




Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810033040/hg2703sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536810033040/hg2703Isup2.hkl |
CCDC reference: 792474
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean
(C-C) = 0.004 Å
- R factor = 0.048
- wR factor = 0.146
- Data-to-parameter ratio = 15.2
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 33 PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 54
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 2
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 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 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 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
2-Chloro-3-nitro-pyridine (0.7899 g, 0.005 mol) and p-toluidine (0.536 g, 0.005 mol) were refluxed in 5 ml ethanol for 5.5 h at 351 K. The mixture was cooled. The residue was then dissolved in a minimum volume of water (10 ml) and extracted with ether (3 x 10 ml). The ethereal layer was washed with water and dried over anhydrous sodium sulfate. Evaporation gave a reddish solid and recrystallization using ethyl acetate yielded red crystals.
Carbon-bound H-atoms were placed in calculated positions (C—H 0.95 to 0.98 Å) and were included in the refinement in the riding model approximation, with Uiso(H) set to 1.2 to 1.5Uequiv(C). The N-bound H-atoms were located in a difference Fourier map but were were refined with a distance restraint of N–H = 0.86±0.01 Å, and with unrestricted Uiso(H).
Studies of pyridine and pyrimidine derivatives related to the title compound are of interest owing to their putative fluorescence properties (Kawai et al. 2001; Abdullah, 2005). As a continuation of structural studies on this class of N-heterocycles (Badaruddin et al., 2009; Fairuz et al., 2010), the title compound, (I), was investigated.
Two independent molecules comprise the asymmetric unit of (I), Figs 1 and 2. While the geometric parameters are in close agreement [r.m.s. deviation of bond distances and angles = 0.0080 Å and 0.849 °, respectively], these differ non-trivially in their conformations. So, while the pyridine groups are virtually super-imposable, the benzene rings are not, Fig. 3. This difference is quantified in the dihedral angles formed between the pyridine and benzene rings, i.e. N2,C1–C5/C6–C11 = 17.42 (16) ° and N5,C13–C17/C18–C23 = 34.64 (16) °. These indicate that there are also twists in the molecules as evidenced by the C6–N3–C5–N2 torsion angle of -11.7 (5) ° and, especially, the C5–N3–C6–C11 torsion angle of 22.3 (5) °. The equivalent torsion angles for the second independent molecule of C18–N6–C17–N5 = 0.8 (5) ° and C17–N6–C18–C23 = 35.9 (5) ° also highlight the differences between the molecules. The nitro groups are co-planar with the pyridine rings to which they are connected as indicated by the O1–N1–C1–C5 and O3–N4–C13–C17 torsion angles of 1.5 (5) and -1.1 (5) °, respectively. Close intramolecular N–H···O and C–H···N interactions are noted, Table 1.
The most notable intermolecular interactions in the crystal structure are of the type C–H···O [which connect the molecules comprising the asymmetric unit], C–H···π and π–π [ring centroid(N2,C1–C5)···centroid(C18–C23) = 3.6442 (19) Å and ring centroid(N5,C13–C17)···centroid(N5,C13–C17)i = 3.722 (2) Å for i: -x, 1 - y, -z] contacts. These serve to connect molecules into the three-dimensional structure, Fig. 4.
For background to the fluorescence properties of compounds related to the title compound, see: Kawai et al. (2001); Abdullah (2005). For the structures of related pyrimidine amine derivatives, see: Badaruddin et al., (2009); Fairuz et al. (2010).
Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997), DIAMOND (Brandenburg, 2006) and Qmol (Gans & Shalloway, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).
C12H11N3O2 | F(000) = 960 |
Mr = 229.24 | Dx = 1.432 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2221 reflections |
a = 10.6557 (12) Å | θ = 3.0–27.8° |
b = 7.1415 (8) Å | µ = 0.10 mm−1 |
c = 27.958 (3) Å | T = 100 K |
β = 91.310 (2)° | Plate, red |
V = 2127.0 (4) Å3 | 0.35 × 0.35 × 0.05 mm |
Z = 8 |
Bruker SMART APEX diffractometer | 3344 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.045 |
Graphite monochromator | θmax = 27.5°, θmin = 1.5° |
ω scans | h = −13→11 |
13178 measured reflections | k = −8→9 |
4804 independent reflections | l = −36→36 |
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.146 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0685P)2 + 0.8145P] where P = (Fo2 + 2Fc2)/3 |
4804 reflections | (Δ/σ)max = 0.001 |
317 parameters | Δρmax = 0.30 e Å−3 |
2 restraints | Δρmin = −0.28 e Å−3 |
C12H11N3O2 | V = 2127.0 (4) Å3 |
Mr = 229.24 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.6557 (12) Å | µ = 0.10 mm−1 |
b = 7.1415 (8) Å | T = 100 K |
c = 27.958 (3) Å | 0.35 × 0.35 × 0.05 mm |
β = 91.310 (2)° |
Bruker SMART APEX diffractometer | 3344 reflections with I > 2σ(I) |
13178 measured reflections | Rint = 0.045 |
4804 independent reflections |
R[F2 > 2σ(F2)] = 0.048 | 2 restraints |
wR(F2) = 0.146 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.30 e Å−3 |
4804 reflections | Δρmin = −0.28 e Å−3 |
317 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. |
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 | ||
O1 | 0.5737 (2) | 0.6059 (3) | 0.07334 (8) | 0.0224 (6) | |
O2 | 0.3802 (2) | 0.6139 (4) | 0.04820 (8) | 0.0265 (6) | |
O3 | 0.1554 (2) | 0.1650 (4) | −0.07299 (8) | 0.0286 (6) | |
O4 | −0.0348 (2) | 0.2379 (4) | −0.09457 (8) | 0.0286 (6) | |
N1 | 0.4595 (3) | 0.5848 (4) | 0.08003 (9) | 0.0186 (6) | |
N2 | 0.4564 (3) | 0.4326 (4) | 0.20794 (9) | 0.0193 (6) | |
N3 | 0.6278 (2) | 0.5089 (4) | 0.16220 (9) | 0.0163 (6) | |
N4 | 0.0469 (3) | 0.2118 (4) | −0.06319 (9) | 0.0207 (6) | |
N5 | 0.0665 (3) | 0.2476 (4) | 0.06993 (9) | 0.0200 (6) | |
N6 | 0.2219 (3) | 0.1555 (4) | 0.01848 (9) | 0.0191 (6) | |
C1 | 0.4176 (3) | 0.5224 (4) | 0.12647 (10) | 0.0171 (7) | |
C2 | 0.2897 (3) | 0.4973 (5) | 0.13170 (11) | 0.0195 (7) | |
H2 | 0.2331 | 0.5196 | 0.1056 | 0.023* | |
C3 | 0.2457 (3) | 0.4396 (5) | 0.17510 (11) | 0.0206 (7) | |
H3A | 0.1586 | 0.4213 | 0.1798 | 0.025* | |
C4 | 0.3327 (3) | 0.4092 (5) | 0.21164 (11) | 0.0211 (7) | |
H4 | 0.3022 | 0.3687 | 0.2416 | 0.025* | |
C5 | 0.5016 (3) | 0.4879 (4) | 0.16576 (11) | 0.0161 (7) | |
C6 | 0.7235 (3) | 0.5118 (4) | 0.19792 (11) | 0.0154 (7) | |
C7 | 0.8350 (3) | 0.5993 (4) | 0.18500 (11) | 0.0169 (7) | |
H7 | 0.8427 | 0.6476 | 0.1535 | 0.020* | |
C8 | 0.9339 (3) | 0.6166 (5) | 0.21729 (11) | 0.0185 (7) | |
H8 | 1.0089 | 0.6759 | 0.2076 | 0.022* | |
C9 | 0.9263 (3) | 0.5489 (5) | 0.26396 (11) | 0.0179 (7) | |
C10 | 0.8168 (3) | 0.4554 (5) | 0.27559 (11) | 0.0184 (7) | |
H10 | 0.8106 | 0.4034 | 0.3067 | 0.022* | |
C11 | 0.7155 (3) | 0.4345 (5) | 0.24348 (11) | 0.0184 (7) | |
H11 | 0.6424 | 0.3686 | 0.2526 | 0.022* | |
C12 | 1.0323 (3) | 0.5790 (5) | 0.29973 (11) | 0.0224 (7) | |
H12A | 1.0097 | 0.5253 | 0.3306 | 0.034* | |
H12B | 1.0478 | 0.7135 | 0.3035 | 0.034* | |
H12C | 1.1083 | 0.5178 | 0.2883 | 0.034* | |
C13 | 0.0149 (3) | 0.2401 (5) | −0.01373 (11) | 0.0183 (7) | |
C14 | −0.1058 (3) | 0.3001 (5) | −0.00485 (12) | 0.0212 (7) | |
H14 | −0.1649 | 0.3152 | −0.0305 | 0.025* | |
C15 | −0.1398 (3) | 0.3376 (5) | 0.04115 (12) | 0.0220 (7) | |
H15 | −0.2214 | 0.3817 | 0.0482 | 0.026* | |
C16 | −0.0491 (3) | 0.3079 (5) | 0.07704 (12) | 0.0222 (7) | |
H16 | −0.0720 | 0.3328 | 0.1091 | 0.027* | |
C17 | 0.1032 (3) | 0.2129 (4) | 0.02481 (11) | 0.0172 (7) | |
C18 | 0.3186 (3) | 0.1221 (5) | 0.05334 (11) | 0.0173 (7) | |
C19 | 0.4414 (3) | 0.1571 (5) | 0.03961 (11) | 0.0189 (7) | |
H19 | 0.4568 | 0.2063 | 0.0087 | 0.023* | |
C20 | 0.5413 (3) | 0.1203 (5) | 0.07102 (11) | 0.0188 (7) | |
H20 | 0.6246 | 0.1423 | 0.0610 | 0.023* | |
C21 | 0.5218 (3) | 0.0519 (5) | 0.11668 (11) | 0.0179 (7) | |
C22 | 0.3992 (3) | 0.0150 (5) | 0.12938 (11) | 0.0188 (7) | |
H22 | 0.3840 | −0.0340 | 0.1603 | 0.023* | |
C23 | 0.2979 (3) | 0.0474 (5) | 0.09839 (11) | 0.0201 (7) | |
H23 | 0.2151 | 0.0187 | 0.1079 | 0.024* | |
C24 | 0.6290 (3) | 0.0200 (5) | 0.15168 (12) | 0.0242 (8) | |
H24A | 0.7084 | 0.0220 | 0.1347 | 0.036* | |
H24B | 0.6189 | −0.1019 | 0.1672 | 0.036* | |
H24C | 0.6296 | 0.1190 | 0.1759 | 0.036* | |
H3 | 0.652 (3) | 0.552 (5) | 0.1350 (8) | 0.022 (10)* | |
H6 | 0.242 (3) | 0.153 (6) | −0.0118 (14) | 0.031 (11)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0175 (13) | 0.0287 (14) | 0.0210 (11) | −0.0020 (10) | −0.0014 (9) | 0.0037 (10) |
O2 | 0.0236 (13) | 0.0349 (15) | 0.0206 (11) | 0.0030 (11) | −0.0063 (10) | 0.0061 (10) |
O3 | 0.0235 (14) | 0.0429 (16) | 0.0195 (12) | 0.0097 (12) | −0.0008 (10) | −0.0016 (11) |
O4 | 0.0288 (14) | 0.0353 (15) | 0.0212 (12) | −0.0007 (12) | −0.0093 (10) | 0.0011 (10) |
N1 | 0.0209 (15) | 0.0172 (15) | 0.0178 (13) | 0.0010 (12) | −0.0025 (11) | 0.0008 (10) |
N2 | 0.0189 (15) | 0.0212 (15) | 0.0179 (13) | −0.0001 (12) | 0.0012 (11) | −0.0003 (11) |
N3 | 0.0131 (14) | 0.0217 (15) | 0.0140 (12) | −0.0016 (11) | −0.0009 (10) | 0.0025 (10) |
N4 | 0.0220 (16) | 0.0199 (15) | 0.0200 (13) | −0.0018 (12) | −0.0040 (11) | 0.0017 (11) |
N5 | 0.0177 (15) | 0.0224 (15) | 0.0198 (13) | 0.0022 (12) | 0.0000 (11) | 0.0008 (11) |
N6 | 0.0172 (15) | 0.0254 (16) | 0.0147 (13) | 0.0025 (12) | −0.0024 (11) | 0.0008 (11) |
C1 | 0.0215 (18) | 0.0143 (16) | 0.0156 (14) | 0.0000 (13) | 0.0000 (12) | −0.0003 (12) |
C2 | 0.0172 (17) | 0.0174 (17) | 0.0236 (16) | 0.0017 (13) | −0.0046 (13) | −0.0006 (13) |
C3 | 0.0127 (17) | 0.0218 (18) | 0.0274 (17) | −0.0001 (14) | 0.0007 (13) | −0.0011 (14) |
C4 | 0.0199 (18) | 0.0232 (18) | 0.0203 (15) | −0.0021 (14) | 0.0024 (13) | −0.0003 (13) |
C5 | 0.0170 (17) | 0.0141 (16) | 0.0173 (14) | −0.0002 (13) | −0.0004 (12) | −0.0032 (11) |
C6 | 0.0116 (16) | 0.0171 (16) | 0.0173 (14) | 0.0012 (13) | −0.0018 (12) | −0.0027 (12) |
C7 | 0.0172 (17) | 0.0164 (16) | 0.0171 (14) | 0.0009 (13) | 0.0009 (12) | −0.0004 (12) |
C8 | 0.0167 (17) | 0.0159 (17) | 0.0229 (16) | 0.0000 (13) | 0.0002 (13) | 0.0001 (12) |
C9 | 0.0185 (17) | 0.0151 (16) | 0.0198 (15) | 0.0028 (13) | −0.0025 (12) | −0.0041 (12) |
C10 | 0.0198 (18) | 0.0206 (17) | 0.0149 (14) | 0.0042 (14) | 0.0019 (12) | 0.0002 (12) |
C11 | 0.0171 (17) | 0.0192 (17) | 0.0189 (15) | 0.0007 (14) | 0.0014 (12) | 0.0001 (13) |
C12 | 0.0232 (19) | 0.0211 (18) | 0.0227 (16) | −0.0005 (15) | −0.0064 (14) | −0.0014 (13) |
C13 | 0.0208 (18) | 0.0162 (16) | 0.0180 (15) | −0.0029 (14) | −0.0017 (12) | 0.0009 (12) |
C14 | 0.0195 (18) | 0.0172 (17) | 0.0265 (17) | −0.0050 (14) | −0.0046 (13) | 0.0044 (13) |
C15 | 0.0148 (17) | 0.0204 (18) | 0.0309 (18) | −0.0001 (14) | 0.0025 (14) | 0.0040 (14) |
C16 | 0.0219 (18) | 0.0226 (18) | 0.0222 (16) | 0.0002 (15) | 0.0038 (13) | 0.0028 (13) |
C17 | 0.0181 (17) | 0.0144 (16) | 0.0190 (15) | −0.0022 (13) | −0.0026 (12) | 0.0020 (12) |
C18 | 0.0205 (18) | 0.0145 (16) | 0.0168 (14) | 0.0019 (13) | −0.0017 (12) | −0.0019 (12) |
C19 | 0.0236 (18) | 0.0169 (17) | 0.0162 (14) | 0.0005 (14) | 0.0032 (12) | 0.0010 (12) |
C20 | 0.0124 (16) | 0.0218 (18) | 0.0223 (16) | 0.0000 (13) | 0.0024 (12) | −0.0021 (13) |
C21 | 0.0172 (17) | 0.0150 (16) | 0.0214 (15) | 0.0029 (13) | −0.0036 (13) | −0.0040 (12) |
C22 | 0.0186 (17) | 0.0214 (18) | 0.0165 (14) | 0.0020 (14) | 0.0011 (12) | 0.0030 (12) |
C23 | 0.0167 (17) | 0.0219 (18) | 0.0217 (15) | −0.0006 (14) | 0.0023 (13) | 0.0030 (13) |
C24 | 0.0235 (19) | 0.0256 (19) | 0.0232 (16) | 0.0044 (15) | −0.0049 (14) | −0.0019 (14) |
O1—N1 | 1.245 (3) | C9—C10 | 1.389 (5) |
O2—N1 | 1.230 (3) | C9—C12 | 1.507 (4) |
O3—N4 | 1.240 (4) | C10—C11 | 1.396 (4) |
O4—N4 | 1.236 (3) | C10—H10 | 0.9500 |
N1—C1 | 1.452 (4) | C11—H11 | 0.9500 |
N2—C4 | 1.335 (4) | C12—H12A | 0.9800 |
N2—C5 | 1.343 (4) | C12—H12B | 0.9800 |
N3—C5 | 1.359 (4) | C12—H12C | 0.9800 |
N3—C6 | 1.412 (4) | C13—C14 | 1.383 (5) |
N3—H3 | 0.867 (15) | C13—C17 | 1.428 (4) |
N4—C13 | 1.446 (4) | C14—C15 | 1.370 (5) |
N5—C16 | 1.324 (4) | C14—H14 | 0.9500 |
N5—C17 | 1.352 (4) | C15—C16 | 1.393 (5) |
N6—C17 | 1.345 (4) | C15—H15 | 0.9500 |
N6—C18 | 1.422 (4) | C16—H16 | 0.9500 |
N6—H6 | 0.88 (4) | C18—C23 | 1.390 (4) |
C1—C2 | 1.386 (5) | C18—C19 | 1.394 (4) |
C1—C5 | 1.422 (4) | C19—C20 | 1.390 (4) |
C2—C3 | 1.374 (4) | C19—H19 | 0.9500 |
C2—H2 | 0.9500 | C20—C21 | 1.387 (4) |
C3—C4 | 1.380 (4) | C20—H20 | 0.9500 |
C3—H3A | 0.9500 | C21—C22 | 1.388 (4) |
C4—H4 | 0.9500 | C21—C24 | 1.505 (4) |
C6—C11 | 1.393 (4) | C22—C23 | 1.388 (4) |
C6—C7 | 1.397 (4) | C22—H22 | 0.9500 |
C7—C8 | 1.377 (4) | C23—H23 | 0.9500 |
C7—H7 | 0.9500 | C24—H24A | 0.9800 |
C8—C9 | 1.396 (4) | C24—H24B | 0.9800 |
C8—H8 | 0.9500 | C24—H24C | 0.9800 |
O2—N1—O1 | 121.9 (3) | C10—C11—H11 | 120.5 |
O2—N1—C1 | 118.6 (3) | C9—C12—H12A | 109.5 |
O1—N1—C1 | 119.5 (2) | C9—C12—H12B | 109.5 |
C4—N2—C5 | 118.6 (3) | H12A—C12—H12B | 109.5 |
C5—N3—C6 | 130.6 (3) | C9—C12—H12C | 109.5 |
C5—N3—H3 | 115 (2) | H12A—C12—H12C | 109.5 |
C6—N3—H3 | 113 (2) | H12B—C12—H12C | 109.5 |
O4—N4—O3 | 121.9 (3) | C14—C13—C17 | 120.4 (3) |
O4—N4—C13 | 118.7 (3) | C14—C13—N4 | 117.1 (3) |
O3—N4—C13 | 119.4 (3) | C17—C13—N4 | 122.5 (3) |
C16—N5—C17 | 119.3 (3) | C15—C14—C13 | 119.7 (3) |
C17—N6—C18 | 129.0 (3) | C15—C14—H14 | 120.2 |
C17—N6—H6 | 113 (3) | C13—C14—H14 | 120.2 |
C18—N6—H6 | 118 (3) | C14—C15—C16 | 116.9 (3) |
C2—C1—C5 | 119.9 (3) | C14—C15—H15 | 121.5 |
C2—C1—N1 | 117.2 (3) | C16—C15—H15 | 121.5 |
C5—C1—N1 | 122.9 (3) | N5—C16—C15 | 125.0 (3) |
C3—C2—C1 | 119.2 (3) | N5—C16—H16 | 117.5 |
C3—C2—H2 | 120.4 | C15—C16—H16 | 117.5 |
C1—C2—H2 | 120.4 | N6—C17—N5 | 118.1 (3) |
C2—C3—C4 | 117.7 (3) | N6—C17—C13 | 123.2 (3) |
C2—C3—H3A | 121.2 | N5—C17—C13 | 118.6 (3) |
C4—C3—H3A | 121.2 | C23—C18—C19 | 119.2 (3) |
N2—C4—C3 | 124.8 (3) | C23—C18—N6 | 123.9 (3) |
N2—C4—H4 | 117.6 | C19—C18—N6 | 116.8 (3) |
C3—C4—H4 | 117.6 | C20—C19—C18 | 120.2 (3) |
N2—C5—N3 | 118.2 (3) | C20—C19—H19 | 119.9 |
N2—C5—C1 | 119.8 (3) | C18—C19—H19 | 119.9 |
N3—C5—C1 | 122.0 (3) | C21—C20—C19 | 121.3 (3) |
C11—C6—C7 | 119.0 (3) | C21—C20—H20 | 119.3 |
C11—C6—N3 | 125.7 (3) | C19—C20—H20 | 119.3 |
C7—C6—N3 | 115.4 (3) | C22—C21—C20 | 117.7 (3) |
C8—C7—C6 | 120.8 (3) | C22—C21—C24 | 120.7 (3) |
C8—C7—H7 | 119.6 | C20—C21—C24 | 121.6 (3) |
C6—C7—H7 | 119.6 | C21—C22—C23 | 122.1 (3) |
C7—C8—C9 | 121.5 (3) | C21—C22—H22 | 118.9 |
C7—C8—H8 | 119.3 | C23—C22—H22 | 118.9 |
C9—C8—H8 | 119.3 | C22—C23—C18 | 119.5 (3) |
C10—C9—C8 | 116.9 (3) | C22—C23—H23 | 120.2 |
C10—C9—C12 | 122.3 (3) | C18—C23—H23 | 120.2 |
C8—C9—C12 | 120.8 (3) | C21—C24—H24A | 109.5 |
C9—C10—C11 | 122.8 (3) | C21—C24—H24B | 109.5 |
C9—C10—H10 | 118.6 | H24A—C24—H24B | 109.5 |
C11—C10—H10 | 118.6 | C21—C24—H24C | 109.5 |
C6—C11—C10 | 118.9 (3) | H24A—C24—H24C | 109.5 |
C6—C11—H11 | 120.5 | H24B—C24—H24C | 109.5 |
O2—N1—C1—C2 | 0.8 (4) | O4—N4—C13—C14 | −1.7 (4) |
O1—N1—C1—C2 | −178.6 (3) | O3—N4—C13—C14 | 177.3 (3) |
O2—N1—C1—C5 | −179.0 (3) | O4—N4—C13—C17 | 179.9 (3) |
O1—N1—C1—C5 | 1.5 (5) | O3—N4—C13—C17 | −1.1 (5) |
C5—C1—C2—C3 | 0.3 (5) | C17—C13—C14—C15 | 1.4 (5) |
N1—C1—C2—C3 | −179.6 (3) | N4—C13—C14—C15 | −177.0 (3) |
C1—C2—C3—C4 | −0.1 (5) | C13—C14—C15—C16 | −1.5 (5) |
C5—N2—C4—C3 | −0.7 (5) | C17—N5—C16—C15 | 0.9 (5) |
C2—C3—C4—N2 | 0.3 (5) | C14—C15—C16—N5 | 0.4 (5) |
C4—N2—C5—N3 | −179.1 (3) | C18—N6—C17—N5 | 0.8 (5) |
C4—N2—C5—C1 | 0.8 (5) | C18—N6—C17—C13 | −179.7 (3) |
C6—N3—C5—N2 | −11.7 (5) | C16—N5—C17—N6 | 178.6 (3) |
C6—N3—C5—C1 | 168.4 (3) | C16—N5—C17—C13 | −0.9 (5) |
C2—C1—C5—N2 | −0.6 (5) | C14—C13—C17—N6 | −179.7 (3) |
N1—C1—C5—N2 | 179.2 (3) | N4—C13—C17—N6 | −1.4 (5) |
C2—C1—C5—N3 | 179.3 (3) | C14—C13—C17—N5 | −0.2 (5) |
N1—C1—C5—N3 | −0.8 (5) | N4—C13—C17—N5 | 178.1 (3) |
C5—N3—C6—C11 | 22.3 (5) | C17—N6—C18—C23 | 35.9 (5) |
C5—N3—C6—C7 | −158.4 (3) | C17—N6—C18—C19 | −148.1 (3) |
C11—C6—C7—C8 | −2.8 (5) | C23—C18—C19—C20 | −1.0 (5) |
N3—C6—C7—C8 | 177.8 (3) | N6—C18—C19—C20 | −177.3 (3) |
C6—C7—C8—C9 | −0.5 (5) | C18—C19—C20—C21 | −1.3 (5) |
C7—C8—C9—C10 | 3.1 (5) | C19—C20—C21—C22 | 2.3 (5) |
C7—C8—C9—C12 | −176.3 (3) | C19—C20—C21—C24 | −177.1 (3) |
C8—C9—C10—C11 | −2.6 (5) | C20—C21—C22—C23 | −1.1 (5) |
C12—C9—C10—C11 | 176.8 (3) | C24—C21—C22—C23 | 178.3 (3) |
C7—C6—C11—C10 | 3.2 (5) | C21—C22—C23—C18 | −1.1 (5) |
N3—C6—C11—C10 | −177.4 (3) | C19—C18—C23—C22 | 2.2 (5) |
C9—C10—C11—C6 | −0.6 (5) | N6—C18—C23—C22 | 178.1 (3) |
Cg1 is the centroid of the C6–C11 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O1 | 0.87 (3) | 1.94 (3) | 2.630 (3) | 136 (3) |
N6—H6···O3 | 0.88 (4) | 1.93 (4) | 2.639 (3) | 137 (3) |
N3—H3···N1 | 0.87 (3) | 2.55 (3) | 2.932 (4) | 108 (2) |
N6—H6···N4 | 0.88 (4) | 2.54 (4) | 2.942 (4) | 109 (2) |
C14—H14···O2i | 0.95 | 2.39 | 3.199 (4) | 143 |
C4—H4···Cg1ii | 0.95 | 2.90 | 3.604 (4) | 132 |
C12—H12b···Cg1iii | 0.98 | 2.80 | 3.654 (4) | 146 |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1, y−1/2, −z+1/2; (iii) −x+2, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C12H11N3O2 |
Mr | 229.24 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 10.6557 (12), 7.1415 (8), 27.958 (3) |
β (°) | 91.310 (2) |
V (Å3) | 2127.0 (4) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.35 × 0.35 × 0.05 |
Data collection | |
Diffractometer | Bruker SMART APEX diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13178, 4804, 3344 |
Rint | 0.045 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.146, 1.04 |
No. of reflections | 4804 |
No. of parameters | 317 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.30, −0.28 |
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), DIAMOND (Brandenburg, 2006) and Qmol (Gans & Shalloway, 2001), publCIF (Westrip, 2010).
Cg1 is the centroid of the C6–C11 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O1 | 0.87 (3) | 1.94 (3) | 2.630 (3) | 136 (3) |
N6—H6···O3 | 0.88 (4) | 1.93 (4) | 2.639 (3) | 137 (3) |
N3—H3···N1 | 0.87 (3) | 2.55 (3) | 2.932 (4) | 108 (2) |
N6—H6···N4 | 0.88 (4) | 2.54 (4) | 2.942 (4) | 109 (2) |
C14—H14···O2i | 0.95 | 2.39 | 3.199 (4) | 143 |
C4—H4···Cg1ii | 0.95 | 2.90 | 3.604 (4) | 132 |
C12—H12b···Cg1iii | 0.98 | 2.80 | 3.654 (4) | 146 |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1, y−1/2, −z+1/2; (iii) −x+2, y+1/2, −z+1/2. |
Studies of pyridine and pyrimidine derivatives related to the title compound are of interest owing to their putative fluorescence properties (Kawai et al. 2001; Abdullah, 2005). As a continuation of structural studies on this class of N-heterocycles (Badaruddin et al., 2009; Fairuz et al., 2010), the title compound, (I), was investigated.
Two independent molecules comprise the asymmetric unit of (I), Figs 1 and 2. While the geometric parameters are in close agreement [r.m.s. deviation of bond distances and angles = 0.0080 Å and 0.849 °, respectively], these differ non-trivially in their conformations. So, while the pyridine groups are virtually super-imposable, the benzene rings are not, Fig. 3. This difference is quantified in the dihedral angles formed between the pyridine and benzene rings, i.e. N2,C1–C5/C6–C11 = 17.42 (16) ° and N5,C13–C17/C18–C23 = 34.64 (16) °. These indicate that there are also twists in the molecules as evidenced by the C6–N3–C5–N2 torsion angle of -11.7 (5) ° and, especially, the C5–N3–C6–C11 torsion angle of 22.3 (5) °. The equivalent torsion angles for the second independent molecule of C18–N6–C17–N5 = 0.8 (5) ° and C17–N6–C18–C23 = 35.9 (5) ° also highlight the differences between the molecules. The nitro groups are co-planar with the pyridine rings to which they are connected as indicated by the O1–N1–C1–C5 and O3–N4–C13–C17 torsion angles of 1.5 (5) and -1.1 (5) °, respectively. Close intramolecular N–H···O and C–H···N interactions are noted, Table 1.
The most notable intermolecular interactions in the crystal structure are of the type C–H···O [which connect the molecules comprising the asymmetric unit], C–H···π and π–π [ring centroid(N2,C1–C5)···centroid(C18–C23) = 3.6442 (19) Å and ring centroid(N5,C13–C17)···centroid(N5,C13–C17)i = 3.722 (2) Å for i: -x, 1 - y, -z] contacts. These serve to connect molecules into the three-dimensional structure, Fig. 4.