Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270111050207/yf3009sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111050207/yf3009Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111050207/yf3009IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111050207/yf3009IIIsup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111050207/yf3009IVsup5.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111050207/yf3009Vsup6.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111050207/yf3009VIsup7.hkl | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270111050207/yf3009Isup8.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270111050207/yf3009IIsup9.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270111050207/yf3009IIIsup10.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270111050207/yf3009IVsup11.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270111050207/yf3009Vsup12.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270111050207/yf3009VIsup13.cml |
CCDC references: 866751; 866752; 866753; 866754; 866755; 866756
For related literature, see: Bernstein et al. (1995); Bondi (1964); Cobo et al. (2008); Day (2005, 2009); Naylor & Wilson (1957); Quiroga et al. (2010); Riddell & Rogerson (1996, 1997); Rowland & Taylor (1996); Tannenbaum et al. (1956); Wood et al. (2009).
A suspension of the appropriate 4-aryl-3-methyl-1-phenyl-4,5-dihydro-1H-pyrazolo[3,4-b]pyridin-6(7H)-one (1 mmol) in dimethylformamide (2 ml) was cooled using an ice–water bath, and then phosphoryl chloride (0.2 ml, 2.1 mmol) was added dropwise. Each reaction mixture was stirred for 30 min at ambient temperature and subsequently heated at 373 K for 5 h. After cooling to ambient temperature by the addition of ice, the reaction mixture was neutralized using sodium hydrogencarbonate solution with vigorous stirring. In each case, the resulting yellow precipitate was collected by filtration, dried and recrystallized from dimethylformamide to afford yellow crystals suitable for single-crystal X-ray diffraction.
All H atoms were located in difference maps and then treated as riding atoms in geometrically idealized positions, with C—H = 0.95 Å (aromatic and formyl H) or 0.98 Å (methyl H), and with Uiso(H) = kUeq(C), where k = 1.5 for the methyl groups, which were permitted to rotate but not to tilt, and 1.2 for all other H atoms.
For all compounds, data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
C20H14ClN3O | F(000) = 1440 |
Mr = 347.79 | Dx = 1.391 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 3829 reflections |
a = 16.784 (3) Å | θ = 2.8–27.5° |
b = 9.6380 (8) Å | µ = 0.24 mm−1 |
c = 21.699 (4) Å | T = 120 K |
β = 108.820 (12)° | Plate, yellow |
V = 3322.5 (9) Å3 | 0.36 × 0.32 × 0.12 mm |
Z = 8 |
Bruker Nonius KappaCCD area-detector diffractometer | 3829 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 2899 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.8° |
ϕ and ω scans | h = −21→21 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −12→12 |
Tmin = 0.918, Tmax = 0.972 | l = −28→26 |
24328 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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.100 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0385P)2 + 3.9079P] where P = (Fo2 + 2Fc2)/3 |
3829 reflections | (Δ/σ)max = 0.001 |
227 parameters | Δρmax = 0.49 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
C20H14ClN3O | V = 3322.5 (9) Å3 |
Mr = 347.79 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 16.784 (3) Å | µ = 0.24 mm−1 |
b = 9.6380 (8) Å | T = 120 K |
c = 21.699 (4) Å | 0.36 × 0.32 × 0.12 mm |
β = 108.820 (12)° |
Bruker Nonius KappaCCD area-detector diffractometer | 3829 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2899 reflections with I > 2σ(I) |
Tmin = 0.918, Tmax = 0.972 | Rint = 0.042 |
24328 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.100 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.49 e Å−3 |
3829 reflections | Δρmin = −0.37 e Å−3 |
227 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.61518 (9) | 0.77753 (14) | 0.30751 (6) | 0.0203 (3) | |
N2 | 0.62845 (9) | 0.87541 (14) | 0.26471 (7) | 0.0208 (3) | |
C3 | 0.63645 (10) | 0.80687 (17) | 0.21430 (8) | 0.0192 (3) | |
C3A | 0.62744 (10) | 0.66021 (17) | 0.22259 (7) | 0.0181 (3) | |
C4 | 0.62831 (10) | 0.53953 (17) | 0.18655 (8) | 0.0184 (3) | |
C5 | 0.62021 (10) | 0.41257 (17) | 0.21619 (8) | 0.0206 (3) | |
C6 | 0.60951 (10) | 0.41769 (17) | 0.27884 (8) | 0.0207 (3) | |
N7 | 0.60520 (9) | 0.52877 (14) | 0.31282 (6) | 0.0202 (3) | |
C7A | 0.61528 (10) | 0.64769 (17) | 0.28342 (8) | 0.0185 (3) | |
C11 | 0.60653 (10) | 0.82139 (17) | 0.36809 (8) | 0.0192 (3) | |
C12 | 0.64242 (10) | 0.74385 (18) | 0.42428 (8) | 0.0215 (3) | |
H12 | 0.6722 | 0.6607 | 0.4228 | 0.026* | |
C13 | 0.63403 (11) | 0.78982 (19) | 0.48259 (8) | 0.0248 (4) | |
H13 | 0.6569 | 0.7365 | 0.5211 | 0.030* | |
C14 | 0.59240 (11) | 0.9133 (2) | 0.48478 (9) | 0.0270 (4) | |
H14 | 0.5879 | 0.9452 | 0.5249 | 0.032* | |
C15 | 0.55732 (11) | 0.99015 (19) | 0.42837 (9) | 0.0265 (4) | |
H15 | 0.5293 | 1.0749 | 0.4302 | 0.032* | |
C16 | 0.56308 (10) | 0.94364 (17) | 0.36920 (8) | 0.0222 (4) | |
H16 | 0.5378 | 0.9945 | 0.3303 | 0.027* | |
C31 | 0.65590 (11) | 0.88296 (18) | 0.16076 (8) | 0.0240 (4) | |
H31A | 0.6667 | 0.9808 | 0.1728 | 0.036* | |
H31B | 0.6079 | 0.8758 | 0.1206 | 0.036* | |
H31C | 0.7058 | 0.8421 | 0.1538 | 0.036* | |
C41 | 0.63590 (10) | 0.55640 (17) | 0.12031 (8) | 0.0187 (3) | |
C42 | 0.56670 (11) | 0.60427 (19) | 0.07000 (8) | 0.0250 (4) | |
H42 | 0.5141 | 0.6163 | 0.0770 | 0.030* | |
C43 | 0.57428 (12) | 0.63463 (19) | 0.00944 (8) | 0.0277 (4) | |
H43 | 0.5267 | 0.6666 | −0.0249 | 0.033* | |
C44 | 0.65076 (12) | 0.61841 (19) | −0.00092 (9) | 0.0288 (4) | |
H44 | 0.6559 | 0.6394 | −0.0423 | 0.035* | |
C45 | 0.72012 (12) | 0.5714 (2) | 0.04917 (9) | 0.0293 (4) | |
H45 | 0.7728 | 0.5608 | 0.0421 | 0.035* | |
C46 | 0.71279 (11) | 0.53974 (18) | 0.10968 (8) | 0.0237 (4) | |
H46 | 0.7603 | 0.5068 | 0.1437 | 0.028* | |
C51 | 0.62123 (13) | 0.27727 (19) | 0.18430 (9) | 0.0299 (4) | |
H51 | 0.6249 | 0.1966 | 0.2103 | 0.036* | |
O51 | 0.61791 (11) | 0.25957 (14) | 0.12891 (7) | 0.0459 (4) | |
Cl61 | 0.59974 (3) | 0.26249 (4) | 0.31752 (2) | 0.02823 (13) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0289 (8) | 0.0157 (7) | 0.0183 (7) | −0.0022 (6) | 0.0103 (6) | −0.0012 (5) |
N2 | 0.0263 (7) | 0.0166 (7) | 0.0206 (7) | −0.0013 (6) | 0.0093 (6) | 0.0014 (6) |
C3 | 0.0210 (8) | 0.0183 (8) | 0.0184 (8) | −0.0013 (6) | 0.0066 (6) | −0.0012 (6) |
C3A | 0.0199 (8) | 0.0181 (8) | 0.0166 (8) | −0.0007 (6) | 0.0063 (6) | −0.0002 (6) |
C4 | 0.0174 (8) | 0.0197 (8) | 0.0169 (8) | 0.0017 (6) | 0.0040 (6) | −0.0001 (6) |
C5 | 0.0253 (9) | 0.0183 (8) | 0.0176 (8) | 0.0005 (7) | 0.0061 (7) | −0.0005 (6) |
C6 | 0.0248 (9) | 0.0176 (8) | 0.0191 (8) | −0.0005 (7) | 0.0066 (7) | 0.0027 (7) |
N7 | 0.0246 (7) | 0.0170 (7) | 0.0197 (7) | −0.0020 (6) | 0.0081 (6) | −0.0006 (6) |
C7A | 0.0212 (8) | 0.0163 (8) | 0.0180 (8) | −0.0014 (6) | 0.0062 (6) | −0.0011 (6) |
C11 | 0.0221 (8) | 0.0201 (8) | 0.0174 (8) | −0.0054 (7) | 0.0092 (6) | −0.0041 (6) |
C12 | 0.0219 (8) | 0.0213 (8) | 0.0224 (8) | −0.0009 (7) | 0.0084 (7) | −0.0020 (7) |
C13 | 0.0244 (9) | 0.0319 (10) | 0.0190 (8) | −0.0054 (7) | 0.0084 (7) | −0.0017 (7) |
C14 | 0.0268 (9) | 0.0330 (10) | 0.0269 (9) | −0.0084 (8) | 0.0166 (7) | −0.0100 (8) |
C15 | 0.0269 (9) | 0.0230 (9) | 0.0351 (10) | −0.0027 (7) | 0.0175 (8) | −0.0072 (8) |
C16 | 0.0232 (8) | 0.0203 (9) | 0.0246 (9) | −0.0035 (7) | 0.0099 (7) | −0.0016 (7) |
C31 | 0.0301 (9) | 0.0203 (9) | 0.0234 (9) | −0.0011 (7) | 0.0113 (7) | 0.0010 (7) |
C41 | 0.0242 (9) | 0.0154 (8) | 0.0172 (8) | 0.0001 (6) | 0.0077 (6) | −0.0018 (6) |
C42 | 0.0228 (9) | 0.0302 (10) | 0.0219 (9) | 0.0029 (7) | 0.0069 (7) | 0.0006 (7) |
C43 | 0.0312 (10) | 0.0303 (10) | 0.0180 (8) | 0.0032 (8) | 0.0031 (7) | 0.0037 (7) |
C44 | 0.0416 (11) | 0.0277 (10) | 0.0196 (9) | −0.0001 (8) | 0.0134 (8) | 0.0010 (7) |
C45 | 0.0302 (10) | 0.0345 (10) | 0.0283 (9) | 0.0040 (8) | 0.0165 (8) | 0.0002 (8) |
C46 | 0.0234 (9) | 0.0251 (9) | 0.0226 (8) | 0.0061 (7) | 0.0073 (7) | 0.0013 (7) |
C51 | 0.0467 (12) | 0.0196 (9) | 0.0259 (9) | 0.0022 (8) | 0.0153 (8) | 0.0004 (7) |
O51 | 0.0934 (13) | 0.0231 (7) | 0.0288 (7) | −0.0026 (8) | 0.0303 (8) | −0.0054 (6) |
Cl61 | 0.0447 (3) | 0.0174 (2) | 0.0234 (2) | −0.00270 (19) | 0.01203 (18) | 0.00244 (17) |
N1—C7A | 1.356 (2) | C14—C15 | 1.389 (3) |
N1—N2 | 1.3911 (19) | C14—H14 | 0.9500 |
N1—C11 | 1.432 (2) | C15—C16 | 1.392 (2) |
N2—C3 | 1.321 (2) | C15—H15 | 0.9500 |
C3—C3A | 1.439 (2) | C16—H16 | 0.9500 |
C3—C31 | 1.496 (2) | C31—H31A | 0.9800 |
C3A—C4 | 1.404 (2) | C31—H31B | 0.9800 |
C3A—C7A | 1.404 (2) | C31—H31C | 0.9800 |
C4—C5 | 1.409 (2) | C41—C42 | 1.391 (2) |
C4—C41 | 1.492 (2) | C41—C46 | 1.392 (2) |
C5—C6 | 1.428 (2) | C42—C43 | 1.392 (2) |
C5—C51 | 1.479 (2) | C42—H42 | 0.9500 |
C6—N7 | 1.315 (2) | C43—C44 | 1.382 (3) |
C6—Cl61 | 1.7486 (17) | C43—H43 | 0.9500 |
N7—C7A | 1.349 (2) | C44—C45 | 1.388 (3) |
C11—C16 | 1.390 (2) | C44—H44 | 0.9500 |
C11—C12 | 1.391 (2) | C45—C46 | 1.391 (2) |
C12—C13 | 1.390 (2) | C45—H45 | 0.9500 |
C12—H12 | 0.9500 | C46—H46 | 0.9500 |
C13—C14 | 1.388 (3) | C51—O51 | 1.197 (2) |
C13—H13 | 0.9500 | C51—H51 | 0.9500 |
C7A—N1—N2 | 110.38 (13) | C15—C14—H14 | 119.9 |
C7A—N1—C11 | 129.72 (14) | C14—C15—C16 | 120.34 (17) |
N2—N1—C11 | 119.87 (13) | C14—C15—H15 | 119.8 |
C3—N2—N1 | 107.13 (13) | C16—C15—H15 | 119.8 |
N2—C3—C3A | 110.16 (14) | C11—C16—C15 | 118.79 (16) |
N2—C3—C31 | 120.25 (15) | C11—C16—H16 | 120.6 |
C3A—C3—C31 | 129.54 (15) | C15—C16—H16 | 120.6 |
C4—C3A—C7A | 118.88 (15) | C3—C31—H31A | 109.5 |
C4—C3A—C3 | 136.35 (15) | C3—C31—H31B | 109.5 |
C7A—C3A—C3 | 104.77 (14) | H31A—C31—H31B | 109.5 |
C3A—C4—C5 | 116.44 (14) | C3—C31—H31C | 109.5 |
C3A—C4—C41 | 117.75 (14) | H31A—C31—H31C | 109.5 |
C5—C4—C41 | 125.81 (14) | H31B—C31—H31C | 109.5 |
C4—C5—C6 | 117.69 (15) | C42—C41—C46 | 119.49 (15) |
C4—C5—C51 | 122.32 (15) | C42—C41—C4 | 118.87 (14) |
C6—C5—C51 | 119.99 (15) | C46—C41—C4 | 121.26 (14) |
N7—C6—C5 | 127.46 (15) | C41—C42—C43 | 120.21 (16) |
N7—C6—Cl61 | 113.37 (12) | C41—C42—H42 | 119.9 |
C5—C6—Cl61 | 119.17 (12) | C43—C42—H42 | 119.9 |
C6—N7—C7A | 112.87 (13) | C44—C43—C42 | 120.17 (16) |
N7—C7A—N1 | 125.87 (14) | C44—C43—H43 | 119.9 |
N7—C7A—C3A | 126.58 (15) | C42—C43—H43 | 119.9 |
N1—C7A—C3A | 107.55 (14) | C43—C44—C45 | 119.88 (16) |
C16—C11—C12 | 121.44 (15) | C43—C44—H44 | 120.1 |
C16—C11—N1 | 118.37 (14) | C45—C44—H44 | 120.1 |
C12—C11—N1 | 120.18 (15) | C44—C45—C46 | 120.23 (17) |
C13—C12—C11 | 118.97 (16) | C44—C45—H45 | 119.9 |
C13—C12—H12 | 120.5 | C46—C45—H45 | 119.9 |
C11—C12—H12 | 120.5 | C45—C46—C41 | 120.01 (16) |
C14—C13—C12 | 120.28 (17) | C45—C46—H46 | 120.0 |
C14—C13—H13 | 119.9 | C41—C46—H46 | 120.0 |
C12—C13—H13 | 119.9 | O51—C51—C5 | 126.26 (17) |
C13—C14—C15 | 120.14 (16) | O51—C51—H51 | 116.9 |
C13—C14—H14 | 119.9 | C5—C51—H51 | 116.9 |
C7A—N1—N2—C3 | 0.20 (18) | C3—C3A—C7A—N7 | −178.79 (16) |
C11—N1—N2—C3 | 178.24 (14) | C4—C3A—C7A—N1 | −178.70 (14) |
N1—N2—C3—C3A | 0.73 (18) | C3—C3A—C7A—N1 | 1.41 (18) |
N1—N2—C3—C31 | −176.85 (14) | C7A—N1—C11—C16 | −144.49 (17) |
N2—C3—C3A—C4 | 178.80 (18) | N2—N1—C11—C16 | 37.9 (2) |
C31—C3—C3A—C4 | −3.9 (3) | C7A—N1—C11—C12 | 36.7 (3) |
N2—C3—C3A—C7A | −1.34 (19) | N2—N1—C11—C12 | −140.93 (16) |
C31—C3—C3A—C7A | 175.94 (17) | C16—C11—C12—C13 | 0.3 (2) |
C7A—C3A—C4—C5 | −2.6 (2) | N1—C11—C12—C13 | 179.13 (15) |
C3—C3A—C4—C5 | 177.25 (18) | C11—C12—C13—C14 | −1.7 (2) |
C7A—C3A—C4—C41 | 176.22 (14) | C12—C13—C14—C15 | 1.4 (3) |
C3—C3A—C4—C41 | −3.9 (3) | C13—C14—C15—C16 | 0.5 (3) |
C3A—C4—C5—C6 | 1.7 (2) | C12—C11—C16—C15 | 1.4 (2) |
C41—C4—C5—C6 | −176.96 (15) | N1—C11—C16—C15 | −177.38 (15) |
C3A—C4—C5—C51 | −179.17 (16) | C14—C15—C16—C11 | −1.8 (3) |
C41—C4—C5—C51 | 2.1 (3) | C3A—C4—C41—C42 | −73.6 (2) |
C4—C5—C6—N7 | 0.9 (3) | C5—C4—C41—C42 | 105.1 (2) |
C51—C5—C6—N7 | −178.24 (17) | C3A—C4—C41—C46 | 99.36 (19) |
C4—C5—C6—Cl61 | −179.69 (12) | C5—C4—C41—C46 | −82.0 (2) |
C51—C5—C6—Cl61 | 1.2 (2) | C46—C41—C42—C43 | 0.3 (3) |
C5—C6—N7—C7A | −2.4 (2) | C4—C41—C42—C43 | 173.40 (16) |
Cl61—C6—N7—C7A | 178.17 (12) | C41—C42—C43—C44 | −0.5 (3) |
C6—N7—C7A—N1 | −178.88 (16) | C42—C43—C44—C45 | 0.2 (3) |
C6—N7—C7A—C3A | 1.4 (2) | C43—C44—C45—C46 | 0.4 (3) |
N2—N1—C7A—N7 | 179.15 (15) | C44—C45—C46—C41 | −0.6 (3) |
C11—N1—C7A—N7 | 1.4 (3) | C42—C41—C46—C45 | 0.2 (3) |
N2—N1—C7A—C3A | −1.05 (18) | C4—C41—C46—C45 | −172.69 (16) |
C11—N1—C7A—C3A | −178.84 (15) | C4—C5—C51—O51 | −10.2 (3) |
C4—C3A—C7A—N7 | 1.1 (3) | C6—C5—C51—O51 | 168.9 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C46—H46···N2i | 0.95 | 2.58 | 3.515 (2) | 169 |
C45—H45···Cg1i | 0.95 | 2.76 | 3.508 (2) | 136 |
Symmetry code: (i) −x+3/2, y−1/2, −z+1/2. |
C21H16ClN3O | Z = 2 |
Mr = 361.82 | F(000) = 376 |
Triclinic, P1 | Dx = 1.419 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.2898 (8) Å | Cell parameters from 3880 reflections |
b = 9.9191 (14) Å | θ = 2.8–27.5° |
c = 10.3666 (10) Å | µ = 0.24 mm−1 |
α = 87.108 (11)° | T = 120 K |
β = 86.808 (8)° | Block, yellow |
γ = 85.088 (12)° | 0.31 × 0.26 × 0.20 mm |
V = 847.08 (17) Å3 |
Bruker Nonius KappaCCD area-detector diffractometer | 3880 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 2544 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.074 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.8° |
ϕ and ω scans | h = −10→10 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −12→12 |
Tmin = 0.929, Tmax = 0.953 | l = −13→13 |
21387 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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0595P)2 + 0.3061P] where P = (Fo2 + 2Fc2)/3 |
3880 reflections | (Δ/σ)max = 0.001 |
237 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.30 e Å−3 |
C21H16ClN3O | γ = 85.088 (12)° |
Mr = 361.82 | V = 847.08 (17) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.2898 (8) Å | Mo Kα radiation |
b = 9.9191 (14) Å | µ = 0.24 mm−1 |
c = 10.3666 (10) Å | T = 120 K |
α = 87.108 (11)° | 0.31 × 0.26 × 0.20 mm |
β = 86.808 (8)° |
Bruker Nonius KappaCCD area-detector diffractometer | 3880 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2544 reflections with I > 2σ(I) |
Tmin = 0.929, Tmax = 0.953 | Rint = 0.074 |
21387 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.31 e Å−3 |
3880 reflections | Δρmin = −0.30 e Å−3 |
237 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.8216 (2) | 0.36034 (18) | 0.45983 (18) | 0.0202 (4) | |
N2 | 0.8403 (2) | 0.22014 (19) | 0.47406 (18) | 0.0231 (5) | |
C3 | 0.7378 (3) | 0.1833 (2) | 0.5691 (2) | 0.0221 (5) | |
C3A | 0.6477 (3) | 0.3001 (2) | 0.6208 (2) | 0.0198 (5) | |
C4 | 0.5268 (3) | 0.3271 (2) | 0.7190 (2) | 0.0195 (5) | |
C5 | 0.4905 (3) | 0.4637 (2) | 0.7485 (2) | 0.0193 (5) | |
C6 | 0.5670 (3) | 0.5641 (2) | 0.6709 (2) | 0.0204 (5) | |
N7 | 0.6692 (2) | 0.54259 (18) | 0.57091 (17) | 0.0199 (4) | |
C7A | 0.7098 (3) | 0.4109 (2) | 0.5509 (2) | 0.0194 (5) | |
C11 | 0.9124 (3) | 0.4268 (2) | 0.3586 (2) | 0.0210 (5) | |
C12 | 0.9105 (3) | 0.5677 (2) | 0.3491 (2) | 0.0236 (5) | |
H12 | 0.8506 | 0.6213 | 0.4115 | 0.028* | |
C13 | 0.9975 (3) | 0.6285 (3) | 0.2469 (2) | 0.0260 (5) | |
H13 | 0.9964 | 0.7245 | 0.2400 | 0.031* | |
C14 | 1.0859 (3) | 0.5521 (3) | 0.1548 (2) | 0.0280 (6) | |
H14 | 1.1441 | 0.5949 | 0.0851 | 0.034* | |
C15 | 1.0878 (3) | 0.4122 (3) | 0.1663 (2) | 0.0291 (6) | |
H15 | 1.1485 | 0.3590 | 0.1040 | 0.035* | |
C16 | 1.0022 (3) | 0.3484 (3) | 0.2675 (2) | 0.0255 (5) | |
H16 | 1.0048 | 0.2524 | 0.2746 | 0.031* | |
C31 | 0.7374 (3) | 0.0363 (2) | 0.6096 (2) | 0.0309 (6) | |
H31A | 0.6364 | 0.0021 | 0.5854 | 0.046* | |
H31B | 0.7457 | 0.0252 | 0.7036 | 0.046* | |
H31C | 0.8299 | −0.0145 | 0.5665 | 0.046* | |
C41 | 0.4377 (3) | 0.2165 (2) | 0.7840 (2) | 0.0207 (5) | |
C42 | 0.3615 (3) | 0.1310 (2) | 0.7071 (2) | 0.0249 (5) | |
H42 | 0.3705 | 0.1431 | 0.6156 | 0.030* | |
C43 | 0.2731 (3) | 0.0290 (2) | 0.7637 (2) | 0.0264 (6) | |
H43 | 0.2216 | −0.0275 | 0.7102 | 0.032* | |
C44 | 0.2585 (3) | 0.0080 (2) | 0.8977 (2) | 0.0260 (6) | |
C45 | 0.3322 (3) | 0.0944 (2) | 0.9731 (2) | 0.0260 (6) | |
H45 | 0.3218 | 0.0829 | 1.0646 | 0.031* | |
C46 | 0.4208 (3) | 0.1972 (2) | 0.9177 (2) | 0.0228 (5) | |
H46 | 0.4702 | 0.2547 | 0.9716 | 0.027* | |
C47 | 0.1682 (3) | −0.1078 (2) | 0.9582 (3) | 0.0353 (7) | |
H47A | 0.1658 | −0.1046 | 1.0526 | 0.053* | |
H47B | 0.2235 | −0.1941 | 0.9317 | 0.053* | |
H47C | 0.0571 | −0.0997 | 0.9294 | 0.053* | |
C51 | 0.3683 (3) | 0.4986 (2) | 0.8547 (2) | 0.0205 (5) | |
H51 | 0.2805 | 0.4433 | 0.8694 | 0.025* | |
O51 | 0.3734 (2) | 0.59303 (16) | 0.92369 (16) | 0.0276 (4) | |
Cl61 | 0.51892 (7) | 0.73502 (6) | 0.69788 (6) | 0.02657 (18) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0215 (10) | 0.0189 (10) | 0.0202 (10) | −0.0022 (8) | 0.0017 (8) | −0.0015 (8) |
N2 | 0.0260 (11) | 0.0199 (10) | 0.0230 (11) | −0.0005 (8) | 0.0003 (9) | −0.0009 (8) |
C3 | 0.0245 (13) | 0.0208 (12) | 0.0209 (12) | −0.0021 (10) | 0.0003 (10) | −0.0018 (10) |
C3A | 0.0203 (12) | 0.0193 (12) | 0.0198 (12) | −0.0010 (9) | −0.0021 (9) | −0.0007 (9) |
C4 | 0.0189 (12) | 0.0201 (12) | 0.0203 (12) | −0.0042 (9) | −0.0036 (9) | −0.0012 (9) |
C5 | 0.0188 (12) | 0.0199 (12) | 0.0197 (12) | −0.0037 (9) | −0.0010 (9) | −0.0021 (9) |
C6 | 0.0202 (12) | 0.0212 (12) | 0.0201 (12) | −0.0018 (9) | −0.0030 (10) | −0.0016 (9) |
N7 | 0.0199 (10) | 0.0199 (10) | 0.0202 (10) | −0.0023 (8) | −0.0013 (8) | −0.0024 (8) |
C7A | 0.0189 (12) | 0.0206 (12) | 0.0190 (12) | −0.0027 (9) | −0.0013 (9) | −0.0018 (9) |
C11 | 0.0190 (12) | 0.0265 (13) | 0.0179 (12) | −0.0043 (10) | −0.0013 (9) | 0.0007 (10) |
C12 | 0.0230 (12) | 0.0254 (13) | 0.0221 (12) | −0.0017 (10) | 0.0003 (10) | −0.0002 (10) |
C13 | 0.0223 (13) | 0.0283 (14) | 0.0277 (13) | −0.0047 (10) | −0.0039 (10) | 0.0033 (11) |
C14 | 0.0223 (13) | 0.0392 (15) | 0.0222 (13) | −0.0059 (11) | 0.0011 (10) | 0.0043 (11) |
C15 | 0.0282 (14) | 0.0369 (15) | 0.0218 (13) | −0.0024 (11) | 0.0043 (10) | −0.0028 (11) |
C16 | 0.0254 (13) | 0.0277 (13) | 0.0230 (13) | −0.0017 (10) | 0.0031 (10) | −0.0016 (10) |
C31 | 0.0389 (15) | 0.0211 (13) | 0.0309 (14) | 0.0004 (11) | 0.0092 (12) | −0.0015 (11) |
C41 | 0.0203 (12) | 0.0181 (11) | 0.0231 (12) | −0.0005 (9) | 0.0029 (10) | −0.0005 (9) |
C42 | 0.0293 (13) | 0.0209 (12) | 0.0248 (13) | −0.0028 (10) | 0.0001 (10) | −0.0040 (10) |
C43 | 0.0261 (13) | 0.0203 (12) | 0.0335 (14) | −0.0052 (10) | 0.0024 (11) | −0.0074 (11) |
C44 | 0.0205 (12) | 0.0191 (12) | 0.0373 (15) | −0.0010 (10) | 0.0072 (11) | −0.0003 (11) |
C45 | 0.0292 (14) | 0.0224 (13) | 0.0251 (13) | −0.0023 (10) | 0.0058 (11) | 0.0034 (10) |
C46 | 0.0251 (13) | 0.0179 (12) | 0.0257 (13) | −0.0014 (10) | 0.0002 (10) | −0.0041 (10) |
C47 | 0.0323 (15) | 0.0211 (13) | 0.0514 (17) | −0.0042 (11) | 0.0096 (13) | 0.0003 (12) |
C51 | 0.0201 (12) | 0.0186 (12) | 0.0224 (12) | −0.0006 (9) | −0.0011 (10) | 0.0005 (10) |
O51 | 0.0311 (10) | 0.0252 (9) | 0.0267 (9) | −0.0037 (7) | 0.0044 (7) | −0.0067 (7) |
Cl61 | 0.0322 (3) | 0.0184 (3) | 0.0286 (3) | −0.0021 (2) | 0.0044 (3) | −0.0020 (2) |
N1—C7A | 1.369 (3) | C15—C16 | 1.389 (3) |
N1—N2 | 1.387 (3) | C15—H15 | 0.9500 |
N1—C11 | 1.425 (3) | C16—H16 | 0.9500 |
N2—C3 | 1.323 (3) | C31—H31A | 0.9800 |
C3—C3A | 1.433 (3) | C31—H31B | 0.9800 |
C3—C31 | 1.497 (3) | C31—H31C | 0.9800 |
C3A—C7A | 1.404 (3) | C41—C46 | 1.390 (3) |
C3A—C4 | 1.408 (3) | C41—C42 | 1.404 (3) |
C4—C5 | 1.407 (3) | C42—C43 | 1.386 (3) |
C4—C41 | 1.488 (3) | C42—H42 | 0.9500 |
C5—C6 | 1.418 (3) | C43—C44 | 1.394 (3) |
C5—C51 | 1.488 (3) | C43—H43 | 0.9500 |
C6—N7 | 1.316 (3) | C44—C45 | 1.389 (3) |
C6—Cl61 | 1.741 (2) | C44—C47 | 1.515 (3) |
N7—C7A | 1.344 (3) | C45—C46 | 1.390 (3) |
C11—C12 | 1.394 (3) | C45—H45 | 0.9500 |
C11—C16 | 1.396 (3) | C46—H46 | 0.9500 |
C12—C13 | 1.390 (3) | C47—H47A | 0.9800 |
C12—H12 | 0.9500 | C47—H47B | 0.9800 |
C13—C14 | 1.386 (3) | C47—H47C | 0.9800 |
C13—H13 | 0.9500 | C51—O51 | 1.211 (3) |
C14—C15 | 1.386 (3) | C51—H51 | 0.9500 |
C14—H14 | 0.9500 | ||
C7A—N1—N2 | 109.91 (17) | C16—C15—H15 | 119.5 |
C7A—N1—C11 | 131.02 (19) | C15—C16—C11 | 119.3 (2) |
N2—N1—C11 | 119.06 (17) | C15—C16—H16 | 120.3 |
C3—N2—N1 | 107.36 (18) | C11—C16—H16 | 120.3 |
N2—C3—C3A | 110.3 (2) | C3—C31—H31A | 109.5 |
N2—C3—C31 | 118.8 (2) | C3—C31—H31B | 109.5 |
C3A—C3—C31 | 130.8 (2) | H31A—C31—H31B | 109.5 |
C7A—C3A—C4 | 117.9 (2) | C3—C31—H31C | 109.5 |
C7A—C3A—C3 | 104.83 (19) | H31A—C31—H31C | 109.5 |
C4—C3A—C3 | 137.3 (2) | H31B—C31—H31C | 109.5 |
C5—C4—C3A | 116.8 (2) | C46—C41—C42 | 118.4 (2) |
C5—C4—C41 | 122.06 (19) | C46—C41—C4 | 123.0 (2) |
C3A—C4—C41 | 121.1 (2) | C42—C41—C4 | 118.5 (2) |
C4—C5—C6 | 118.29 (19) | C43—C42—C41 | 120.5 (2) |
C4—C5—C51 | 119.44 (19) | C43—C42—H42 | 119.7 |
C6—C5—C51 | 122.2 (2) | C41—C42—H42 | 119.7 |
N7—C6—C5 | 126.2 (2) | C42—C43—C44 | 121.1 (2) |
N7—C6—Cl61 | 113.51 (17) | C42—C43—H43 | 119.4 |
C5—C6—Cl61 | 120.22 (17) | C44—C43—H43 | 119.4 |
C6—N7—C7A | 113.97 (19) | C45—C44—C43 | 117.9 (2) |
N7—C7A—N1 | 126.1 (2) | C45—C44—C47 | 121.4 (2) |
N7—C7A—C3A | 126.5 (2) | C43—C44—C47 | 120.7 (2) |
N1—C7A—C3A | 107.44 (19) | C44—C45—C46 | 121.5 (2) |
C12—C11—C16 | 120.3 (2) | C44—C45—H45 | 119.2 |
C12—C11—N1 | 121.0 (2) | C46—C45—H45 | 119.2 |
C16—C11—N1 | 118.8 (2) | C45—C46—C41 | 120.4 (2) |
C13—C12—C11 | 119.1 (2) | C45—C46—H46 | 119.8 |
C13—C12—H12 | 120.5 | C41—C46—H46 | 119.8 |
C11—C12—H12 | 120.5 | C44—C47—H47A | 109.5 |
C14—C13—C12 | 121.3 (2) | C44—C47—H47B | 109.5 |
C14—C13—H13 | 119.3 | H47A—C47—H47B | 109.5 |
C12—C13—H13 | 119.3 | C44—C47—H47C | 109.5 |
C15—C14—C13 | 118.9 (2) | H47A—C47—H47C | 109.5 |
C15—C14—H14 | 120.6 | H47B—C47—H47C | 109.5 |
C13—C14—H14 | 120.6 | O51—C51—C5 | 124.3 (2) |
C14—C15—C16 | 121.1 (2) | O51—C51—H51 | 117.8 |
C14—C15—H15 | 119.5 | C5—C51—H51 | 117.8 |
C7A—N1—N2—C3 | 2.2 (2) | C4—C3A—C7A—N1 | −178.64 (19) |
C11—N1—N2—C3 | −176.78 (19) | C3—C3A—C7A—N1 | 3.3 (2) |
N1—N2—C3—C3A | 0.0 (3) | C7A—N1—C11—C12 | 8.1 (4) |
N1—N2—C3—C31 | −177.3 (2) | N2—N1—C11—C12 | −173.2 (2) |
N2—C3—C3A—C7A | −2.1 (3) | C7A—N1—C11—C16 | −171.1 (2) |
C31—C3—C3A—C7A | 174.7 (2) | N2—N1—C11—C16 | 7.7 (3) |
N2—C3—C3A—C4 | −179.5 (3) | C16—C11—C12—C13 | 0.8 (3) |
C31—C3—C3A—C4 | −2.7 (5) | N1—C11—C12—C13 | −178.3 (2) |
C7A—C3A—C4—C5 | −6.7 (3) | C11—C12—C13—C14 | −0.1 (4) |
C3—C3A—C4—C5 | 170.5 (3) | C12—C13—C14—C15 | −0.5 (4) |
C7A—C3A—C4—C41 | 170.9 (2) | C13—C14—C15—C16 | 0.4 (4) |
C3—C3A—C4—C41 | −12.0 (4) | C14—C15—C16—C11 | 0.3 (4) |
C3A—C4—C5—C6 | 5.2 (3) | C12—C11—C16—C15 | −0.9 (4) |
C41—C4—C5—C6 | −172.2 (2) | N1—C11—C16—C15 | 178.2 (2) |
C3A—C4—C5—C51 | −177.7 (2) | C5—C4—C41—C46 | −53.5 (3) |
C41—C4—C5—C51 | 4.8 (3) | C3A—C4—C41—C46 | 129.1 (2) |
C4—C5—C6—N7 | 0.9 (4) | C5—C4—C41—C42 | 123.8 (2) |
C51—C5—C6—N7 | −176.0 (2) | C3A—C4—C41—C42 | −53.6 (3) |
C4—C5—C6—Cl61 | 176.80 (17) | C46—C41—C42—C43 | −0.7 (3) |
C51—C5—C6—Cl61 | −0.2 (3) | C4—C41—C42—C43 | −178.1 (2) |
C5—C6—N7—C7A | −5.2 (3) | C41—C42—C43—C44 | −0.4 (4) |
Cl61—C6—N7—C7A | 178.65 (16) | C42—C43—C44—C45 | 1.4 (4) |
C6—N7—C7A—N1 | −175.2 (2) | C42—C43—C44—C47 | −177.1 (2) |
C6—N7—C7A—C3A | 3.6 (3) | C43—C44—C45—C46 | −1.3 (4) |
N2—N1—C7A—N7 | 175.5 (2) | C47—C44—C45—C46 | 177.3 (2) |
C11—N1—C7A—N7 | −5.7 (4) | C44—C45—C46—C41 | 0.1 (4) |
N2—N1—C7A—C3A | −3.5 (2) | C42—C41—C46—C45 | 0.8 (3) |
C11—N1—C7A—C3A | 175.3 (2) | C4—C41—C46—C45 | 178.1 (2) |
C4—C3A—C7A—N7 | 2.4 (4) | C4—C5—C51—O51 | 147.5 (2) |
C3—C3A—C7A—N7 | −175.7 (2) | C6—C5—C51—O51 | −35.6 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14···O51i | 0.95 | 2.46 | 3.319 (3) | 150 |
C46—H46···O51ii | 0.95 | 2.41 | 3.348 (3) | 170 |
Symmetry codes: (i) x+1, y, z−1; (ii) −x+1, −y+1, −z+2. |
C20H13Cl2N3O | F(000) = 1568 |
Mr = 382.23 | Dx = 1.497 Mg m−3 |
Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2n 2ab | Cell parameters from 3898 reflections |
a = 20.868 (3) Å | θ = 2.6–27.5° |
b = 9.603 (4) Å | µ = 0.40 mm−1 |
c = 16.924 (9) Å | T = 120 K |
V = 3391 (2) Å3 | Block, yellow |
Z = 8 | 0.40 × 0.37 × 0.28 mm |
Bruker Nonius KappaCCD area-detector diffractometer | 3898 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 2444 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.080 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.6° |
ϕ and ω scans | h = −26→27 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −12→12 |
Tmin = 0.857, Tmax = 0.897 | l = −21→21 |
34307 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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.147 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0644P)2 + 2.799P] where P = (Fo2 + 2Fc2)/3 |
3898 reflections | (Δ/σ)max = 0.001 |
236 parameters | Δρmax = 0.62 e Å−3 |
0 restraints | Δρmin = −0.46 e Å−3 |
C20H13Cl2N3O | V = 3391 (2) Å3 |
Mr = 382.23 | Z = 8 |
Orthorhombic, Pbcn | Mo Kα radiation |
a = 20.868 (3) Å | µ = 0.40 mm−1 |
b = 9.603 (4) Å | T = 120 K |
c = 16.924 (9) Å | 0.40 × 0.37 × 0.28 mm |
Bruker Nonius KappaCCD area-detector diffractometer | 3898 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2444 reflections with I > 2σ(I) |
Tmin = 0.857, Tmax = 0.897 | Rint = 0.080 |
34307 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.147 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.62 e Å−3 |
3898 reflections | Δρmin = −0.46 e Å−3 |
236 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.43927 (11) | 0.4788 (2) | 0.66113 (14) | 0.0232 (6) | |
N2 | 0.47888 (11) | 0.3796 (3) | 0.62658 (14) | 0.0264 (6) | |
C3 | 0.52893 (13) | 0.4473 (3) | 0.59765 (17) | 0.0246 (6) | |
C3A | 0.52391 (13) | 0.5935 (3) | 0.61389 (16) | 0.0234 (6) | |
C4 | 0.55968 (13) | 0.7145 (3) | 0.59974 (17) | 0.0240 (6) | |
C5 | 0.53149 (14) | 0.8418 (3) | 0.62180 (17) | 0.0267 (7) | |
C6 | 0.46982 (14) | 0.8384 (3) | 0.65700 (17) | 0.0255 (6) | |
N7 | 0.43615 (11) | 0.7264 (3) | 0.67574 (13) | 0.0227 (5) | |
C7A | 0.46463 (13) | 0.6076 (3) | 0.65297 (17) | 0.0227 (6) | |
C11 | 0.38016 (13) | 0.4364 (3) | 0.69734 (17) | 0.0241 (6) | |
C12 | 0.32457 (14) | 0.5114 (3) | 0.68410 (17) | 0.0256 (6) | |
H12 | 0.3252 | 0.5924 | 0.6518 | 0.031* | |
C13 | 0.26811 (14) | 0.4671 (3) | 0.71837 (18) | 0.0278 (7) | |
H13 | 0.2297 | 0.5180 | 0.7097 | 0.033* | |
C14 | 0.26690 (14) | 0.3485 (3) | 0.76548 (18) | 0.0304 (7) | |
H14 | 0.2279 | 0.3187 | 0.7889 | 0.036* | |
C15 | 0.32279 (14) | 0.2740 (3) | 0.77806 (18) | 0.0290 (7) | |
H15 | 0.3220 | 0.1925 | 0.8099 | 0.035* | |
C16 | 0.37991 (14) | 0.3179 (3) | 0.74446 (17) | 0.0263 (6) | |
H16 | 0.4184 | 0.2675 | 0.7535 | 0.032* | |
C31 | 0.57808 (14) | 0.3692 (3) | 0.55090 (18) | 0.0277 (7) | |
H31A | 0.6166 | 0.3556 | 0.5832 | 0.042* | |
H31B | 0.5891 | 0.4224 | 0.5034 | 0.042* | |
H31C | 0.5607 | 0.2783 | 0.5355 | 0.042* | |
C41 | 0.62387 (13) | 0.7041 (3) | 0.56150 (17) | 0.0239 (6) | |
C42 | 0.67115 (13) | 0.6204 (3) | 0.59601 (18) | 0.0278 (7) | |
H42 | 0.6623 | 0.5737 | 0.6442 | 0.033* | |
C43 | 0.73058 (14) | 0.6049 (3) | 0.56092 (18) | 0.0285 (7) | |
H43 | 0.7627 | 0.5487 | 0.5847 | 0.034* | |
C44 | 0.74209 (14) | 0.6729 (3) | 0.49054 (17) | 0.0264 (7) | |
Cl44 | 0.81663 (3) | 0.65380 (9) | 0.44439 (4) | 0.0317 (2) | |
C45 | 0.69610 (14) | 0.7551 (3) | 0.45423 (18) | 0.0274 (7) | |
H45 | 0.7050 | 0.8000 | 0.4055 | 0.033* | |
C46 | 0.63714 (14) | 0.7706 (3) | 0.49004 (17) | 0.0274 (7) | |
H46 | 0.6053 | 0.8270 | 0.4658 | 0.033* | |
C51 | 0.56620 (16) | 0.9771 (3) | 0.6167 (2) | 0.0366 (8) | |
H51 | 0.5414 | 1.0595 | 0.6116 | 0.044* | |
O51 | 0.62385 (11) | 0.9889 (3) | 0.61878 (15) | 0.0447 (6) | |
Cl61 | 0.43227 (3) | 0.99479 (8) | 0.68206 (5) | 0.0307 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0223 (13) | 0.0221 (14) | 0.0252 (13) | 0.0003 (10) | 0.0022 (10) | −0.0020 (10) |
N2 | 0.0250 (13) | 0.0255 (14) | 0.0287 (14) | 0.0038 (10) | −0.0012 (10) | −0.0034 (11) |
C3 | 0.0242 (15) | 0.0261 (16) | 0.0234 (15) | 0.0008 (12) | −0.0035 (12) | −0.0015 (13) |
C3A | 0.0240 (15) | 0.0292 (16) | 0.0169 (14) | 0.0008 (12) | −0.0030 (11) | 0.0008 (12) |
C4 | 0.0221 (15) | 0.0298 (17) | 0.0200 (14) | −0.0009 (12) | −0.0026 (11) | 0.0025 (12) |
C5 | 0.0252 (16) | 0.0268 (17) | 0.0279 (16) | −0.0041 (12) | −0.0013 (12) | 0.0020 (13) |
C6 | 0.0273 (16) | 0.0238 (16) | 0.0252 (15) | 0.0009 (12) | −0.0051 (12) | −0.0039 (12) |
N7 | 0.0222 (12) | 0.0234 (13) | 0.0226 (13) | −0.0002 (10) | −0.0023 (10) | −0.0012 (10) |
C7A | 0.0230 (15) | 0.0214 (15) | 0.0237 (15) | 0.0012 (12) | −0.0037 (12) | −0.0012 (12) |
C11 | 0.0227 (15) | 0.0242 (16) | 0.0253 (15) | −0.0037 (12) | 0.0009 (12) | −0.0038 (12) |
C12 | 0.0284 (15) | 0.0245 (16) | 0.0240 (15) | −0.0001 (12) | −0.0036 (12) | 0.0017 (13) |
C13 | 0.0237 (15) | 0.0303 (18) | 0.0294 (16) | −0.0007 (12) | −0.0001 (12) | −0.0051 (13) |
C14 | 0.0276 (16) | 0.0319 (18) | 0.0317 (17) | −0.0076 (13) | 0.0051 (13) | −0.0011 (14) |
C15 | 0.0344 (17) | 0.0251 (16) | 0.0276 (17) | −0.0056 (13) | 0.0003 (13) | −0.0004 (13) |
C16 | 0.0271 (16) | 0.0259 (16) | 0.0260 (15) | 0.0012 (12) | −0.0033 (12) | −0.0029 (13) |
C31 | 0.0280 (16) | 0.0263 (17) | 0.0287 (16) | 0.0024 (12) | −0.0011 (12) | −0.0036 (13) |
C41 | 0.0203 (15) | 0.0270 (16) | 0.0245 (15) | −0.0038 (12) | −0.0006 (12) | −0.0003 (12) |
C42 | 0.0246 (16) | 0.0348 (18) | 0.0239 (16) | −0.0035 (13) | −0.0022 (12) | 0.0023 (13) |
C43 | 0.0229 (15) | 0.0355 (18) | 0.0270 (16) | −0.0025 (13) | −0.0039 (12) | 0.0017 (14) |
C44 | 0.0229 (15) | 0.0299 (17) | 0.0263 (16) | −0.0059 (12) | 0.0011 (12) | −0.0053 (13) |
Cl44 | 0.0241 (4) | 0.0390 (5) | 0.0319 (4) | −0.0015 (3) | 0.0050 (3) | −0.0020 (3) |
C45 | 0.0284 (16) | 0.0289 (17) | 0.0250 (16) | −0.0026 (13) | 0.0035 (12) | 0.0013 (13) |
C46 | 0.0299 (16) | 0.0242 (16) | 0.0280 (17) | −0.0004 (13) | −0.0030 (12) | 0.0011 (13) |
C51 | 0.0342 (19) | 0.031 (2) | 0.045 (2) | −0.0048 (14) | 0.0085 (15) | −0.0004 (15) |
O51 | 0.0371 (14) | 0.0469 (16) | 0.0501 (15) | −0.0153 (11) | 0.0119 (11) | −0.0122 (12) |
Cl61 | 0.0292 (4) | 0.0236 (4) | 0.0393 (4) | 0.0019 (3) | −0.0033 (3) | −0.0033 (3) |
N1—C7A | 1.352 (4) | C14—C15 | 1.385 (4) |
N1—N2 | 1.390 (3) | C14—H14 | 0.9500 |
N1—C11 | 1.436 (4) | C15—C16 | 1.386 (4) |
N2—C3 | 1.324 (4) | C15—H15 | 0.9500 |
C3—C3A | 1.435 (4) | C16—H16 | 0.9500 |
C3—C31 | 1.497 (4) | C31—H31A | 0.9800 |
C3A—C4 | 1.402 (4) | C31—H31B | 0.9800 |
C3A—C7A | 1.409 (4) | C31—H31C | 0.9800 |
C4—C5 | 1.407 (4) | C41—C46 | 1.395 (4) |
C4—C41 | 1.491 (4) | C41—C42 | 1.400 (4) |
C5—C6 | 1.419 (4) | C42—C43 | 1.383 (4) |
C5—C51 | 1.490 (4) | C42—H42 | 0.9500 |
C6—N7 | 1.323 (4) | C43—C44 | 1.380 (4) |
C6—Cl61 | 1.746 (3) | C43—H43 | 0.9500 |
N7—C7A | 1.343 (4) | C44—C45 | 1.386 (4) |
C11—C12 | 1.384 (4) | C44—Cl44 | 1.750 (3) |
C11—C16 | 1.390 (4) | C45—C46 | 1.380 (4) |
C12—C13 | 1.381 (4) | C45—H45 | 0.9500 |
C12—H12 | 0.9500 | C46—H46 | 0.9500 |
C13—C14 | 1.390 (4) | C51—O51 | 1.209 (4) |
C13—H13 | 0.9500 | C51—H51 | 0.9500 |
C7A—N1—N2 | 110.6 (2) | C13—C14—H14 | 120.1 |
C7A—N1—C11 | 129.7 (2) | C14—C15—C16 | 120.3 (3) |
N2—N1—C11 | 119.7 (2) | C14—C15—H15 | 119.9 |
C3—N2—N1 | 106.7 (2) | C16—C15—H15 | 119.9 |
N2—C3—C3A | 110.6 (2) | C15—C16—C11 | 119.2 (3) |
N2—C3—C31 | 119.3 (3) | C15—C16—H16 | 120.4 |
C3A—C3—C31 | 129.9 (3) | C11—C16—H16 | 120.4 |
C4—C3A—C7A | 117.9 (3) | C3—C31—H31A | 109.5 |
C4—C3A—C3 | 137.7 (3) | C3—C31—H31B | 109.5 |
C7A—C3A—C3 | 104.3 (2) | H31A—C31—H31B | 109.5 |
C3A—C4—C5 | 116.9 (3) | C3—C31—H31C | 109.5 |
C3A—C4—C41 | 119.8 (3) | H31A—C31—H31C | 109.5 |
C5—C4—C41 | 123.3 (3) | H31B—C31—H31C | 109.5 |
C4—C5—C6 | 118.1 (3) | C46—C41—C42 | 119.0 (3) |
C4—C5—C51 | 122.6 (3) | C46—C41—C4 | 121.6 (3) |
C6—C5—C51 | 119.0 (3) | C42—C41—C4 | 119.4 (3) |
N7—C6—C5 | 127.0 (3) | C43—C42—C41 | 121.0 (3) |
N7—C6—Cl61 | 113.7 (2) | C43—C42—H42 | 119.5 |
C5—C6—Cl61 | 119.3 (2) | C41—C42—H42 | 119.5 |
C6—N7—C7A | 112.7 (2) | C44—C43—C42 | 118.4 (3) |
N7—C7A—N1 | 125.1 (3) | C44—C43—H43 | 120.8 |
N7—C7A—C3A | 127.2 (3) | C42—C43—H43 | 120.8 |
N1—C7A—C3A | 107.7 (2) | C43—C44—C45 | 122.1 (3) |
C12—C11—C16 | 121.1 (3) | C43—C44—Cl44 | 119.4 (2) |
C12—C11—N1 | 120.2 (3) | C45—C44—Cl44 | 118.5 (2) |
C16—C11—N1 | 118.7 (3) | C46—C45—C44 | 119.0 (3) |
C13—C12—C11 | 119.1 (3) | C46—C45—H45 | 120.5 |
C13—C12—H12 | 120.4 | C44—C45—H45 | 120.5 |
C11—C12—H12 | 120.4 | C45—C46—C41 | 120.5 (3) |
C12—C13—C14 | 120.6 (3) | C45—C46—H46 | 119.7 |
C12—C13—H13 | 119.7 | C41—C46—H46 | 119.7 |
C14—C13—H13 | 119.7 | O51—C51—C5 | 124.3 (3) |
C15—C14—C13 | 119.7 (3) | O51—C51—H51 | 117.8 |
C15—C14—H14 | 120.1 | C5—C51—H51 | 117.8 |
C7A—N1—N2—C3 | 0.5 (3) | C4—C3A—C7A—N1 | −179.2 (2) |
C11—N1—N2—C3 | 179.4 (2) | C3—C3A—C7A—N1 | 2.3 (3) |
N1—N2—C3—C3A | 1.0 (3) | C7A—N1—C11—C12 | 43.0 (4) |
N1—N2—C3—C31 | −175.3 (2) | N2—N1—C11—C12 | −135.7 (3) |
N2—C3—C3A—C4 | 179.8 (3) | C7A—N1—C11—C16 | −138.1 (3) |
C31—C3—C3A—C4 | −4.4 (6) | N2—N1—C11—C16 | 43.2 (4) |
N2—C3—C3A—C7A | −2.1 (3) | C16—C11—C12—C13 | −0.1 (4) |
C31—C3—C3A—C7A | 173.7 (3) | N1—C11—C12—C13 | 178.8 (3) |
C7A—C3A—C4—C5 | −3.6 (4) | C11—C12—C13—C14 | −0.1 (4) |
C3—C3A—C4—C5 | 174.3 (3) | C12—C13—C14—C15 | −0.1 (5) |
C7A—C3A—C4—C41 | 177.5 (2) | C13—C14—C15—C16 | 0.5 (5) |
C3—C3A—C4—C41 | −4.6 (5) | C14—C15—C16—C11 | −0.7 (4) |
C3A—C4—C5—C6 | 0.5 (4) | C12—C11—C16—C15 | 0.5 (4) |
C41—C4—C5—C6 | 179.3 (3) | N1—C11—C16—C15 | −178.4 (3) |
C3A—C4—C5—C51 | 174.5 (3) | C3A—C4—C41—C46 | 120.3 (3) |
C41—C4—C5—C51 | −6.7 (4) | C5—C4—C41—C46 | −58.5 (4) |
C4—C5—C6—N7 | 3.8 (5) | C3A—C4—C41—C42 | −56.7 (4) |
C51—C5—C6—N7 | −170.4 (3) | C5—C4—C41—C42 | 124.6 (3) |
C4—C5—C6—Cl61 | −177.9 (2) | C46—C41—C42—C43 | 1.0 (4) |
C51—C5—C6—Cl61 | 7.9 (4) | C4—C41—C42—C43 | 178.0 (3) |
C5—C6—N7—C7A | −4.2 (4) | C41—C42—C43—C44 | −0.6 (5) |
Cl61—C6—N7—C7A | 177.35 (19) | C42—C43—C44—C45 | −0.3 (5) |
C6—N7—C7A—N1 | −176.5 (3) | C42—C43—C44—Cl44 | −179.4 (2) |
C6—N7—C7A—C3A | 0.6 (4) | C43—C44—C45—C46 | 0.7 (5) |
N2—N1—C7A—N7 | 175.8 (2) | Cl44—C44—C45—C46 | 179.9 (2) |
C11—N1—C7A—N7 | −3.1 (5) | C44—C45—C46—C41 | −0.3 (4) |
N2—N1—C7A—C3A | −1.8 (3) | C42—C41—C46—C45 | −0.5 (4) |
C11—N1—C7A—C3A | 179.4 (3) | C4—C41—C46—C45 | −177.5 (3) |
C4—C3A—C7A—N7 | 3.3 (4) | C4—C5—C51—O51 | −24.9 (5) |
C3—C3A—C7A—N7 | −175.2 (3) | C6—C5—C51—O51 | 149.1 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C15—H15···O51i | 0.95 | 2.56 | 3.433 (4) | 153 |
C43—H43···O51ii | 0.95 | 2.50 | 3.381 (4) | 154 |
C42—H42···Cg1iii | 0.95 | 2.75 | 3.653 (4) | 160 |
Symmetry codes: (i) −x+1, y−1, −z+3/2; (ii) −x+3/2, y−1/2, z; (iii) −x+1, y, −z+3/2. |
C20H13BrClN3O | Z = 2 |
Mr = 426.68 | F(000) = 428 |
Triclinic, P1 | Dx = 1.633 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.3826 (11) Å | Cell parameters from 3981 reflections |
b = 9.7781 (12) Å | θ = 2.8–27.5° |
c = 10.1072 (6) Å | µ = 2.54 mm−1 |
α = 108.077 (10)° | T = 120 K |
β = 99.353 (9)° | Block, yellow |
γ = 90.911 (10)° | 0.36 × 0.27 × 0.20 mm |
V = 867.61 (16) Å3 |
Bruker Nonius KappaCCD area-detector diffractometer | 3981 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 3098 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.8° |
ϕ and ω scans | h = −12→12 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −12→12 |
Tmin = 0.440, Tmax = 0.604 | l = −13→13 |
23897 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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.077 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0282P)2 + 0.7864P] where P = (Fo2 + 2Fc2)/3 |
3981 reflections | (Δ/σ)max = 0.001 |
236 parameters | Δρmax = 0.63 e Å−3 |
0 restraints | Δρmin = −0.42 e Å−3 |
C20H13BrClN3O | γ = 90.911 (10)° |
Mr = 426.68 | V = 867.61 (16) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.3826 (11) Å | Mo Kα radiation |
b = 9.7781 (12) Å | µ = 2.54 mm−1 |
c = 10.1072 (6) Å | T = 120 K |
α = 108.077 (10)° | 0.36 × 0.27 × 0.20 mm |
β = 99.353 (9)° |
Bruker Nonius KappaCCD area-detector diffractometer | 3981 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 3098 reflections with I > 2σ(I) |
Tmin = 0.440, Tmax = 0.604 | Rint = 0.048 |
23897 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.077 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.63 e Å−3 |
3981 reflections | Δρmin = −0.42 e Å−3 |
236 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.5591 (2) | 0.5642 (2) | 0.2414 (2) | 0.0219 (5) | |
N2 | 0.4424 (2) | 0.5963 (2) | 0.1562 (2) | 0.0246 (5) | |
C3 | 0.3337 (3) | 0.5050 (3) | 0.1457 (3) | 0.0208 (5) | |
C3A | 0.3758 (3) | 0.4078 (3) | 0.2234 (2) | 0.0189 (5) | |
C4 | 0.3111 (3) | 0.2948 (3) | 0.2552 (2) | 0.0182 (5) | |
C5 | 0.3977 (3) | 0.2322 (3) | 0.3460 (2) | 0.0194 (5) | |
C6 | 0.5421 (2) | 0.2922 (3) | 0.4011 (2) | 0.0179 (5) | |
N7 | 0.6066 (2) | 0.3995 (2) | 0.3760 (2) | 0.0193 (4) | |
C7A | 0.5224 (3) | 0.4528 (3) | 0.2853 (2) | 0.0189 (5) | |
C11 | 0.6915 (3) | 0.6513 (3) | 0.2750 (3) | 0.0228 (5) | |
C12 | 0.8222 (3) | 0.5968 (3) | 0.3124 (3) | 0.0252 (6) | |
H12 | 0.8243 | 0.5011 | 0.3168 | 0.030* | |
C13 | 0.9504 (3) | 0.6838 (3) | 0.3436 (3) | 0.0302 (6) | |
H13 | 1.0402 | 0.6470 | 0.3693 | 0.036* | |
C14 | 0.9479 (3) | 0.8222 (3) | 0.3375 (3) | 0.0378 (7) | |
H14 | 1.0353 | 0.8813 | 0.3598 | 0.045* | |
C15 | 0.8166 (4) | 0.8752 (3) | 0.2986 (3) | 0.0395 (8) | |
H15 | 0.8152 | 0.9706 | 0.2938 | 0.047* | |
C16 | 0.6875 (3) | 0.7912 (3) | 0.2667 (3) | 0.0315 (6) | |
H16 | 0.5981 | 0.8280 | 0.2398 | 0.038* | |
C31 | 0.1896 (3) | 0.5170 (3) | 0.0624 (3) | 0.0268 (6) | |
H31A | 0.1937 | 0.6030 | 0.0324 | 0.040* | |
H31B | 0.1150 | 0.5249 | 0.1214 | 0.040* | |
H31C | 0.1659 | 0.4312 | −0.0211 | 0.040* | |
C41 | 0.1542 (2) | 0.2508 (3) | 0.2015 (2) | 0.0189 (5) | |
C42 | 0.0599 (3) | 0.2681 (3) | 0.2984 (3) | 0.0230 (5) | |
H42 | 0.0967 | 0.3061 | 0.3968 | 0.028* | |
C43 | −0.0869 (3) | 0.2303 (3) | 0.2520 (3) | 0.0231 (5) | |
H43 | −0.1510 | 0.2417 | 0.3178 | 0.028* | |
C44 | −0.1387 (3) | 0.1756 (3) | 0.1078 (3) | 0.0216 (5) | |
Br44 | −0.34042 (3) | 0.12129 (3) | 0.04510 (3) | 0.03122 (10) | |
C45 | −0.0484 (3) | 0.1582 (3) | 0.0099 (3) | 0.0217 (5) | |
H45 | −0.0858 | 0.1205 | −0.0885 | 0.026* | |
C46 | 0.0987 (3) | 0.1969 (3) | 0.0581 (2) | 0.0199 (5) | |
H46 | 0.1620 | 0.1863 | −0.0083 | 0.024* | |
C51 | 0.3466 (3) | 0.1035 (3) | 0.3776 (3) | 0.0241 (6) | |
H51 | 0.4019 | 0.0814 | 0.4549 | 0.029* | |
O51 | 0.24153 (19) | 0.0246 (2) | 0.31414 (19) | 0.0306 (4) | |
Cl61 | 0.65220 (6) | 0.22130 (7) | 0.51739 (6) | 0.02490 (15) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0203 (11) | 0.0221 (11) | 0.0241 (11) | −0.0002 (9) | 0.0021 (9) | 0.0096 (9) |
N2 | 0.0251 (11) | 0.0259 (12) | 0.0255 (12) | 0.0053 (9) | 0.0054 (9) | 0.0116 (10) |
C3 | 0.0208 (12) | 0.0227 (13) | 0.0208 (13) | 0.0023 (10) | 0.0075 (10) | 0.0075 (10) |
C3A | 0.0167 (12) | 0.0188 (12) | 0.0196 (12) | 0.0006 (10) | 0.0030 (10) | 0.0042 (10) |
C4 | 0.0164 (11) | 0.0208 (12) | 0.0149 (12) | 0.0002 (10) | 0.0038 (9) | 0.0016 (10) |
C5 | 0.0184 (12) | 0.0210 (13) | 0.0178 (12) | −0.0007 (10) | 0.0040 (10) | 0.0043 (10) |
C6 | 0.0167 (12) | 0.0195 (12) | 0.0161 (12) | 0.0027 (10) | 0.0027 (9) | 0.0036 (10) |
N7 | 0.0170 (10) | 0.0212 (11) | 0.0189 (10) | −0.0003 (8) | 0.0019 (8) | 0.0060 (9) |
C7A | 0.0182 (12) | 0.0195 (12) | 0.0198 (13) | 0.0001 (10) | 0.0067 (10) | 0.0058 (10) |
C11 | 0.0259 (13) | 0.0225 (13) | 0.0196 (12) | −0.0060 (11) | 0.0078 (10) | 0.0046 (10) |
C12 | 0.0232 (13) | 0.0307 (15) | 0.0211 (13) | −0.0050 (11) | 0.0049 (11) | 0.0074 (11) |
C13 | 0.0250 (14) | 0.0435 (17) | 0.0210 (14) | −0.0114 (12) | 0.0041 (11) | 0.0096 (12) |
C14 | 0.0450 (18) | 0.0406 (18) | 0.0231 (14) | −0.0215 (14) | 0.0077 (13) | 0.0037 (13) |
C15 | 0.056 (2) | 0.0272 (15) | 0.0360 (17) | −0.0141 (14) | 0.0167 (15) | 0.0071 (13) |
C16 | 0.0408 (17) | 0.0242 (14) | 0.0322 (15) | −0.0013 (12) | 0.0133 (13) | 0.0096 (12) |
C31 | 0.0235 (13) | 0.0313 (15) | 0.0296 (14) | 0.0023 (11) | 0.0020 (11) | 0.0167 (12) |
C41 | 0.0138 (11) | 0.0205 (12) | 0.0230 (13) | −0.0020 (10) | 0.0000 (10) | 0.0095 (10) |
C42 | 0.0191 (12) | 0.0293 (14) | 0.0193 (13) | −0.0017 (10) | 0.0017 (10) | 0.0067 (11) |
C43 | 0.0186 (12) | 0.0239 (13) | 0.0284 (14) | 0.0012 (10) | 0.0071 (11) | 0.0093 (11) |
C44 | 0.0156 (12) | 0.0165 (12) | 0.0324 (14) | 0.0003 (10) | 0.0013 (10) | 0.0087 (11) |
Br44 | 0.01564 (13) | 0.03375 (17) | 0.04062 (18) | −0.00322 (10) | −0.00055 (11) | 0.00958 (13) |
C45 | 0.0222 (13) | 0.0196 (12) | 0.0207 (13) | 0.0007 (10) | −0.0021 (10) | 0.0055 (10) |
C46 | 0.0199 (12) | 0.0209 (13) | 0.0191 (12) | 0.0014 (10) | 0.0035 (10) | 0.0066 (10) |
C51 | 0.0221 (13) | 0.0269 (14) | 0.0245 (13) | 0.0002 (11) | 0.0011 (11) | 0.0112 (11) |
O51 | 0.0272 (10) | 0.0313 (10) | 0.0331 (11) | −0.0098 (8) | −0.0038 (8) | 0.0154 (9) |
Cl61 | 0.0183 (3) | 0.0309 (3) | 0.0274 (3) | −0.0004 (2) | −0.0017 (2) | 0.0151 (3) |
N1—C7A | 1.356 (3) | C14—C15 | 1.389 (5) |
N1—N2 | 1.383 (3) | C14—H14 | 0.9500 |
N1—C11 | 1.427 (3) | C15—C16 | 1.387 (4) |
N2—C3 | 1.314 (3) | C15—H15 | 0.9500 |
C3—C3A | 1.432 (3) | C16—H16 | 0.9500 |
C3—C31 | 1.500 (3) | C31—H31A | 0.9800 |
C3A—C4 | 1.399 (3) | C31—H31B | 0.9800 |
C3A—C7A | 1.417 (3) | C31—H31C | 0.9800 |
C4—C5 | 1.414 (3) | C41—C46 | 1.387 (3) |
C4—C41 | 1.490 (3) | C41—C42 | 1.398 (3) |
C5—C6 | 1.419 (3) | C42—C43 | 1.385 (3) |
C5—C51 | 1.482 (3) | C42—H42 | 0.9500 |
C6—N7 | 1.314 (3) | C43—C44 | 1.387 (4) |
C6—Cl61 | 1.751 (2) | C43—H43 | 0.9500 |
N7—C7A | 1.346 (3) | C44—C45 | 1.378 (4) |
C11—C12 | 1.388 (4) | C44—Br44 | 1.907 (2) |
C11—C16 | 1.397 (4) | C45—C46 | 1.391 (3) |
C12—C13 | 1.396 (3) | C45—H45 | 0.9500 |
C12—H12 | 0.9500 | C46—H46 | 0.9500 |
C13—C14 | 1.374 (4) | C51—O51 | 1.200 (3) |
C13—H13 | 0.9500 | C51—H51 | 0.9500 |
C7A—N1—N2 | 110.9 (2) | C15—C14—H14 | 120.2 |
C7A—N1—C11 | 130.3 (2) | C16—C15—C14 | 121.2 (3) |
N2—N1—C11 | 118.7 (2) | C16—C15—H15 | 119.4 |
C3—N2—N1 | 106.8 (2) | C14—C15—H15 | 119.4 |
N2—C3—C3A | 111.1 (2) | C15—C16—C11 | 118.6 (3) |
N2—C3—C31 | 118.9 (2) | C15—C16—H16 | 120.7 |
C3A—C3—C31 | 130.0 (2) | C11—C16—H16 | 120.7 |
C4—C3A—C7A | 118.0 (2) | C3—C31—H31A | 109.5 |
C4—C3A—C3 | 137.7 (2) | C3—C31—H31B | 109.5 |
C7A—C3A—C3 | 104.1 (2) | H31A—C31—H31B | 109.5 |
C3A—C4—C5 | 117.4 (2) | C3—C31—H31C | 109.5 |
C3A—C4—C41 | 120.1 (2) | H31A—C31—H31C | 109.5 |
C5—C4—C41 | 122.4 (2) | H31B—C31—H31C | 109.5 |
C4—C5—C6 | 117.3 (2) | C46—C41—C42 | 119.1 (2) |
C4—C5—C51 | 122.7 (2) | C46—C41—C4 | 121.8 (2) |
C6—C5—C51 | 119.8 (2) | C42—C41—C4 | 119.1 (2) |
N7—C6—C5 | 127.4 (2) | C43—C42—C41 | 120.6 (2) |
N7—C6—Cl61 | 113.59 (17) | C43—C42—H42 | 119.7 |
C5—C6—Cl61 | 119.02 (18) | C41—C42—H42 | 119.7 |
C6—N7—C7A | 113.5 (2) | C42—C43—C44 | 118.8 (2) |
N7—C7A—N1 | 126.6 (2) | C42—C43—H43 | 120.6 |
N7—C7A—C3A | 126.3 (2) | C44—C43—H43 | 120.6 |
N1—C7A—C3A | 107.0 (2) | C45—C44—C43 | 121.9 (2) |
C12—C11—C16 | 120.7 (2) | C45—C44—Br44 | 119.59 (19) |
C12—C11—N1 | 120.5 (2) | C43—C44—Br44 | 118.54 (19) |
C16—C11—N1 | 118.8 (2) | C44—C45—C46 | 118.6 (2) |
C11—C12—C13 | 119.4 (3) | C44—C45—H45 | 120.7 |
C11—C12—H12 | 120.3 | C46—C45—H45 | 120.7 |
C13—C12—H12 | 120.3 | C41—C46—C45 | 121.0 (2) |
C14—C13—C12 | 120.5 (3) | C41—C46—H46 | 119.5 |
C14—C13—H13 | 119.7 | C45—C46—H46 | 119.5 |
C12—C13—H13 | 119.7 | O51—C51—C5 | 125.8 (2) |
C13—C14—C15 | 119.6 (3) | O51—C51—H51 | 117.1 |
C13—C14—H14 | 120.2 | C5—C51—H51 | 117.1 |
C7A—N1—N2—C3 | −0.5 (3) | C4—C3A—C7A—N1 | −178.7 (2) |
C11—N1—N2—C3 | −177.7 (2) | C3—C3A—C7A—N1 | −1.6 (3) |
N1—N2—C3—C3A | −0.5 (3) | C7A—N1—C11—C12 | 27.5 (4) |
N1—N2—C3—C31 | 178.1 (2) | N2—N1—C11—C12 | −155.9 (2) |
N2—C3—C3A—C4 | 177.6 (3) | C7A—N1—C11—C16 | −153.7 (3) |
C31—C3—C3A—C4 | −0.8 (5) | N2—N1—C11—C16 | 22.8 (3) |
N2—C3—C3A—C7A | 1.3 (3) | C16—C11—C12—C13 | 0.8 (4) |
C31—C3—C3A—C7A | −177.1 (2) | N1—C11—C12—C13 | 179.5 (2) |
C7A—C3A—C4—C5 | −0.8 (3) | C11—C12—C13—C14 | 0.0 (4) |
C3—C3A—C4—C5 | −176.7 (3) | C12—C13—C14—C15 | −0.6 (4) |
C7A—C3A—C4—C41 | 175.4 (2) | C13—C14—C15—C16 | 0.5 (4) |
C3—C3A—C4—C41 | −0.5 (4) | C14—C15—C16—C11 | 0.3 (4) |
C3A—C4—C5—C6 | 1.9 (3) | C12—C11—C16—C15 | −0.9 (4) |
C41—C4—C5—C6 | −174.1 (2) | N1—C11—C16—C15 | −179.6 (2) |
C3A—C4—C5—C51 | −174.3 (2) | C3A—C4—C41—C46 | 62.7 (3) |
C41—C4—C5—C51 | 9.7 (4) | C5—C4—C41—C46 | −121.4 (3) |
C4—C5—C6—N7 | −1.0 (4) | C3A—C4—C41—C42 | −115.5 (3) |
C51—C5—C6—N7 | 175.4 (2) | C5—C4—C41—C42 | 60.5 (3) |
C4—C5—C6—Cl61 | 178.45 (17) | C46—C41—C42—C43 | 0.8 (4) |
C51—C5—C6—Cl61 | −5.2 (3) | C4—C41—C42—C43 | 179.0 (2) |
C5—C6—N7—C7A | −1.3 (4) | C41—C42—C43—C44 | −0.3 (4) |
Cl61—C6—N7—C7A | 179.29 (17) | C42—C43—C44—C45 | −0.2 (4) |
C6—N7—C7A—N1 | 179.1 (2) | C42—C43—C44—Br44 | 179.10 (18) |
C6—N7—C7A—C3A | 2.7 (3) | C43—C44—C45—C46 | 0.0 (4) |
N2—N1—C7A—N7 | −175.7 (2) | Br44—C44—C45—C46 | −179.24 (17) |
C11—N1—C7A—N7 | 1.1 (4) | C42—C41—C46—C45 | −1.0 (4) |
N2—N1—C7A—C3A | 1.4 (3) | C4—C41—C46—C45 | −179.2 (2) |
C11—N1—C7A—C3A | 178.1 (2) | C44—C45—C46—C41 | 0.6 (4) |
C4—C3A—C7A—N7 | −1.7 (4) | C4—C5—C51—O51 | 13.8 (4) |
C3—C3A—C7A—N7 | 175.5 (2) | C6—C5—C51—O51 | −162.3 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14···O51i | 0.95 | 2.55 | 3.448 (4) | 157 |
C45—H45···O51ii | 0.95 | 2.49 | 3.397 (3) | 160 |
Symmetry codes: (i) x+1, y+1, z; (ii) −x, −y, −z. |
C21H16ClN3O2 | Z = 2 |
Mr = 377.82 | F(000) = 392 |
Triclinic, P1 | Dx = 1.449 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.6972 (8) Å | Cell parameters from 3975 reflections |
b = 10.039 (2) Å | θ = 2.9–27.5° |
c = 10.090 (2) Å | µ = 0.24 mm−1 |
α = 85.23 (2)° | T = 120 K |
β = 80.856 (16)° | Block, yellow |
γ = 86.665 (16)° | 0.28 × 0.19 × 0.14 mm |
V = 865.9 (3) Å3 |
Bruker Nonius KappaCCD area-detector diffractometer | 3975 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 3265 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.9° |
ϕ and ω scans | h = −11→11 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −13→13 |
Tmin = 0.935, Tmax = 0.968 | l = −13→13 |
21671 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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.090 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0348P)2 + 0.4672P] where P = (Fo2 + 2Fc2)/3 |
3975 reflections | (Δ/σ)max = 0.001 |
246 parameters | Δρmax = 0.30 e Å−3 |
0 restraints | Δρmin = −0.34 e Å−3 |
C21H16ClN3O2 | γ = 86.665 (16)° |
Mr = 377.82 | V = 865.9 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.6972 (8) Å | Mo Kα radiation |
b = 10.039 (2) Å | µ = 0.24 mm−1 |
c = 10.090 (2) Å | T = 120 K |
α = 85.23 (2)° | 0.28 × 0.19 × 0.14 mm |
β = 80.856 (16)° |
Bruker Nonius KappaCCD area-detector diffractometer | 3975 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 3265 reflections with I > 2σ(I) |
Tmin = 0.935, Tmax = 0.968 | Rint = 0.038 |
21671 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.090 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.30 e Å−3 |
3975 reflections | Δρmin = −0.34 e Å−3 |
246 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.16793 (15) | 0.54294 (13) | 0.63866 (12) | 0.0194 (3) | |
N2 | 0.14578 (15) | 0.52771 (13) | 0.77795 (13) | 0.0228 (3) | |
C3 | 0.24644 (18) | 0.43253 (16) | 0.81293 (15) | 0.0223 (3) | |
C3A | 0.33834 (17) | 0.38108 (15) | 0.69550 (15) | 0.0190 (3) | |
C4 | 0.45894 (17) | 0.28283 (14) | 0.66688 (15) | 0.0183 (3) | |
C5 | 0.50117 (17) | 0.25515 (14) | 0.53084 (15) | 0.0179 (3) | |
C6 | 0.42944 (17) | 0.33498 (15) | 0.43277 (15) | 0.0186 (3) | |
N7 | 0.32598 (14) | 0.43468 (12) | 0.45534 (12) | 0.0186 (3) | |
C7A | 0.28076 (17) | 0.45262 (15) | 0.58685 (15) | 0.0180 (3) | |
C11 | 0.07659 (17) | 0.64308 (15) | 0.57297 (15) | 0.0195 (3) | |
C12 | 0.09100 (18) | 0.65774 (15) | 0.43325 (16) | 0.0219 (3) | |
H12 | 0.1589 | 0.5988 | 0.3796 | 0.026* | |
C13 | 0.00439 (19) | 0.76016 (16) | 0.37292 (17) | 0.0252 (3) | |
H13 | 0.0137 | 0.7707 | 0.2776 | 0.030* | |
C14 | −0.09519 (18) | 0.84688 (16) | 0.45008 (17) | 0.0259 (3) | |
H14 | −0.1524 | 0.9172 | 0.4081 | 0.031* | |
C15 | −0.11012 (19) | 0.82955 (16) | 0.58915 (17) | 0.0263 (3) | |
H15 | −0.1790 | 0.8880 | 0.6425 | 0.032* | |
C16 | −0.02577 (18) | 0.72775 (16) | 0.65167 (16) | 0.0232 (3) | |
H16 | −0.0377 | 0.7160 | 0.7471 | 0.028* | |
C31 | 0.2456 (2) | 0.39059 (19) | 0.95881 (16) | 0.0305 (4) | |
H31A | 0.3393 | 0.4211 | 0.9875 | 0.046* | |
H31B | 0.2442 | 0.2928 | 0.9725 | 0.046* | |
H31C | 0.1528 | 0.4304 | 1.0121 | 0.046* | |
C41 | 0.54140 (17) | 0.21477 (15) | 0.77338 (14) | 0.0188 (3) | |
C42 | 0.61300 (18) | 0.29186 (16) | 0.85291 (15) | 0.0218 (3) | |
H42 | 0.6010 | 0.3866 | 0.8424 | 0.026* | |
C43 | 0.70168 (18) | 0.23279 (16) | 0.94730 (15) | 0.0226 (3) | |
H43 | 0.7497 | 0.2866 | 1.0007 | 0.027* | |
C44 | 0.71917 (18) | 0.09370 (16) | 0.96246 (15) | 0.0224 (3) | |
C45 | 0.64676 (19) | 0.01550 (16) | 0.88497 (15) | 0.0239 (3) | |
H45 | 0.6579 | −0.0793 | 0.8963 | 0.029* | |
C46 | 0.55879 (18) | 0.07495 (15) | 0.79166 (15) | 0.0210 (3) | |
H46 | 0.5097 | 0.0207 | 0.7395 | 0.025* | |
O47 | 0.80345 (14) | 0.02424 (12) | 1.05122 (11) | 0.0287 (3) | |
C47 | 0.8873 (2) | 0.10160 (19) | 1.12636 (17) | 0.0314 (4) | |
H47A | 0.9590 | 0.1579 | 1.0641 | 0.047* | |
H47B | 0.9466 | 0.0414 | 1.1832 | 0.047* | |
H47C | 0.8136 | 0.1584 | 1.1832 | 0.047* | |
C51 | 0.62544 (17) | 0.15076 (15) | 0.49429 (15) | 0.0197 (3) | |
H51 | 0.7044 | 0.1361 | 0.5497 | 0.024* | |
O51 | 0.63380 (14) | 0.08308 (12) | 0.39951 (11) | 0.0278 (3) | |
Cl61 | 0.48404 (5) | 0.31069 (4) | 0.26223 (4) | 0.02477 (11) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0205 (6) | 0.0191 (6) | 0.0181 (6) | 0.0048 (5) | −0.0033 (5) | −0.0023 (5) |
N2 | 0.0251 (7) | 0.0243 (7) | 0.0180 (6) | 0.0045 (5) | −0.0027 (5) | −0.0015 (5) |
C3 | 0.0226 (8) | 0.0223 (8) | 0.0214 (8) | 0.0030 (6) | −0.0031 (6) | −0.0022 (6) |
C3A | 0.0212 (7) | 0.0174 (7) | 0.0189 (7) | 0.0011 (6) | −0.0049 (6) | −0.0017 (6) |
C4 | 0.0199 (7) | 0.0159 (7) | 0.0198 (7) | −0.0008 (6) | −0.0047 (6) | −0.0018 (6) |
C5 | 0.0183 (7) | 0.0159 (7) | 0.0199 (7) | 0.0008 (6) | −0.0043 (6) | −0.0023 (5) |
C6 | 0.0199 (7) | 0.0181 (7) | 0.0183 (7) | −0.0004 (6) | −0.0037 (6) | −0.0034 (5) |
N7 | 0.0188 (6) | 0.0175 (6) | 0.0199 (6) | 0.0016 (5) | −0.0044 (5) | −0.0032 (5) |
C7A | 0.0177 (7) | 0.0164 (7) | 0.0204 (7) | 0.0005 (5) | −0.0041 (5) | −0.0027 (5) |
C11 | 0.0176 (7) | 0.0161 (7) | 0.0249 (8) | 0.0008 (6) | −0.0051 (6) | −0.0005 (6) |
C12 | 0.0200 (7) | 0.0201 (8) | 0.0250 (8) | 0.0033 (6) | −0.0028 (6) | −0.0016 (6) |
C13 | 0.0251 (8) | 0.0236 (8) | 0.0266 (8) | 0.0008 (6) | −0.0057 (6) | 0.0024 (6) |
C14 | 0.0229 (8) | 0.0190 (8) | 0.0353 (9) | 0.0039 (6) | −0.0074 (7) | 0.0027 (7) |
C15 | 0.0254 (8) | 0.0187 (8) | 0.0342 (9) | 0.0059 (6) | −0.0034 (7) | −0.0046 (6) |
C16 | 0.0232 (8) | 0.0218 (8) | 0.0249 (8) | 0.0028 (6) | −0.0044 (6) | −0.0044 (6) |
C31 | 0.0329 (9) | 0.0348 (10) | 0.0209 (8) | 0.0119 (7) | −0.0017 (7) | 0.0003 (7) |
C41 | 0.0198 (7) | 0.0196 (7) | 0.0167 (7) | 0.0042 (6) | −0.0028 (6) | −0.0026 (6) |
C42 | 0.0243 (8) | 0.0193 (8) | 0.0218 (7) | 0.0039 (6) | −0.0048 (6) | −0.0029 (6) |
C43 | 0.0226 (8) | 0.0263 (8) | 0.0197 (7) | 0.0020 (6) | −0.0047 (6) | −0.0066 (6) |
C44 | 0.0201 (7) | 0.0291 (8) | 0.0168 (7) | 0.0062 (6) | −0.0031 (6) | 0.0005 (6) |
C45 | 0.0293 (8) | 0.0188 (8) | 0.0223 (8) | 0.0047 (6) | −0.0032 (6) | 0.0006 (6) |
C46 | 0.0242 (8) | 0.0197 (8) | 0.0191 (7) | 0.0009 (6) | −0.0034 (6) | −0.0022 (6) |
O47 | 0.0304 (6) | 0.0312 (7) | 0.0255 (6) | 0.0074 (5) | −0.0117 (5) | 0.0012 (5) |
C47 | 0.0277 (9) | 0.0447 (11) | 0.0227 (8) | 0.0057 (8) | −0.0095 (7) | −0.0023 (7) |
C51 | 0.0208 (7) | 0.0176 (7) | 0.0205 (7) | 0.0012 (6) | −0.0037 (6) | −0.0006 (6) |
O51 | 0.0318 (6) | 0.0252 (6) | 0.0275 (6) | 0.0086 (5) | −0.0079 (5) | −0.0096 (5) |
Cl61 | 0.0307 (2) | 0.0246 (2) | 0.01870 (18) | 0.00654 (15) | −0.00483 (14) | −0.00329 (14) |
N1—C7A | 1.3677 (19) | C15—C16 | 1.390 (2) |
N1—N2 | 1.3847 (17) | C15—H15 | 0.9500 |
N1—C11 | 1.4299 (19) | C16—H16 | 0.9500 |
N2—C3 | 1.322 (2) | C31—H31A | 0.9800 |
C3—C3A | 1.436 (2) | C31—H31B | 0.9800 |
C3—C31 | 1.496 (2) | C31—H31C | 0.9800 |
C3A—C7A | 1.404 (2) | C41—C42 | 1.396 (2) |
C3A—C4 | 1.410 (2) | C41—C46 | 1.403 (2) |
C4—C5 | 1.410 (2) | C42—C43 | 1.393 (2) |
C4—C41 | 1.484 (2) | C42—H42 | 0.9500 |
C5—C6 | 1.420 (2) | C43—C44 | 1.394 (2) |
C5—C51 | 1.486 (2) | C43—H43 | 0.9500 |
C6—N7 | 1.3158 (19) | C44—O47 | 1.3678 (18) |
C6—Cl61 | 1.7443 (15) | C44—C45 | 1.393 (2) |
N7—C7A | 1.3466 (19) | C45—C46 | 1.382 (2) |
C11—C12 | 1.392 (2) | C45—H45 | 0.9500 |
C11—C16 | 1.395 (2) | C46—H46 | 0.9500 |
C12—C13 | 1.395 (2) | O47—C47 | 1.431 (2) |
C12—H12 | 0.9500 | C47—H47A | 0.9800 |
C13—C14 | 1.387 (2) | C47—H47B | 0.9800 |
C13—H13 | 0.9500 | C47—H47C | 0.9800 |
C14—C15 | 1.386 (2) | C51—O51 | 1.2090 (19) |
C14—H14 | 0.9500 | C51—H51 | 0.9500 |
C7A—N1—N2 | 110.00 (12) | C15—C16—C11 | 119.37 (15) |
C7A—N1—C11 | 130.74 (13) | C15—C16—H16 | 120.3 |
N2—N1—C11 | 119.26 (12) | C11—C16—H16 | 120.3 |
C3—N2—N1 | 107.32 (12) | C3—C31—H31A | 109.5 |
N2—C3—C3A | 110.44 (13) | C3—C31—H31B | 109.5 |
N2—C3—C31 | 119.35 (14) | H31A—C31—H31B | 109.5 |
C3A—C3—C31 | 130.15 (14) | C3—C31—H31C | 109.5 |
C7A—C3A—C4 | 118.09 (13) | H31A—C31—H31C | 109.5 |
C7A—C3A—C3 | 104.59 (13) | H31B—C31—H31C | 109.5 |
C4—C3A—C3 | 137.30 (14) | C42—C41—C46 | 118.43 (14) |
C3A—C4—C5 | 116.64 (13) | C42—C41—C4 | 119.15 (13) |
C3A—C4—C41 | 121.97 (13) | C46—C41—C4 | 122.30 (13) |
C5—C4—C41 | 121.36 (13) | C43—C42—C41 | 121.40 (15) |
C4—C5—C6 | 118.12 (13) | C43—C42—H42 | 119.3 |
C4—C5—C51 | 119.30 (13) | C41—C42—H42 | 119.3 |
C6—C5—C51 | 122.46 (13) | C42—C43—C44 | 119.19 (14) |
N7—C6—C5 | 126.51 (14) | C42—C43—H43 | 120.4 |
N7—C6—Cl61 | 113.28 (11) | C44—C43—H43 | 120.4 |
C5—C6—Cl61 | 120.13 (11) | O47—C44—C45 | 115.37 (14) |
C6—N7—C7A | 113.75 (13) | O47—C44—C43 | 124.62 (14) |
N7—C7A—N1 | 125.90 (13) | C45—C44—C43 | 120.01 (14) |
N7—C7A—C3A | 126.50 (13) | C46—C45—C44 | 120.41 (15) |
N1—C7A—C3A | 107.59 (13) | C46—C45—H45 | 119.8 |
C12—C11—C16 | 120.39 (14) | C44—C45—H45 | 119.8 |
C12—C11—N1 | 120.92 (13) | C45—C46—C41 | 120.54 (14) |
C16—C11—N1 | 118.68 (14) | C45—C46—H46 | 119.7 |
C11—C12—C13 | 119.12 (15) | C41—C46—H46 | 119.7 |
C11—C12—H12 | 120.4 | C44—O47—C47 | 116.76 (13) |
C13—C12—H12 | 120.4 | O47—C47—H47A | 109.5 |
C14—C13—C12 | 120.99 (15) | O47—C47—H47B | 109.5 |
C14—C13—H13 | 119.5 | H47A—C47—H47B | 109.5 |
C12—C13—H13 | 119.5 | O47—C47—H47C | 109.5 |
C15—C14—C13 | 119.16 (15) | H47A—C47—H47C | 109.5 |
C15—C14—H14 | 120.4 | H47B—C47—H47C | 109.5 |
C13—C14—H14 | 120.4 | O51—C51—C5 | 125.05 (14) |
C14—C15—C16 | 120.93 (15) | O51—C51—H51 | 117.5 |
C14—C15—H15 | 119.5 | C5—C51—H51 | 117.5 |
C16—C15—H15 | 119.5 | ||
C7A—N1—N2—C3 | 1.97 (17) | C3—C3A—C7A—N1 | 2.36 (17) |
C11—N1—N2—C3 | −178.18 (13) | C7A—N1—C11—C12 | 2.5 (2) |
N1—N2—C3—C3A | −0.41 (18) | N2—N1—C11—C12 | −177.36 (14) |
N1—N2—C3—C31 | −177.83 (14) | C7A—N1—C11—C16 | −176.44 (15) |
N2—C3—C3A—C7A | −1.22 (18) | N2—N1—C11—C16 | 3.7 (2) |
C31—C3—C3A—C7A | 175.84 (17) | C16—C11—C12—C13 | 1.5 (2) |
N2—C3—C3A—C4 | −179.58 (17) | N1—C11—C12—C13 | −177.43 (14) |
C31—C3—C3A—C4 | −2.5 (3) | C11—C12—C13—C14 | 0.0 (2) |
C7A—C3A—C4—C5 | −6.2 (2) | C12—C13—C14—C15 | −1.0 (2) |
C3—C3A—C4—C5 | 171.99 (17) | C13—C14—C15—C16 | 0.7 (2) |
C7A—C3A—C4—C41 | 171.81 (14) | C14—C15—C16—C11 | 0.8 (2) |
C3—C3A—C4—C41 | −10.0 (3) | C12—C11—C16—C15 | −1.8 (2) |
C3A—C4—C5—C6 | 5.2 (2) | N1—C11—C16—C15 | 177.07 (14) |
C41—C4—C5—C6 | −172.87 (13) | C3A—C4—C41—C42 | −55.9 (2) |
C3A—C4—C5—C51 | −178.84 (13) | C5—C4—C41—C42 | 122.02 (16) |
C41—C4—C5—C51 | 3.1 (2) | C3A—C4—C41—C46 | 128.27 (16) |
C4—C5—C6—N7 | 0.3 (2) | C5—C4—C41—C46 | −53.8 (2) |
C51—C5—C6—N7 | −175.51 (14) | C46—C41—C42—C43 | 0.9 (2) |
C4—C5—C6—Cl61 | 176.88 (11) | C4—C41—C42—C43 | −175.12 (14) |
C51—C5—C6—Cl61 | 1.0 (2) | C41—C42—C43—C44 | 0.0 (2) |
C5—C6—N7—C7A | −4.5 (2) | C42—C43—C44—O47 | 179.83 (14) |
Cl61—C6—N7—C7A | 178.77 (10) | C42—C43—C44—C45 | −0.8 (2) |
C6—N7—C7A—N1 | −175.59 (14) | O47—C44—C45—C46 | −179.85 (14) |
C6—N7—C7A—C3A | 3.2 (2) | C43—C44—C45—C46 | 0.7 (2) |
N2—N1—C7A—N7 | 176.27 (14) | C44—C45—C46—C41 | 0.1 (2) |
C11—N1—C7A—N7 | −3.6 (3) | C42—C41—C46—C45 | −0.9 (2) |
N2—N1—C7A—C3A | −2.74 (17) | C4—C41—C46—C45 | 174.91 (14) |
C11—N1—C7A—C3A | 177.43 (14) | C45—C44—O47—C47 | 176.21 (14) |
C4—C3A—C7A—N7 | 2.1 (2) | C43—C44—O47—C47 | −4.4 (2) |
C3—C3A—C7A—N7 | −176.64 (14) | C4—C5—C51—O51 | 150.72 (16) |
C4—C3A—C7A—N1 | −178.89 (13) | C6—C5—C51—O51 | −33.5 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14···O51i | 0.95 | 2.43 | 3.312 (2) | 154 |
C46—H46···O51ii | 0.95 | 2.36 | 3.300 (2) | 171 |
Symmetry codes: (i) x−1, y+1, z; (ii) −x+1, −y, −z+1. |
C20H13ClN4O3 | F(000) = 808 |
Mr = 392.79 | Dx = 1.469 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4073 reflections |
a = 11.7839 (13) Å | θ = 3.3–27.5° |
b = 9.9890 (4) Å | µ = 0.25 mm−1 |
c = 15.71 (2) Å | T = 120 K |
β = 106.084 (8)° | Plate, yellow |
V = 1776 (2) Å3 | 0.39 × 0.29 × 0.14 mm |
Z = 4 |
Bruker Nonius KappaCCD area-detector diffractometer | 4073 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 2914 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.049 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.3° |
ϕ and ω scans | h = −15→15 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −12→12 |
Tmin = 0.910, Tmax = 0.966 | l = −20→20 |
25554 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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.134 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0651P)2 + 0.8224P] where P = (Fo2 + 2Fc2)/3 |
4073 reflections | (Δ/σ)max = 0.001 |
254 parameters | Δρmax = 0.42 e Å−3 |
0 restraints | Δρmin = −0.34 e Å−3 |
C20H13ClN4O3 | V = 1776 (2) Å3 |
Mr = 392.79 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.7839 (13) Å | µ = 0.25 mm−1 |
b = 9.9890 (4) Å | T = 120 K |
c = 15.71 (2) Å | 0.39 × 0.29 × 0.14 mm |
β = 106.084 (8)° |
Bruker Nonius KappaCCD area-detector diffractometer | 4073 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2914 reflections with I > 2σ(I) |
Tmin = 0.910, Tmax = 0.966 | Rint = 0.049 |
25554 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.134 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.42 e Å−3 |
4073 reflections | Δρmin = −0.34 e Å−3 |
254 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.57391 (14) | 0.20314 (17) | 0.53040 (11) | 0.0256 (4) | |
N2 | 0.57099 (15) | 0.12065 (17) | 0.45850 (11) | 0.0268 (4) | |
C3 | 0.47614 (17) | 0.1523 (2) | 0.39466 (13) | 0.0251 (4) | |
C3A | 0.41296 (17) | 0.2582 (2) | 0.42304 (13) | 0.0237 (4) | |
C4 | 0.31283 (17) | 0.3357 (2) | 0.38427 (13) | 0.0229 (4) | |
C5 | 0.28078 (17) | 0.4330 (2) | 0.43806 (13) | 0.0230 (4) | |
C6 | 0.35375 (18) | 0.4473 (2) | 0.52615 (14) | 0.0251 (4) | |
N7 | 0.45157 (14) | 0.37954 (17) | 0.56384 (11) | 0.0247 (4) | |
C7A | 0.47828 (17) | 0.2862 (2) | 0.51058 (13) | 0.0237 (4) | |
C11 | 0.67273 (17) | 0.1966 (2) | 0.60716 (13) | 0.0255 (4) | |
C12 | 0.66881 (18) | 0.2578 (2) | 0.68585 (14) | 0.0282 (5) | |
H12 | 0.6001 | 0.3049 | 0.6891 | 0.034* | |
C13 | 0.76613 (19) | 0.2494 (2) | 0.75969 (14) | 0.0302 (5) | |
H13 | 0.7639 | 0.2923 | 0.8132 | 0.036* | |
C14 | 0.86635 (19) | 0.1794 (2) | 0.75659 (15) | 0.0321 (5) | |
H14 | 0.9324 | 0.1738 | 0.8074 | 0.039* | |
C15 | 0.86862 (19) | 0.1176 (2) | 0.67776 (15) | 0.0327 (5) | |
H15 | 0.9366 | 0.0683 | 0.6752 | 0.039* | |
C16 | 0.77317 (18) | 0.1265 (2) | 0.60263 (14) | 0.0299 (5) | |
H16 | 0.7763 | 0.0854 | 0.5488 | 0.036* | |
C31 | 0.44492 (18) | 0.0781 (2) | 0.30880 (13) | 0.0290 (5) | |
H31A | 0.4994 | 0.0028 | 0.3126 | 0.044* | |
H31B | 0.4509 | 0.1384 | 0.2611 | 0.044* | |
H31C | 0.3639 | 0.0442 | 0.2964 | 0.044* | |
C41 | 0.25175 (17) | 0.3180 (2) | 0.28819 (13) | 0.0232 (4) | |
C42 | 0.28974 (19) | 0.3947 (2) | 0.22727 (14) | 0.0289 (5) | |
H42 | 0.3509 | 0.4585 | 0.2479 | 0.035* | |
C43 | 0.23928 (19) | 0.3790 (2) | 0.13676 (14) | 0.0300 (5) | |
H43 | 0.2642 | 0.4318 | 0.0950 | 0.036* | |
C44 | 0.15134 (18) | 0.2836 (2) | 0.10952 (13) | 0.0271 (5) | |
C45 | 0.11408 (18) | 0.2037 (2) | 0.16809 (14) | 0.0289 (5) | |
H45 | 0.0550 | 0.1375 | 0.1471 | 0.035* | |
C46 | 0.16431 (18) | 0.2218 (2) | 0.25805 (14) | 0.0270 (4) | |
H46 | 0.1390 | 0.1684 | 0.2994 | 0.032* | |
N44 | 0.09402 (17) | 0.2684 (2) | 0.01403 (12) | 0.0339 (4) | |
O41 | 0.12160 (17) | 0.34620 (19) | −0.03747 (10) | 0.0478 (5) | |
O42 | 0.02258 (16) | 0.17746 (19) | −0.01044 (11) | 0.0512 (5) | |
C51 | 0.17321 (18) | 0.5163 (2) | 0.40463 (14) | 0.0270 (4) | |
H51 | 0.1567 | 0.5824 | 0.4430 | 0.032* | |
O51 | 0.10541 (12) | 0.50510 (15) | 0.33157 (10) | 0.0315 (4) | |
Cl61 | 0.31718 (5) | 0.56456 (5) | 0.59607 (3) | 0.03116 (16) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0239 (8) | 0.0288 (9) | 0.0223 (9) | 0.0033 (7) | 0.0034 (7) | −0.0020 (7) |
N2 | 0.0274 (9) | 0.0279 (9) | 0.0258 (9) | 0.0009 (7) | 0.0084 (7) | −0.0039 (7) |
C3 | 0.0238 (10) | 0.0255 (10) | 0.0263 (10) | 0.0003 (8) | 0.0074 (8) | −0.0004 (9) |
C3A | 0.0233 (9) | 0.0250 (10) | 0.0221 (10) | −0.0016 (8) | 0.0053 (8) | −0.0013 (8) |
C4 | 0.0214 (9) | 0.0233 (10) | 0.0237 (10) | −0.0042 (8) | 0.0057 (8) | 0.0001 (8) |
C5 | 0.0218 (9) | 0.0232 (10) | 0.0242 (10) | 0.0000 (8) | 0.0066 (8) | 0.0011 (8) |
C6 | 0.0266 (10) | 0.0235 (10) | 0.0258 (10) | −0.0014 (8) | 0.0084 (8) | −0.0003 (8) |
N7 | 0.0249 (8) | 0.0255 (9) | 0.0235 (9) | −0.0002 (7) | 0.0064 (7) | −0.0016 (7) |
C7A | 0.0234 (10) | 0.0259 (10) | 0.0216 (10) | 0.0007 (8) | 0.0060 (8) | −0.0006 (8) |
C11 | 0.0230 (10) | 0.0249 (10) | 0.0256 (10) | −0.0002 (8) | 0.0019 (8) | 0.0035 (8) |
C12 | 0.0259 (10) | 0.0305 (11) | 0.0265 (11) | 0.0019 (9) | 0.0045 (9) | 0.0021 (9) |
C13 | 0.0349 (11) | 0.0294 (11) | 0.0245 (11) | 0.0002 (9) | 0.0054 (9) | 0.0034 (9) |
C14 | 0.0292 (11) | 0.0318 (12) | 0.0295 (11) | −0.0007 (9) | −0.0015 (9) | 0.0058 (10) |
C15 | 0.0270 (11) | 0.0327 (12) | 0.0353 (12) | 0.0028 (9) | 0.0031 (9) | 0.0047 (10) |
C16 | 0.0305 (11) | 0.0289 (11) | 0.0298 (11) | 0.0025 (9) | 0.0074 (9) | 0.0005 (9) |
C31 | 0.0281 (10) | 0.0312 (11) | 0.0269 (11) | 0.0011 (9) | 0.0061 (9) | −0.0059 (9) |
C41 | 0.0214 (9) | 0.0245 (10) | 0.0238 (10) | 0.0020 (8) | 0.0065 (8) | −0.0009 (8) |
C42 | 0.0300 (11) | 0.0296 (11) | 0.0264 (11) | −0.0086 (9) | 0.0064 (9) | −0.0025 (9) |
C43 | 0.0348 (11) | 0.0309 (11) | 0.0255 (11) | −0.0043 (10) | 0.0104 (9) | 0.0009 (9) |
C44 | 0.0287 (10) | 0.0312 (11) | 0.0206 (10) | 0.0018 (9) | 0.0055 (8) | −0.0006 (9) |
C45 | 0.0249 (10) | 0.0321 (11) | 0.0274 (11) | −0.0057 (9) | 0.0035 (9) | −0.0021 (9) |
C46 | 0.0265 (10) | 0.0297 (11) | 0.0250 (10) | −0.0031 (9) | 0.0075 (9) | 0.0014 (9) |
N44 | 0.0373 (10) | 0.0398 (11) | 0.0240 (9) | −0.0029 (9) | 0.0075 (8) | −0.0038 (9) |
O41 | 0.0659 (12) | 0.0532 (11) | 0.0232 (8) | −0.0090 (9) | 0.0106 (8) | 0.0038 (8) |
O42 | 0.0544 (11) | 0.0635 (12) | 0.0300 (9) | −0.0257 (10) | 0.0020 (8) | −0.0097 (9) |
C51 | 0.0281 (10) | 0.0251 (11) | 0.0286 (11) | 0.0016 (9) | 0.0091 (9) | −0.0004 (9) |
O51 | 0.0266 (7) | 0.0350 (9) | 0.0302 (8) | 0.0032 (7) | 0.0031 (6) | −0.0011 (7) |
Cl61 | 0.0351 (3) | 0.0316 (3) | 0.0263 (3) | 0.0059 (2) | 0.0077 (2) | −0.0050 (2) |
N1—C7A | 1.364 (2) | C14—H14 | 0.9500 |
N1—N2 | 1.391 (3) | C15—C16 | 1.389 (3) |
N1—C11 | 1.427 (3) | C15—H15 | 0.9500 |
N2—C3 | 1.317 (3) | C16—H16 | 0.9500 |
C3—C3A | 1.433 (3) | C31—H31A | 0.9800 |
C3—C31 | 1.493 (3) | C31—H31B | 0.9800 |
C3A—C4 | 1.402 (3) | C31—H31C | 0.9800 |
C3A—C7A | 1.405 (3) | C41—C46 | 1.392 (3) |
C4—C5 | 1.406 (3) | C41—C42 | 1.393 (3) |
C4—C41 | 1.492 (3) | C42—C43 | 1.390 (3) |
C5—C6 | 1.419 (3) | C42—H42 | 0.9500 |
C5—C51 | 1.485 (3) | C43—C44 | 1.385 (3) |
C6—N7 | 1.326 (3) | C43—H43 | 0.9500 |
C6—Cl61 | 1.740 (2) | C44—C45 | 1.378 (3) |
N7—C7A | 1.347 (3) | C44—N44 | 1.472 (3) |
C11—C12 | 1.391 (3) | C45—C46 | 1.384 (3) |
C11—C16 | 1.394 (3) | C45—H45 | 0.9500 |
C12—C13 | 1.389 (3) | C46—H46 | 0.9500 |
C12—H12 | 0.9500 | N44—O42 | 1.226 (2) |
C13—C14 | 1.385 (3) | N44—O41 | 1.228 (3) |
C13—H13 | 0.9500 | C51—O51 | 1.208 (3) |
C14—C15 | 1.391 (4) | C51—H51 | 0.9500 |
C7A—N1—N2 | 110.01 (16) | C16—C15—H15 | 119.4 |
C7A—N1—C11 | 130.54 (17) | C14—C15—H15 | 119.4 |
N2—N1—C11 | 119.32 (17) | C15—C16—C11 | 119.2 (2) |
C3—N2—N1 | 107.51 (17) | C15—C16—H16 | 120.4 |
N2—C3—C3A | 110.17 (18) | C11—C16—H16 | 120.4 |
N2—C3—C31 | 120.88 (18) | C3—C31—H31A | 109.5 |
C3A—C3—C31 | 128.91 (18) | C3—C31—H31B | 109.5 |
C4—C3A—C7A | 118.79 (18) | H31A—C31—H31B | 109.5 |
C4—C3A—C3 | 136.04 (19) | C3—C31—H31C | 109.5 |
C7A—C3A—C3 | 105.10 (17) | H31A—C31—H31C | 109.5 |
C3A—C4—C5 | 117.05 (19) | H31B—C31—H31C | 109.5 |
C3A—C4—C41 | 119.06 (17) | C46—C41—C42 | 119.63 (19) |
C5—C4—C41 | 123.74 (18) | C46—C41—C4 | 122.03 (18) |
C4—C5—C6 | 117.66 (18) | C42—C41—C4 | 118.21 (18) |
C4—C5—C51 | 121.32 (18) | C43—C42—C41 | 120.8 (2) |
C6—C5—C51 | 121.02 (18) | C43—C42—H42 | 119.6 |
N7—C6—C5 | 126.92 (18) | C41—C42—H42 | 119.6 |
N7—C6—Cl61 | 113.48 (16) | C44—C43—C42 | 117.72 (19) |
C5—C6—Cl61 | 119.60 (16) | C44—C43—H43 | 121.1 |
C6—N7—C7A | 113.56 (18) | C42—C43—H43 | 121.1 |
N7—C7A—N1 | 126.86 (18) | C45—C44—C43 | 122.8 (2) |
N7—C7A—C3A | 125.93 (19) | C45—C44—N44 | 118.65 (19) |
N1—C7A—C3A | 107.21 (17) | C43—C44—N44 | 118.57 (18) |
C12—C11—C16 | 120.24 (19) | C44—C45—C46 | 118.7 (2) |
C12—C11—N1 | 120.68 (19) | C44—C45—H45 | 120.6 |
C16—C11—N1 | 119.07 (19) | C46—C45—H45 | 120.6 |
C13—C12—C11 | 119.5 (2) | C45—C46—C41 | 120.28 (19) |
C13—C12—H12 | 120.3 | C45—C46—H46 | 119.9 |
C11—C12—H12 | 120.3 | C41—C46—H46 | 119.9 |
C14—C13—C12 | 121.1 (2) | O42—N44—O41 | 123.1 (2) |
C14—C13—H13 | 119.5 | O42—N44—C44 | 118.49 (18) |
C12—C13—H13 | 119.5 | O41—N44—C44 | 118.38 (19) |
C13—C14—C15 | 118.8 (2) | O51—C51—C5 | 123.97 (19) |
C13—C14—H14 | 120.6 | O51—C51—H51 | 118.0 |
C15—C14—H14 | 120.6 | C5—C51—H51 | 118.0 |
C16—C15—C14 | 121.1 (2) | ||
C7A—N1—N2—C3 | 0.6 (2) | C7A—N1—C11—C12 | 17.0 (3) |
C11—N1—N2—C3 | −175.59 (18) | N2—N1—C11—C12 | −167.68 (18) |
N1—N2—C3—C3A | 0.0 (2) | C7A—N1—C11—C16 | −163.7 (2) |
N1—N2—C3—C31 | −177.80 (18) | N2—N1—C11—C16 | 11.6 (3) |
N2—C3—C3A—C4 | 176.1 (2) | C16—C11—C12—C13 | 0.5 (3) |
C31—C3—C3A—C4 | −6.3 (4) | N1—C11—C12—C13 | 179.76 (19) |
N2—C3—C3A—C7A | −0.6 (2) | C11—C12—C13—C14 | −0.9 (3) |
C31—C3—C3A—C7A | 177.0 (2) | C12—C13—C14—C15 | 0.3 (3) |
C7A—C3A—C4—C5 | −3.3 (3) | C13—C14—C15—C16 | 0.9 (3) |
C3—C3A—C4—C5 | −179.7 (2) | C14—C15—C16—C11 | −1.3 (3) |
C7A—C3A—C4—C41 | 172.52 (17) | C12—C11—C16—C15 | 0.6 (3) |
C3—C3A—C4—C41 | −3.8 (3) | N1—C11—C16—C15 | −178.68 (19) |
C3A—C4—C5—C6 | 1.6 (3) | C3A—C4—C41—C46 | 87.2 (2) |
C41—C4—C5—C6 | −173.97 (18) | C5—C4—C41—C46 | −97.3 (2) |
C3A—C4—C5—C51 | −177.27 (18) | C3A—C4—C41—C42 | −88.6 (2) |
C41—C4—C5—C51 | 7.1 (3) | C5—C4—C41—C42 | 87.0 (2) |
C4—C5—C6—N7 | 1.1 (3) | C46—C41—C42—C43 | 1.7 (3) |
C51—C5—C6—N7 | −179.94 (19) | C4—C41—C42—C43 | 177.56 (19) |
C4—C5—C6—Cl61 | −179.17 (14) | C41—C42—C43—C44 | −0.8 (3) |
C51—C5—C6—Cl61 | −0.3 (3) | C42—C43—C44—C45 | −1.0 (3) |
C5—C6—N7—C7A | −2.0 (3) | C42—C43—C44—N44 | 178.01 (19) |
Cl61—C6—N7—C7A | 178.32 (14) | C43—C44—C45—C46 | 1.8 (3) |
C6—N7—C7A—N1 | 178.88 (18) | N44—C44—C45—C46 | −177.24 (19) |
C6—N7—C7A—C3A | 0.1 (3) | C44—C45—C46—C41 | −0.8 (3) |
N2—N1—C7A—N7 | 179.99 (18) | C42—C41—C46—C45 | −0.9 (3) |
C11—N1—C7A—N7 | −4.4 (3) | C4—C41—C46—C45 | −176.60 (19) |
N2—N1—C7A—C3A | −1.0 (2) | C45—C44—N44—O42 | −6.3 (3) |
C11—N1—C7A—C3A | 174.63 (19) | C43—C44—N44—O42 | 174.6 (2) |
C4—C3A—C7A—N7 | 2.6 (3) | C45—C44—N44—O41 | 174.9 (2) |
C3—C3A—C7A—N7 | 179.99 (19) | C43—C44—N44—O41 | −4.1 (3) |
C4—C3A—C7A—N1 | −176.40 (17) | C4—C5—C51—O51 | 1.8 (3) |
C3—C3A—C7A—N1 | 1.0 (2) | C6—C5—C51—O51 | −177.05 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
C45—H45···O51i | 0.95 | 2.41 | 3.261 (5) | 150 |
Symmetry code: (i) −x, y−1/2, −z+1/2. |
Experimental details
(I) | (II) | (III) | (IV) | |
Crystal data | ||||
Chemical formula | C20H14ClN3O | C21H16ClN3O | C20H13Cl2N3O | C20H13BrClN3O |
Mr | 347.79 | 361.82 | 382.23 | 426.68 |
Crystal system, space group | Monoclinic, C2/c | Triclinic, P1 | Orthorhombic, Pbcn | Triclinic, P1 |
Temperature (K) | 120 | 120 | 120 | 120 |
a, b, c (Å) | 16.784 (3), 9.6380 (8), 21.699 (4) | 8.2898 (8), 9.9191 (14), 10.3666 (10) | 20.868 (3), 9.603 (4), 16.924 (9) | 9.3826 (11), 9.7781 (12), 10.1072 (6) |
α, β, γ (°) | 90, 108.820 (12), 90 | 87.108 (11), 86.808 (8), 85.088 (12) | 90, 90, 90 | 108.077 (10), 99.353 (9), 90.911 (10) |
V (Å3) | 3322.5 (9) | 847.08 (17) | 3391 (2) | 867.61 (16) |
Z | 8 | 2 | 8 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.24 | 0.24 | 0.40 | 2.54 |
Crystal size (mm) | 0.36 × 0.32 × 0.12 | 0.31 × 0.26 × 0.20 | 0.40 × 0.37 × 0.28 | 0.36 × 0.27 × 0.20 |
Data collection | ||||
Diffractometer | Bruker Nonius KappaCCD area-detector diffractometer | Bruker Nonius KappaCCD area-detector diffractometer | Bruker Nonius KappaCCD area-detector diffractometer | Bruker Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.918, 0.972 | 0.929, 0.953 | 0.857, 0.897 | 0.440, 0.604 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24328, 3829, 2899 | 21387, 3880, 2544 | 34307, 3898, 2444 | 23897, 3981, 3098 |
Rint | 0.042 | 0.074 | 0.080 | 0.048 |
(sin θ/λ)max (Å−1) | 0.650 | 0.649 | 0.650 | 0.650 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.100, 1.05 | 0.050, 0.130, 1.03 | 0.053, 0.147, 1.08 | 0.036, 0.077, 1.05 |
No. of reflections | 3829 | 3880 | 3898 | 3981 |
No. of parameters | 227 | 237 | 236 | 236 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.49, −0.37 | 0.31, −0.30 | 0.62, −0.46 | 0.63, −0.42 |
(V) | (VI) | |
Crystal data | ||
Chemical formula | C21H16ClN3O2 | C20H13ClN4O3 |
Mr | 377.82 | 392.79 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/c |
Temperature (K) | 120 | 120 |
a, b, c (Å) | 8.6972 (8), 10.039 (2), 10.090 (2) | 11.7839 (13), 9.9890 (4), 15.71 (2) |
α, β, γ (°) | 85.23 (2), 80.856 (16), 86.665 (16) | 90, 106.084 (8), 90 |
V (Å3) | 865.9 (3) | 1776 (2) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.24 | 0.25 |
Crystal size (mm) | 0.28 × 0.19 × 0.14 | 0.39 × 0.29 × 0.14 |
Data collection | ||
Diffractometer | Bruker Nonius KappaCCD area-detector diffractometer | Bruker Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.935, 0.968 | 0.910, 0.966 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 21671, 3975, 3265 | 25554, 4073, 2914 |
Rint | 0.038 | 0.049 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.090, 1.06 | 0.048, 0.134, 1.09 |
No. of reflections | 3975 | 4073 |
No. of parameters | 246 | 254 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.30, −0.34 | 0.42, −0.34 |
Computer programs: COLLECT (Nonius, 1999), DIRAX/LSQ (Duisenberg et al., 2000), EVALCCD (Duisenberg et al., 2003), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
Compound | N2—N1—C11—C12 | C3A—C4—C41—C42 | C4—C5—C51—O51 |
(I) | -140.93 (16) | -73.6 (2) | -10.2 (3) |
(II) | -173.2 (2) | -53.6 (3) | 147.5 (2) |
(III) | -135.7 (3) | -56.7 (4) | -24.9 (5) |
(IV) | -155.9 (2) | -115.5 (3) | 13.8 (4) |
(V) | -177.26 (14) | -55.9 (2) | 150.72 (16) |
(VI) | -167.68 (18) | -88.6 (2) | 1.8 (3) |
Cg1 represents the centroid of the C11–C16 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
Compound (I) | ||||
C46—H46···N2i | 0.95 | 2.58 | 3.515 (2) | 169 |
C45—H45···Cg1i | 0.95 | 2.76 | 3.508 (2) | 136 |
Compound (II) | ||||
C14—H14···O51ii | 0.95 | 2.46 | 3.319 (3) | 150 |
C46—H46···O51iii | 0.95 | 2.41 | 3.348 (3) | 170 |
Compound (III) | ||||
C15—H15···O51iv | 0.95 | 2.56 | 3.433 (4) | 153 |
C43—H43···O51v | 0.95 | 2.50 | 3.381 (4) | 154 |
C42—H42···Cg1vi | 0.95 | 2.75 | 3.653 (4) | 160 |
Compound (IV) | ||||
C14—H14···O51vii | 0.95 | 2.55 | 3.448 (4) | 157 |
C45—H45···O51viii | 0.95 | 2.49 | 3.397 (3) | 160 |
Compound (V) | ||||
C14—H14···O51ix | 0.95 | 2.43 | 3.312 (2) | 154 |
C46—H46···O51x | 0.95 | 2.36 | 3.300 (2) | 171 |
Compound (VI) | ||||
C45—H45···O51xi | 0.95 | 2.41 | 3.261 (2) | 150 |
Symmetry codes: (i) -x + 3/2, y - 1/2, -z + 1/2; (ii) x + 1, y, z - 1; (iii) -x + 1, -y + 1, -z + 2; (iv) -x + 1, y - 1, -z + 3/2; (v) -x + 3/2, y - 1/2, z; (vi) -x + 1, y, -z + 3/2; (vii) x + 1, y + 1, z; (viii) -x, -y, -z; (ix) x - 1, y + 1, z; (x) -x + 1, -y, -z + 1; (xi) -x, y - 1/2, -z + 1/2. |
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We have recently described the preparation of a series of 6-chloropyrazolo[3,4-b]pyridine-5-carbaldehydes via tandem chlorination-formylation of pyrazolopyridinones under Vilsmeier–Haack conditions (Quiroga et al., 2010). These compounds are intended for use as precursors in the synthesis of new fused heterocyclic systems with potential bioactivity. Here we report the molecular and supramolecular structures of six closely-related 4-aryl-6-chloro-3-methyl-1-phenyl-pyrazolo[3,4-b]pyridine-5-carbaldehydes, (I)–(VI) (Figs. 1–6).
Despite differing by only the single substituent R at atom C44 (see scheme and Figs. 1–6), compounds (I)–(VI) show some interesting variation in their crystallization characteristics. Compound (III), where R = Cl, might well be expected to be isomorphous either with (II), where R = Me, or with (IV), where R = Br. In the event, (III) crystallizes in the orthorhombic space group Pbcn, while (II) and (IV) both crystallize in the triclinic space group P1, as does (V), where R = OMe, while the nitro derivative (VI) crystallizes in the monoclinic space group P21/c. Thus, these six rather similar compounds crystallize in no fewer than four different space groups (P1, P21/c, C2/c and Pbcn) spanning three crystal systems. Despite their common space group, the unit-cell dimensions of (II) and (IV) differ in that (II) has all the unit-cell angles less than 90° and quite similar in value, while (IV) has all the unit-cell angles greater than 90° and spanning a range of ca 17°. Despite their different space groups, the effective molecular volumes for (II), R = Me, and (III), R = Cl, as calculated from Vcell/Z (see Crystal data), are identical within experimental uncertainty, while the molecular volume of (IV), R = Br, is greater by only ca 2.4%.
None of the molecules of (I)–(VI) exhibit any internal symmetry and all of them are conformationally chiral. However, the centrosymmetric space groups all accommodate equal numbers of the two conformational enantiomers. The reference molecules of (I)–(VI) were selected to have the same sign for the torsion angles N2—N1—C11—C12 defining the orientation of the C11–C16 ring relative to the fused ring system (Table 1 and Figs. 1–6), where the individual values span a range of ca 40°. Similarly, the torsion angles C3A—C4—C41—C42, defining the orientation of the C41–C46 ring relative to the fused ring system, vary quite widely, spanning a range of ca 60°. While it is perhaps tempting to associate the variable orientation of the substituted C41–C46 aryl ring with the fact that donors forming part of this ring participate in hydrogen bonding in each of (I)–(VI), such an interpretation could not be convincingly applied to the orientation of the unsubstituted C11–C16 aryl ring, since the location of the donor unit C14—H14, active in (II), (IV) and (V), is unaffected by the value of the torsion angle N2—N1—C11—C12.
Perhaps the most striking feature of the molecular conformations in (I)–(VI) concerns the orientation of the formyl group (Table 1 and Figs. 1–6), where the formyl O atom is directed towards atom Cl61 in (II) and (V) but away from it in all the other compounds. This type of behaviour has been noted previously in a series of N6-substituted 2-amino-4-chloro-5-formylpyrimidines (Cobo et al., 2008). A number of factors, including intra- and intermolecular hydrogen bonds and electrostatic factors, were considered as possibly underlying the occurrence of the two different formyl conformations, but no single factor was regarded in that work as providing a fully satisfactory interpretation of the observed behaviour. Likewise for (I)–(VI) here, no clear and simple interpretation of the formyl orientation presents itself.
The supramolecular assembly in (I)–(VI) is dominated by C—H···O hydrogen bonds (Table 2), but there is a C—H···N hydrogen bond in (I) and there are C—H···π(arene) hydrogen bonds in (I) and (III), where both compounds utilize the aryl ring (C11—C16) as the acceptor. Intermolecular contacts of C—H···O type have been regarded as structurally insignificant if: (a) the H···O distance exceeds 2.60 Å (cf. Bondi, 1964; Rowland & Taylor, 1996); (b) the C—H···O angle is less than 130° (cf. Wood et al., 2009); or (c) if the C—H bond concerned forms part of a methyl group. Such C—H bonds are of low acidity, and methyl groups H3C—E are likely to be undergoing very rapid rotation about the C—E bonds (Riddell & Rogerson, 1996, 1997), particularly when bonded to aryl rings where the sixfold rotational barriers are typically only a few J mol-1 (Tannenbaum et al., 1956; Naylor & Wilson, 1957). For compounds crystallizing in different space groups, very different patterns of supramolecular assembly are observed, but the three compounds which crystallize in space group P1, (II), (IV) and (V), all have rather similar hydrogen-bonded structures, albeit with differences in detail.
In the structure of (I), in space group C2/c, a combination of one C—H···N and one C—H···π(arene) hydrogen bonds links molecules related by the 21 screw axis along (3/4, y, 1/4) to form a chain of rings running parallel to the [010] direction (Fig. 7). Four chains of the type, each containing molecules related to one another by one of the four screw axes along (1/4, y, 1/4), (1/4, y, 3/4), (3/4, y, 1/4) and (3/4, y, 3/4), pass through each unit cell, but there are no direction-specific interactions between adjacent chains.
There are two C—H···O hydrogen bonds in the structures of each of (II), (IV) and (V) (Table 2). One of these hydrogen bonds, where the donor forms part of the C41–C46 ring, links pairs of molecules related by inversion, forming centrosymmetric R22(14) (Bernstein et al., 1995) rings in each of (II) and (V) (Figs. 8 and 12) and a centrosymmetric R22(16) ring in (IV) (Fig. 11). The second hydrogen bond, which utilizes the same donor atom in each of the three compounds, links molecules related by translation into C(12) chains running parallel to the [101], [110] and [110] directions in (II), (IV) and (V), respectively. The combination of the two C—H···O hydrogen bonds leads in each case to the formation of a chain of edge-fused rings. In (II), this chain of rings contains R22(14) rings centred at (1/2 + n, 1/2, 1 - n), where n represents an integer, alternating with R42(26) rings centred at (n, 1/2, 3/2 - n) (Fig. 8); in (IV), R22(16) rings centred at (n, n, 0) alternate with R42(28) rings centred at (1/2 + n, 1/2 + n, 1/2) (Fig. 11); and in (V), R22(14) rings centred at (1/2 + n, -n, 0) alternate with R42(26) rings centred at (n, 1/2 - n, 1/2) (Fig. 12), where in every case n represents an integer.
The hydrogen-bonded assembly in (III) is two-dimensional and of considerably greater complexity than the other hydrogen-bonded structures reported here. However, it can be straightforwardly analysed in terms of a one-dimensional sub-structure. Atom C15 in the molecule at (x, y, z) acts as hydrogen-bond donor to atom O51 in the molecule at (-x + 1, y - 1, -z + 3/2), while atom C15 at (-x + 1, y - 1, -z + 3/2) in turn acts as donor to atom O51 at (x, y - 2, z), so forming a C(11) chain running parallel to the [010] direction. There are, in fact, two such chains around the 21 screw axis along (1/2, y, 3/4), related to one another by a unit translation along [010], and these two chains are linked to one another by a C—H···π(arene)(-x + 1, y, -z + 3/2) hydrogen bond to form a one-dimensional substructure (Fig. 9).
The action of the second C—H···O hydrogen bond in (III) is to link the double chains which run parallel to [010] into a sheet. Atoms C43 in the molecules at (x, y, z) and (-x + 1, y - 1, -z + 3/2), which are both components of a chain along (1/2, y, 1/2), act as hydrogen-bond donors to atoms O51 in the molecules at (-x + 3/2, y - 1/2, z) and (x - 1/2, y - 3/2, -z + 3/2), respectively, which themselves form parts of C(11) chains along (1, y, 3/4) and (0, y, 3/4), respectively, so leading to the formation of a sheet lying parallel to (001) (Fig. 10). This sheet lies in the domain 0.5 < z < 1.0, and a second sheet, related to the first by inversion, lies in the domain 0 < z < 1/2, but there are no direction-specific interactions between adjacent sheets. Thus, in (III), despite having a constitution and steric properties, as manifested by the molecular volume, very similar to those of (II) and (IV), not only crystallizes in a different crystal system but also adopts a very different, and much more complex, pattern of supramolecular assembly.
In the structure of (VI), in space group P21/c, a single C—H···O hydrogen bond links molecules related by the 21 screw axis along (0, y, 1/4) into a simple C(8) chain. Two such chains, related to one another by inversion, pass through each unit cell, but there are no direction-specific interactions between adjacent chains. It is interesting to note that (VI), where R = NO2 and thus having the largest number of potential hydrogen-bond acceptors within each molecule, in fact has the simplest hydrogen-bonded structure in this series.
The wide range of space groups observed here, together with the different modes of hydrogen-bonded assembly, certainly suggest that series of this type might provide an interesting challenge for structure-prediction algorithms (Day et al., 2005, 2009).