 | 0.049* | |
H6B | 0.8338 | 0.4608 | 0.2362 | 0.049* | |
H6C | 0.6539 | 0.5016 | 0.3072 | 0.049* | |
N1 | 0.5786 (5) | 0.40307 (12) | 0.5059 (2) | 0.0251 (5) | |
O1 | −0.0546 (4) | 0.28618 (11) | 0.2237 (2) | 0.0307 (5) | |
O2 | 0.2377 (4) | 0.22114 (11) | 0.1208 (2) | 0.0295 (4) | |
O3 | 0.7786 (5) | 0.41582 (14) | 0.6254 (2) | 0.0459 (6) | |
O4 | 0.3272 (4) | 0.42156 (12) | 0.4695 (2) | 0.0358 (5) | |
C2 | 0.2965 (6) | 0.36225 (15) | 0.1475 (3) | 0.0232 (5) | |
C3 | 0.5172 (6) | 0.39874 (14) | 0.2488 (3) | 0.0215 (5) | |
C4 | 0.6506 (5) | 0.35992 (15) | 0.3963 (3) | 0.0219 (5) | |
H4 | 0.8623 | 0.3571 | 0.4308 | 0.026* | |
C5 | 0.5249 (6) | 0.28390 (14) | 0.3825 (3) | 0.0222 (5) | |
H5A | 0.4685 | 0.2745 | 0.462 | 0.027* | |
H5B | 0.6679 | 0.248 | 0.3866 | 0.027* | |
S1 | 0.21473 (13) | 0.28001 (4) | 0.20910 (6) | 0.02130 (17) | |
Br1 | 0.07361 (7) | 0.387274 (17) | −0.04923 (3) | 0.03772 (14) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C6 | 0.0387 (16) | 0.0305 (15) | 0.0264 (14) | −0.0061 (12) | 0.0123 (13) | 0.0006 (12) |
N1 | 0.0302 (13) | 0.0261 (12) | 0.0163 (11) | −0.0013 (9) | 0.0073 (10) | 0.0003 (9) |
O1 | 0.0237 (10) | 0.0391 (12) | 0.0313 (11) | −0.0022 (8) | 0.0136 (9) | 0.0002 (9) |
O2 | 0.0348 (11) | 0.0294 (10) | 0.0250 (10) | −0.0061 (8) | 0.0134 (9) | −0.0084 (8) |
O3 | 0.0472 (14) | 0.0566 (15) | 0.0197 (11) | 0.0039 (11) | 0.0006 (10) | −0.0108 (10) |
O4 | 0.0310 (11) | 0.0434 (13) | 0.0356 (11) | 0.0009 (9) | 0.0166 (10) | −0.0090 (10) |
C2 | 0.0249 (13) | 0.0273 (13) | 0.0154 (12) | 0.0004 (11) | 0.0068 (11) | 0.0017 (10) |
C3 | 0.0221 (12) | 0.0259 (14) | 0.0181 (12) | 0.0022 (10) | 0.0100 (11) | 0.0012 (10) |
C4 | 0.0193 (12) | 0.0285 (13) | 0.0155 (12) | −0.0004 (10) | 0.0050 (10) | −0.0010 (10) |
C5 | 0.0230 (13) | 0.0259 (13) | 0.0152 (12) | 0.0027 (10) | 0.0055 (10) | 0.0023 (10) |
S1 | 0.0213 (3) | 0.0248 (3) | 0.0168 (3) | −0.0020 (2) | 0.0072 (3) | −0.0012 (2) |
Br1 | 0.0440 (2) | 0.0395 (2) | 0.01639 (17) | −0.00632 (13) | −0.00001 (13) | 0.00559 (11) |
S1—C2 | 1.754 (3) | N1—O3 | 1.220 (3) |
C2—C3 | 1.332 (4) | O1—S1 | 1.439 (2) |
C3—C4 | 1.520 (4) | O2—S1 | 1.438 (2) |
C4—C5 | 1.524 (4) | C6—H6A | 0.96 |
C5—S1 | 1.784 (3) | C6—H6B | 0.96 |
C6—C3 | 1.487 (4) | C6—H6C | 0.96 |
C2—Br1 | 1.868 (3) | C4—H4 | 0.98 |
N1—C4 | 1.522 (3) | C5—H5A | 0.97 |
N1—O4 | 1.217 (3) | C5—H5B | 0.97 |
S1—C2—C3 | 114.65 (19) | N1—C4—C5 | 109.2 (2) |
S1—C2—Br1 | 117.29 (14) | C3—C4—H4 | 109.7 |
C2—C3—C4 | 112.8 (2) | N1—C4—H4 | 109.7 |
C2—C3—C6 | 127.7 (2) | C5—C4—H4 | 109.7 |
C3—C6—H6A | 109.5 | C4—C5—S1 | 106.72 (17) |
C3—C6—H6B | 109.5 | C4—C5—H5A | 110.4 |
H6A—C6—H6B | 109.5 | S1—C5—H5A | 110.4 |
C3—C6—H6C | 109.5 | C4—C5—H5B | 110.4 |
H6A—C6—H6C | 109.5 | S1—C5—H5B | 110.4 |
H6B—C6—H6C | 109.5 | H5A—C5—H5B | 108.6 |
O4—N1—O3 | 124.7 (2) | O2—S1—O1 | 116.83 (12) |
O4—N1—C4 | 118.2 (2) | O2—S1—C2 | 110.15 (12) |
O3—N1—C4 | 117.1 (2) | O1—S1—C2 | 110.11 (12) |
C3—C2—Br1 | 128.1 (2) | O2—S1—C5 | 111.24 (12) |
C6—C3—C4 | 119.6 (2) | O1—S1—C5 | 112.35 (12) |
C3—C4—N1 | 108.2 (2) | C2—S1—C5 | 93.78 (12) |
C3—C4—C5 | 110.5 (2) | ||
S1—C2—C3—C6 | 178.7 (2) | C3—C4—C5—S1 | −12.9 (3) |
Br1—C2—C3—C6 | −0.1 (4) | N1—C4—C5—S1 | 105.9 (2) |
S1—C2—C3—C4 | 0.4 (3) | C3—C2—S1—O2 | −121.6 (2) |
Br1—C2—C3—C4 | −178.38 (19) | Br1—C2—S1—O2 | 57.32 (18) |
C2—C3—C4—N1 | −110.9 (3) | C3—C2—S1—O1 | 108.2 (2) |
C6—C3—C4—N1 | 70.6 (3) | Br1—C2—S1—O1 | −72.94 (17) |
C2—C3—C4—C5 | 8.5 (3) | C3—C2—S1—C5 | −7.3 (2) |
C6—C3—C4—C5 | −170.0 (2) | Br1—C2—S1—C5 | 171.59 (16) |
O4—N1—C4—C3 | 49.1 (3) | C4—C5—S1—O2 | 124.68 (18) |
O3—N1—C4—C3 | −131.8 (3) | C4—C5—S1—O1 | −102.21 (19) |
O4—N1—C4—C5 | −71.2 (3) | C4—C5—S1—C2 | 11.35 (19) |
O3—N1—C4—C5 | 108.0 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5A···O2i | 0.97 | 2.34 | 3.286 (3) | 163 |
C4—H4···O2ii | 0.98 | 2.5 | 3.238 (3) | 132 |
C4—H4···O4iii | 0.98 | 2.52 | 3.388 (3) | 147 |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x+1, −y+1/2, z+1/2; (iii) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C5H6BrNO4S |
Mr | 256.08 |
Crystal system, space group | Monoclinic, P121/c1 |
Temperature (K) | 185 |
a, b, c (Å) | 5.0733 (10), 18.465 (4), 10.029 (2) |
β (°) | 115.12 (3) |
V (Å3) | 850.6 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 5.05 |
Crystal size (mm) | 0.31 × 0.24 × 0.11 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (HKL2002; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.287, 0.574 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7018, 1933, 1603 |
Rint | 0.040 |
(sin θ/λ)max (Å−1) | 0.648 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.073, 1.07 |
No. of reflections | 1933 |
No. of parameters | 111 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.34, −0.53 |
Computer programs: COLLECT (Nonius, 1998), HKL SCALEPACK (Otwinowski & Minor, 1997), HKL DENZO (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and ATOMS (Dowty, 1997), WinGX (Farrugia, 1999).
S1—C2 | 1.754 (3) | C5—S1 | 1.784 (3) |
C2—C3 | 1.332 (4) | C6—C3 | 1.487 (4) |
C3—C4 | 1.520 (4) | C2—Br1 | 1.868 (3) |
C4—C5 | 1.524 (4) | N1—C4 | 1.522 (3) |
S1—C2—C3 | 114.65 (19) | C2—C3—C4 | 112.8 (2) |
S1—C2—Br1 | 117.29 (14) | C2—C3—C6 | 127.7 (2) |
Br1—C2—C3—C6 | −0.1 (4) | S1—C2—C3—C4 | 0.4 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5A···O2i | 0.97 | 2.34 | 3.286 (3) | 163 |
C4—H4···O2ii | 0.98 | 2.5 | 3.238 (3) | 132 |
C4—H4···O4iii | 0.98 | 2.52 | 3.388 (3) | 147 |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x+1, −y+1/2, z+1/2; (iii) x+1, y, z. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- Purchase subscription
- Reduced-price subscriptions
- If you have already subscribed, you may need to register
Thiolene 1,1-dioxides are an easily accessible class of heterocyclic compounds and among their derivatives are compounds with useful properties. Nitro-containing thiolene 1,1-dioxides have proved to be models for studying theoretical problems such as allyl-vinyl isomerization and oxime-nitronic tautomerism (Perekalin et al., 1994). The introduction of a halogen atom into the ring of nitrothiolene 1,1-dioxide leads to the appearance of specific properties. Bromo derivatives of 3-methyl-4-nitro-thiolene 1,1-dioxide have been shown to undergo halo- and prototropic rearrangements under mild conditions (Efremova et al., 2002). The title compound, 2-bromo-3-methyl-4-nitro-2-thiolene 1,1-dioxide, (I), is the major product formed during these transformations. \sch
One molecule of (I) is contained in the asymmetric unit, with all atomic positions located on general positions. The structure of (I) is very similar to that of the structural isomer, 4-bromo-3-methyl-4-nitro-2-thiolene 1,1-dioxide, (II) (Efremova et al., 2003). The bond lengths and angles for both isomers are comparable (Table 1). The five-membered heterocyclic ring in both compounds has an envelope conformation, with atoms S1, C2, C3 and C4 in the same plane, as expected, due to the sp2 hybridization of atoms C2 and C3. Atom C5 is out of this plane by 0.218 (6) Å, pointing away from the nitro group on C4 towards the less sterically hindered side of the molecule (Fig. 1). In the isomer, (II), with both the bromine and the nitro group on C4, atom C5 points above the plane towards the nitro group.
The packing of the molecules in (I) is mainly dependent on three weak hydrogen bonds, C5—H5A··· O2, C4—H4···O2 and C4—H4···O4 (Table 2), consistent with previous observations (Desiraju & Steiner, 1999). These hydrogen bonds are the result of the electron-withdrawing nature of the sulfonyl and nitro groups. The Mulliken population analysis (Mulliken, 1955) for a molecule of (I) from Hartree-Fock calculations using a 3–21 G(*) basis set (Wavefunction, 2000) confirmed that the O atoms of these two groups carry significant negative atomic charges. The average atomic charge on the O atoms in the sulfonyl group is −0.56 (1) e, and the average atomic charge on the O atoms in the nitro group is −0.374 (4) e. Atoms H4 and H5A are in close proximity to the –SO2 and –NO2 groups, which makes them the most positively charged H atoms in the compound. The Mulliken population analysis verified this, with atomic charges of 0.321 (3) and 0.325 (2) e for atoms H4 and H5A, respectively. For comparison, the H atoms in the C6 methyl group have an average atomic charge of 0.255 (11) e, and atom H5B has an atomic charge of 0.304 (2) e.
These hydrogen-bonding interactions result in a layered network of molecules of (I) perpendicular to the b axis (Fig. 2). Also within these sheets, there is a short intermolecular interaction of 3.002 (3) Å between atom Br1 and atom O3 on the nitro group. The Mulliken population analysis showed that the Br atom has a very small positive atomic charge [0.080 (1) e], consistent with an unexpected weak attractive interaction with O3.