Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101012574/gg1076sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101012574/gg1076Isup2.hkl |
CCDC reference: 174843
A sample of (I) was obtained from Aldrich. Crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation of a solution in ethanol.
Compound (I) crystallized in the monoclinic system; space group P21/n was assumed from the systematic absences. H atoms were treated as riding atoms with a C—H distance of 0.95 Å and an N—H distance of 0.88 Å.
Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2001); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PRPKAPPA (Ferguson, 1999).
C7H5N3O2S | F(000) = 400 |
Mr = 195.20 | Dx = 1.649 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 3.7715 (2) Å | Cell parameters from 1785 reflections |
b = 15.6399 (8) Å | θ = 3.0–27.5° |
c = 13.3484 (9) Å | µ = 0.38 mm−1 |
β = 93.252 (2)° | T = 150 K |
V = 786.10 (8) Å3 | Needle, yellow |
Z = 4 | 0.48 × 0.10 × 0.02 mm |
Nonius KappaCCD diffractometer | 1785 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 1252 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.061 |
ϕ scans, and ω scans with κ offsets | θmax = 27.5°, θmin = 3.0° |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | h = −4→4 |
Tmin = 0.837, Tmax = 0.990 | k = −20→20 |
8740 measured reflections | l = −17→17 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.108 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0528P)2] where P = (Fo2 + 2Fc2)/3 |
1785 reflections | (Δ/σ)max < 0.001 |
118 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.38 e Å−3 |
C7H5N3O2S | V = 786.10 (8) Å3 |
Mr = 195.20 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 3.7715 (2) Å | µ = 0.38 mm−1 |
b = 15.6399 (8) Å | T = 150 K |
c = 13.3484 (9) Å | 0.48 × 0.10 × 0.02 mm |
β = 93.252 (2)° |
Nonius KappaCCD diffractometer | 1785 independent reflections |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | 1252 reflections with I > 2σ(I) |
Tmin = 0.837, Tmax = 0.990 | Rint = 0.061 |
8740 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.108 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.32 e Å−3 |
1785 reflections | Δρmin = −0.38 e Å−3 |
118 parameters |
Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm [Fox, G·C. & Holmes, K·C. (1966). Acta Cryst. 20, 886–891] which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the 'size' command in the SHELXL97 input file. |
Geometry. Mean-plane data from the final SHELXL97 refinement run:- |
x | y | z | Uiso*/Ueq | ||
S1 | 0.13369 (14) | 0.59656 (4) | 0.73695 (4) | 0.0212 (2) | |
C2 | 0.2747 (5) | 0.55738 (15) | 0.62235 (16) | 0.0194 (5) | |
N2 | 0.4038 (4) | 0.60932 (12) | 0.55432 (13) | 0.0222 (4) | |
N3 | 0.2508 (5) | 0.47380 (11) | 0.60927 (13) | 0.0191 (4) | |
C4 | 0.1075 (5) | 0.43604 (14) | 0.69082 (15) | 0.0168 (5) | |
C5 | 0.0369 (5) | 0.34875 (14) | 0.69966 (16) | 0.0200 (5) | |
C6 | −0.1067 (5) | 0.31891 (14) | 0.78566 (16) | 0.0204 (5) | |
C7 | −0.1796 (5) | 0.37582 (15) | 0.86222 (15) | 0.0181 (5) | |
N7 | −0.3315 (5) | 0.34311 (13) | 0.95236 (13) | 0.0238 (5) | |
O71 | −0.3864 (4) | 0.26500 (11) | 0.95848 (12) | 0.0351 (5) | |
O72 | −0.4024 (4) | 0.39324 (11) | 1.01911 (12) | 0.0324 (4) | |
C8 | −0.1189 (5) | 0.46298 (14) | 0.85607 (15) | 0.0173 (5) | |
C9 | 0.0242 (5) | 0.49212 (14) | 0.76966 (16) | 0.0173 (5) | |
H21 | 0.4774 | 0.5883 | 0.4980 | 0.027* | |
H22 | 0.4155 | 0.6647 | 0.5657 | 0.027* | |
H5 | 0.0872 | 0.3105 | 0.6471 | 0.024* | |
H6 | −0.1558 | 0.2597 | 0.7928 | 0.025* | |
H8 | −0.1731 | 0.5008 | 0.9088 | 0.021* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0260 (3) | 0.0155 (3) | 0.0226 (3) | 0.0001 (2) | 0.0053 (2) | −0.0009 (2) |
C2 | 0.0147 (11) | 0.0208 (14) | 0.0224 (12) | 0.0009 (9) | −0.0011 (9) | 0.0011 (10) |
N2 | 0.0311 (11) | 0.0167 (11) | 0.0196 (10) | −0.0021 (8) | 0.0084 (8) | −0.0023 (8) |
N3 | 0.0205 (10) | 0.0184 (11) | 0.0187 (10) | 0.0008 (7) | 0.0027 (7) | −0.0005 (8) |
C4 | 0.0145 (11) | 0.0167 (13) | 0.0193 (12) | 0.0007 (8) | 0.0005 (8) | −0.0005 (9) |
C5 | 0.0216 (12) | 0.0175 (13) | 0.0208 (12) | 0.0019 (9) | 0.0009 (9) | −0.0025 (9) |
C6 | 0.0213 (13) | 0.0155 (13) | 0.0246 (13) | 0.0020 (9) | 0.0015 (9) | 0.0009 (10) |
C7 | 0.0154 (11) | 0.0198 (13) | 0.0194 (11) | 0.0009 (9) | 0.0028 (8) | 0.0021 (9) |
N7 | 0.0236 (11) | 0.0231 (12) | 0.0249 (11) | 0.0010 (8) | 0.0033 (8) | 0.0028 (9) |
O71 | 0.0518 (11) | 0.0170 (10) | 0.0382 (11) | −0.0036 (8) | 0.0164 (8) | 0.0056 (8) |
O72 | 0.0478 (11) | 0.0251 (10) | 0.0256 (9) | 0.0002 (8) | 0.0136 (8) | −0.0038 (8) |
C8 | 0.0169 (11) | 0.0192 (13) | 0.0159 (11) | 0.0023 (9) | 0.0011 (8) | −0.0021 (9) |
C9 | 0.0155 (11) | 0.0142 (12) | 0.0218 (12) | 0.0008 (8) | −0.0016 (9) | −0.0008 (9) |
S1—C2 | 1.758 (2) | C2—N2 | 1.331 (3) |
C2—N3 | 1.321 (3) | C7—N7 | 1.455 (3) |
N3—C4 | 1.376 (3) | N7—O71 | 1.243 (2) |
C4—C5 | 1.397 (3) | N7—O72 | 1.228 (2) |
C5—C6 | 1.378 (3) | N2—H21 | 0.8800 |
C6—C7 | 1.394 (3) | N2—H22 | 0.8800 |
C7—C8 | 1.386 (3) | C5—H5 | 0.9500 |
C8—C9 | 1.378 (3) | C6—H6 | 0.9500 |
C9—S1 | 1.746 (2) | C8—H8 | 0.9500 |
C4—C9 | 1.419 (3) | ||
C9—S1—C2 | 88.80 (10) | C5—C6—H6 | 120.1 |
N3—C2—N2 | 122.58 (19) | C7—C6—H6 | 120.1 |
N3—C2—S1 | 115.99 (16) | C8—C7—C6 | 123.0 (2) |
N2—C2—S1 | 121.42 (17) | C8—C7—N7 | 117.99 (19) |
C2—N2—H21 | 120.0 | C6—C7—N7 | 119.0 (2) |
C2—N2—H22 | 120.0 | O72—N7—O71 | 122.43 (18) |
H21—N2—H22 | 120.0 | O72—N7—C7 | 119.21 (19) |
C2—N3—C4 | 110.30 (18) | O71—N7—C7 | 118.36 (19) |
N3—C4—C5 | 124.86 (19) | C9—C8—C7 | 116.7 (2) |
N3—C4—C9 | 115.8 (2) | C9—C8—H8 | 121.7 |
C5—C4—C9 | 119.34 (19) | C7—C8—H8 | 121.7 |
C6—C5—C4 | 119.1 (2) | C8—C9—C4 | 122.0 (2) |
C6—C5—H5 | 120.4 | C8—C9—S1 | 128.90 (17) |
C4—C5—H5 | 120.4 | C4—C9—S1 | 109.10 (16) |
C5—C6—C7 | 119.8 (2) | ||
C6—C7—N7—O71 | 1.0 (3) | C8—C7—N7—O71 | −179.93 (17) |
C6—C7—N7—O72 | −178.61 (18) | C8—C7—N7—O72 | 0.4 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H21···N3i | 0.88 | 2.05 | 2.912 (2) | 165 |
N2—H22···O71ii | 0.88 | 2.54 | 3.119 (2) | 124 |
N2—H22···O71iii | 0.88 | 2.41 | 3.051 (2) | 130 |
C8—H8···O72iv | 0.95 | 2.53 | 3.381 (3) | 149 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x−1/2, y+1/2, −z+3/2; (iii) −x+1/2, y+1/2, −z+3/2; (iv) −x−1, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C7H5N3O2S |
Mr | 195.20 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 150 |
a, b, c (Å) | 3.7715 (2), 15.6399 (8), 13.3484 (9) |
β (°) | 93.252 (2) |
V (Å3) | 786.10 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.38 |
Crystal size (mm) | 0.48 × 0.10 × 0.02 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.837, 0.990 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8740, 1785, 1252 |
Rint | 0.061 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.108, 1.01 |
No. of reflections | 1785 |
No. of parameters | 118 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.32, −0.38 |
Computer programs: KappaCCD Server Software (Nonius, 1997), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXS97 (Sheldrick, 1997), PLATON (Spek, 2001), SHELXL97 (Sheldrick, 1997) and PRPKAPPA (Ferguson, 1999).
S1—C2 | 1.758 (2) | C8—C9 | 1.378 (3) |
C2—N3 | 1.321 (3) | C9—S1 | 1.746 (2) |
N3—C4 | 1.376 (3) | C4—C9 | 1.419 (3) |
C4—C5 | 1.397 (3) | C2—N2 | 1.331 (3) |
C5—C6 | 1.378 (3) | C7—N7 | 1.455 (3) |
C6—C7 | 1.394 (3) | N7—O71 | 1.243 (2) |
C7—C8 | 1.386 (3) | N7—O72 | 1.228 (2) |
C6—C7—N7—O71 | 1.0 (3) | C6—C7—N7—O72 | −178.61 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H21···N3i | 0.88 | 2.05 | 2.912 (2) | 165 |
N2—H22···O71ii | 0.88 | 2.54 | 3.119 (2) | 124 |
N2—H22···O71iii | 0.88 | 2.41 | 3.051 (2) | 130 |
C8—H8···O72iv | 0.95 | 2.53 | 3.381 (3) | 149 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x−1/2, y+1/2, −z+3/2; (iii) −x+1/2, y+1/2, −z+3/2; (iv) −x−1, −y+1, −z+2. |
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In nitroanilines where the amino and nitro substituents are remote from one another such that intramolecular hydrogen-bond formation is precluded, the molecules generally act as double donors and double acceptors of hydrogen bonds; the resulting supramolecular structures can be either two-dimensional (Ploug-Sørensen & Andersen, 1986; Tonogaki et al., 1993; Ellena et al., 1999; Cannon et al., 2001) or three-dimensional (Ferguson et al., 2001). The effect of introducing an excess of hydrogen-bond acceptors, as in 3,5-dinitroaniline (Glidewell et al., 2001), can be unexpected; in this compound, not all of the N—H bonds are engaged in the hydrogen bonding, despite the excess of acceptors over donors. Pursuing this theme, we have now investigated the molecular and supramolecular structure of 2-amino-6-nitrobenzothiazole, (I), where the ring N atom provides an additional hydrogen-bond acceptor site, so giving an excess of acceptors over donors.
Molecules of (I) (Fig. 1) are linked by N—H···O, N—H···N and C—H···O hydrogen bonds (Table 2) into a three-dimensional framework, which is reinforced by aromatic π–π-stacking interactions; the framework structure can readily be analysed in terms of the low-dimensional motifs generated by the individual hydrogen bonds in turn.
The amino N2 atom acts as hydrogen-bond donor, via H22, in a nearly planar three-centre system where the two acceptors are O71 atoms in two different molecules (Table 2). Atom N2 at (x, y, z) acts as donor to O71 at (1/2 - x, 1/2 + y, 3/2 - z), so producing a C(9) chain running parallel to the [010] direction and generated by the 21 axis along (1/4, y, 3/4); at the same time, N2 at (x, y, z) also acts as donor to O71 at (-1/2 - x, 1/2 + y, 3/2 - z), producing a similar C(9) spiral chain around the 21 axis along (-0.25, y, 3/4). The combination of these two one-dimensional motifs generates a sheet parallel to (001) in the form of a (4,4)-net (Batten & Robson, 1998) built from a single type of R33(20) ring (Fig. 2). This sheet is reinforced by aromatic π–π-stacking interactions; in molecules related by translation along the [100] direction, the interplanar spacing is ca 3.38 Å and there is π–π overlap between the carbocyclic ring of the molecule at (x, y, z) with the heterocyclic ring of the molecule at (-1 + x, y, z), with a centroid offset of ca 1.24 Å (Fig. 2); propagation of this interaction by translation gives a sheared-stack motif.
There are two (001) sheets passing through each unit cell, one in the domain -0.02 < z < 0.52 and the other in the domain 0.48 < z < 1.02, and these sheets are linked into a three-dimensional framework by almost linear N—H···N hydrogen bonds, whose effect is reinforced by C—H···O hydrogen bonds (Table 2). The amino N2 atom at (x, y, z) lies in the domain 0.48 < z < 1.02 and acts as hydrogen-bond donor, via H21, to the thiazole N3 atom in the molecule at (1 - x, 1 - y, 1 - z), which lies in the domain -0.02 < z < 0.48; N2 at (1 - x, 1 - y, 1 - z), in turn, acts as donor to N3 at (x, y, z), so generating a centrosymmetric R22(8) motif (Fig. 3). Similarly, N2 at (1/2 - x, 1/2 + y, 3/2 - z), which also lies in the domain 0.48 < z < 1.02, acts as donor to N3 at (-1/2 + x, 3/2 - y, 1/2 + z), which lies in the domain 0.98 < z < 1.52. In this manner, each (001) sheet is linked to its two immediate neighbours, so generating a continuous three-dimensional array.
Atom C8 at (x, y, z), in the domain 0.48 < z < 1.02, acts as hydrogen-bond donor to the nitro O72 atom at (-1 - x, 1 - y, 2 - z), which is in the domain -0.02 < z < 0.52. In so doing, it generates a centrosymmetric R22(10) motif, and the propagation of this motif of paired C—H···O hydrogen bonds again serves to link each (001) sheet to each of its neighbours. The combination of these two cyclic motifs generates a C22(14)[R22(8)][R22(10)] chain of rings running parallel to the [201] direction (Fig. 3)
In the isomeric 2-amino-4-nitrobenzothiazole, (II) [Cambridge Structural Database (CSD; Allen & Kennard, 1993) refcode ZUHVUT (Lokaj et al., 1996)], the hydrogen bonding links the molecules into (101) sheets (Fig. 4) rather than into a three-dimensional array. A combination of N—H···O and N—H···N hydrogen bonds generates a checkerboard array of R22(8) and R66(32) rings; the resulting net is of (4,4)-type (Batten & Robson, 1998) if the dimeric units produced by the R22(8) motif are regarded as the nodes of this net.
Within the molecule of (I), the C2—N2 and C2—N3 distances are very similar (Table 1); both the exocyclic C—N bonds are short for their types (Allen et al., 1987) and there is evidence for quinonoid-type bond fixation within the aryl ring, indicating that forms (Ia) and (Ib) both contribute to the overall structure.