




Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536808037069/tk2325sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536808037069/tk2325Isup2.hkl |
CCDC reference: 712448
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean
(C-C) = 0.002 Å
- R factor = 0.028
- wR factor = 0.079
- Data-to-parameter ratio = 35.5
checkCIF/PLATON results
No syntax errors found
Alert level C Value of measurement temperature given = 100.000 Value of melting point given = 0.000 PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.17
Alert level G PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels .......... 2
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
p-Tosylhydrazine (2 mmol) was added to a refluxing ethanolic solution (50 ml) of 5-bromosalicylaldehyde (2 mmol). The mixture was stirred for 2 h. After cooling, the colorless crystalline solid was isolated by filtration, washed with cold ethanol, and recrystallized from an ethanol solution of (I).
H atoms bound to O1 and N2 were located from a difference Fourier map and refined freely. The remaining H atoms were positioned geometrically and refined as riding model with C—H = 0.93 - 0.96 Å, and with Uiso(H) = 1.2-1.5Ueq(C). A rotating group model was used for the methyl group. The highest residual electron density peak (1.28 eÅ-3) was located 0.64 Å from Br1 and the deepest hole (-0.59 eÅ-3) was located 0.59 Å from Br1.
Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).
C14H13BrN2O3S | F(000) = 744 |
Mr = 369.23 | Dx = 1.647 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 9995 reflections |
a = 15.8890 (3) Å | θ = 2.5–37.4° |
b = 9.8502 (2) Å | µ = 2.91 mm−1 |
c = 9.8702 (2) Å | T = 100 K |
β = 105.475 (1)° | Block, colourless |
V = 1488.78 (5) Å3 | 0.45 × 0.34 × 0.31 mm |
Z = 4 |
Bruker SMART APEXII CCD area-detector diffractometer | 7057 independent reflections |
Radiation source: fine-focus sealed tube | 5961 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
ϕ and ω scans | θmax = 36.0°, θmin = 1.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | h = −26→25 |
Tmin = 0.308, Tmax = 0.407 | k = −16→16 |
41486 measured reflections | l = −16→16 |
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)] = 0.028 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.079 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0378P)2 + 0.5647P] where P = (Fo2 + 2Fc2)/3 |
7057 reflections | (Δ/σ)max = 0.003 |
199 parameters | Δρmax = 1.28 e Å−3 |
0 restraints | Δρmin = −0.59 e Å−3 |
C14H13BrN2O3S | V = 1488.78 (5) Å3 |
Mr = 369.23 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 15.8890 (3) Å | µ = 2.91 mm−1 |
b = 9.8502 (2) Å | T = 100 K |
c = 9.8702 (2) Å | 0.45 × 0.34 × 0.31 mm |
β = 105.475 (1)° |
Bruker SMART APEXII CCD area-detector diffractometer | 7057 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | 5961 reflections with I > 2σ(I) |
Tmin = 0.308, Tmax = 0.407 | Rint = 0.035 |
41486 measured reflections |
R[F2 > 2σ(F2)] = 0.028 | 0 restraints |
wR(F2) = 0.079 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 1.28 e Å−3 |
7057 reflections | Δρmin = −0.59 e Å−3 |
199 parameters |
Experimental. The low-temperature data was collected with the Oxford Cyrosystem Cobra low-temperature attachment. |
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. |
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. |
x | y | z | Uiso*/Ueq | ||
Br1 | 1.191754 (8) | 0.636650 (14) | 1.149579 (15) | 0.02941 (4) | |
S1 | 0.645085 (17) | 0.74186 (3) | 0.60027 (3) | 0.01571 (5) | |
O1 | 0.91105 (6) | 0.56509 (11) | 0.60615 (10) | 0.02610 (17) | |
O2 | 0.67053 (6) | 0.78504 (9) | 0.47792 (9) | 0.02295 (16) | |
O3 | 0.57441 (5) | 0.80755 (8) | 0.63807 (9) | 0.02088 (15) | |
N1 | 0.80775 (6) | 0.71072 (9) | 0.72484 (10) | 0.01769 (15) | |
N2 | 0.73002 (6) | 0.77064 (9) | 0.73584 (10) | 0.01728 (15) | |
C1 | 0.97310 (8) | 0.58383 (12) | 0.72937 (13) | 0.02124 (19) | |
C2 | 1.05653 (9) | 0.53277 (14) | 0.74093 (15) | 0.0272 (2) | |
H2A | 1.0683 | 0.4878 | 0.6652 | 0.033* | |
C3 | 1.12225 (8) | 0.54873 (14) | 0.86523 (15) | 0.0279 (2) | |
H3A | 1.1778 | 0.5144 | 0.8729 | 0.033* | |
C4 | 1.10429 (8) | 0.61625 (12) | 0.97777 (14) | 0.0237 (2) | |
C5 | 1.02200 (8) | 0.66843 (12) | 0.96797 (13) | 0.02211 (19) | |
H5A | 1.0110 | 0.7138 | 1.0441 | 0.027* | |
C6 | 0.95532 (7) | 0.65296 (11) | 0.84359 (12) | 0.01914 (18) | |
C7 | 0.86985 (7) | 0.70900 (11) | 0.83885 (12) | 0.01990 (18) | |
H7A | 0.8600 | 0.7445 | 0.9206 | 0.024* | |
C8 | 0.62834 (7) | 0.56588 (10) | 0.59177 (11) | 0.01615 (16) | |
C9 | 0.66712 (8) | 0.48649 (11) | 0.50865 (12) | 0.02087 (19) | |
H9A | 0.6983 | 0.5265 | 0.4518 | 0.025* | |
C10 | 0.65842 (8) | 0.34621 (11) | 0.51211 (13) | 0.0223 (2) | |
H10A | 0.6841 | 0.2924 | 0.4567 | 0.027* | |
C11 | 0.61190 (7) | 0.28427 (11) | 0.59702 (12) | 0.01949 (18) | |
C12 | 0.57195 (8) | 0.36678 (11) | 0.67689 (13) | 0.02032 (18) | |
H12A | 0.5393 | 0.3271 | 0.7318 | 0.024* | |
C13 | 0.58016 (7) | 0.50714 (11) | 0.67562 (12) | 0.01874 (17) | |
H13A | 0.5539 | 0.5612 | 0.7300 | 0.022* | |
C14 | 0.60620 (9) | 0.13240 (11) | 0.60308 (15) | 0.0257 (2) | |
H14A | 0.6230 | 0.0935 | 0.5250 | 0.039* | |
H14B | 0.5473 | 0.1063 | 0.5986 | 0.039* | |
H14C | 0.6446 | 0.1003 | 0.6894 | 0.039* | |
H1N2 | 0.7171 (12) | 0.7519 (19) | 0.812 (2) | 0.027 (4)* | |
H1O1 | 0.8634 (18) | 0.596 (3) | 0.615 (3) | 0.057 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.01916 (6) | 0.02972 (7) | 0.03454 (8) | −0.00490 (4) | −0.00119 (5) | 0.00973 (5) |
S1 | 0.01756 (10) | 0.01561 (10) | 0.01476 (10) | 0.00098 (7) | 0.00568 (8) | 0.00033 (7) |
O1 | 0.0248 (4) | 0.0345 (5) | 0.0198 (4) | 0.0064 (3) | 0.0074 (3) | 0.0009 (3) |
O2 | 0.0322 (4) | 0.0216 (3) | 0.0178 (4) | 0.0002 (3) | 0.0114 (3) | 0.0031 (3) |
O3 | 0.0191 (3) | 0.0196 (3) | 0.0246 (4) | 0.0042 (3) | 0.0069 (3) | −0.0005 (3) |
N1 | 0.0164 (4) | 0.0173 (3) | 0.0206 (4) | 0.0000 (3) | 0.0071 (3) | 0.0001 (3) |
N2 | 0.0165 (4) | 0.0191 (4) | 0.0171 (4) | −0.0003 (3) | 0.0059 (3) | −0.0025 (3) |
C1 | 0.0217 (5) | 0.0216 (4) | 0.0217 (5) | 0.0026 (4) | 0.0081 (4) | 0.0037 (4) |
C2 | 0.0245 (5) | 0.0295 (5) | 0.0305 (6) | 0.0072 (4) | 0.0122 (5) | 0.0035 (5) |
C3 | 0.0208 (5) | 0.0282 (5) | 0.0359 (7) | 0.0051 (4) | 0.0095 (5) | 0.0075 (5) |
C4 | 0.0172 (4) | 0.0233 (5) | 0.0290 (6) | −0.0010 (4) | 0.0035 (4) | 0.0069 (4) |
C5 | 0.0189 (5) | 0.0213 (4) | 0.0251 (5) | −0.0017 (4) | 0.0042 (4) | 0.0007 (4) |
C6 | 0.0178 (4) | 0.0181 (4) | 0.0218 (5) | 0.0002 (3) | 0.0057 (4) | 0.0017 (3) |
C7 | 0.0181 (4) | 0.0199 (4) | 0.0219 (5) | −0.0005 (3) | 0.0057 (4) | −0.0023 (4) |
C8 | 0.0168 (4) | 0.0161 (4) | 0.0154 (4) | −0.0003 (3) | 0.0040 (3) | −0.0008 (3) |
C9 | 0.0253 (5) | 0.0193 (4) | 0.0211 (5) | −0.0006 (4) | 0.0114 (4) | −0.0023 (4) |
C10 | 0.0263 (5) | 0.0184 (4) | 0.0238 (5) | 0.0005 (4) | 0.0094 (4) | −0.0037 (4) |
C11 | 0.0181 (4) | 0.0174 (4) | 0.0209 (5) | −0.0002 (3) | 0.0015 (4) | 0.0004 (3) |
C12 | 0.0187 (4) | 0.0201 (4) | 0.0228 (5) | −0.0018 (3) | 0.0067 (4) | 0.0016 (4) |
C13 | 0.0175 (4) | 0.0197 (4) | 0.0205 (4) | −0.0001 (3) | 0.0075 (3) | −0.0002 (3) |
C14 | 0.0291 (6) | 0.0171 (4) | 0.0286 (6) | −0.0001 (4) | 0.0035 (5) | 0.0009 (4) |
Br1—C4 | 1.8947 (13) | C5—H5A | 0.9300 |
S1—O3 | 1.4292 (8) | C6—C7 | 1.4551 (16) |
S1—O2 | 1.4363 (9) | C7—H7A | 0.9300 |
S1—N2 | 1.6518 (10) | C8—C9 | 1.3907 (15) |
S1—C8 | 1.7524 (10) | C8—C13 | 1.3943 (15) |
O1—C1 | 1.3585 (16) | C9—C10 | 1.3900 (16) |
O1—H1O1 | 0.84 (3) | C9—H9A | 0.9300 |
N1—C7 | 1.2837 (15) | C10—C11 | 1.3971 (17) |
N1—N2 | 1.3989 (13) | C10—H10A | 0.9300 |
N2—H1N2 | 0.852 (19) | C11—C12 | 1.3972 (16) |
C1—C2 | 1.3937 (17) | C11—C14 | 1.5008 (16) |
C1—C6 | 1.4087 (16) | C12—C13 | 1.3891 (15) |
C2—C3 | 1.392 (2) | C12—H12A | 0.9300 |
C2—H2A | 0.9300 | C13—H13A | 0.9300 |
C3—C4 | 1.388 (2) | C14—H14A | 0.9600 |
C3—H3A | 0.9300 | C14—H14B | 0.9600 |
C4—C5 | 1.3840 (17) | C14—H14C | 0.9600 |
C5—C6 | 1.3995 (17) | ||
O3—S1—O2 | 120.16 (5) | C1—C6—C7 | 122.85 (11) |
O3—S1—N2 | 103.88 (5) | N1—C7—C6 | 121.72 (10) |
O2—S1—N2 | 106.13 (5) | N1—C7—H7A | 119.1 |
O3—S1—C8 | 109.91 (5) | C6—C7—H7A | 119.1 |
O2—S1—C8 | 109.02 (5) | C9—C8—C13 | 121.11 (10) |
N2—S1—C8 | 106.82 (5) | C9—C8—S1 | 119.93 (8) |
C1—O1—H1O1 | 108.2 (18) | C13—C8—S1 | 118.85 (8) |
C7—N1—N2 | 115.19 (9) | C10—C9—C8 | 118.81 (10) |
N1—N2—S1 | 114.34 (7) | C10—C9—H9A | 120.6 |
N1—N2—H1N2 | 113.8 (13) | C8—C9—H9A | 120.6 |
S1—N2—H1N2 | 110.0 (13) | C9—C10—C11 | 121.39 (10) |
O1—C1—C2 | 118.13 (11) | C9—C10—H10A | 119.3 |
O1—C1—C6 | 121.98 (10) | C11—C10—H10A | 119.3 |
C2—C1—C6 | 119.89 (12) | C10—C11—C12 | 118.51 (10) |
C3—C2—C1 | 120.33 (12) | C10—C11—C14 | 120.42 (11) |
C3—C2—H2A | 119.8 | C12—C11—C14 | 121.07 (11) |
C1—C2—H2A | 119.8 | C13—C12—C11 | 121.06 (10) |
C4—C3—C2 | 119.57 (11) | C13—C12—H12A | 119.5 |
C4—C3—H3A | 120.2 | C11—C12—H12A | 119.5 |
C2—C3—H3A | 120.2 | C12—C13—C8 | 119.09 (10) |
C5—C4—C3 | 120.94 (12) | C12—C13—H13A | 120.5 |
C5—C4—Br1 | 118.48 (10) | C8—C13—H13A | 120.5 |
C3—C4—Br1 | 120.58 (9) | C11—C14—H14A | 109.5 |
C4—C5—C6 | 120.05 (12) | C11—C14—H14B | 109.5 |
C4—C5—H5A | 120.0 | H14A—C14—H14B | 109.5 |
C6—C5—H5A | 120.0 | C11—C14—H14C | 109.5 |
C5—C6—C1 | 119.22 (11) | H14A—C14—H14C | 109.5 |
C5—C6—C7 | 117.93 (10) | H14B—C14—H14C | 109.5 |
C7—N1—N2—S1 | −166.98 (8) | C5—C6—C7—N1 | 173.17 (11) |
O3—S1—N2—N1 | 177.80 (7) | C1—C6—C7—N1 | −7.24 (17) |
O2—S1—N2—N1 | −54.59 (9) | O3—S1—C8—C9 | 155.48 (9) |
C8—S1—N2—N1 | 61.63 (8) | O2—S1—C8—C9 | 21.84 (11) |
O1—C1—C2—C3 | −179.66 (12) | N2—S1—C8—C9 | −92.44 (10) |
C6—C1—C2—C3 | 0.54 (19) | O3—S1—C8—C13 | −28.24 (10) |
C1—C2—C3—C4 | −0.2 (2) | O2—S1—C8—C13 | −161.87 (9) |
C2—C3—C4—C5 | −0.25 (19) | N2—S1—C8—C13 | 83.85 (9) |
C2—C3—C4—Br1 | 178.81 (10) | C13—C8—C9—C10 | −1.12 (18) |
C3—C4—C5—C6 | 0.31 (18) | S1—C8—C9—C10 | 175.08 (9) |
Br1—C4—C5—C6 | −178.78 (9) | C8—C9—C10—C11 | −0.07 (19) |
C4—C5—C6—C1 | 0.06 (17) | C9—C10—C11—C12 | 1.54 (18) |
C4—C5—C6—C7 | 179.67 (11) | C9—C10—C11—C14 | −177.72 (12) |
O1—C1—C6—C5 | 179.73 (11) | C10—C11—C12—C13 | −1.87 (18) |
C2—C1—C6—C5 | −0.48 (17) | C14—C11—C12—C13 | 177.39 (11) |
O1—C1—C6—C7 | 0.14 (17) | C11—C12—C13—C8 | 0.73 (18) |
C2—C1—C6—C7 | 179.92 (11) | C9—C8—C13—C12 | 0.80 (17) |
N2—N1—C7—C6 | −178.58 (10) | S1—C8—C13—C12 | −175.44 (9) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H1N2···O2i | 0.851 (19) | 2.002 (19) | 2.8476 (13) | 172.4 (19) |
O1—H1O1···N1 | 0.84 (3) | 1.94 (3) | 2.6740 (14) | 146 (3) |
C7—H7A···O1i | 0.93 | 2.60 | 3.3793 (15) | 142 |
C10—H10A···Br1ii | 0.93 | 2.91 | 3.8082 (12) | 164 |
C12—H12A···O3iii | 0.93 | 2.49 | 3.3691 (15) | 158 |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x+2, y−1/2, −z+3/2; (iii) −x+1, y−1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C14H13BrN2O3S |
Mr | 369.23 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 15.8890 (3), 9.8502 (2), 9.8702 (2) |
β (°) | 105.475 (1) |
V (Å3) | 1488.78 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.91 |
Crystal size (mm) | 0.45 × 0.34 × 0.31 |
Data collection | |
Diffractometer | Bruker SMART APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2005) |
Tmin, Tmax | 0.308, 0.407 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 41486, 7057, 5961 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.827 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.079, 1.06 |
No. of reflections | 7057 |
No. of parameters | 199 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.28, −0.59 |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H1N2···O2i | 0.851 (19) | 2.002 (19) | 2.8476 (13) | 172.4 (19) |
O1—H1O1···N1 | 0.84 (3) | 1.94 (3) | 2.6740 (14) | 146 (3) |
C7—H7A···O1i | 0.93 | 2.60 | 3.3793 (15) | 142 |
C10—H10A···Br1ii | 0.93 | 2.91 | 3.8082 (12) | 164 |
C12—H12A···O3iii | 0.93 | 2.49 | 3.3691 (15) | 158 |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x+2, y−1/2, −z+3/2; (iii) −x+1, y−1/2, −z+3/2. |
Sulfonamides were the first class of antimicrobial agents to be discovered. They inhibit dihydropteroate synthetase in the bacterial folic acid pathway. Although their clinical role has diminished, they are still useful in certain situations, because of their efficacy and low cost (Krygowski et al., 1998). Sulfonamides (e.g. sulfanilamide, sulfamethoxazole, sulfafurazole) are structural analogues of p-aminobenzoic acid (PABA) and compete with PABA to block its conversion to dihydrofolic acid. These agents are generally used in combination with other drugs to prevent or treat a number of bacterial and parasitic infections (Tierney et al., 2006). With regard to all of the above, we report herein the crystal structure of the title compound, (I).
Bond lengths and angles in (I), Fig. 1, are comparable with those in related structures (Mehrabi et al., 2008; Ali et al. 2007). An intramolecular O—H···N hydrogen bond is noted which generates a S(6) ring motif. The two benzene rings make the dihedral angle of 86.47 (6)°. Intermolecular N—H···O and C—H···O interactions link neighbouring molecules via R22(13) ring motifs to form 1-D extended chains along the c-axis, Fig. 2 and Table 1. The crystal structure is further stabilized by intermolecular N—H···O, C—H···Br, C—H···O and π···π [Cg1···Cg1 = 3.9548 (8) Å; symmetry code: 2 - x, 1 - y, 2 - z] interactions.