Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802016938/lh6001sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802016938/lh6001Isup2.hkl |
CCDC reference: 198971
Crystals of the title compound were separated from a partially evaporated ethanol solution containing an equimolar amount of 3-aminobenzoic acid.
All thiazole H atoms were included in the refinement, at calculated positions, as riding models, with C—H set to 0.95 Å and N—H set to 0.88 Å. H1W was initially located on difference syntheses, while H2W was generated at the most probable position based on the position of H1W and the position of adjacent symmetry-generated water molecules. Both H1W and H2W were restrained to an O—H distance of 0.83 Å and an H···H distance of 1.35 Å, while displacement parameters were refined as riding models.
Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON97 (Spek, 1997); software used to prepare material for publication: SHELXL97.
C7H5N3O2S·H2O | F(000) = 440 |
Mr = 213.22 | Dx = 1.621 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5386 reflections |
a = 3.8930 (2) Å | θ = 2.9–32.0° |
b = 10.8743 (5) Å | µ = 0.35 mm−1 |
c = 20.6378 (8) Å | T = 150 K |
β = 91.335 (4)° | Block, yellow |
V = 873.44 (7) Å3 | 0.20 × 0.15 × 0.10 mm |
Z = 4 |
Bruker–Nonius KappaCCD area-detector diffractometer | 1504 independent reflections |
Radiation source: Bruker–Nonius FR591 rotating anode | 1247 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
Detector resolution: 9.091 pixels mm-1 | θmax = 25.0°, θmin = 3.5° |
ϕ and ω scans | h = −4→4 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | k = −12→12 |
Tmin = 0.933, Tmax = 0.970 | l = −20→24 |
5105 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.105 | H-atom parameters constrained |
S = 1.14 | w = 1/[σ2(Fo2) + (0.0469P)2 + 0.3321P] where P = (Fo2 + 2Fc2)/3 |
1504 reflections | (Δ/σ)max < 0.001 |
133 parameters | Δρmax = 0.32 e Å−3 |
2 restraints | Δρmin = −0.25 e Å−3 |
C7H5N3O2S·H2O | V = 873.44 (7) Å3 |
Mr = 213.22 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 3.8930 (2) Å | µ = 0.35 mm−1 |
b = 10.8743 (5) Å | T = 150 K |
c = 20.6378 (8) Å | 0.20 × 0.15 × 0.10 mm |
β = 91.335 (4)° |
Bruker–Nonius KappaCCD area-detector diffractometer | 1504 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 1247 reflections with I > 2σ(I) |
Tmin = 0.933, Tmax = 0.970 | Rint = 0.037 |
5105 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 2 restraints |
wR(F2) = 0.105 | H-atom parameters constrained |
S = 1.14 | Δρmax = 0.32 e Å−3 |
1504 reflections | Δρmin = −0.25 e Å−3 |
133 parameters |
x | y | z | Uiso*/Ueq | ||
S1 | −0.04243 (15) | 0.76601 (5) | 0.09002 (3) | 0.0302 (2) | |
C2 | −0.2356 (5) | 0.64834 (19) | 0.04280 (10) | 0.0278 (5) | |
N21 | −0.3748 (5) | 0.67345 (17) | −0.01460 (9) | 0.0339 (5) | |
H21 | −0.4729 | 0.6146 | −0.0377 | 0.042* | |
H22 | −0.3695 | 0.7490 | −0.0298 | 0.042* | |
N3 | −0.2317 (5) | 0.53787 (16) | 0.06927 (9) | 0.0284 (5) | |
C4 | −0.0054 (6) | 0.4381 (2) | 0.16807 (11) | 0.0302 (5) | |
H4 | −0.0853 | 0.3591 | 0.1550 | 0.038* | |
C5 | 0.1677 (6) | 0.4525 (2) | 0.22604 (11) | 0.0301 (5) | |
H5 | 0.2085 | 0.3833 | 0.2533 | 0.038* | |
C6 | 0.2843 (6) | 0.56838 (19) | 0.24521 (10) | 0.0273 (5) | |
N61 | 0.4724 (5) | 0.58028 (17) | 0.30589 (9) | 0.0322 (5) | |
O61 | 0.5502 (5) | 0.48605 (15) | 0.33659 (8) | 0.0417 (5) | |
O62 | 0.5517 (5) | 0.68351 (15) | 0.32564 (8) | 0.0439 (5) | |
C7 | 0.2336 (5) | 0.67269 (19) | 0.20707 (10) | 0.0274 (5) | |
H7 | 0.3154 | 0.7511 | 0.2206 | 0.034* | |
C8 | 0.0599 (5) | 0.65679 (19) | 0.14898 (10) | 0.0260 (5) | |
C9 | −0.0638 (6) | 0.5403 (2) | 0.12820 (11) | 0.0262 (5) | |
O1W | 0.2649 (10) | 0.0608 (2) | 0.03261 (11) | 0.1058 (12) | |
H1W | 0.306 | 0.040 | 0.0709 | 0.132* | |
H2W | 0.221 | 0.009 | 0.0053 | 0.132* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0355 (4) | 0.0179 (3) | 0.0371 (4) | −0.0024 (2) | −0.0021 (3) | −0.0003 (2) |
C2 | 0.0273 (12) | 0.0211 (12) | 0.0353 (13) | 0.0017 (9) | 0.0043 (9) | −0.0047 (9) |
N21 | 0.0433 (12) | 0.0199 (10) | 0.0382 (12) | −0.0002 (9) | −0.0036 (9) | −0.0029 (8) |
N3 | 0.0273 (11) | 0.0206 (10) | 0.0376 (11) | −0.0008 (8) | 0.0048 (8) | −0.0028 (8) |
C4 | 0.0299 (13) | 0.0168 (11) | 0.0441 (14) | −0.0021 (9) | 0.0060 (10) | −0.0015 (9) |
C5 | 0.0318 (13) | 0.0173 (11) | 0.0413 (14) | 0.0018 (9) | 0.0055 (10) | 0.0030 (9) |
C6 | 0.0235 (12) | 0.0248 (12) | 0.0340 (13) | 0.0019 (9) | 0.0057 (9) | −0.0003 (9) |
N61 | 0.0316 (11) | 0.0247 (11) | 0.0404 (12) | 0.0015 (9) | 0.0029 (8) | 0.0002 (8) |
O61 | 0.0582 (12) | 0.0261 (9) | 0.0406 (10) | 0.0036 (8) | −0.0046 (8) | 0.0067 (7) |
O62 | 0.0571 (12) | 0.0253 (9) | 0.0487 (11) | −0.0038 (8) | −0.0135 (8) | −0.0025 (8) |
C7 | 0.0252 (12) | 0.0181 (11) | 0.0388 (13) | −0.0010 (9) | 0.0040 (9) | −0.0025 (9) |
C8 | 0.0241 (12) | 0.0169 (11) | 0.0371 (13) | 0.0008 (9) | 0.0056 (9) | 0.0011 (9) |
C9 | 0.0217 (11) | 0.0218 (11) | 0.0351 (13) | 0.0001 (9) | 0.0046 (9) | −0.0031 (9) |
O1W | 0.223 (4) | 0.0400 (14) | 0.0523 (15) | −0.0334 (17) | −0.0421 (19) | 0.0132 (10) |
S1—C8 | 1.740 (2) | C5—H5 | 0.95 |
S1—C2 | 1.766 (2) | C6—C7 | 1.392 (3) |
C2—N3 | 1.320 (3) | C6—N61 | 1.442 (3) |
C2—N21 | 1.320 (3) | N61—O62 | 1.231 (2) |
N21—H21 | 0.88 | N61—O61 | 1.239 (2) |
N21—H22 | 0.88 | C7—C8 | 1.373 (3) |
N3—C9 | 1.367 (3) | C7—H7 | 0.95 |
C4—C5 | 1.368 (3) | C8—C9 | 1.418 (3) |
C4—C9 | 1.399 (3) | O1W—H1W | 0.84 |
C4—H4 | 0.95 | O1W—H2W | 0.81 |
C5—C6 | 1.394 (3) | ||
C8—S1—C2 | 88.80 (10) | C7—C6—N61 | 118.72 (19) |
N3—C2—N21 | 124.1 (2) | C5—C6—N61 | 118.90 (19) |
N3—C2—S1 | 115.50 (17) | O62—N61—O61 | 121.9 (2) |
N21—C2—S1 | 120.40 (16) | O62—N61—C6 | 119.20 (18) |
C2—N21—H21 | 120.0 | O61—N61—C6 | 118.91 (18) |
C2—N21—H22 | 120.0 | C8—C7—C6 | 116.8 (2) |
H21—N21—H22 | 120.0 | C8—C7—H7 | 121.6 |
C2—N3—C9 | 110.56 (18) | C6—C7—H7 | 121.6 |
C5—C4—C9 | 119.6 (2) | C7—C8—C9 | 122.23 (19) |
C5—C4—H4 | 120.2 | C7—C8—S1 | 128.65 (17) |
C9—C4—H4 | 120.2 | C9—C8—S1 | 109.12 (16) |
C4—C5—C6 | 120.2 (2) | N3—C9—C4 | 125.2 (2) |
C4—C5—H5 | 119.9 | N3—C9—C8 | 115.99 (19) |
C6—C5—H5 | 119.9 | C4—C9—C8 | 118.9 (2) |
C7—C6—C5 | 122.4 (2) | H1W—O1W—H2W | 120 |
C8—S1—C2—N3 | 1.44 (17) | C6—C7—C8—C9 | 0.0 (3) |
C8—S1—C2—N21 | −179.22 (19) | C6—C7—C8—S1 | −179.32 (16) |
N21—C2—N3—C9 | 178.79 (19) | C2—S1—C8—C7 | 178.9 (2) |
S1—C2—N3—C9 | −1.9 (2) | C2—S1—C8—C9 | −0.53 (15) |
C9—C4—C5—C6 | 0.1 (3) | C2—N3—C9—C4 | −178.1 (2) |
C4—C5—C6—C7 | −0.4 (3) | C2—N3—C9—C8 | 1.5 (3) |
C4—C5—C6—N61 | −178.67 (19) | C5—C4—C9—N3 | 179.75 (19) |
C7—C6—N61—O62 | 7.6 (3) | C5—C4—C9—C8 | 0.2 (3) |
C5—C6—N61—O62 | −174.1 (2) | C7—C8—C9—N3 | −179.88 (19) |
C7—C6—N61—O61 | −172.27 (19) | S1—C8—C9—N3 | −0.4 (2) |
C5—C6—N61—O61 | 6.0 (3) | C7—C8—C9—C4 | −0.3 (3) |
C5—C6—C7—C8 | 0.3 (3) | S1—C8—C9—C4 | 179.16 (16) |
N61—C6—C7—C8 | 178.58 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
N21—H21···N3i | 0.88 | 2.11 | 2.970 (3) | 165 |
N21—H22···O1Wii | 0.88 | 2.11 | 2.946 (3) | 159 |
O1W—H1W···O61iii | 0.84 | 2.06 | 2.894 (3) | 175 |
O1W—H2W···O1Wiv | 0.81 | 2.17 | 2.772 (6) | 132 |
O1W—H2W···O1Wv | 0.81 | 2.30 | 2.651 (8) | 107 |
Symmetry codes: (i) −x−1, −y+1, −z; (ii) −x, −y+1, −z; (iii) −x+1, y−1/2, −z+1/2; (iv) −x, −y, −z; (v) −x+1, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | C7H5N3O2S·H2O |
Mr | 213.22 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 150 |
a, b, c (Å) | 3.8930 (2), 10.8743 (5), 20.6378 (8) |
β (°) | 91.335 (4) |
V (Å3) | 873.44 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.35 |
Crystal size (mm) | 0.20 × 0.15 × 0.10 |
Data collection | |
Diffractometer | Bruker–Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.933, 0.970 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5105, 1504, 1247 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.105, 1.14 |
No. of reflections | 1504 |
No. of parameters | 133 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.32, −0.25 |
Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), DENZO and COLLECT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON97 (Spek, 1997), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
N21—H21···N3i | 0.88 | 2.11 | 2.970 (3) | 165 |
N21—H22···O1Wii | 0.88 | 2.11 | 2.946 (3) | 159 |
O1W—H1W···O61iii | 0.84 | 2.06 | 2.894 (3) | 175 |
O1W—H2W···O1Wiv | 0.81 | 2.17 | 2.772 (6) | 132 |
O1W—H2W···O1Wv | 0.81 | 2.30 | 2.651 (8) | 107 |
Symmetry codes: (i) −x−1, −y+1, −z; (ii) −x, −y+1, −z; (iii) −x+1, y−1/2, −z+1/2; (iv) −x, −y, −z; (v) −x+1, −y, −z. |
A multitude of crystal structures of 2-aminobenzo-1,3-thiazole, and its derivatives, have been determined and provide an interesting subset of compounds in the 2-amino-1,3-thiazole range. Of the structures reported, most are pure organics that have fragments attached to the amino N atom. The structure of 2-aminobenzo-1,3-thiazole itself is unknown, but of the ring-substituted compounds, the structures of the 6-fluoro (Jai-nhuknan et al., 1997), and both 4-nitro (Lokaj et al., 1996) and 6-nitro (Glidewell et al., 2001) analogues have been determined. In these three cases, the recorded hydrogen-bonding patterns are noteworthy, as well as the bond distances in the two nitro derivatives. In 2-amino-4-nitrobenzo-1,3-thiazole, the C2—N21 and C2—N3 distances are equal to within 2σ [1.315 (2) and 1.312 (2) Å, respectively], a feature indicating complete π-electron delocalization. The bond distances in 2-amino-6-nitrobenzo-1,3-thiazole are less equal [1.331 (3) and 1.321 (3) Å], whereas for 2-amino-6-fluorobenzo-1,3-thiazole [1.358 (2) and 1.295 (2) Å] the bond distances are more acentric than the average values [1.336 (17) and 1.313 (11) Å; Allen et al., 1987]. The hydrogen-bonding patterns in all three structures includes a dimer formation about the N21—H···N3 association and for both nitro analogues at least one nitro O atom is also involved in the hydrogen-bonding array. In this paper, the single-crystal structure of 2-amino-6-nitrobenzo-1,3-thiazole hydrate, (I), is reported as an addition to the non-hydrate structure. The hydrate structure was obtained from attempts to produce adducts of 2-amino-6-nitrobenzo-1,3-thiazole with aromatic carboxylic acids, as done for 2-aminobenzo-1,3-thiazole (Lynch et al., 1998, 1999).
The structure of (I) (Fig. 1) comprises the thiazole molecule associated in an extensive hydrogen-bonded network with the water molecule. Hydrogen-bonding geometries are listed in Table 2. The bond lengths across the N21—C2—N3 site show a similar pattern as in the 4-nitro analogue, with both bond lengths being equal [1.320 (3) Å]. The formation of dimers via the N21—H···N3 association is expected for these types of compounds, but the location of the water molecule so near to a symmetry element provides an interesting hydrogen-bonding network (Fig. 2). The water network extends parallel to the a axis, while the thiazoles are inclined to the (100) plane. The water O atom is bound by the second amino H atom, while H1W associates to a nitroO atom. The suggested position of H2W allows for a three-centre association, linking two symmetry-generated water molecules.