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The supramolecular structures of the title compounds, 2-phenyl-5-
p-tolyl-1,5,6,10b-tetrahydropyrazolo[1,5-
c]quinazoline, C
23H
21N
3, (I), 5-(4-bromophenyl)-2-phenyl-1,5,6,10b-tetrahydropyrazolo[1,5-
c]quinazoline, C
22H
18BrN
3, (II), 2-(4-chlorophenyl)-5-phenyl-1,5,6,10b-tetrahydropyrazolo[1,5-
c]quinazoline, C
22H
18ClN
3, (III), and 5-(4-bromophenyl)-2-(4-chlorophenyl)-1,5,6,10b-tetrahydropyrazolo[1,5-
c]quinazoline, C
22H
17BrClN
3, (IV), are of two general types. Compounds (I), (II) and (III) form base-paired dimers
via N—H
N hydrogen bonds, where (I) and (II) are isomorphous, while in (IV), there are no conventional hydrogen bonds.
Supporting information
CCDC references: 187944; 187945; 187946; 187947
For compounds (I) to (IV), a catalytic amount of acetic acid was added to an
equimolar solution of the relevant dihydropyrazole starting material and
aromatic aldehyde, and stirred at room temperature for between 5 and 10 min.
The resulting precipitates were filtered off and washed with fresh ethanol to
yield white solids. Crystals suitable for X-ray diffraction were obtained by
slow evaporation from dimethylformamide and ethyl acetate solution for (I),
diffusion using hexane and ethyl acetate solutions for (II) and (III), and
slow evaporation from an ethyl acetate solution for (IV). For (I), yield 86%,
m.p. 486 K. Analysis found: C 81.47, H 6.12, N 12.31%; calculated for
C23H21N3: C 81.38, H 6.24, N 12.38%. For (II), yield 92%, m.p. 536 K.
Analysis found: C 65.23, H 4.39, N 10.28%; calculated for C22H18BrN3: C
65.36, H 4.49, N 10.39%. For (III), yield 81%, m.p. 507 K. Analysis found: C
73.46, H 5.05, N 11.65%; calculated for C22H18ClN3: C 73.43, H 5.04, N
11.68%. For (IV), yield 85%, m.p. 487 K. Analysis found: C 60.19, H 3.81, N
9.48%. calculated for C22H17BrClN3: C 60.23, H 3.91, N 9.58%.
Compounds (I), (II) and (IV) crystallized in the triclinic system; space group
P1 was assumed and confirmed by the analysis. The disordered arene
group in (IV) was modelled as two regular hexagons, each formed using the
SHELXL AFIX 6 instruction and refined using the PART instruction
(SHELXL97; Sheldrick, 1997). Refinement of a tied site occupancy factor
for each group indicated an 0.5 occupancy for each group. That this should be
the case is indicated by the fact that, for the C21A—C26A group, there could
be short intermolecular contacts in the range 2.72–3.11 Å for the group of
atoms C22A—C24A in the molecule at (1 - x, -y, 2 - z).
Thus, there is correlated disorder of these arene groups, in which alternate
arene groups interchange between conformations A and B for each
centrosymmetric pair. An attempt was made to refine the structure in the
spacegroup P1. The resulting refinement would not stabilize, with high
oscillating shifts for atoms and with large correlations between refined
paramenters. An attempt to split Cl54 into two discrete atoms was not
successful. Compound (III) crystallized in the monoclinic system; spacegroup
C2/c or Cc from the systematic absences,
C2/c confirmed by the analysis. In compounds (I)-(IV), all H
atoms were treated as riding atoms, with C—H = 0.95–1.00 Å and N—H =
0.88 Å.
Data collection: SMART (Bruker, 1997) for (I); KappaCCD Server Software (Nonius, 1997) for (II), (III), (IV). Cell refinement: SMART for (I); DENZO-SMN (Otwinowski & Minor, 1997) for (II), (III), (IV). Data reduction: SHELXTL (Bruker, 1997) for (I); DENZO-SMN for (II), (III), (IV). For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976) and PLATON (Spek, 2002); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).
(I) 2-Phenyl-5-
p-tolyl-1,5,6,10
b-tetrahydropyrazolo[1,5-
c]quinazoline
top
Crystal data top
C23H21N3 | Z = 2 |
Mr = 339.43 | F(000) = 360 |
Triclinic, P1 | Dx = 1.284 Mg m−3 |
Hall symbol: -P_1 | Melting point: 486 K |
a = 8.5292 (12) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.7291 (16) Å | Cell parameters from 3993 reflections |
c = 11.0469 (16) Å | θ = 2.0–29.1° |
α = 109.417 (2)° | µ = 0.08 mm−1 |
β = 91.555 (3)° | T = 120 K |
γ = 110.945 (3)° | Plate, colourless |
V = 878.1 (2) Å3 | 0.18 × 0.08 × 0.04 mm |
Data collection top
Bruker SMART1000 CCD area-detector diffractometer | 3993 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 3451 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.014 |
ϕ scans, and ω scans with κ offsets | θmax = 29.1°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | h = −11→7 |
Tmin = 0.986, Tmax = 0.997 | k = −13→14 |
5532 measured reflections | l = −12→14 |
Refinement top
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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.146 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.064P)2 + 0.6107P] where P = (Fo2 + 2Fc2)/3 |
3993 reflections | (Δ/σ)max < 0.001 |
235 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
Crystal data top
C23H21N3 | γ = 110.945 (3)° |
Mr = 339.43 | V = 878.1 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.5292 (12) Å | Mo Kα radiation |
b = 10.7291 (16) Å | µ = 0.08 mm−1 |
c = 11.0469 (16) Å | T = 120 K |
α = 109.417 (2)° | 0.18 × 0.08 × 0.04 mm |
β = 91.555 (3)° | |
Data collection top
Bruker SMART1000 CCD area-detector diffractometer | 3993 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | 3451 reflections with I > 2σ(I) |
Tmin = 0.986, Tmax = 0.997 | Rint = 0.014 |
5532 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.146 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.31 e Å−3 |
3993 reflections | Δρmin = −0.27 e Å−3 |
235 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | −0.0964 (2) | 0.32820 (17) | 0.07315 (15) | 0.0254 (3) | |
C2 | −0.1893 (2) | 0.27201 (17) | 0.17058 (15) | 0.0220 (3) | |
C21 | −0.2816 (2) | 0.11914 (17) | 0.14714 (16) | 0.0250 (3) | |
C22 | −0.2744 (2) | 0.01508 (19) | 0.03366 (18) | 0.0316 (4) | |
C23 | −0.3597 (3) | −0.1300 (2) | 0.01091 (19) | 0.0367 (4) | |
C24 | −0.4517 (3) | −0.17209 (19) | 0.10157 (19) | 0.0366 (4) | |
C25 | −0.4631 (3) | −0.0698 (2) | 0.21335 (19) | 0.0361 (4) | |
C26 | −0.3797 (2) | 0.07498 (19) | 0.23625 (17) | 0.0308 (4) | |
N3 | −0.18664 (16) | 0.37314 (14) | 0.27518 (13) | 0.0219 (3) | |
N4 | −0.10372 (16) | 0.50609 (14) | 0.26040 (13) | 0.0205 (3) | |
C5 | −0.01454 (19) | 0.62216 (16) | 0.38439 (15) | 0.0210 (3) | |
C51 | 0.0368 (2) | 0.76551 (17) | 0.36454 (15) | 0.0229 (3) | |
C52 | −0.0666 (2) | 0.78595 (19) | 0.27976 (19) | 0.0309 (4) | |
C53 | −0.0208 (3) | 0.9180 (2) | 0.2660 (2) | 0.0364 (4) | |
C54 | 0.1276 (3) | 1.03339 (19) | 0.33691 (19) | 0.0336 (4) | |
C57 | 0.1753 (3) | 1.1759 (2) | 0.3205 (2) | 0.0494 (6) | |
C55 | 0.2277 (3) | 1.0129 (2) | 0.4227 (2) | 0.0404 (5) | |
C56 | 0.1847 (2) | 0.8811 (2) | 0.43577 (19) | 0.0344 (4) | |
N6 | 0.12726 (17) | 0.60072 (15) | 0.43579 (13) | 0.0247 (3) | |
C6a | 0.23539 (19) | 0.56458 (16) | 0.35389 (15) | 0.0206 (3) | |
C7 | 0.3963 (2) | 0.57803 (18) | 0.40415 (17) | 0.0266 (3) | |
C8 | 0.5050 (2) | 0.54256 (19) | 0.3212 (2) | 0.0310 (4) | |
C9 | 0.4581 (2) | 0.49409 (18) | 0.18768 (19) | 0.0319 (4) | |
C10 | 0.2977 (2) | 0.47751 (17) | 0.13729 (17) | 0.0269 (3) | |
C10a | 0.18454 (19) | 0.51076 (16) | 0.21805 (15) | 0.0211 (3) | |
C10b | 0.0068 (2) | 0.48573 (16) | 0.16049 (15) | 0.0215 (3) | |
H1A | −0.1764 | 0.3200 | 0.0016 | 0.030* | |
H1B | −0.0214 | 0.2780 | 0.0362 | 0.030* | |
H22 | −0.2106 | 0.0435 | −0.0286 | 0.038* | |
H23 | −0.3547 | −0.2001 | −0.0669 | 0.044* | |
H24 | −0.5071 | −0.2711 | 0.0872 | 0.044* | |
H25 | −0.5284 | −0.0991 | 0.2746 | 0.043* | |
H26 | −0.3890 | 0.1445 | 0.3126 | 0.037* | |
H5 | −0.0962 | 0.6204 | 0.4477 | 0.025* | |
H52 | −0.1695 | 0.7091 | 0.2308 | 0.037* | |
H53 | −0.0925 | 0.9296 | 0.2069 | 0.044* | |
H57A | 0.2545 | 1.2521 | 0.3976 | 0.074* | |
H57B | 0.0726 | 1.1949 | 0.3101 | 0.074* | |
H57C | 0.2298 | 1.1732 | 0.2432 | 0.074* | |
H55 | 0.3283 | 1.0908 | 0.4739 | 0.049* | |
H56 | 0.2574 | 0.8698 | 0.4943 | 0.041* | |
H6 | 0.1530 | 0.6273 | 0.5212 | 0.030* | |
H7 | 0.4305 | 0.6117 | 0.4956 | 0.032* | |
H8 | 0.6132 | 0.5516 | 0.3562 | 0.037* | |
H9 | 0.5346 | 0.4724 | 0.1312 | 0.038* | |
H10 | 0.2646 | 0.4427 | 0.0456 | 0.032* | |
H10B | 0.0138 | 0.5498 | 0.1109 | 0.026* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0284 (8) | 0.0216 (8) | 0.0211 (7) | 0.0039 (6) | 0.0029 (6) | 0.0080 (6) |
C2 | 0.0218 (7) | 0.0217 (7) | 0.0213 (7) | 0.0056 (6) | 0.0017 (6) | 0.0097 (6) |
C21 | 0.0261 (8) | 0.0216 (8) | 0.0251 (8) | 0.0053 (6) | −0.0001 (6) | 0.0104 (6) |
C22 | 0.0373 (10) | 0.0246 (8) | 0.0299 (9) | 0.0080 (7) | 0.0052 (7) | 0.0108 (7) |
C23 | 0.0452 (11) | 0.0235 (9) | 0.0347 (9) | 0.0092 (8) | 0.0016 (8) | 0.0075 (7) |
C24 | 0.0403 (10) | 0.0217 (8) | 0.0398 (10) | 0.0021 (7) | −0.0028 (8) | 0.0132 (7) |
C25 | 0.0389 (10) | 0.0300 (9) | 0.0342 (9) | 0.0027 (8) | 0.0030 (8) | 0.0173 (8) |
C26 | 0.0342 (9) | 0.0263 (9) | 0.0269 (8) | 0.0046 (7) | 0.0030 (7) | 0.0114 (7) |
N3 | 0.0197 (6) | 0.0207 (6) | 0.0253 (7) | 0.0054 (5) | 0.0031 (5) | 0.0111 (5) |
N4 | 0.0204 (6) | 0.0185 (6) | 0.0229 (6) | 0.0062 (5) | 0.0042 (5) | 0.0094 (5) |
C5 | 0.0210 (7) | 0.0217 (7) | 0.0203 (7) | 0.0089 (6) | 0.0047 (6) | 0.0071 (6) |
C51 | 0.0228 (7) | 0.0205 (7) | 0.0253 (7) | 0.0090 (6) | 0.0078 (6) | 0.0073 (6) |
C52 | 0.0266 (8) | 0.0233 (8) | 0.0422 (10) | 0.0078 (7) | 0.0015 (7) | 0.0136 (7) |
C53 | 0.0390 (10) | 0.0296 (9) | 0.0468 (11) | 0.0165 (8) | 0.0063 (8) | 0.0182 (8) |
C54 | 0.0407 (10) | 0.0212 (8) | 0.0395 (10) | 0.0120 (7) | 0.0175 (8) | 0.0109 (7) |
C57 | 0.0687 (15) | 0.0232 (9) | 0.0550 (13) | 0.0146 (10) | 0.0201 (11) | 0.0155 (9) |
C55 | 0.0398 (11) | 0.0235 (9) | 0.0421 (11) | 0.0002 (8) | 0.0000 (8) | 0.0064 (8) |
C56 | 0.0335 (9) | 0.0286 (9) | 0.0337 (9) | 0.0058 (7) | −0.0020 (7) | 0.0099 (7) |
N6 | 0.0243 (7) | 0.0335 (8) | 0.0188 (6) | 0.0133 (6) | 0.0036 (5) | 0.0102 (6) |
C6a | 0.0202 (7) | 0.0178 (7) | 0.0257 (7) | 0.0062 (6) | 0.0044 (6) | 0.0114 (6) |
C7 | 0.0224 (8) | 0.0243 (8) | 0.0341 (9) | 0.0075 (6) | 0.0021 (6) | 0.0137 (7) |
C8 | 0.0201 (8) | 0.0262 (8) | 0.0493 (11) | 0.0095 (7) | 0.0060 (7) | 0.0164 (8) |
C9 | 0.0263 (8) | 0.0234 (8) | 0.0464 (10) | 0.0102 (7) | 0.0171 (8) | 0.0120 (7) |
C10 | 0.0291 (8) | 0.0198 (7) | 0.0294 (8) | 0.0067 (6) | 0.0106 (7) | 0.0089 (6) |
C10a | 0.0219 (7) | 0.0157 (7) | 0.0251 (7) | 0.0048 (6) | 0.0057 (6) | 0.0095 (6) |
C10b | 0.0244 (7) | 0.0211 (7) | 0.0196 (7) | 0.0074 (6) | 0.0042 (6) | 0.0096 (6) |
Geometric parameters (Å, º) top
C1—C2 | 1.512 (2) | C52—H52 | 0.9500 |
C1—C10b | 1.539 (2) | C53—C54 | 1.389 (3) |
C1—H1A | 0.9900 | C53—H53 | 0.9500 |
C1—H1B | 0.9900 | C54—C55 | 1.380 (3) |
C2—N3 | 1.288 (2) | C54—C57 | 1.510 (3) |
C2—C21 | 1.470 (2) | C57—H57A | 0.9800 |
C21—C22 | 1.395 (2) | C57—H57B | 0.9800 |
C21—C26 | 1.402 (2) | C57—H57C | 0.9800 |
C22—C23 | 1.391 (2) | C55—C56 | 1.386 (3) |
C22—H22 | 0.9500 | C55—H55 | 0.9500 |
C23—C24 | 1.383 (3) | C56—H56 | 0.9500 |
C23—H23 | 0.9500 | N6—C6a | 1.374 (2) |
C24—C25 | 1.386 (3) | N6—H6 | 0.8857 |
C24—H24 | 0.9500 | C6a—C7 | 1.406 (2) |
C25—C26 | 1.387 (2) | C6a—C10a | 1.408 (2) |
C25—H25 | 0.9500 | C7—C8 | 1.383 (2) |
C26—H26 | 0.9500 | C7—H7 | 0.9500 |
N3—N4 | 1.4147 (18) | C8—C9 | 1.384 (3) |
N4—C5 | 1.4620 (19) | C8—H8 | 0.9500 |
N4—C10b | 1.483 (2) | C9—C10 | 1.390 (3) |
C5—N6 | 1.445 (2) | C9—H9 | 0.9500 |
C5—C51 | 1.534 (2) | C10—C10a | 1.392 (2) |
C5—H5 | 1.0000 | C10—H10 | 0.9500 |
C51—C56 | 1.388 (2) | C10a—C10b | 1.522 (2) |
C51—C52 | 1.391 (2) | C10b—H10B | 1.0000 |
C52—C53 | 1.391 (2) | | |
| | | |
C2—C1—C10b | 100.55 (12) | C54—C53—H53 | 119.3 |
C2—C1—H1A | 111.7 | C52—C53—H53 | 119.3 |
C10b—C1—H1A | 111.7 | C55—C54—C53 | 117.62 (17) |
C2—C1—H1B | 111.7 | C55—C54—C57 | 121.77 (19) |
C10b—C1—H1B | 111.7 | C53—C54—C57 | 120.61 (19) |
H1A—C1—H1B | 109.4 | C54—C57—H57A | 109.5 |
N3—C2—C21 | 122.94 (14) | C54—C57—H57B | 109.5 |
N3—C2—C1 | 112.68 (14) | H57A—C57—H57B | 109.5 |
C21—C2—C1 | 124.29 (14) | C54—C57—H57C | 109.5 |
C22—C21—C26 | 118.82 (15) | H57A—C57—H57C | 109.5 |
C22—C21—C2 | 119.95 (15) | H57B—C57—H57C | 109.5 |
C26—C21—C2 | 121.23 (15) | C54—C55—C56 | 121.52 (18) |
C23—C22—C21 | 120.53 (17) | C54—C55—H55 | 119.2 |
C23—C22—H22 | 119.7 | C56—C55—H55 | 119.2 |
C21—C22—H22 | 119.7 | C55—C56—C51 | 120.91 (18) |
C24—C23—C22 | 120.05 (18) | C55—C56—H56 | 119.5 |
C24—C23—H23 | 120.0 | C51—C56—H56 | 119.5 |
C22—C23—H23 | 120.0 | C6a—N6—C5 | 118.73 (13) |
C23—C24—C25 | 120.00 (17) | C6a—N6—H6 | 121.5 |
C23—C24—H24 | 120.0 | C5—N6—H6 | 118.7 |
C25—C24—H24 | 120.0 | N6—C6a—C7 | 120.66 (15) |
C24—C25—C26 | 120.30 (17) | N6—C6a—C10a | 120.15 (14) |
C24—C25—H25 | 119.9 | C7—C6a—C10a | 119.18 (15) |
C26—C25—H25 | 119.9 | C8—C7—C6a | 120.35 (16) |
C25—C26—C21 | 120.26 (17) | C8—C7—H7 | 119.8 |
C25—C26—H26 | 119.9 | C6a—C7—H7 | 119.8 |
C21—C26—H26 | 119.9 | C7—C8—C9 | 120.78 (16) |
C2—N3—N4 | 108.49 (12) | C7—C8—H8 | 119.6 |
N3—N4—C5 | 112.26 (12) | C9—C8—H8 | 119.6 |
N3—N4—C10b | 107.96 (11) | C8—C9—C10 | 119.14 (16) |
C5—N4—C10b | 114.03 (12) | C8—C9—H9 | 120.4 |
N6—C5—N4 | 110.75 (12) | C10—C9—H9 | 120.4 |
N6—C5—C51 | 113.52 (13) | C9—C10—C10a | 121.52 (16) |
N4—C5—C51 | 108.56 (12) | C9—C10—H10 | 119.2 |
N6—C5—H5 | 107.9 | C10a—C10—H10 | 119.2 |
N4—C5—H5 | 107.9 | C10—C10a—C6a | 118.98 (15) |
C51—C5—H5 | 107.9 | C10—C10a—C10b | 120.53 (14) |
C56—C51—C52 | 117.99 (16) | C6a—C10a—C10b | 120.46 (13) |
C56—C51—C5 | 120.66 (15) | N4—C10b—C10a | 112.68 (12) |
C52—C51—C5 | 121.28 (14) | N4—C10b—C1 | 100.43 (12) |
C51—C52—C53 | 120.55 (17) | C10a—C10b—C1 | 112.68 (13) |
C51—C52—H52 | 119.7 | N4—C10b—H10B | 110.2 |
C53—C52—H52 | 119.7 | C10a—C10b—H10B | 110.2 |
C54—C53—C52 | 121.39 (18) | C1—C10b—H10B | 110.2 |
| | | |
C10b—C1—C2—N3 | 16.10 (18) | C53—C54—C55—C56 | 1.6 (3) |
C10b—C1—C2—C21 | −167.19 (15) | C57—C54—C55—C56 | −178.92 (19) |
N3—C2—C21—C22 | −177.79 (16) | C54—C55—C56—C51 | −1.4 (3) |
C1—C2—C21—C22 | 5.8 (2) | C52—C51—C56—C55 | 0.0 (3) |
N3—C2—C21—C26 | 3.1 (3) | C5—C51—C56—C55 | −176.97 (17) |
C1—C2—C21—C26 | −173.30 (16) | N4—C5—N6—C6a | 46.58 (18) |
C26—C21—C22—C23 | −1.5 (3) | C51—C5—N6—C6a | −75.85 (18) |
C2—C21—C22—C23 | 179.34 (17) | C5—N6—C6a—C7 | 163.73 (14) |
C21—C22—C23—C24 | −0.5 (3) | C5—N6—C6a—C10a | −17.5 (2) |
C22—C23—C24—C25 | 1.9 (3) | N6—C6a—C7—C8 | −179.47 (15) |
C23—C24—C25—C26 | −1.4 (3) | C10a—C6a—C7—C8 | 1.8 (2) |
C24—C25—C26—C21 | −0.6 (3) | C6a—C7—C8—C9 | 0.3 (3) |
C22—C21—C26—C25 | 2.1 (3) | C7—C8—C9—C10 | −1.8 (3) |
C2—C21—C26—C25 | −178.80 (16) | C8—C9—C10—C10a | 1.1 (3) |
C21—C2—N3—N4 | −173.44 (14) | C9—C10—C10a—C6a | 1.0 (2) |
C1—C2—N3—N4 | 3.32 (18) | C9—C10—C10a—C10b | −177.39 (14) |
C2—N3—N4—C5 | −149.36 (13) | N6—C6a—C10a—C10 | 178.81 (14) |
C2—N3—N4—C10b | −22.83 (16) | C7—C6a—C10a—C10 | −2.4 (2) |
N3—N4—C5—N6 | 67.19 (16) | N6—C6a—C10a—C10b | −2.8 (2) |
C10b—N4—C5—N6 | −55.99 (16) | C7—C6a—C10a—C10b | 176.00 (14) |
N3—N4—C5—C51 | −167.53 (12) | N3—N4—C10b—C10a | −88.85 (14) |
C10b—N4—C5—C51 | 69.28 (15) | C5—N4—C10b—C10a | 36.64 (17) |
N6—C5—C51—C56 | −24.1 (2) | N3—N4—C10b—C1 | 31.27 (14) |
N4—C5—C51—C56 | −147.76 (16) | C5—N4—C10b—C1 | 156.76 (12) |
N6—C5—C51—C52 | 158.96 (15) | C10—C10a—C10b—N4 | 171.16 (13) |
N4—C5—C51—C52 | 35.3 (2) | C6a—C10a—C10b—N4 | −7.25 (19) |
C56—C51—C52—C53 | 1.0 (3) | C10—C10a—C10b—C1 | 58.37 (19) |
C5—C51—C52—C53 | 177.94 (16) | C6a—C10a—C10b—C1 | −120.04 (15) |
C51—C52—C53—C54 | −0.7 (3) | C2—C1—C10b—N4 | −27.02 (15) |
C52—C53—C54—C55 | −0.6 (3) | C2—C1—C10b—C10a | 93.11 (15) |
C52—C53—C54—C57 | 179.92 (19) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N6—H6···N3i | 0.88 | 2.26 | 3.122 (2) | 164 |
C53—H53···Cg4ii | 0.95 | 2.75 | 3.635 (3) | 156 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, y+1, z. |
(II) 5-(4-Bromophenyl)-2-phenyl-1,5,6,10
b-tetrahydropyrazolo[1,5-
c]quinazoline
top
Crystal data top
C22H18BrN3 | Z = 2 |
Mr = 404.30 | F(000) = 412 |
Triclinic, P1 | Dx = 1.541 Mg m−3 |
Hall symbol: -P_1 | Melting point: 536 K |
a = 8.5110 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.7015 (3) Å | Cell parameters from 3775 reflections |
c = 11.0357 (3) Å | θ = 3.1–27.5° |
α = 110.036 (2)° | µ = 2.37 mm−1 |
β = 92.1613 (15)° | T = 120 K |
γ = 110.3276 (10)° | Block, colourless |
V = 871.37 (4) Å3 | 0.25 × 0.15 × 0.10 mm |
Data collection top
Nonius KappaCCD area-detector diffractometer | 3775 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 3235 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.056 |
ϕ scans, and ω scans with κ offsets | θmax = 27.5°, θmin = 3.1° |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | h = −11→11 |
Tmin = 0.719, Tmax = 0.789 | k = −13→13 |
12439 measured reflections | l = −12→12 |
Refinement top
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.091 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0481P)2 + 0.3379P] where P = (Fo2 + 2Fc2)/3 |
3775 reflections | (Δ/σ)max = 0.002 |
235 parameters | Δρmax = 0.46 e Å−3 |
0 restraints | Δρmin = −0.65 e Å−3 |
Crystal data top
C22H18BrN3 | γ = 110.3276 (10)° |
Mr = 404.30 | V = 871.37 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.5110 (2) Å | Mo Kα radiation |
b = 10.7015 (3) Å | µ = 2.37 mm−1 |
c = 11.0357 (3) Å | T = 120 K |
α = 110.036 (2)° | 0.25 × 0.15 × 0.10 mm |
β = 92.1613 (15)° | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 3775 independent reflections |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | 3235 reflections with I > 2σ(I) |
Tmin = 0.719, Tmax = 0.789 | Rint = 0.056 |
12439 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.091 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.46 e Å−3 |
3775 reflections | Δρmin = −0.65 e Å−3 |
235 parameters | |
Special details top
Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm
(Fox & Holmes, 1966) which effectively corrects for absorption effects. High
redundancy data were used in the scaling program hence the 'multi-scan' code
word was used. No transmission coefficients are available from the program
(only scale factors for each frame). The scale factors in the experimental
table are calculated from the 'size' command in the SHELXL97 input
file. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | −0.0934 (3) | 0.3248 (2) | 0.0737 (2) | 0.0196 (5) | |
C2 | −0.1889 (3) | 0.2714 (2) | 0.1704 (2) | 0.0158 (4) | |
C21 | −0.2816 (3) | 0.1186 (2) | 0.1466 (2) | 0.0173 (5) | |
C22 | −0.2733 (3) | 0.0127 (2) | 0.0335 (2) | 0.0218 (5) | |
C23 | −0.3613 (3) | −0.1332 (3) | 0.0093 (2) | 0.0255 (5) | |
C24 | −0.4549 (3) | −0.1728 (3) | 0.0995 (2) | 0.0252 (5) | |
C25 | −0.4656 (3) | −0.0681 (3) | 0.2114 (3) | 0.0268 (5) | |
C26 | −0.3812 (3) | 0.0767 (3) | 0.2346 (2) | 0.0223 (5) | |
N3 | −0.1874 (2) | 0.37453 (19) | 0.27450 (18) | 0.0165 (4) | |
N4 | −0.1042 (2) | 0.50691 (19) | 0.25962 (17) | 0.0150 (4) | |
C5 | −0.0151 (3) | 0.6246 (2) | 0.3854 (2) | 0.0156 (4) | |
C51 | 0.0352 (3) | 0.7676 (2) | 0.3661 (2) | 0.0164 (4) | |
C52 | −0.0686 (3) | 0.7859 (2) | 0.2782 (2) | 0.0230 (5) | |
C53 | −0.0243 (3) | 0.9169 (3) | 0.2625 (2) | 0.0242 (5) | |
C54 | 0.1236 (3) | 1.0297 (2) | 0.3372 (2) | 0.0200 (5) | |
Br54 | 0.18587 (3) | 1.20894 (2) | 0.31532 (2) | 0.02693 (10) | |
C55 | 0.2251 (3) | 1.0155 (3) | 0.4269 (2) | 0.0266 (5) | |
C56 | 0.1808 (3) | 0.8840 (3) | 0.4400 (2) | 0.0244 (5) | |
N6 | 0.1274 (2) | 0.6049 (2) | 0.43881 (18) | 0.0182 (4) | |
C6a | 0.2379 (3) | 0.5701 (2) | 0.3575 (2) | 0.0162 (4) | |
C7 | 0.4000 (3) | 0.5874 (2) | 0.4103 (2) | 0.0202 (5) | |
C8 | 0.5106 (3) | 0.5531 (2) | 0.3276 (3) | 0.0242 (5) | |
C9 | 0.4627 (3) | 0.5023 (2) | 0.1932 (3) | 0.0254 (5) | |
C10 | 0.3009 (3) | 0.4823 (2) | 0.1408 (2) | 0.0215 (5) | |
C10a | 0.1860 (3) | 0.5139 (2) | 0.2207 (2) | 0.0168 (4) | |
C10b | 0.0071 (3) | 0.4842 (2) | 0.1601 (2) | 0.0159 (4) | |
H1A | −0.1723 | 0.3136 | −0.0010 | 0.024* | |
H1B | −0.0167 | 0.2744 | 0.0404 | 0.024* | |
H22 | −0.2073 | 0.0397 | −0.0275 | 0.026* | |
H23 | −0.3570 | −0.2050 | −0.0688 | 0.031* | |
H24 | −0.5118 | −0.2718 | 0.0846 | 0.030* | |
H25 | −0.5311 | −0.0957 | 0.2725 | 0.032* | |
H26 | −0.3911 | 0.1479 | 0.3107 | 0.027* | |
H5 | −0.0968 | 0.6236 | 0.4482 | 0.019* | |
H52 | −0.1710 | 0.7080 | 0.2283 | 0.028* | |
H53 | −0.0945 | 0.9284 | 0.2015 | 0.029* | |
H55 | 0.3247 | 1.0950 | 0.4795 | 0.032* | |
H56 | 0.2521 | 0.8737 | 0.5011 | 0.029* | |
H6 | 0.1532 | 0.6314 | 0.5242 | 0.022* | |
H7 | 0.4342 | 0.6226 | 0.5026 | 0.024* | |
H8 | 0.6202 | 0.5648 | 0.3637 | 0.029* | |
H9 | 0.5398 | 0.4811 | 0.1371 | 0.030* | |
H10 | 0.2678 | 0.4463 | 0.0483 | 0.026* | |
H10B | 0.0117 | 0.5456 | 0.1084 | 0.019* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0227 (12) | 0.0171 (11) | 0.0136 (11) | 0.0017 (9) | 0.0027 (9) | 0.0055 (9) |
C2 | 0.0166 (11) | 0.0152 (11) | 0.0148 (11) | 0.0048 (9) | 0.0008 (8) | 0.0065 (9) |
C21 | 0.0190 (11) | 0.0160 (11) | 0.0164 (11) | 0.0037 (9) | −0.0002 (8) | 0.0090 (9) |
C22 | 0.0247 (13) | 0.0201 (12) | 0.0190 (12) | 0.0064 (10) | 0.0028 (9) | 0.0080 (9) |
C23 | 0.0322 (14) | 0.0191 (12) | 0.0234 (13) | 0.0100 (10) | 0.0002 (10) | 0.0062 (10) |
C24 | 0.0283 (13) | 0.0155 (11) | 0.0285 (13) | 0.0027 (10) | −0.0018 (10) | 0.0110 (10) |
C25 | 0.0278 (13) | 0.0234 (12) | 0.0272 (14) | 0.0027 (10) | 0.0044 (10) | 0.0146 (10) |
C26 | 0.0262 (13) | 0.0186 (11) | 0.0197 (12) | 0.0057 (10) | 0.0039 (9) | 0.0073 (9) |
N3 | 0.0180 (9) | 0.0143 (9) | 0.0186 (10) | 0.0054 (7) | 0.0034 (7) | 0.0086 (7) |
N4 | 0.0180 (9) | 0.0126 (9) | 0.0142 (9) | 0.0043 (7) | 0.0043 (7) | 0.0066 (7) |
C5 | 0.0172 (11) | 0.0151 (10) | 0.0148 (11) | 0.0068 (9) | 0.0043 (8) | 0.0052 (8) |
C51 | 0.0188 (11) | 0.0164 (11) | 0.0164 (11) | 0.0087 (9) | 0.0068 (8) | 0.0066 (9) |
C52 | 0.0193 (12) | 0.0175 (11) | 0.0283 (13) | 0.0038 (9) | −0.0006 (9) | 0.0080 (10) |
C53 | 0.0254 (13) | 0.0215 (12) | 0.0299 (14) | 0.0102 (10) | 0.0024 (10) | 0.0139 (10) |
C54 | 0.0276 (13) | 0.0150 (11) | 0.0205 (12) | 0.0099 (9) | 0.0104 (9) | 0.0078 (9) |
Br54 | 0.03910 (17) | 0.01496 (14) | 0.02808 (17) | 0.00948 (11) | 0.00988 (11) | 0.01025 (10) |
C55 | 0.0288 (13) | 0.0170 (12) | 0.0271 (13) | 0.0042 (10) | −0.0029 (10) | 0.0059 (10) |
C56 | 0.0284 (13) | 0.0190 (12) | 0.0219 (12) | 0.0067 (10) | −0.0031 (10) | 0.0064 (10) |
N6 | 0.0224 (10) | 0.0219 (10) | 0.0127 (9) | 0.0104 (8) | 0.0029 (7) | 0.0075 (8) |
C6a | 0.0193 (11) | 0.0106 (10) | 0.0202 (12) | 0.0050 (8) | 0.0042 (9) | 0.0082 (8) |
C7 | 0.0225 (12) | 0.0152 (11) | 0.0224 (12) | 0.0052 (9) | 0.0013 (9) | 0.0091 (9) |
C8 | 0.0169 (12) | 0.0189 (12) | 0.0381 (15) | 0.0069 (9) | 0.0047 (10) | 0.0123 (10) |
C9 | 0.0220 (12) | 0.0183 (12) | 0.0359 (15) | 0.0084 (10) | 0.0145 (10) | 0.0087 (10) |
C10 | 0.0275 (13) | 0.0129 (10) | 0.0219 (12) | 0.0055 (9) | 0.0095 (9) | 0.0058 (9) |
C10a | 0.0209 (11) | 0.0109 (10) | 0.0191 (11) | 0.0043 (9) | 0.0061 (9) | 0.0078 (8) |
C10b | 0.0211 (11) | 0.0150 (10) | 0.0132 (11) | 0.0063 (9) | 0.0061 (8) | 0.0075 (8) |
Geometric parameters (Å, º) top
C1—C2 | 1.511 (3) | C51—C52 | 1.396 (3) |
C1—C10b | 1.537 (3) | C52—C53 | 1.393 (3) |
C1—H1A | 0.9900 | C52—H52 | 0.9500 |
C1—H1B | 0.9900 | C53—C54 | 1.380 (3) |
C2—N3 | 1.288 (3) | C53—H53 | 0.9500 |
C2—C21 | 1.469 (3) | C54—C55 | 1.370 (3) |
C21—C22 | 1.393 (3) | C54—Br54 | 1.908 (2) |
C21—C26 | 1.400 (3) | C55—C56 | 1.385 (3) |
C22—C23 | 1.399 (3) | C55—H55 | 0.9500 |
C22—H22 | 0.9500 | C56—H56 | 0.9500 |
C23—C24 | 1.385 (4) | N6—C6a | 1.380 (3) |
C23—H23 | 0.9500 | N6—H6 | 0.8800 |
C24—C25 | 1.386 (4) | C6a—C7 | 1.402 (3) |
C24—H24 | 0.9500 | C6a—C10a | 1.407 (3) |
C25—C26 | 1.388 (3) | C7—C8 | 1.389 (3) |
C25—H25 | 0.9500 | C7—H7 | 0.9500 |
C26—H26 | 0.9500 | C8—C9 | 1.382 (4) |
N3—N4 | 1.416 (2) | C8—H8 | 0.9500 |
N4—C5 | 1.465 (3) | C9—C10 | 1.388 (4) |
N4—C10b | 1.490 (3) | C9—H9 | 0.9500 |
C5—N6 | 1.440 (3) | C10—C10a | 1.392 (3) |
C5—C51 | 1.531 (3) | C10—H10 | 0.9500 |
C5—H5 | 1.0000 | C10a—C10b | 1.519 (3) |
C51—C56 | 1.382 (3) | C10b—H10B | 1.0000 |
| | | |
C2—C1—C10b | 101.04 (17) | C53—C52—H52 | 119.5 |
C2—C1—H1A | 111.6 | C51—C52—H52 | 119.5 |
C10b—C1—H1A | 111.6 | C54—C53—C52 | 118.7 (2) |
C2—C1—H1B | 111.6 | C54—C53—H53 | 120.6 |
C10b—C1—H1B | 111.6 | C52—C53—H53 | 120.6 |
H1A—C1—H1B | 109.4 | C55—C54—C53 | 121.4 (2) |
N3—C2—C21 | 122.95 (19) | C55—C54—Br54 | 119.68 (17) |
N3—C2—C1 | 112.81 (18) | C53—C54—Br54 | 118.94 (18) |
C21—C2—C1 | 124.17 (19) | C54—C55—C56 | 119.2 (2) |
C22—C21—C26 | 118.9 (2) | C54—C55—H55 | 120.4 |
C22—C21—C2 | 119.8 (2) | C56—C55—H55 | 120.4 |
C26—C21—C2 | 121.2 (2) | C51—C56—C55 | 121.4 (2) |
C21—C22—C23 | 120.5 (2) | C51—C56—H56 | 119.3 |
C21—C22—H22 | 119.8 | C55—C56—H56 | 119.3 |
C23—C22—H22 | 119.8 | C6a—N6—C5 | 118.43 (18) |
C24—C23—C22 | 119.8 (2) | C6a—N6—H6 | 121.1 |
C24—C23—H23 | 120.1 | C5—N6—H6 | 119.3 |
C22—C23—H23 | 120.1 | N6—C6a—C7 | 120.5 (2) |
C23—C24—C25 | 120.1 (2) | N6—C6a—C10a | 119.8 (2) |
C23—C24—H24 | 119.9 | C7—C6a—C10a | 119.7 (2) |
C25—C24—H24 | 119.9 | C8—C7—C6a | 120.0 (2) |
C24—C25—C26 | 120.3 (2) | C8—C7—H7 | 120.0 |
C24—C25—H25 | 119.9 | C6a—C7—H7 | 120.0 |
C26—C25—H25 | 119.9 | C9—C8—C7 | 120.6 (2) |
C25—C26—C21 | 120.3 (2) | C9—C8—H8 | 119.7 |
C25—C26—H26 | 119.8 | C7—C8—H8 | 119.7 |
C21—C26—H26 | 119.8 | C8—C9—C10 | 119.4 (2) |
C2—N3—N4 | 108.54 (17) | C8—C9—H9 | 120.3 |
N3—N4—C5 | 111.94 (17) | C10—C9—H9 | 120.3 |
N3—N4—C10b | 108.09 (16) | C9—C10—C10a | 121.5 (2) |
C5—N4—C10b | 114.10 (17) | C9—C10—H10 | 119.3 |
N6—C5—N4 | 111.18 (17) | C10a—C10—H10 | 119.3 |
N6—C5—C51 | 113.15 (18) | C10—C10a—C6a | 118.7 (2) |
N4—C5—C51 | 108.57 (17) | C10—C10a—C10b | 120.1 (2) |
N6—C5—H5 | 107.9 | C6a—C10a—C10b | 121.17 (19) |
N4—C5—H5 | 107.9 | N4—C10b—C10a | 112.59 (17) |
C51—C5—H5 | 107.9 | N4—C10b—C1 | 100.49 (16) |
C56—C51—C52 | 118.2 (2) | C10a—C10b—C1 | 113.07 (18) |
C56—C51—C5 | 120.7 (2) | N4—C10b—H10B | 110.1 |
C52—C51—C5 | 121.01 (19) | C10a—C10b—H10B | 110.1 |
C53—C52—C51 | 121.0 (2) | C1—C10b—H10B | 110.1 |
| | | |
C10b—C1—C2—N3 | 14.9 (2) | C53—C54—C55—C56 | 1.9 (4) |
C10b—C1—C2—C21 | −168.15 (19) | Br54—C54—C55—C56 | −178.56 (19) |
N3—C2—C21—C22 | −178.0 (2) | C52—C51—C56—C55 | −0.8 (4) |
C1—C2—C21—C22 | 5.3 (3) | C5—C51—C56—C55 | −177.8 (2) |
N3—C2—C21—C26 | 3.0 (3) | C54—C55—C56—C51 | −1.0 (4) |
C1—C2—C21—C26 | −173.7 (2) | N4—C5—N6—C6a | 47.4 (3) |
C26—C21—C22—C23 | −0.8 (3) | C51—C5—N6—C6a | −75.0 (2) |
C2—C21—C22—C23 | −179.8 (2) | C5—N6—C6a—C7 | 162.77 (19) |
C21—C22—C23—C24 | −1.2 (4) | C5—N6—C6a—C10a | −18.6 (3) |
C22—C23—C24—C25 | 2.0 (4) | N6—C6a—C7—C8 | −179.5 (2) |
C23—C24—C25—C26 | −0.8 (4) | C10a—C6a—C7—C8 | 1.9 (3) |
C24—C25—C26—C21 | −1.3 (4) | C6a—C7—C8—C9 | 0.2 (3) |
C22—C21—C26—C25 | 2.1 (3) | C7—C8—C9—C10 | −1.5 (3) |
C2—C21—C26—C25 | −179.0 (2) | C8—C9—C10—C10a | 0.7 (3) |
C21—C2—N3—N4 | −173.10 (18) | C9—C10—C10a—C6a | 1.4 (3) |
C1—C2—N3—N4 | 3.9 (2) | C9—C10—C10a—C10b | −177.1 (2) |
C2—N3—N4—C5 | −148.81 (18) | N6—C6a—C10a—C10 | 178.77 (19) |
C2—N3—N4—C10b | −22.3 (2) | C7—C6a—C10a—C10 | −2.6 (3) |
N3—N4—C5—N6 | 67.9 (2) | N6—C6a—C10a—C10b | −2.8 (3) |
C10b—N4—C5—N6 | −55.3 (2) | C7—C6a—C10a—C10b | 175.81 (19) |
N3—N4—C5—C51 | −167.02 (16) | N3—N4—C10b—C10a | −90.6 (2) |
C10b—N4—C5—C51 | 69.8 (2) | C5—N4—C10b—C10a | 34.6 (2) |
N6—C5—C51—C56 | −24.7 (3) | N3—N4—C10b—C1 | 30.0 (2) |
N4—C5—C51—C56 | −148.6 (2) | C5—N4—C10b—C1 | 155.21 (18) |
N6—C5—C51—C52 | 158.4 (2) | C10—C10a—C10b—N4 | 172.67 (18) |
N4—C5—C51—C52 | 34.4 (3) | C6a—C10a—C10b—N4 | −5.8 (3) |
C56—C51—C52—C53 | 1.8 (3) | C10—C10a—C10b—C1 | 59.6 (3) |
C5—C51—C52—C53 | 178.8 (2) | C6a—C10a—C10b—C1 | −118.8 (2) |
C51—C52—C53—C54 | −1.0 (4) | C2—C1—C10b—N4 | −25.6 (2) |
C52—C53—C54—C55 | −0.9 (4) | C2—C1—C10b—C10a | 94.6 (2) |
C52—C53—C54—Br54 | 179.56 (18) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N6—H6···N3i | 0.88 | 2.25 | 3.105 (3) | 162 |
C53—H53···Cg4ii | 0.95 | 2.71 | 3.588 (3) | 154 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, y+1, z. |
(III) 2-(4-Chlorophenyl)-5-phenyl-1,5,6,10
b-tetrahydropyrazolo[1,5-
c]quinazoline
top
Crystal data top
C22H18ClN3 | Dx = 1.362 Mg m−3 |
Mr = 359.84 | Melting point: 507 K |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 21.2115 (3) Å | Cell parameters from 4002 reflections |
b = 11.1385 (2) Å | θ = 3.0–27.5° |
c = 17.5948 (4) Å | µ = 0.23 mm−1 |
β = 122.427 (1)° | T = 120 K |
V = 3508.84 (11) Å3 | Block, colourless |
Z = 8 | 0.46 × 0.32 × 0.10 mm |
F(000) = 1504 | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 4002 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 3286 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.085 |
ϕ scans, and ω scans with κ offsets | θmax = 27.5°, θmin = 3.0° |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | h = −27→27 |
Tmin = 0.902, Tmax = 0.978 | k = −14→13 |
15078 measured reflections | l = −22→22 |
Refinement top
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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0694P)2 + 2.7737P] where P = (Fo2 + 2Fc2)/3 |
4002 reflections | (Δ/σ)max = 0.001 |
235 parameters | Δρmax = 0.39 e Å−3 |
0 restraints | Δρmin = −0.54 e Å−3 |
Crystal data top
C22H18ClN3 | V = 3508.84 (11) Å3 |
Mr = 359.84 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 21.2115 (3) Å | µ = 0.23 mm−1 |
b = 11.1385 (2) Å | T = 120 K |
c = 17.5948 (4) Å | 0.46 × 0.32 × 0.10 mm |
β = 122.427 (1)° | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 4002 independent reflections |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | 3286 reflections with I > 2σ(I) |
Tmin = 0.902, Tmax = 0.978 | Rint = 0.085 |
15078 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.39 e Å−3 |
4002 reflections | Δρmin = −0.54 e Å−3 |
235 parameters | |
Special details top
Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm
(Fox & Holmes, 1966) which effectively corrects for absorption effects. High
redundancy data were used in the scaling program hence the 'multi-scan' code
word was used. No transmission coefficients are available from the program
(only scale factors for each frame). The scale factors in the experimental
table are calculated from the 'size' command in the SHELXL97 input
file. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.77274 (9) | 0.01251 (14) | 0.32135 (11) | 0.0190 (3) | |
C2 | 0.77913 (8) | −0.00754 (13) | 0.41001 (11) | 0.0162 (3) | |
C21 | 0.82236 (8) | −0.10520 (14) | 0.47191 (11) | 0.0178 (3) | |
C22 | 0.86868 (9) | −0.17558 (15) | 0.45584 (12) | 0.0222 (4) | |
C23 | 0.90480 (9) | −0.27575 (15) | 0.50815 (12) | 0.0233 (4) | |
C24 | 0.89436 (9) | −0.30657 (15) | 0.57673 (11) | 0.0213 (3) | |
Cl24 | 0.93393 (2) | −0.43768 (4) | 0.63743 (3) | 0.02595 (14) | |
C25 | 0.85056 (10) | −0.23629 (16) | 0.59595 (12) | 0.0248 (4) | |
C26 | 0.81529 (10) | −0.13634 (15) | 0.54418 (12) | 0.0233 (4) | |
N3 | 0.73520 (7) | 0.06174 (11) | 0.42018 (9) | 0.0172 (3) | |
N4 | 0.69178 (7) | 0.12878 (12) | 0.34064 (9) | 0.0167 (3) | |
C5 | 0.66763 (9) | 0.24480 (14) | 0.35434 (11) | 0.0173 (3) | |
C51 | 0.60380 (8) | 0.29047 (15) | 0.26276 (11) | 0.0184 (3) | |
C52 | 0.55424 (9) | 0.21002 (16) | 0.19710 (12) | 0.0224 (4) | |
C53 | 0.49483 (9) | 0.25135 (17) | 0.11479 (12) | 0.0267 (4) | |
C54 | 0.48380 (10) | 0.37354 (18) | 0.09770 (13) | 0.0308 (4) | |
C55 | 0.53205 (10) | 0.45374 (18) | 0.16297 (14) | 0.0308 (4) | |
C56 | 0.59190 (9) | 0.41280 (16) | 0.24502 (12) | 0.0241 (4) | |
N6 | 0.72870 (7) | 0.32985 (12) | 0.39952 (9) | 0.0196 (3) | |
C6a | 0.78374 (8) | 0.32935 (14) | 0.37973 (10) | 0.0163 (3) | |
C7 | 0.83771 (9) | 0.42042 (15) | 0.41312 (11) | 0.0209 (3) | |
C8 | 0.89153 (9) | 0.42294 (16) | 0.39114 (12) | 0.0245 (4) | |
C9 | 0.89286 (9) | 0.33560 (16) | 0.33574 (13) | 0.0259 (4) | |
C10 | 0.84045 (9) | 0.24437 (15) | 0.30419 (11) | 0.0212 (3) | |
C10a | 0.78591 (8) | 0.23873 (14) | 0.32564 (10) | 0.0163 (3) | |
C10b | 0.73224 (8) | 0.13351 (14) | 0.29347 (11) | 0.0170 (3) | |
H1A | 0.7430 | −0.0513 | 0.2773 | 0.023* | |
H1B | 0.8224 | 0.0174 | 0.3290 | 0.023* | |
H22 | 0.8755 | −0.1544 | 0.4084 | 0.027* | |
H23 | 0.9364 | −0.3227 | 0.4970 | 0.028* | |
H25 | 0.8450 | −0.2569 | 0.6444 | 0.030* | |
H26 | 0.7857 | −0.0878 | 0.5577 | 0.028* | |
H5 | 0.6472 | 0.2319 | 0.3934 | 0.021* | |
H52 | 0.5610 | 0.1262 | 0.2086 | 0.027* | |
H53 | 0.4617 | 0.1956 | 0.0702 | 0.032* | |
H54 | 0.4434 | 0.4018 | 0.0415 | 0.037* | |
H55 | 0.5244 | 0.5376 | 0.1518 | 0.037* | |
H56 | 0.6249 | 0.4689 | 0.2893 | 0.029* | |
H6 | 0.7391 | 0.3624 | 0.4506 | 0.023* | |
H7 | 0.8375 | 0.4809 | 0.4511 | 0.025* | |
H8 | 0.9279 | 0.4851 | 0.4143 | 0.029* | |
H9 | 0.9291 | 0.3384 | 0.3198 | 0.031* | |
H10 | 0.8416 | 0.1839 | 0.2669 | 0.025* | |
H10B | 0.6964 | 0.1371 | 0.2268 | 0.020* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0210 (8) | 0.0177 (8) | 0.0219 (8) | 0.0003 (6) | 0.0139 (7) | −0.0006 (6) |
C2 | 0.0154 (7) | 0.0152 (7) | 0.0197 (8) | −0.0050 (6) | 0.0105 (6) | −0.0032 (6) |
C21 | 0.0158 (7) | 0.0176 (8) | 0.0191 (8) | −0.0041 (6) | 0.0088 (6) | −0.0028 (6) |
C22 | 0.0229 (8) | 0.0228 (8) | 0.0263 (9) | 0.0001 (6) | 0.0167 (7) | 0.0023 (7) |
C23 | 0.0207 (8) | 0.0236 (8) | 0.0285 (9) | 0.0025 (6) | 0.0150 (7) | 0.0023 (7) |
C24 | 0.0153 (7) | 0.0246 (8) | 0.0193 (8) | −0.0036 (6) | 0.0062 (7) | 0.0019 (7) |
Cl24 | 0.0197 (2) | 0.0276 (3) | 0.0255 (2) | 0.00038 (15) | 0.00878 (18) | 0.00796 (16) |
C25 | 0.0266 (9) | 0.0304 (9) | 0.0197 (8) | −0.0014 (7) | 0.0139 (7) | 0.0018 (7) |
C26 | 0.0260 (9) | 0.0246 (8) | 0.0237 (9) | 0.0006 (7) | 0.0162 (7) | −0.0025 (7) |
N3 | 0.0160 (6) | 0.0177 (7) | 0.0185 (7) | −0.0026 (5) | 0.0096 (6) | 0.0003 (5) |
N4 | 0.0167 (6) | 0.0182 (7) | 0.0187 (7) | −0.0007 (5) | 0.0119 (6) | 0.0002 (5) |
C5 | 0.0171 (7) | 0.0188 (8) | 0.0214 (8) | −0.0021 (6) | 0.0139 (7) | −0.0035 (6) |
C51 | 0.0144 (7) | 0.0233 (8) | 0.0228 (8) | −0.0003 (6) | 0.0135 (7) | −0.0020 (7) |
C52 | 0.0172 (8) | 0.0260 (9) | 0.0273 (9) | −0.0028 (6) | 0.0142 (7) | −0.0039 (7) |
C53 | 0.0159 (8) | 0.0403 (10) | 0.0242 (9) | −0.0018 (7) | 0.0109 (7) | −0.0049 (8) |
C54 | 0.0176 (8) | 0.0449 (11) | 0.0282 (10) | 0.0073 (8) | 0.0112 (7) | 0.0053 (9) |
C55 | 0.0265 (9) | 0.0296 (10) | 0.0352 (11) | 0.0073 (7) | 0.0159 (8) | 0.0065 (8) |
C56 | 0.0207 (8) | 0.0248 (9) | 0.0279 (9) | 0.0006 (7) | 0.0138 (7) | −0.0015 (7) |
N6 | 0.0186 (7) | 0.0229 (7) | 0.0197 (7) | −0.0037 (5) | 0.0119 (6) | −0.0072 (6) |
C6a | 0.0141 (7) | 0.0174 (7) | 0.0158 (7) | 0.0011 (6) | 0.0070 (6) | 0.0017 (6) |
C7 | 0.0186 (8) | 0.0195 (8) | 0.0190 (8) | −0.0021 (6) | 0.0063 (7) | −0.0002 (6) |
C8 | 0.0164 (8) | 0.0248 (9) | 0.0263 (9) | −0.0053 (6) | 0.0075 (7) | 0.0048 (7) |
C9 | 0.0175 (8) | 0.0315 (9) | 0.0326 (10) | 0.0004 (7) | 0.0161 (7) | 0.0078 (8) |
C10 | 0.0220 (8) | 0.0221 (8) | 0.0252 (9) | 0.0022 (6) | 0.0165 (7) | 0.0029 (7) |
C10a | 0.0141 (7) | 0.0182 (8) | 0.0162 (7) | 0.0004 (6) | 0.0080 (6) | 0.0026 (6) |
C10b | 0.0179 (7) | 0.0185 (8) | 0.0184 (8) | −0.0004 (6) | 0.0124 (7) | −0.0016 (6) |
Geometric parameters (Å, º) top
C1—C2 | 1.508 (2) | C51—C52 | 1.393 (2) |
C1—C10b | 1.531 (2) | C52—C53 | 1.393 (2) |
C1—H1A | 0.9900 | C52—H52 | 0.9500 |
C1—H1B | 0.9900 | C53—C54 | 1.386 (3) |
C2—N3 | 1.294 (2) | C53—H53 | 0.9500 |
C2—C21 | 1.463 (2) | C54—C55 | 1.380 (3) |
C21—C22 | 1.399 (2) | C54—H54 | 0.9500 |
C21—C26 | 1.401 (2) | C55—C56 | 1.392 (3) |
C22—C23 | 1.387 (2) | C55—H55 | 0.9500 |
C22—H22 | 0.9500 | C56—H56 | 0.9500 |
C23—C24 | 1.382 (2) | N6—C6a | 1.3857 (19) |
C23—H23 | 0.9500 | N6—H6 | 0.8800 |
C24—C25 | 1.388 (2) | C6a—C7 | 1.401 (2) |
C24—Cl24 | 1.7367 (17) | C6a—C10a | 1.405 (2) |
C25—C26 | 1.378 (2) | C7—C8 | 1.388 (2) |
C25—H25 | 0.9500 | C7—H7 | 0.9500 |
C26—H26 | 0.9500 | C8—C9 | 1.388 (3) |
N3—N4 | 1.4079 (19) | C8—H8 | 0.9500 |
N4—C5 | 1.457 (2) | C9—C10 | 1.384 (2) |
N4—C10b | 1.4804 (18) | C9—H9 | 0.9500 |
C5—N6 | 1.450 (2) | C10—C10a | 1.398 (2) |
C5—C51 | 1.533 (2) | C10—H10 | 0.9500 |
C5—H5 | 1.0000 | C10a—C10b | 1.516 (2) |
C51—C56 | 1.390 (2) | C10b—H10B | 1.0000 |
| | | |
C2—C1—C10b | 100.69 (12) | C53—C52—H52 | 119.7 |
C2—C1—H1A | 111.6 | C51—C52—H52 | 119.7 |
C10b—C1—H1A | 111.6 | C54—C53—C52 | 120.22 (17) |
C2—C1—H1B | 111.6 | C54—C53—H53 | 119.9 |
C10b—C1—H1B | 111.6 | C52—C53—H53 | 119.9 |
H1A—C1—H1B | 109.4 | C55—C54—C53 | 119.44 (17) |
N3—C2—C21 | 123.42 (14) | C55—C54—H54 | 120.3 |
N3—C2—C1 | 112.51 (14) | C53—C54—H54 | 120.3 |
C21—C2—C1 | 123.58 (13) | C54—C55—C56 | 120.52 (18) |
C22—C21—C26 | 118.23 (15) | C54—C55—H55 | 119.7 |
C22—C21—C2 | 119.60 (14) | C56—C55—H55 | 119.7 |
C26—C21—C2 | 122.03 (14) | C51—C56—C55 | 120.57 (17) |
C23—C22—C21 | 120.97 (15) | C51—C56—H56 | 119.7 |
C23—C22—H22 | 119.5 | C55—C56—H56 | 119.7 |
C21—C22—H22 | 119.5 | C6a—N6—C5 | 119.01 (13) |
C24—C23—C22 | 119.29 (15) | C6a—N6—H6 | 118.3 |
C24—C23—H23 | 120.4 | C5—N6—H6 | 119.4 |
C22—C23—H23 | 120.4 | N6—C6a—C7 | 120.05 (14) |
C23—C24—C25 | 120.94 (16) | N6—C6a—C10a | 120.74 (14) |
C23—C24—Cl24 | 119.66 (13) | C7—C6a—C10a | 119.21 (14) |
C25—C24—Cl24 | 119.36 (13) | C8—C7—C6a | 120.46 (15) |
C26—C25—C24 | 119.45 (15) | C8—C7—H7 | 119.8 |
C26—C25—H25 | 120.3 | C6a—C7—H7 | 119.8 |
C24—C25—H25 | 120.3 | C9—C8—C7 | 120.72 (16) |
C25—C26—C21 | 121.04 (15) | C9—C8—H8 | 119.6 |
C25—C26—H26 | 119.5 | C7—C8—H8 | 119.6 |
C21—C26—H26 | 119.5 | C10—C9—C8 | 118.82 (15) |
C2—N3—N4 | 108.33 (12) | C10—C9—H9 | 120.6 |
N3—N4—C5 | 113.99 (12) | C8—C9—H9 | 120.6 |
N3—N4—C10b | 108.02 (11) | C9—C10—C10a | 121.87 (16) |
C5—N4—C10b | 114.96 (12) | C9—C10—H10 | 119.1 |
N6—C5—N4 | 112.34 (12) | C10a—C10—H10 | 119.1 |
N6—C5—C51 | 112.67 (13) | C10—C10a—C6a | 118.90 (14) |
N4—C5—C51 | 108.13 (13) | C10—C10a—C10b | 119.90 (14) |
N6—C5—H5 | 107.8 | C6a—C10a—C10b | 121.16 (13) |
N4—C5—H5 | 107.8 | N4—C10b—C10a | 111.29 (12) |
C51—C5—H5 | 107.8 | N4—C10b—C1 | 100.57 (12) |
C56—C51—C52 | 118.61 (16) | C10a—C10b—C1 | 112.39 (12) |
C56—C51—C5 | 120.86 (15) | N4—C10b—H10B | 110.7 |
C52—C51—C5 | 120.46 (15) | C10a—C10b—H10B | 110.7 |
C53—C52—C51 | 120.62 (17) | C1—C10b—H10B | 110.7 |
| | | |
C10b—C1—C2—N3 | 15.76 (16) | C52—C53—C54—C55 | −0.2 (3) |
C10b—C1—C2—C21 | −172.08 (14) | C53—C54—C55—C56 | 0.7 (3) |
N3—C2—C21—C22 | −179.85 (15) | C52—C51—C56—C55 | −0.6 (2) |
C1—C2—C21—C22 | 8.8 (2) | C5—C51—C56—C55 | −177.46 (15) |
N3—C2—C21—C26 | 4.5 (2) | C54—C55—C56—C51 | −0.4 (3) |
C1—C2—C21—C26 | −166.82 (15) | N4—C5—N6—C6a | 36.79 (19) |
C26—C21—C22—C23 | 2.0 (2) | C51—C5—N6—C6a | −85.64 (16) |
C2—C21—C22—C23 | −173.79 (15) | C5—N6—C6a—C7 | 171.52 (14) |
C21—C22—C23—C24 | 0.4 (3) | C5—N6—C6a—C10a | −8.0 (2) |
C22—C23—C24—C25 | −2.4 (3) | N6—C6a—C7—C8 | −177.80 (15) |
C22—C23—C24—Cl24 | 175.44 (13) | C10a—C6a—C7—C8 | 1.7 (2) |
C23—C24—C25—C26 | 1.9 (3) | C6a—C7—C8—C9 | 0.1 (3) |
Cl24—C24—C25—C26 | −175.94 (13) | C7—C8—C9—C10 | −1.3 (3) |
C24—C25—C26—C21 | 0.6 (3) | C8—C9—C10—C10a | 0.8 (3) |
C22—C21—C26—C25 | −2.5 (2) | C9—C10—C10a—C6a | 0.9 (2) |
C2—C21—C26—C25 | 173.16 (15) | C9—C10—C10a—C10b | −176.81 (15) |
C21—C2—N3—N4 | −168.43 (13) | N6—C6a—C10a—C10 | 177.33 (14) |
C1—C2—N3—N4 | 3.74 (17) | C7—C6a—C10a—C10 | −2.1 (2) |
C2—N3—N4—C5 | −152.17 (13) | N6—C6a—C10a—C10b | −5.0 (2) |
C2—N3—N4—C10b | −23.08 (15) | C7—C6a—C10a—C10b | 175.56 (14) |
N3—N4—C5—N6 | 71.45 (15) | N3—N4—C10b—C10a | −87.84 (14) |
C10b—N4—C5—N6 | −54.05 (17) | C5—N4—C10b—C10a | 40.70 (17) |
N3—N4—C5—C51 | −163.59 (12) | N3—N4—C10b—C1 | 31.41 (14) |
C10b—N4—C5—C51 | 70.92 (15) | C5—N4—C10b—C1 | 159.95 (13) |
N6—C5—C51—C56 | −25.73 (19) | C10—C10a—C10b—N4 | 166.26 (14) |
N4—C5—C51—C56 | −150.49 (14) | C6a—C10a—C10b—N4 | −11.4 (2) |
N6—C5—C51—C52 | 157.43 (13) | C10—C10a—C10b—C1 | 54.33 (19) |
N4—C5—C51—C52 | 32.66 (18) | C6a—C10a—C10b—C1 | −123.36 (15) |
C56—C51—C52—C53 | 1.1 (2) | C2—C1—C10b—N4 | −26.90 (14) |
C5—C51—C52—C53 | 178.05 (14) | C2—C1—C10b—C10a | 91.55 (14) |
C51—C52—C53—C54 | −0.8 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N6—H6···N3i | 0.88 | 2.20 | 3.083 (2) | 178 |
C1—H1A···Cg3ii | 0.99 | 2.44 | 3.407 (2) | 166 |
C22—H22···Cg5ii | 0.95 | 2.88 | 3.739 (2) | 152 |
Symmetry codes: (i) −x+3/2, −y+1/2, −z+1; (ii) −x+3/2, y−1/2, −z+1/2. |
(IV) 5-(4-Bromophenyl)-2-(4-chlorophenyl)-1,5,6,10
b-tetrahydropyrazolo[1,5-
c] quinazoline
top
Crystal data top
C22H17BrClN3 | Z = 2 |
Mr = 438.75 | F(000) = 444 |
Triclinic, P1 | Dx = 1.556 Mg m−3 |
Hall symbol: -P_1 | Melting point: 487 K |
a = 5.5560 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.2526 (2) Å | Cell parameters from 4188 reflections |
c = 14.0827 (3) Å | θ = 3.0–27.4° |
α = 77.9230 (9)° | µ = 2.37 mm−1 |
β = 83.0060 (8)° | T = 120 K |
γ = 87.814 (1)° | Block, colourless |
V = 930.41 (3) Å3 | 0.35 × 0.10 × 0.08 mm |
Data collection top
Nonius KappaCCD area-detector diffractometer | 4188 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 3683 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.068 |
ϕ scans, and ω scans with κ offsets | θmax = 27.4°, θmin = 3.0° |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | h = −7→7 |
Tmin = 0.492, Tmax = 0.843 | k = −15→15 |
14350 measured reflections | l = −18→18 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.080 | w = 1/[σ2(Fo2) + (0.0266P)2 + 0.6775P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
4188 reflections | Δρmax = 0.49 e Å−3 |
269 parameters | Δρmin = −0.68 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0130 (12) |
Crystal data top
C22H17BrClN3 | γ = 87.814 (1)° |
Mr = 438.75 | V = 930.41 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 5.5560 (1) Å | Mo Kα radiation |
b = 12.2526 (2) Å | µ = 2.37 mm−1 |
c = 14.0827 (3) Å | T = 120 K |
α = 77.9230 (9)° | 0.35 × 0.10 × 0.08 mm |
β = 83.0060 (8)° | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 4188 independent reflections |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | 3683 reflections with I > 2σ(I) |
Tmin = 0.492, Tmax = 0.843 | Rint = 0.068 |
14350 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.080 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.49 e Å−3 |
4188 reflections | Δρmin = −0.68 e Å−3 |
269 parameters | |
Special details top
Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm
(Fox & Holmes, 1966) which effectively corrects for absorption effects. High
redundancy data were used in the scaling program hence the 'multi-scan' code
word was used. No transmission coefficients are available from the program
(only scale factors for each frame). The scale factors in the experimental
table are calculated from the 'size' command in the SHELXL97 input
file. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Cl24 | 0.57185 (14) | 1.26302 (5) | 1.00319 (4) | 0.04059 (18) | |
C1 | 0.0630 (4) | 0.8853 (2) | 0.78261 (17) | 0.0248 (5) | |
C2 | 0.2741 (4) | 0.96410 (17) | 0.75248 (16) | 0.0189 (4) | |
C21A | 0.3609 (9) | 1.0332 (4) | 0.8164 (2) | 0.0189 (4) | 0.50 |
C22A | 0.2721 (6) | 1.0162 (3) | 0.9149 (2) | 0.0191 (9) | 0.50 |
C23A | 0.3461 (6) | 1.0846 (3) | 0.9729 (2) | 0.0204 (9) | 0.50 |
C24A | 0.5088 (8) | 1.1699 (3) | 0.9324 (4) | 0.0139 (14) | 0.50 |
C25A | 0.5975 (9) | 1.1868 (5) | 0.8339 (4) | 0.0173 (17) | 0.50 |
C26A | 0.5235 (11) | 1.1185 (5) | 0.7758 (3) | 0.0130 (14) | 0.50 |
C21B | 0.3370 (8) | 1.0470 (4) | 0.8080 (2) | 0.0175 (11) | 0.50 |
C22B | 0.1737 (6) | 1.0680 (3) | 0.8853 (2) | 0.0201 (9) | 0.50 |
C23B | 0.2354 (7) | 1.1400 (3) | 0.9424 (2) | 0.0243 (10) | 0.50 |
C24B | 0.4603 (8) | 1.1911 (4) | 0.9224 (4) | 0.0225 (17) | 0.50 |
C25B | 0.6236 (7) | 1.1701 (6) | 0.8451 (5) | 0.025 (2) | 0.50 |
C26B | 0.5620 (8) | 1.0980 (6) | 0.7879 (4) | 0.0165 (17) | 0.50 |
N3 | 0.3764 (3) | 0.96414 (14) | 0.66559 (13) | 0.0171 (4) | |
N4 | 0.2497 (3) | 0.89011 (14) | 0.62532 (12) | 0.0161 (4) | |
C5 | 0.4110 (4) | 0.83725 (17) | 0.55841 (14) | 0.0158 (4) | |
C51 | 0.2592 (4) | 0.77798 (17) | 0.50144 (14) | 0.0152 (4) | |
C52 | 0.0743 (4) | 0.83624 (17) | 0.45246 (15) | 0.0178 (4) | |
C53 | −0.0574 (4) | 0.78592 (17) | 0.39556 (15) | 0.0185 (4) | |
C54 | −0.0027 (4) | 0.67636 (18) | 0.38782 (15) | 0.0180 (4) | |
Br54 | −0.17399 (4) | 0.608703 (18) | 0.306946 (16) | 0.02505 (9) | |
C55 | 0.1785 (4) | 0.61751 (19) | 0.43595 (17) | 0.0238 (5) | |
C56 | 0.3076 (4) | 0.66836 (18) | 0.49269 (16) | 0.0217 (5) | |
N6 | 0.5854 (3) | 0.76567 (15) | 0.61147 (13) | 0.0176 (4) | |
C6a | 0.4967 (4) | 0.68993 (17) | 0.69533 (16) | 0.0189 (4) | |
C7 | 0.6372 (4) | 0.59733 (19) | 0.73284 (18) | 0.0254 (5) | |
C8 | 0.5521 (5) | 0.5233 (2) | 0.81712 (19) | 0.0329 (6) | |
C9 | 0.3246 (5) | 0.5388 (2) | 0.86507 (18) | 0.0341 (6) | |
C10 | 0.1850 (4) | 0.6310 (2) | 0.82896 (17) | 0.0270 (5) | |
C10a | 0.2685 (4) | 0.70822 (17) | 0.74441 (15) | 0.0179 (4) | |
C10b | 0.1165 (4) | 0.81048 (18) | 0.70763 (15) | 0.0180 (4) | |
H1A | −0.0942 | 0.9254 | 0.7763 | 0.030* | |
H1B | 0.0644 | 0.8423 | 0.8504 | 0.030* | |
H22A | 0.1609 | 0.9579 | 0.9426 | 0.023* | 0.50 |
H23A | 0.2854 | 1.0730 | 1.0402 | 0.024* | 0.50 |
H25A | 0.7087 | 1.2451 | 0.8062 | 0.021* | 0.50 |
H26A | 0.5842 | 1.1301 | 0.7085 | 0.016* | 0.50 |
H22B | 0.0200 | 1.0331 | 0.8990 | 0.024* | 0.50 |
H23B | 0.1237 | 1.1544 | 0.9952 | 0.029* | 0.50 |
H25B | 0.7773 | 1.2049 | 0.8314 | 0.030* | 0.50 |
H26B | 0.6736 | 1.0837 | 0.7351 | 0.020* | 0.50 |
H5 | 0.5030 | 0.8976 | 0.5104 | 0.019* | |
H52 | 0.0378 | 0.9112 | 0.4580 | 0.021* | |
H53 | −0.1829 | 0.8260 | 0.3625 | 0.022* | |
H55 | 0.2147 | 0.5426 | 0.4303 | 0.029* | |
H56 | 0.4315 | 0.6274 | 0.5262 | 0.026* | |
H6 | 0.7087 | 0.7403 | 0.5765 | 0.021* | |
H7 | 0.7926 | 0.5854 | 0.7000 | 0.030* | |
H8 | 0.6501 | 0.4613 | 0.8424 | 0.039* | |
H9 | 0.2645 | 0.4867 | 0.9222 | 0.041* | |
H10 | 0.0297 | 0.6419 | 0.8623 | 0.032* | |
H10B | −0.0381 | 0.7878 | 0.6880 | 0.022* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl24 | 0.0711 (5) | 0.0325 (3) | 0.0238 (3) | −0.0193 (3) | −0.0073 (3) | −0.0143 (3) |
C1 | 0.0207 (10) | 0.0305 (12) | 0.0271 (12) | −0.0071 (9) | 0.0047 (9) | −0.0178 (10) |
C2 | 0.0191 (9) | 0.0196 (10) | 0.0200 (10) | −0.0022 (8) | 0.0000 (8) | −0.0097 (8) |
C21A | 0.0191 (9) | 0.0196 (10) | 0.0200 (10) | −0.0022 (8) | 0.0000 (8) | −0.0097 (8) |
C22A | 0.020 (2) | 0.021 (2) | 0.018 (2) | −0.0055 (18) | −0.0022 (17) | −0.0077 (18) |
C23A | 0.023 (2) | 0.023 (2) | 0.015 (2) | 0.0009 (19) | −0.0007 (17) | −0.0057 (18) |
C24A | 0.019 (2) | 0.009 (2) | 0.016 (3) | 0.002 (2) | −0.009 (2) | −0.004 (2) |
C25A | 0.024 (3) | 0.015 (3) | 0.012 (3) | −0.003 (2) | 0.001 (2) | −0.004 (2) |
C26A | 0.017 (2) | 0.010 (3) | 0.011 (3) | 0.006 (2) | −0.005 (2) | 0.001 (2) |
C21B | 0.022 (2) | 0.019 (3) | 0.013 (2) | 0.0022 (19) | −0.0043 (17) | −0.0068 (18) |
C22B | 0.021 (2) | 0.022 (2) | 0.018 (2) | −0.0008 (19) | 0.0010 (17) | −0.0074 (18) |
C23B | 0.034 (3) | 0.028 (2) | 0.014 (2) | −0.002 (2) | 0.0012 (19) | −0.0110 (19) |
C24B | 0.037 (3) | 0.018 (3) | 0.015 (3) | 0.007 (3) | −0.013 (2) | −0.007 (2) |
C25B | 0.028 (4) | 0.016 (3) | 0.032 (4) | −0.005 (3) | −0.015 (3) | −0.002 (3) |
C26B | 0.018 (3) | 0.016 (3) | 0.014 (3) | 0.007 (2) | −0.005 (2) | 0.001 (2) |
N3 | 0.0204 (8) | 0.0162 (8) | 0.0174 (9) | −0.0012 (7) | −0.0039 (7) | −0.0086 (7) |
N4 | 0.0181 (8) | 0.0165 (8) | 0.0159 (9) | −0.0003 (7) | −0.0024 (7) | −0.0084 (7) |
C5 | 0.0177 (9) | 0.0159 (10) | 0.0144 (10) | −0.0004 (8) | −0.0007 (8) | −0.0053 (8) |
C51 | 0.0166 (9) | 0.0175 (10) | 0.0123 (10) | −0.0015 (8) | 0.0011 (7) | −0.0061 (8) |
C52 | 0.0213 (10) | 0.0154 (10) | 0.0178 (11) | 0.0011 (8) | −0.0031 (8) | −0.0058 (8) |
C53 | 0.0193 (10) | 0.0200 (10) | 0.0165 (10) | 0.0009 (8) | −0.0037 (8) | −0.0038 (8) |
C54 | 0.0187 (10) | 0.0216 (10) | 0.0155 (10) | −0.0021 (8) | −0.0016 (8) | −0.0081 (8) |
Br54 | 0.02558 (13) | 0.02700 (14) | 0.02849 (15) | −0.00012 (9) | −0.01032 (9) | −0.01510 (10) |
C55 | 0.0236 (11) | 0.0198 (11) | 0.0330 (13) | 0.0038 (9) | −0.0089 (9) | −0.0141 (9) |
C56 | 0.0203 (10) | 0.0215 (11) | 0.0267 (12) | 0.0054 (9) | −0.0085 (9) | −0.0105 (9) |
N6 | 0.0138 (8) | 0.0221 (9) | 0.0178 (9) | 0.0012 (7) | −0.0010 (7) | −0.0070 (7) |
C6a | 0.0193 (10) | 0.0186 (10) | 0.0222 (11) | −0.0029 (8) | −0.0078 (8) | −0.0086 (8) |
C7 | 0.0282 (11) | 0.0207 (11) | 0.0318 (13) | −0.0002 (9) | −0.0131 (10) | −0.0104 (9) |
C8 | 0.0484 (15) | 0.0182 (11) | 0.0362 (14) | −0.0023 (11) | −0.0239 (12) | −0.0038 (10) |
C9 | 0.0539 (16) | 0.0249 (12) | 0.0243 (13) | −0.0204 (12) | −0.0150 (11) | 0.0023 (10) |
C10 | 0.0331 (12) | 0.0297 (12) | 0.0202 (12) | −0.0166 (10) | −0.0053 (9) | −0.0056 (9) |
C10a | 0.0207 (10) | 0.0198 (10) | 0.0156 (10) | −0.0079 (8) | −0.0042 (8) | −0.0069 (8) |
C10b | 0.0159 (9) | 0.0229 (11) | 0.0175 (11) | −0.0053 (8) | 0.0002 (8) | −0.0096 (8) |
Geometric parameters (Å, º) top
Cl24—C24A | 1.735 (4) | N4—C5 | 1.455 (3) |
Cl24—C24B | 1.758 (4) | N4—C10b | 1.488 (3) |
C1—C2 | 1.510 (3) | C5—N6 | 1.450 (3) |
C1—C10b | 1.534 (3) | C5—C51 | 1.529 (3) |
C1—H1A | 0.9900 | C5—H5 | 1.0000 |
C1—H1B | 0.9900 | C51—C56 | 1.388 (3) |
C2—N3 | 1.285 (3) | C51—C52 | 1.397 (3) |
C2—C21B | 1.480 (4) | C52—C53 | 1.393 (3) |
C2—C21A | 1.488 (4) | C52—H52 | 0.9500 |
C21A—C22A | 1.3900 | C53—C54 | 1.389 (3) |
C21A—C26A | 1.3900 | C53—H53 | 0.9500 |
C22A—C23A | 1.3900 | C54—C55 | 1.378 (3) |
C22A—H22A | 0.9500 | C54—Br54 | 1.900 (2) |
C23A—C24A | 1.3900 | C55—C56 | 1.387 (3) |
C23A—H23A | 0.9500 | C55—H55 | 0.9500 |
C24A—C25A | 1.3900 | C56—H56 | 0.9500 |
C25A—C26A | 1.3900 | N6—C6a | 1.390 (3) |
C25A—H25A | 0.9500 | N6—H6 | 0.8800 |
C26A—H26A | 0.9500 | C6a—C7 | 1.399 (3) |
C21B—C22B | 1.3900 | C6a—C10a | 1.402 (3) |
C21B—C26B | 1.3900 | C7—C8 | 1.378 (4) |
C22B—C23B | 1.3900 | C7—H7 | 0.9500 |
C22B—H22B | 0.9500 | C8—C9 | 1.385 (4) |
C23B—C24B | 1.3900 | C8—H8 | 0.9500 |
C23B—H23B | 0.9500 | C9—C10 | 1.387 (4) |
C24B—C25B | 1.3900 | C9—H9 | 0.9500 |
C25B—C26B | 1.3900 | C10—C10a | 1.399 (3) |
C25B—H25B | 0.9500 | C10—H10 | 0.9500 |
C26B—H26B | 0.9500 | C10a—C10b | 1.518 (3) |
N3—N4 | 1.415 (2) | C10b—H10B | 1.0000 |
| | | |
C2—C1—C10b | 100.36 (16) | N6—C5—N4 | 109.97 (16) |
C2—C1—H1A | 111.7 | N6—C5—C51 | 114.40 (16) |
C10b—C1—H1A | 111.7 | N4—C5—C51 | 109.08 (16) |
C2—C1—H1B | 111.7 | N6—C5—H5 | 107.7 |
C10b—C1—H1B | 111.7 | N4—C5—H5 | 107.7 |
H1A—C1—H1B | 109.5 | C51—C5—H5 | 107.7 |
N3—C2—C21B | 121.5 (2) | C56—C51—C52 | 118.40 (19) |
N3—C2—C21A | 122.8 (2) | C56—C51—C5 | 121.66 (18) |
N3—C2—C1 | 112.92 (18) | C52—C51—C5 | 119.86 (18) |
C21B—C2—C1 | 124.9 (2) | C53—C52—C51 | 120.89 (19) |
C21A—C2—C1 | 124.3 (2) | C53—C52—H52 | 119.6 |
C22A—C21A—C26A | 120.0 | C51—C52—H52 | 119.6 |
C22A—C21A—C2 | 120.5 (3) | C54—C53—C52 | 119.16 (19) |
C26A—C21A—C2 | 119.5 (3) | C54—C53—H53 | 120.4 |
C21A—C22A—C23A | 120.0 | C52—C53—H53 | 120.4 |
C21A—C22A—H22A | 120.0 | C55—C54—C53 | 120.72 (19) |
C23A—C22A—H22A | 120.0 | C55—C54—Br54 | 119.82 (16) |
C24A—C23A—C22A | 120.0 | C53—C54—Br54 | 119.44 (15) |
C24A—C23A—H23A | 120.0 | C54—C55—C56 | 119.6 (2) |
C22A—C23A—H23A | 120.0 | C54—C55—H55 | 120.2 |
C25A—C24A—C23A | 120.0 | C56—C55—H55 | 120.2 |
C25A—C24A—Cl24 | 120.8 (3) | C55—C56—C51 | 121.2 (2) |
C23A—C24A—Cl24 | 118.8 (3) | C55—C56—H56 | 119.4 |
C24A—C25A—C26A | 120.0 | C51—C56—H56 | 119.4 |
C24A—C25A—H25A | 120.0 | C6a—N6—C5 | 117.60 (16) |
C26A—C25A—H25A | 120.0 | C6a—N6—H6 | 114.3 |
C25A—C26A—C21A | 120.0 | C5—N6—H6 | 117.0 |
C25A—C26A—H26A | 120.0 | N6—C6a—C7 | 120.4 (2) |
C21A—C26A—H26A | 120.0 | N6—C6a—C10a | 119.88 (19) |
C22B—C21B—C26B | 120.0 | C7—C6a—C10a | 119.7 (2) |
C22B—C21B—C2 | 119.0 (3) | C8—C7—C6a | 120.6 (2) |
C26B—C21B—C2 | 120.9 (3) | C8—C7—H7 | 119.7 |
C21B—C22B—C23B | 120.0 | C6a—C7—H7 | 119.7 |
C21B—C22B—H22B | 120.0 | C7—C8—C9 | 120.4 (2) |
C23B—C22B—H22B | 120.0 | C7—C8—H8 | 119.8 |
C22B—C23B—C24B | 120.0 | C9—C8—H8 | 119.8 |
C22B—C23B—H23B | 120.0 | C8—C9—C10 | 119.5 (2) |
C24B—C23B—H23B | 120.0 | C8—C9—H9 | 120.3 |
C25B—C24B—C23B | 120.0 | C10—C9—H9 | 120.3 |
C25B—C24B—Cl24 | 116.7 (3) | C9—C10—C10a | 121.3 (2) |
C23B—C24B—Cl24 | 122.4 (3) | C9—C10—H10 | 119.3 |
C24B—C25B—C26B | 120.0 | C10a—C10—H10 | 119.3 |
C24B—C25B—H25B | 120.0 | C10—C10a—C6a | 118.5 (2) |
C26B—C25B—H25B | 120.0 | C10—C10a—C10b | 120.60 (19) |
C25B—C26B—C21B | 120.0 | C6a—C10a—C10b | 120.85 (18) |
C25B—C26B—H26B | 120.0 | N4—C10b—C10a | 112.50 (16) |
C21B—C26B—H26B | 120.0 | N4—C10b—C1 | 100.20 (16) |
C2—N3—N4 | 108.33 (16) | C10a—C10b—C1 | 112.66 (18) |
N3—N4—C5 | 111.42 (15) | N4—C10b—H10B | 110.4 |
N3—N4—C10b | 107.92 (15) | C10a—C10b—H10B | 110.4 |
C5—N4—C10b | 114.33 (16) | C1—C10b—H10B | 110.4 |
| | | |
C10b—C1—C2—N3 | 18.2 (2) | N3—N4—C5—N6 | 65.5 (2) |
C10b—C1—C2—C21B | −171.4 (3) | C10b—N4—C5—N6 | −57.2 (2) |
C10b—C1—C2—C21A | −160.5 (3) | N3—N4—C5—C51 | −168.29 (15) |
N3—C2—C21A—C22A | −168.8 (3) | C10b—N4—C5—C51 | 69.0 (2) |
C21B—C2—C21A—C22A | 106 (2) | N6—C5—C51—C56 | −7.4 (3) |
C1—C2—C21A—C22A | 9.8 (5) | N4—C5—C51—C56 | −131.0 (2) |
N3—C2—C21A—C26A | 14.1 (4) | N6—C5—C51—C52 | 175.91 (17) |
C21B—C2—C21A—C26A | −71 (2) | N4—C5—C51—C52 | 52.3 (2) |
C1—C2—C21A—C26A | −167.3 (3) | C56—C51—C52—C53 | −0.5 (3) |
C26A—C21A—C22A—C23A | 0.0 | C5—C51—C52—C53 | 176.34 (18) |
C2—C21A—C22A—C23A | −177.1 (4) | C51—C52—C53—C54 | 0.0 (3) |
C21A—C22A—C23A—C24A | 0.0 | C52—C53—C54—C55 | 0.3 (3) |
C22A—C23A—C24A—C25A | 0.0 | C52—C53—C54—Br54 | −177.93 (15) |
C22A—C23A—C24A—Cl24 | 173.1 (4) | C53—C54—C55—C56 | 0.0 (3) |
C24B—Cl24—C24A—C25A | 78.7 (12) | Br54—C54—C55—C56 | 178.19 (17) |
C24B—Cl24—C24A—C23A | −94.3 (13) | C54—C55—C56—C51 | −0.5 (3) |
C23A—C24A—C25A—C26A | 0.0 | C52—C51—C56—C55 | 0.8 (3) |
Cl24—C24A—C25A—C26A | −172.9 (4) | C5—C51—C56—C55 | −176.0 (2) |
C24A—C25A—C26A—C21A | 0.0 | N4—C5—N6—C6a | 49.9 (2) |
C22A—C21A—C26A—C25A | 0.0 | C51—C5—N6—C6a | −73.2 (2) |
C2—C21A—C26A—C25A | 177.1 (4) | C5—N6—C6a—C7 | 160.41 (18) |
N3—C2—C21B—C22B | 159.1 (2) | C5—N6—C6a—C10a | −21.6 (3) |
C21A—C2—C21B—C22B | −100 (2) | N6—C6a—C7—C8 | 178.6 (2) |
C1—C2—C21B—C22B | −10.5 (4) | C10a—C6a—C7—C8 | 0.7 (3) |
N3—C2—C21B—C26B | −25.1 (4) | C6a—C7—C8—C9 | 0.9 (3) |
C21A—C2—C21B—C26B | 76 (2) | C7—C8—C9—C10 | −1.6 (4) |
C1—C2—C21B—C26B | 165.3 (3) | C8—C9—C10—C10a | 0.6 (3) |
C26B—C21B—C22B—C23B | 0.0 | C9—C10—C10a—C6a | 0.9 (3) |
C2—C21B—C22B—C23B | 175.8 (3) | C9—C10—C10a—C10b | −178.2 (2) |
C21B—C22B—C23B—C24B | 0.0 | N6—C6a—C10a—C10 | −179.54 (19) |
C22B—C23B—C24B—C25B | 0.0 | C7—C6a—C10a—C10 | −1.6 (3) |
C22B—C23B—C24B—Cl24 | −168.6 (4) | N6—C6a—C10a—C10b | −0.5 (3) |
C24A—Cl24—C24B—C25B | −62.5 (12) | C7—C6a—C10a—C10b | 177.53 (18) |
C24A—Cl24—C24B—C23B | 106.4 (13) | N3—N4—C10b—C10a | −88.41 (19) |
C23B—C24B—C25B—C26B | 0.0 | C5—N4—C10b—C10a | 36.2 (2) |
Cl24—C24B—C25B—C26B | 169.2 (4) | N3—N4—C10b—C1 | 31.47 (19) |
C24B—C25B—C26B—C21B | 0.0 | C5—N4—C10b—C1 | 156.04 (17) |
C22B—C21B—C26B—C25B | 0.0 | C10—C10a—C10b—N4 | 172.09 (18) |
C2—C21B—C26B—C25B | −175.8 (3) | C6a—C10a—C10b—N4 | −7.0 (3) |
C21B—C2—N3—N4 | −169.4 (2) | C10—C10a—C10b—C1 | 59.7 (2) |
C21A—C2—N3—N4 | −179.9 (3) | C6a—C10a—C10b—C1 | −119.3 (2) |
C1—C2—N3—N4 | 1.4 (2) | C2—C1—C10b—N4 | −28.2 (2) |
C2—N3—N4—C5 | −147.98 (17) | C2—C1—C10b—C10a | 91.6 (2) |
C2—N3—N4—C10b | −21.7 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N6—H6···Cg5i | 0.88 | 2.82 | 3.666 (2) | 163 |
C10b—H10B···N6ii | 1.00 | 2.52 | 3.500 (3) | 168 |
Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z. |
Experimental details
| (I) | (II) | (III) | (IV) |
Crystal data |
Chemical formula | C23H21N3 | C22H18BrN3 | C22H18ClN3 | C22H17BrClN3 |
Mr | 339.43 | 404.30 | 359.84 | 438.75 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 | Monoclinic, C2/c | Triclinic, P1 |
Temperature (K) | 120 | 120 | 120 | 120 |
a, b, c (Å) | 8.5292 (12), 10.7291 (16), 11.0469 (16) | 8.5110 (2), 10.7015 (3), 11.0357 (3) | 21.2115 (3), 11.1385 (2), 17.5948 (4) | 5.5560 (1), 12.2526 (2), 14.0827 (3) |
α, β, γ (°) | 109.417 (2), 91.555 (3), 110.945 (3) | 110.036 (2), 92.1613 (15), 110.3276 (10) | 90, 122.427 (1), 90 | 77.9230 (9), 83.0060 (8), 87.814 (1) |
V (Å3) | 878.1 (2) | 871.37 (4) | 3508.84 (11) | 930.41 (3) |
Z | 2 | 2 | 8 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.08 | 2.37 | 0.23 | 2.37 |
Crystal size (mm) | 0.18 × 0.08 × 0.04 | 0.25 × 0.15 × 0.10 | 0.46 × 0.32 × 0.10 | 0.35 × 0.10 × 0.08 |
|
Data collection |
Diffractometer | Bruker SMART1000 CCD area-detector diffractometer | Nonius KappaCCD area-detector diffractometer | Nonius KappaCCD area-detector diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1997) | Multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | Multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | Multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.986, 0.997 | 0.719, 0.789 | 0.902, 0.978 | 0.492, 0.843 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5532, 3993, 3451 | 12439, 3775, 3235 | 15078, 4002, 3286 | 14350, 4188, 3683 |
Rint | 0.014 | 0.056 | 0.085 | 0.068 |
(sin θ/λ)max (Å−1) | 0.684 | 0.650 | 0.649 | 0.648 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.146, 1.06 | 0.037, 0.091, 1.03 | 0.047, 0.130, 1.01 | 0.034, 0.080, 1.05 |
No. of reflections | 3993 | 3775 | 4002 | 4188 |
No. of parameters | 235 | 235 | 235 | 269 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.31, −0.27 | 0.46, −0.65 | 0.39, −0.54 | 0.49, −0.68 |
Selected geometric parameters (Å, º) for (I) topC1—C2 | 1.512 (2) | N6—C6a | 1.374 (2) |
C1—C10b | 1.539 (2) | C6a—C7 | 1.406 (2) |
C2—N3 | 1.288 (2) | C6a—C10a | 1.408 (2) |
C2—C21 | 1.470 (2) | C7—C8 | 1.383 (2) |
N3—N4 | 1.4147 (18) | C8—C9 | 1.384 (3) |
N4—C5 | 1.4620 (19) | C9—C10 | 1.390 (3) |
N4—C10b | 1.483 (2) | C10—C10a | 1.392 (2) |
C5—N6 | 1.445 (2) | C10a—C10b | 1.522 (2) |
| | | |
C2—C1—C10b | 100.55 (12) | C8—C7—C6a | 120.35 (16) |
N3—C2—C1 | 112.68 (14) | C7—C8—C9 | 120.78 (16) |
C2—N3—N4 | 108.49 (12) | C8—C9—C10 | 119.14 (16) |
N3—N4—C5 | 112.26 (12) | C9—C10—C10a | 121.52 (16) |
N3—N4—C10b | 107.96 (11) | C10—C10a—C6a | 118.98 (15) |
C5—N4—C10b | 114.03 (12) | C10—C10a—C10b | 120.53 (14) |
N6—C5—N4 | 110.75 (12) | C6a—C10a—C10b | 120.46 (13) |
C6a—N6—C5 | 118.73 (13) | N4—C10b—C10a | 112.68 (12) |
N6—C6a—C7 | 120.66 (15) | N4—C10b—C1 | 100.43 (12) |
N6—C6a—C10a | 120.15 (14) | C10a—C10b—C1 | 112.68 (13) |
C7—C6a—C10a | 119.18 (15) | | |
| | | |
N3—C2—C21—C22 | −177.79 (16) | N6—C5—C51—C56 | −24.1 (2) |
C1—C2—C21—C22 | 5.8 (2) | N4—C5—C51—C56 | −147.76 (16) |
N3—C2—C21—C26 | 3.1 (3) | N6—C5—C51—C52 | 158.96 (15) |
C1—C2—C21—C26 | −173.30 (16) | N4—C5—C51—C52 | 35.3 (2) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N6—H6···N3i | 0.88 | 2.26 | 3.122 (2) | 164 |
C53—H53···Cg4ii | 0.95 | 2.75 | 3.635 (3) | 156 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, y+1, z. |
Selected geometric parameters (Å, º) for (II) topC1—C2 | 1.511 (3) | C6a—C7 | 1.402 (3) |
C1—C10b | 1.537 (3) | C6a—C10a | 1.407 (3) |
C2—N3 | 1.288 (3) | C7—C8 | 1.389 (3) |
N3—N4 | 1.416 (2) | C8—C9 | 1.382 (4) |
N4—C5 | 1.465 (3) | C9—C10 | 1.388 (4) |
N4—C10b | 1.490 (3) | C10—C10a | 1.392 (3) |
C5—N6 | 1.440 (3) | C10a—C10b | 1.519 (3) |
N6—C6a | 1.380 (3) | | |
| | | |
C2—C1—C10b | 101.04 (17) | C8—C7—C6a | 120.0 (2) |
N3—C2—C1 | 112.81 (18) | C9—C8—C7 | 120.6 (2) |
C2—N3—N4 | 108.54 (17) | C8—C9—C10 | 119.4 (2) |
N3—N4—C5 | 111.94 (17) | C9—C10—C10a | 121.5 (2) |
N3—N4—C10b | 108.09 (16) | C10—C10a—C6a | 118.7 (2) |
C5—N4—C10b | 114.10 (17) | C10—C10a—C10b | 120.1 (2) |
N6—C5—N4 | 111.18 (17) | C6a—C10a—C10b | 121.17 (19) |
C6a—N6—C5 | 118.43 (18) | N4—C10b—C10a | 112.59 (17) |
N6—C6a—C7 | 120.5 (2) | N4—C10b—C1 | 100.49 (16) |
N6—C6a—C10a | 119.8 (2) | C10a—C10b—C1 | 113.07 (18) |
C7—C6a—C10a | 119.7 (2) | | |
| | | |
N3—C2—C21—C22 | −178.0 (2) | N6—C5—C51—C56 | −24.7 (3) |
C1—C2—C21—C22 | 5.3 (3) | N4—C5—C51—C56 | −148.6 (2) |
N3—C2—C21—C26 | 3.0 (3) | N6—C5—C51—C52 | 158.4 (2) |
C1—C2—C21—C26 | −173.7 (2) | N4—C5—C51—C52 | 34.4 (3) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N6—H6···N3i | 0.88 | 2.25 | 3.105 (3) | 162 |
C53—H53···Cg4ii | 0.95 | 2.71 | 3.588 (3) | 154 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, y+1, z. |
Selected geometric parameters (Å, º) for (III) topC1—C2 | 1.508 (2) | C6a—C7 | 1.401 (2) |
C1—C10b | 1.531 (2) | C6a—C10a | 1.405 (2) |
C2—N3 | 1.294 (2) | C7—C8 | 1.388 (2) |
N3—N4 | 1.4079 (19) | C8—C9 | 1.388 (3) |
N4—C5 | 1.457 (2) | C9—C10 | 1.384 (2) |
N4—C10b | 1.4804 (18) | C10—C10a | 1.398 (2) |
C5—N6 | 1.450 (2) | C10a—C10b | 1.516 (2) |
N6—C6a | 1.3857 (19) | | |
| | | |
C2—C1—C10b | 100.69 (12) | C8—C7—C6a | 120.46 (15) |
N3—C2—C1 | 112.51 (14) | C9—C8—C7 | 120.72 (16) |
C2—N3—N4 | 108.33 (12) | C10—C9—C8 | 118.82 (15) |
N3—N4—C5 | 113.99 (12) | C9—C10—C10a | 121.87 (16) |
N3—N4—C10b | 108.02 (11) | C10—C10a—C6a | 118.90 (14) |
C5—N4—C10b | 114.96 (12) | C10—C10a—C10b | 119.90 (14) |
N6—C5—N4 | 112.34 (12) | C6a—C10a—C10b | 121.16 (13) |
C6a—N6—C5 | 119.01 (13) | N4—C10b—C10a | 111.29 (12) |
N6—C6a—C7 | 120.05 (14) | N4—C10b—C1 | 100.57 (12) |
N6—C6a—C10a | 120.74 (14) | C10a—C10b—C1 | 112.39 (12) |
C7—C6a—C10a | 119.21 (14) | | |
| | | |
N3—C2—C21—C22 | −179.85 (15) | N6—C5—C51—C56 | −25.73 (19) |
C1—C2—C21—C22 | 8.8 (2) | N4—C5—C51—C56 | −150.49 (14) |
N3—C2—C21—C26 | 4.5 (2) | N6—C5—C51—C52 | 157.43 (13) |
C1—C2—C21—C26 | −166.82 (15) | N4—C5—C51—C52 | 32.66 (18) |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
N6—H6···N3i | 0.88 | 2.20 | 3.083 (2) | 178 |
C1—H1A···Cg3ii | 0.99 | 2.44 | 3.407 (2) | 166 |
C22—H22···Cg5ii | 0.95 | 2.88 | 3.739 (2) | 152 |
Symmetry codes: (i) −x+3/2, −y+1/2, −z+1; (ii) −x+3/2, y−1/2, −z+1/2. |
Selected geometric parameters (Å, º) for (IV) topC1—C2 | 1.510 (3) | N6—C6a | 1.390 (3) |
C1—C10b | 1.534 (3) | C6a—C7 | 1.399 (3) |
C2—N3 | 1.285 (3) | C6a—C10a | 1.402 (3) |
N3—N4 | 1.415 (2) | C7—C8 | 1.378 (4) |
N4—C5 | 1.455 (3) | C8—C9 | 1.385 (4) |
N4—C10b | 1.488 (3) | C9—C10 | 1.387 (4) |
C5—N6 | 1.450 (3) | C10—C10a | 1.399 (3) |
C5—C51 | 1.529 (3) | C10a—C10b | 1.518 (3) |
| | | |
C2—C1—C10b | 100.36 (16) | C8—C7—C6a | 120.6 (2) |
N3—C2—C1 | 112.92 (18) | C7—C8—C9 | 120.4 (2) |
C2—N3—N4 | 108.33 (16) | C8—C9—C10 | 119.5 (2) |
N3—N4—C5 | 111.42 (15) | C9—C10—C10a | 121.3 (2) |
N3—N4—C10b | 107.92 (15) | C10—C10a—C6a | 118.5 (2) |
C5—N4—C10b | 114.33 (16) | C10—C10a—C10b | 120.60 (19) |
N6—C5—N4 | 109.97 (16) | C6a—C10a—C10b | 120.85 (18) |
C6a—N6—C5 | 117.60 (16) | N4—C10b—C10a | 112.50 (16) |
N6—C6a—C7 | 120.4 (2) | N4—C10b—C1 | 100.20 (16) |
N6—C6a—C10a | 119.88 (19) | C10a—C10b—C1 | 112.66 (18) |
C7—C6a—C10a | 119.7 (2) | | |
| | | |
N3—C2—C21A—C22A | −168.8 (3) | N6—C5—C51—C56 | −7.4 (3) |
N3—C2—C21A—C26A | 14.1 (4) | N4—C5—C51—C56 | −131.0 (2) |
N3—C2—C21B—C22B | 159.1 (2) | N6—C5—C51—C52 | 175.91 (17) |
N3—C2—C21B—C26B | −25.1 (4) | N4—C5—C51—C52 | 52.3 (2) |
Hydrogen-bond geometry (Å, º) for (IV) top
D—H···A | D—H | H···A | D···A | D—H···A |
N6—H6···Cg5i | 0.88 | 2.82 | 3.666 (2) | 163 |
C10b—H10B···N6ii | 1.00 | 2.52 | 3.500 (3) | 168 |
Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z. |
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The quinazoline skeleton is an important pharmacophore that occurs frequently in the medicinal chemistry literature (Fry et al., 1994). Pyrazolo[1,5-c]quinazolinones have been shown to be potent amino acid antagonists (McQuaid et al., 1992), antiinflammatory agents, immunosuppressants, and antiasthmatic and antiallergenic agents (Casey et al., 1980).
We report herein the synthesis and the crystal structure of four 2,4-diaryl-1,5,6,10b-tetrahydropyrazolo[1,5-c]quinazolines (see Scheme). In this scheme, the synthesis of these compounds was achieved in a four-step sequence, starting with a known condensation of o-nitrobenzaldehyde with the corresponding acetophenone, followed by reaction with hydrazine to afford the pyrazole ring formation, then reduction of the nitro group to amino, and finally a new cyclocondensation with different benzaldehydes to yield the desired compounds; (I) has R = H and R1 = CH3, (II) has R = H and R1 = Br, (III) has R = Cl and R1 = H, and (IV) has R = Cl and R1 = Br. Compounds (I), (II) and (IV) crystallize in the triclinic spacegroup P1, and (III) in the monoclinic space group C2/c. \sch
In the molecular structure of (IV), the arene ring attached to C2 is disordered, each with 50% site occupancy. The indications are that this is a correlated disorder. In all four compounds, the bonds and angles of the tricyclic moiety are similar, and identical within experimental error for the isomorphous compounds (I) and (II) (Tables 1, 3, 5 and 7; Figs. 1 to 4). The pyrazole rings are C10b envelopes and the tetrahydropyrimidine rings have half-chair conformations (Cremer & Pople, 1975). The conformations of the arene substituents are very similar in compounds (I), (II) and (III), with, for example, the N3—C2—C21—C22 torsion angles being -177.79 (16), -178.0 (3) and 179.85 (15)°, respectively, and the N4—C5—C51—C52 angles 35.3 (2), 34.4(3 and 32.7 (3)°, respectively. In (IV), the arene ring defined by atoms C21—C26 is disordered and the N4—C5—C51—C52 angle is 52.3 (2)°. These and related torsion angles are detailed in Tables 1, 3, 5 and 7.
In compounds (I)-(III), the molecules form R22(10) base-paired rings (Bernstein et al., 1995); H6···N3 distances are 2.26, 2.25 and 2.20 Å, for (I), (II) and (III), respectively, N6···N3 distances are 3.122 (2), 3.105 (3) and 3.083 (2) Å, for (I), (II) and (III), respectively, and the angles at H6 are 164, 162 and 178°, respectively, with atom N3 being in the molecules at (-x, 1 - y, 1 - z) for (I) and (II), and at (3/2 - x, 1/2 - y, 1 - z) for (III) (Tables 2, 4 and 6). Fig. 5 displays this base-paired ring for (II) as an example.
What is unexpected, however, despite the close conformational similarities of the tricyclic moieties in the four structures, is that (IV) does not form the N6···N3 hydrogen bond. Instead, there is an N—H···π(arene) interaction involving N6—H6 and the C51—C56 arene ring at (x - 1, y, z), with a perpendicular distance from atom H6 to the ring of 2.57 Å (Table 8). This interaction links the molecules in chains along the a axis (Fig. 6). In addition, there is a short intermolecular C10b—H10B···N6(x + 1, y, z) contact, with H···N 2.52 Å, C···N 3.500 (3) Å and an angle at H of 168°. This seems to be adventitious and in conjunction with the N—H···π contact, as the contacts around atom N6 are not close to being tetrahedral; H10B(x - 1, y, z)···N6—H6 is 155°, H10B(x - 1, y, z)···N6—C6a is 63° and H10B(x - 1, y, z)···N6—C7 is 92°.
In compounds (I) and (II), there is an intermolecular C—H···π(arene) interaction involving C53—H53 and the C21—C26 arene ring [centroid Cg4 at (x, 1 + y, z), Tables 2 and 4]. These link the molecules into a chain which runs along the b axis; Fig. 7 shows this chain for (II). In compound (III), there are two such interactions between C1—H1A and the C6a—C10a ring (centroid Cg3), and between C22—H22 and the C51—C56 ring (centroid Cg5); both these centroids are in the symmetry-related molecules at (3/2 - x, y - 1/2, 1/2 - z). These interactions form spiral chains formed by molecules related by the screw axis (3/4,y,1/4) and by symmetry-related screw axes. These chains run parallel to the b axis (Table 6 and Fig. 8). There is also a short intermolecular Cl24···Cl24(2 - x, y, 3/2 - z) contact in (III), with a Cl···Cl distance of 3.4118 (6) Å.
There are no π···π stacking interactions of significance in any of the four crystal structures. There is a potential solvent void of 35.6 Å3 per unit-cell volume of 3508.8 Å3 in (III), but there was no evidence of excess electron density in this volume. There are no solvent accessible voids in the other three structures.