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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, C23H21N3, (I), 5-(4-bromo­phenyl)-2-phenyl-1,5,6,10b-tetra­hydro­pyrazolo­[1,5-c]­quinazoline, C22H18BrN3, (II), 2-(4-chlorophenyl)-5-phenyl-1,5,6,10b-tetrahydropyrazolo[1,5-c]quinazoline, C22H18ClN3, (III), and 5-(4-bromo­phenyl)-2-(4-chlorophenyl)-1,5,6,10b-tetrahydropyrazolo[1,5-c]quinazoline, C22H17BrClN3, (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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102006200/gg1111sup1.cif
Contains datablocks global, I, II, III, IV

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102006200/gg1111Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102006200/gg1111IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102006200/gg1111IIIsup4.hkl
Contains datablock III

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102006200/gg1111IVsup5.hkl
Contains datablock IV

CCDC references: 187944; 187945; 187946; 187947

Comment top

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.

Experimental top

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%.

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. A view of the molecule of (I) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. A view of the molecule of (II) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 3] Fig. 3. A view of the molecule of (III) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 4] Fig. 4. A view of the molecule of (IV) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. The minor component of the disordered arene ring has been omitted.
[Figure 5] Fig. 5. A view of the R22(10) ring structure in (II), similar to those found in (I) and (III). The atoms labelled with an asterisk (*) are at symmetry position (-x, 1 - y, 1 - z).
[Figure 6] Fig. 6. A view of the N—H···π(arene) interaction involving N6—H6 and the C51—C56 ring in (IV), linking molecules along the a axis. The atoms labelled with an asterisk (*) or hash sign (#) are at symmetry positions (x + 1, y, z) and (x - 1, y, z), respectively. Please check these added symmetry codes are correct.
[Figure 7] Fig. 7. A view of the chain along the b axis formed by the C—H···π(arene) interaction between C53—H53 and the C21—C26 ring in (II). The atom labelled with an asterisk (*) is in the molecule at (x, 1 + y, z) and that labelled with a hash sign (#) is in the molecule at (x, 1 - y, z).
[Figure 8] Fig. 8. A stereoview of the spiral chain formed by C1A—H1A···π(Cg3) and C22—H22···π(Cg5) in (III).
(I) 2-Phenyl-5-p-tolyl-1,5,6,10b-tetrahydropyrazolo[1,5-c]quinazoline top
Crystal data top
C23H21N3Z = 2
Mr = 339.43F(000) = 360
Triclinic, P1Dx = 1.284 Mg m3
Hall symbol: -P_1Melting point: 486 K
a = 8.5292 (12) ÅMo Kα radiation, λ = 0.71073 Å
b = 10.7291 (16) ÅCell parameters from 3993 reflections
c = 11.0469 (16) Åθ = 2.0–29.1°
α = 109.417 (2)°µ = 0.08 mm1
β = 91.555 (3)°T = 120 K
γ = 110.945 (3)°Plate, colourless
V = 878.1 (2) Å30.18 × 0.08 × 0.04 mm
Data collection top
Bruker SMART1000 CCD area-detector
diffractometer
3993 independent reflections
Radiation source: fine-focus sealed X-ray tube3451 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.014
ϕ scans, and ω scans with κ offsetsθmax = 29.1°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
h = 117
Tmin = 0.986, Tmax = 0.997k = 1314
5532 measured reflectionsl = 1214
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.146H-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 parametersΔρmax = 0.31 e Å3
0 restraintsΔρmin = 0.27 e Å3
Crystal data top
C23H21N3γ = 110.945 (3)°
Mr = 339.43V = 878.1 (2) Å3
Triclinic, P1Z = 2
a = 8.5292 (12) ÅMo Kα radiation
b = 10.7291 (16) ŵ = 0.08 mm1
c = 11.0469 (16) ÅT = 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 = 0.997Rint = 0.014
5532 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0520 restraints
wR(F2) = 0.146H-atom parameters constrained
S = 1.06Δρmax = 0.31 e Å3
3993 reflectionsΔρmin = 0.27 e Å3
235 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.0964 (2)0.32820 (17)0.07315 (15)0.0254 (3)
C20.1893 (2)0.27201 (17)0.17058 (15)0.0220 (3)
C210.2816 (2)0.11914 (17)0.14714 (16)0.0250 (3)
C220.2744 (2)0.01508 (19)0.03366 (18)0.0316 (4)
C230.3597 (3)0.1300 (2)0.01091 (19)0.0367 (4)
C240.4517 (3)0.17209 (19)0.10157 (19)0.0366 (4)
C250.4631 (3)0.0698 (2)0.21335 (19)0.0361 (4)
C260.3797 (2)0.07498 (19)0.23625 (17)0.0308 (4)
N30.18664 (16)0.37314 (14)0.27518 (13)0.0219 (3)
N40.10372 (16)0.50609 (14)0.26040 (13)0.0205 (3)
C50.01454 (19)0.62216 (16)0.38439 (15)0.0210 (3)
C510.0368 (2)0.76551 (17)0.36454 (15)0.0229 (3)
C520.0666 (2)0.78595 (19)0.27976 (19)0.0309 (4)
C530.0208 (3)0.9180 (2)0.2660 (2)0.0364 (4)
C540.1276 (3)1.03339 (19)0.33691 (19)0.0336 (4)
C570.1753 (3)1.1759 (2)0.3205 (2)0.0494 (6)
C550.2277 (3)1.0129 (2)0.4227 (2)0.0404 (5)
C560.1847 (2)0.8811 (2)0.43577 (19)0.0344 (4)
N60.12726 (17)0.60072 (15)0.43579 (13)0.0247 (3)
C6a0.23539 (19)0.56458 (16)0.35389 (15)0.0206 (3)
C70.3963 (2)0.57803 (18)0.40415 (17)0.0266 (3)
C80.5050 (2)0.54256 (19)0.3212 (2)0.0310 (4)
C90.4581 (2)0.49409 (18)0.18768 (19)0.0319 (4)
C100.2977 (2)0.47751 (17)0.13729 (17)0.0269 (3)
C10a0.18454 (19)0.51076 (16)0.21805 (15)0.0211 (3)
C10b0.0068 (2)0.48573 (16)0.16049 (15)0.0215 (3)
H1A0.17640.32000.00160.030*
H1B0.02140.27800.03620.030*
H220.21060.04350.02860.038*
H230.35470.20010.06690.044*
H240.50710.27110.08720.044*
H250.52840.09910.27460.043*
H260.38900.14450.31260.037*
H50.09620.62040.44770.025*
H520.16950.70910.23080.037*
H530.09250.92960.20690.044*
H57A0.25451.25210.39760.074*
H57B0.07261.19490.31010.074*
H57C0.22981.17320.24320.074*
H550.32831.09080.47390.049*
H560.25740.86980.49430.041*
H60.15300.62730.52120.030*
H70.43050.61170.49560.032*
H80.61320.55160.35620.037*
H90.53460.47240.13120.038*
H100.26460.44270.04560.032*
H10B0.01380.54980.11090.026*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0284 (8)0.0216 (8)0.0211 (7)0.0039 (6)0.0029 (6)0.0080 (6)
C20.0218 (7)0.0217 (7)0.0213 (7)0.0056 (6)0.0017 (6)0.0097 (6)
C210.0261 (8)0.0216 (8)0.0251 (8)0.0053 (6)0.0001 (6)0.0104 (6)
C220.0373 (10)0.0246 (8)0.0299 (9)0.0080 (7)0.0052 (7)0.0108 (7)
C230.0452 (11)0.0235 (9)0.0347 (9)0.0092 (8)0.0016 (8)0.0075 (7)
C240.0403 (10)0.0217 (8)0.0398 (10)0.0021 (7)0.0028 (8)0.0132 (7)
C250.0389 (10)0.0300 (9)0.0342 (9)0.0027 (8)0.0030 (8)0.0173 (8)
C260.0342 (9)0.0263 (9)0.0269 (8)0.0046 (7)0.0030 (7)0.0114 (7)
N30.0197 (6)0.0207 (6)0.0253 (7)0.0054 (5)0.0031 (5)0.0111 (5)
N40.0204 (6)0.0185 (6)0.0229 (6)0.0062 (5)0.0042 (5)0.0094 (5)
C50.0210 (7)0.0217 (7)0.0203 (7)0.0089 (6)0.0047 (6)0.0071 (6)
C510.0228 (7)0.0205 (7)0.0253 (7)0.0090 (6)0.0078 (6)0.0073 (6)
C520.0266 (8)0.0233 (8)0.0422 (10)0.0078 (7)0.0015 (7)0.0136 (7)
C530.0390 (10)0.0296 (9)0.0468 (11)0.0165 (8)0.0063 (8)0.0182 (8)
C540.0407 (10)0.0212 (8)0.0395 (10)0.0120 (7)0.0175 (8)0.0109 (7)
C570.0687 (15)0.0232 (9)0.0550 (13)0.0146 (10)0.0201 (11)0.0155 (9)
C550.0398 (11)0.0235 (9)0.0421 (11)0.0002 (8)0.0000 (8)0.0064 (8)
C560.0335 (9)0.0286 (9)0.0337 (9)0.0058 (7)0.0020 (7)0.0099 (7)
N60.0243 (7)0.0335 (8)0.0188 (6)0.0133 (6)0.0036 (5)0.0102 (6)
C6a0.0202 (7)0.0178 (7)0.0257 (7)0.0062 (6)0.0044 (6)0.0114 (6)
C70.0224 (8)0.0243 (8)0.0341 (9)0.0075 (6)0.0021 (6)0.0137 (7)
C80.0201 (8)0.0262 (8)0.0493 (11)0.0095 (7)0.0060 (7)0.0164 (8)
C90.0263 (8)0.0234 (8)0.0464 (10)0.0102 (7)0.0171 (8)0.0120 (7)
C100.0291 (8)0.0198 (7)0.0294 (8)0.0067 (6)0.0106 (7)0.0089 (6)
C10a0.0219 (7)0.0157 (7)0.0251 (7)0.0048 (6)0.0057 (6)0.0095 (6)
C10b0.0244 (7)0.0211 (7)0.0196 (7)0.0074 (6)0.0042 (6)0.0096 (6)
Geometric parameters (Å, º) top
C1—C21.512 (2)C52—H520.9500
C1—C10b1.539 (2)C53—C541.389 (3)
C1—H1A0.9900C53—H530.9500
C1—H1B0.9900C54—C551.380 (3)
C2—N31.288 (2)C54—C571.510 (3)
C2—C211.470 (2)C57—H57A0.9800
C21—C221.395 (2)C57—H57B0.9800
C21—C261.402 (2)C57—H57C0.9800
C22—C231.391 (2)C55—C561.386 (3)
C22—H220.9500C55—H550.9500
C23—C241.383 (3)C56—H560.9500
C23—H230.9500N6—C6a1.374 (2)
C24—C251.386 (3)N6—H60.8857
C24—H240.9500C6a—C71.406 (2)
C25—C261.387 (2)C6a—C10a1.408 (2)
C25—H250.9500C7—C81.383 (2)
C26—H260.9500C7—H70.9500
N3—N41.4147 (18)C8—C91.384 (3)
N4—C51.4620 (19)C8—H80.9500
N4—C10b1.483 (2)C9—C101.390 (3)
C5—N61.445 (2)C9—H90.9500
C5—C511.534 (2)C10—C10a1.392 (2)
C5—H51.0000C10—H100.9500
C51—C561.388 (2)C10a—C10b1.522 (2)
C51—C521.391 (2)C10b—H10B1.0000
C52—C531.391 (2)
C2—C1—C10b100.55 (12)C54—C53—H53119.3
C2—C1—H1A111.7C52—C53—H53119.3
C10b—C1—H1A111.7C55—C54—C53117.62 (17)
C2—C1—H1B111.7C55—C54—C57121.77 (19)
C10b—C1—H1B111.7C53—C54—C57120.61 (19)
H1A—C1—H1B109.4C54—C57—H57A109.5
N3—C2—C21122.94 (14)C54—C57—H57B109.5
N3—C2—C1112.68 (14)H57A—C57—H57B109.5
C21—C2—C1124.29 (14)C54—C57—H57C109.5
C22—C21—C26118.82 (15)H57A—C57—H57C109.5
C22—C21—C2119.95 (15)H57B—C57—H57C109.5
C26—C21—C2121.23 (15)C54—C55—C56121.52 (18)
C23—C22—C21120.53 (17)C54—C55—H55119.2
C23—C22—H22119.7C56—C55—H55119.2
C21—C22—H22119.7C55—C56—C51120.91 (18)
C24—C23—C22120.05 (18)C55—C56—H56119.5
C24—C23—H23120.0C51—C56—H56119.5
C22—C23—H23120.0C6a—N6—C5118.73 (13)
C23—C24—C25120.00 (17)C6a—N6—H6121.5
C23—C24—H24120.0C5—N6—H6118.7
C25—C24—H24120.0N6—C6a—C7120.66 (15)
C24—C25—C26120.30 (17)N6—C6a—C10a120.15 (14)
C24—C25—H25119.9C7—C6a—C10a119.18 (15)
C26—C25—H25119.9C8—C7—C6a120.35 (16)
C25—C26—C21120.26 (17)C8—C7—H7119.8
C25—C26—H26119.9C6a—C7—H7119.8
C21—C26—H26119.9C7—C8—C9120.78 (16)
C2—N3—N4108.49 (12)C7—C8—H8119.6
N3—N4—C5112.26 (12)C9—C8—H8119.6
N3—N4—C10b107.96 (11)C8—C9—C10119.14 (16)
C5—N4—C10b114.03 (12)C8—C9—H9120.4
N6—C5—N4110.75 (12)C10—C9—H9120.4
N6—C5—C51113.52 (13)C9—C10—C10a121.52 (16)
N4—C5—C51108.56 (12)C9—C10—H10119.2
N6—C5—H5107.9C10a—C10—H10119.2
N4—C5—H5107.9C10—C10a—C6a118.98 (15)
C51—C5—H5107.9C10—C10a—C10b120.53 (14)
C56—C51—C52117.99 (16)C6a—C10a—C10b120.46 (13)
C56—C51—C5120.66 (15)N4—C10b—C10a112.68 (12)
C52—C51—C5121.28 (14)N4—C10b—C1100.43 (12)
C51—C52—C53120.55 (17)C10a—C10b—C1112.68 (13)
C51—C52—H52119.7N4—C10b—H10B110.2
C53—C52—H52119.7C10a—C10b—H10B110.2
C54—C53—C52121.39 (18)C1—C10b—H10B110.2
C10b—C1—C2—N316.10 (18)C53—C54—C55—C561.6 (3)
C10b—C1—C2—C21167.19 (15)C57—C54—C55—C56178.92 (19)
N3—C2—C21—C22177.79 (16)C54—C55—C56—C511.4 (3)
C1—C2—C21—C225.8 (2)C52—C51—C56—C550.0 (3)
N3—C2—C21—C263.1 (3)C5—C51—C56—C55176.97 (17)
C1—C2—C21—C26173.30 (16)N4—C5—N6—C6a46.58 (18)
C26—C21—C22—C231.5 (3)C51—C5—N6—C6a75.85 (18)
C2—C21—C22—C23179.34 (17)C5—N6—C6a—C7163.73 (14)
C21—C22—C23—C240.5 (3)C5—N6—C6a—C10a17.5 (2)
C22—C23—C24—C251.9 (3)N6—C6a—C7—C8179.47 (15)
C23—C24—C25—C261.4 (3)C10a—C6a—C7—C81.8 (2)
C24—C25—C26—C210.6 (3)C6a—C7—C8—C90.3 (3)
C22—C21—C26—C252.1 (3)C7—C8—C9—C101.8 (3)
C2—C21—C26—C25178.80 (16)C8—C9—C10—C10a1.1 (3)
C21—C2—N3—N4173.44 (14)C9—C10—C10a—C6a1.0 (2)
C1—C2—N3—N43.32 (18)C9—C10—C10a—C10b177.39 (14)
C2—N3—N4—C5149.36 (13)N6—C6a—C10a—C10178.81 (14)
C2—N3—N4—C10b22.83 (16)C7—C6a—C10a—C102.4 (2)
N3—N4—C5—N667.19 (16)N6—C6a—C10a—C10b2.8 (2)
C10b—N4—C5—N655.99 (16)C7—C6a—C10a—C10b176.00 (14)
N3—N4—C5—C51167.53 (12)N3—N4—C10b—C10a88.85 (14)
C10b—N4—C5—C5169.28 (15)C5—N4—C10b—C10a36.64 (17)
N6—C5—C51—C5624.1 (2)N3—N4—C10b—C131.27 (14)
N4—C5—C51—C56147.76 (16)C5—N4—C10b—C1156.76 (12)
N6—C5—C51—C52158.96 (15)C10—C10a—C10b—N4171.16 (13)
N4—C5—C51—C5235.3 (2)C6a—C10a—C10b—N47.25 (19)
C56—C51—C52—C531.0 (3)C10—C10a—C10b—C158.37 (19)
C5—C51—C52—C53177.94 (16)C6a—C10a—C10b—C1120.04 (15)
C51—C52—C53—C540.7 (3)C2—C1—C10b—N427.02 (15)
C52—C53—C54—C550.6 (3)C2—C1—C10b—C10a93.11 (15)
C52—C53—C54—C57179.92 (19)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N6—H6···N3i0.882.263.122 (2)164
C53—H53···Cg4ii0.952.753.635 (3)156
Symmetry codes: (i) x, y+1, z+1; (ii) x, y+1, z.
(II) 5-(4-Bromophenyl)-2-phenyl-1,5,6,10b-tetrahydropyrazolo[1,5-c]quinazoline top
Crystal data top
C22H18BrN3Z = 2
Mr = 404.30F(000) = 412
Triclinic, P1Dx = 1.541 Mg m3
Hall symbol: -P_1Melting point: 536 K
a = 8.5110 (2) ÅMo Kα radiation, λ = 0.71073 Å
b = 10.7015 (3) ÅCell parameters from 3775 reflections
c = 11.0357 (3) Åθ = 3.1–27.5°
α = 110.036 (2)°µ = 2.37 mm1
β = 92.1613 (15)°T = 120 K
γ = 110.3276 (10)°Block, colourless
V = 871.37 (4) Å30.25 × 0.15 × 0.10 mm
Data collection top
Nonius KappaCCD area-detector
diffractometer
3775 independent reflections
Radiation source: fine-focus sealed X-ray tube3235 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.056
ϕ scans, and ω scans with κ offsetsθmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan
(DENZO-SMN; Otwinowski & Minor, 1997)
h = 1111
Tmin = 0.719, Tmax = 0.789k = 1313
12439 measured reflectionsl = 1212
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.091H-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 parametersΔρmax = 0.46 e Å3
0 restraintsΔρmin = 0.65 e Å3
Crystal data top
C22H18BrN3γ = 110.3276 (10)°
Mr = 404.30V = 871.37 (4) Å3
Triclinic, P1Z = 2
a = 8.5110 (2) ÅMo Kα radiation
b = 10.7015 (3) ŵ = 2.37 mm1
c = 11.0357 (3) ÅT = 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 = 0.789Rint = 0.056
12439 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.091H-atom parameters constrained
S = 1.03Δρmax = 0.46 e Å3
3775 reflectionsΔρmin = 0.65 e Å3
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
xyzUiso*/Ueq
C10.0934 (3)0.3248 (2)0.0737 (2)0.0196 (5)
C20.1889 (3)0.2714 (2)0.1704 (2)0.0158 (4)
C210.2816 (3)0.1186 (2)0.1466 (2)0.0173 (5)
C220.2733 (3)0.0127 (2)0.0335 (2)0.0218 (5)
C230.3613 (3)0.1332 (3)0.0093 (2)0.0255 (5)
C240.4549 (3)0.1728 (3)0.0995 (2)0.0252 (5)
C250.4656 (3)0.0681 (3)0.2114 (3)0.0268 (5)
C260.3812 (3)0.0767 (3)0.2346 (2)0.0223 (5)
N30.1874 (2)0.37453 (19)0.27450 (18)0.0165 (4)
N40.1042 (2)0.50691 (19)0.25962 (17)0.0150 (4)
C50.0151 (3)0.6246 (2)0.3854 (2)0.0156 (4)
C510.0352 (3)0.7676 (2)0.3661 (2)0.0164 (4)
C520.0686 (3)0.7859 (2)0.2782 (2)0.0230 (5)
C530.0243 (3)0.9169 (3)0.2625 (2)0.0242 (5)
C540.1236 (3)1.0297 (2)0.3372 (2)0.0200 (5)
Br540.18587 (3)1.20894 (2)0.31532 (2)0.02693 (10)
C550.2251 (3)1.0155 (3)0.4269 (2)0.0266 (5)
C560.1808 (3)0.8840 (3)0.4400 (2)0.0244 (5)
N60.1274 (2)0.6049 (2)0.43881 (18)0.0182 (4)
C6a0.2379 (3)0.5701 (2)0.3575 (2)0.0162 (4)
C70.4000 (3)0.5874 (2)0.4103 (2)0.0202 (5)
C80.5106 (3)0.5531 (2)0.3276 (3)0.0242 (5)
C90.4627 (3)0.5023 (2)0.1932 (3)0.0254 (5)
C100.3009 (3)0.4823 (2)0.1408 (2)0.0215 (5)
C10a0.1860 (3)0.5139 (2)0.2207 (2)0.0168 (4)
C10b0.0071 (3)0.4842 (2)0.1601 (2)0.0159 (4)
H1A0.17230.31360.00100.024*
H1B0.01670.27440.04040.024*
H220.20730.03970.02750.026*
H230.35700.20500.06880.031*
H240.51180.27180.08460.030*
H250.53110.09570.27250.032*
H260.39110.14790.31070.027*
H50.09680.62360.44820.019*
H520.17100.70800.22830.028*
H530.09450.92840.20150.029*
H550.32471.09500.47950.032*
H560.25210.87370.50110.029*
H60.15320.63140.52420.022*
H70.43420.62260.50260.024*
H80.62020.56480.36370.029*
H90.53980.48110.13710.030*
H100.26780.44630.04830.026*
H10B0.01170.54560.10840.019*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0227 (12)0.0171 (11)0.0136 (11)0.0017 (9)0.0027 (9)0.0055 (9)
C20.0166 (11)0.0152 (11)0.0148 (11)0.0048 (9)0.0008 (8)0.0065 (9)
C210.0190 (11)0.0160 (11)0.0164 (11)0.0037 (9)0.0002 (8)0.0090 (9)
C220.0247 (13)0.0201 (12)0.0190 (12)0.0064 (10)0.0028 (9)0.0080 (9)
C230.0322 (14)0.0191 (12)0.0234 (13)0.0100 (10)0.0002 (10)0.0062 (10)
C240.0283 (13)0.0155 (11)0.0285 (13)0.0027 (10)0.0018 (10)0.0110 (10)
C250.0278 (13)0.0234 (12)0.0272 (14)0.0027 (10)0.0044 (10)0.0146 (10)
C260.0262 (13)0.0186 (11)0.0197 (12)0.0057 (10)0.0039 (9)0.0073 (9)
N30.0180 (9)0.0143 (9)0.0186 (10)0.0054 (7)0.0034 (7)0.0086 (7)
N40.0180 (9)0.0126 (9)0.0142 (9)0.0043 (7)0.0043 (7)0.0066 (7)
C50.0172 (11)0.0151 (10)0.0148 (11)0.0068 (9)0.0043 (8)0.0052 (8)
C510.0188 (11)0.0164 (11)0.0164 (11)0.0087 (9)0.0068 (8)0.0066 (9)
C520.0193 (12)0.0175 (11)0.0283 (13)0.0038 (9)0.0006 (9)0.0080 (10)
C530.0254 (13)0.0215 (12)0.0299 (14)0.0102 (10)0.0024 (10)0.0139 (10)
C540.0276 (13)0.0150 (11)0.0205 (12)0.0099 (9)0.0104 (9)0.0078 (9)
Br540.03910 (17)0.01496 (14)0.02808 (17)0.00948 (11)0.00988 (11)0.01025 (10)
C550.0288 (13)0.0170 (12)0.0271 (13)0.0042 (10)0.0029 (10)0.0059 (10)
C560.0284 (13)0.0190 (12)0.0219 (12)0.0067 (10)0.0031 (10)0.0064 (10)
N60.0224 (10)0.0219 (10)0.0127 (9)0.0104 (8)0.0029 (7)0.0075 (8)
C6a0.0193 (11)0.0106 (10)0.0202 (12)0.0050 (8)0.0042 (9)0.0082 (8)
C70.0225 (12)0.0152 (11)0.0224 (12)0.0052 (9)0.0013 (9)0.0091 (9)
C80.0169 (12)0.0189 (12)0.0381 (15)0.0069 (9)0.0047 (10)0.0123 (10)
C90.0220 (12)0.0183 (12)0.0359 (15)0.0084 (10)0.0145 (10)0.0087 (10)
C100.0275 (13)0.0129 (10)0.0219 (12)0.0055 (9)0.0095 (9)0.0058 (9)
C10a0.0209 (11)0.0109 (10)0.0191 (11)0.0043 (9)0.0061 (9)0.0078 (8)
C10b0.0211 (11)0.0150 (10)0.0132 (11)0.0063 (9)0.0061 (8)0.0075 (8)
Geometric parameters (Å, º) top
C1—C21.511 (3)C51—C521.396 (3)
C1—C10b1.537 (3)C52—C531.393 (3)
C1—H1A0.9900C52—H520.9500
C1—H1B0.9900C53—C541.380 (3)
C2—N31.288 (3)C53—H530.9500
C2—C211.469 (3)C54—C551.370 (3)
C21—C221.393 (3)C54—Br541.908 (2)
C21—C261.400 (3)C55—C561.385 (3)
C22—C231.399 (3)C55—H550.9500
C22—H220.9500C56—H560.9500
C23—C241.385 (4)N6—C6a1.380 (3)
C23—H230.9500N6—H60.8800
C24—C251.386 (4)C6a—C71.402 (3)
C24—H240.9500C6a—C10a1.407 (3)
C25—C261.388 (3)C7—C81.389 (3)
C25—H250.9500C7—H70.9500
C26—H260.9500C8—C91.382 (4)
N3—N41.416 (2)C8—H80.9500
N4—C51.465 (3)C9—C101.388 (4)
N4—C10b1.490 (3)C9—H90.9500
C5—N61.440 (3)C10—C10a1.392 (3)
C5—C511.531 (3)C10—H100.9500
C5—H51.0000C10a—C10b1.519 (3)
C51—C561.382 (3)C10b—H10B1.0000
C2—C1—C10b101.04 (17)C53—C52—H52119.5
C2—C1—H1A111.6C51—C52—H52119.5
C10b—C1—H1A111.6C54—C53—C52118.7 (2)
C2—C1—H1B111.6C54—C53—H53120.6
C10b—C1—H1B111.6C52—C53—H53120.6
H1A—C1—H1B109.4C55—C54—C53121.4 (2)
N3—C2—C21122.95 (19)C55—C54—Br54119.68 (17)
N3—C2—C1112.81 (18)C53—C54—Br54118.94 (18)
C21—C2—C1124.17 (19)C54—C55—C56119.2 (2)
C22—C21—C26118.9 (2)C54—C55—H55120.4
C22—C21—C2119.8 (2)C56—C55—H55120.4
C26—C21—C2121.2 (2)C51—C56—C55121.4 (2)
C21—C22—C23120.5 (2)C51—C56—H56119.3
C21—C22—H22119.8C55—C56—H56119.3
C23—C22—H22119.8C6a—N6—C5118.43 (18)
C24—C23—C22119.8 (2)C6a—N6—H6121.1
C24—C23—H23120.1C5—N6—H6119.3
C22—C23—H23120.1N6—C6a—C7120.5 (2)
C23—C24—C25120.1 (2)N6—C6a—C10a119.8 (2)
C23—C24—H24119.9C7—C6a—C10a119.7 (2)
C25—C24—H24119.9C8—C7—C6a120.0 (2)
C24—C25—C26120.3 (2)C8—C7—H7120.0
C24—C25—H25119.9C6a—C7—H7120.0
C26—C25—H25119.9C9—C8—C7120.6 (2)
C25—C26—C21120.3 (2)C9—C8—H8119.7
C25—C26—H26119.8C7—C8—H8119.7
C21—C26—H26119.8C8—C9—C10119.4 (2)
C2—N3—N4108.54 (17)C8—C9—H9120.3
N3—N4—C5111.94 (17)C10—C9—H9120.3
N3—N4—C10b108.09 (16)C9—C10—C10a121.5 (2)
C5—N4—C10b114.10 (17)C9—C10—H10119.3
N6—C5—N4111.18 (17)C10a—C10—H10119.3
N6—C5—C51113.15 (18)C10—C10a—C6a118.7 (2)
N4—C5—C51108.57 (17)C10—C10a—C10b120.1 (2)
N6—C5—H5107.9C6a—C10a—C10b121.17 (19)
N4—C5—H5107.9N4—C10b—C10a112.59 (17)
C51—C5—H5107.9N4—C10b—C1100.49 (16)
C56—C51—C52118.2 (2)C10a—C10b—C1113.07 (18)
C56—C51—C5120.7 (2)N4—C10b—H10B110.1
C52—C51—C5121.01 (19)C10a—C10b—H10B110.1
C53—C52—C51121.0 (2)C1—C10b—H10B110.1
C10b—C1—C2—N314.9 (2)C53—C54—C55—C561.9 (4)
C10b—C1—C2—C21168.15 (19)Br54—C54—C55—C56178.56 (19)
N3—C2—C21—C22178.0 (2)C52—C51—C56—C550.8 (4)
C1—C2—C21—C225.3 (3)C5—C51—C56—C55177.8 (2)
N3—C2—C21—C263.0 (3)C54—C55—C56—C511.0 (4)
C1—C2—C21—C26173.7 (2)N4—C5—N6—C6a47.4 (3)
C26—C21—C22—C230.8 (3)C51—C5—N6—C6a75.0 (2)
C2—C21—C22—C23179.8 (2)C5—N6—C6a—C7162.77 (19)
C21—C22—C23—C241.2 (4)C5—N6—C6a—C10a18.6 (3)
C22—C23—C24—C252.0 (4)N6—C6a—C7—C8179.5 (2)
C23—C24—C25—C260.8 (4)C10a—C6a—C7—C81.9 (3)
C24—C25—C26—C211.3 (4)C6a—C7—C8—C90.2 (3)
C22—C21—C26—C252.1 (3)C7—C8—C9—C101.5 (3)
C2—C21—C26—C25179.0 (2)C8—C9—C10—C10a0.7 (3)
C21—C2—N3—N4173.10 (18)C9—C10—C10a—C6a1.4 (3)
C1—C2—N3—N43.9 (2)C9—C10—C10a—C10b177.1 (2)
C2—N3—N4—C5148.81 (18)N6—C6a—C10a—C10178.77 (19)
C2—N3—N4—C10b22.3 (2)C7—C6a—C10a—C102.6 (3)
N3—N4—C5—N667.9 (2)N6—C6a—C10a—C10b2.8 (3)
C10b—N4—C5—N655.3 (2)C7—C6a—C10a—C10b175.81 (19)
N3—N4—C5—C51167.02 (16)N3—N4—C10b—C10a90.6 (2)
C10b—N4—C5—C5169.8 (2)C5—N4—C10b—C10a34.6 (2)
N6—C5—C51—C5624.7 (3)N3—N4—C10b—C130.0 (2)
N4—C5—C51—C56148.6 (2)C5—N4—C10b—C1155.21 (18)
N6—C5—C51—C52158.4 (2)C10—C10a—C10b—N4172.67 (18)
N4—C5—C51—C5234.4 (3)C6a—C10a—C10b—N45.8 (3)
C56—C51—C52—C531.8 (3)C10—C10a—C10b—C159.6 (3)
C5—C51—C52—C53178.8 (2)C6a—C10a—C10b—C1118.8 (2)
C51—C52—C53—C541.0 (4)C2—C1—C10b—N425.6 (2)
C52—C53—C54—C550.9 (4)C2—C1—C10b—C10a94.6 (2)
C52—C53—C54—Br54179.56 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N6—H6···N3i0.882.253.105 (3)162
C53—H53···Cg4ii0.952.713.588 (3)154
Symmetry codes: (i) x, y+1, z+1; (ii) x, y+1, z.
(III) 2-(4-Chlorophenyl)-5-phenyl-1,5,6,10b-tetrahydropyrazolo[1,5-c]quinazoline top
Crystal data top
C22H18ClN3Dx = 1.362 Mg m3
Mr = 359.84Melting point: 507 K
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 21.2115 (3) ÅCell parameters from 4002 reflections
b = 11.1385 (2) Åθ = 3.0–27.5°
c = 17.5948 (4) ŵ = 0.23 mm1
β = 122.427 (1)°T = 120 K
V = 3508.84 (11) Å3Block, colourless
Z = 80.46 × 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 tube3286 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.085
ϕ scans, and ω scans with κ offsetsθmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan
(DENZO-SMN; Otwinowski & Minor, 1997)
h = 2727
Tmin = 0.902, Tmax = 0.978k = 1413
15078 measured reflectionsl = 2222
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.130H-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 parametersΔρmax = 0.39 e Å3
0 restraintsΔρmin = 0.54 e Å3
Crystal data top
C22H18ClN3V = 3508.84 (11) Å3
Mr = 359.84Z = 8
Monoclinic, C2/cMo Kα radiation
a = 21.2115 (3) ŵ = 0.23 mm1
b = 11.1385 (2) ÅT = 120 K
c = 17.5948 (4) Å0.46 × 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 = 0.978Rint = 0.085
15078 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0470 restraints
wR(F2) = 0.130H-atom parameters constrained
S = 1.01Δρmax = 0.39 e Å3
4002 reflectionsΔρmin = 0.54 e Å3
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
xyzUiso*/Ueq
C10.77274 (9)0.01251 (14)0.32135 (11)0.0190 (3)
C20.77913 (8)0.00754 (13)0.41001 (11)0.0162 (3)
C210.82236 (8)0.10520 (14)0.47191 (11)0.0178 (3)
C220.86868 (9)0.17558 (15)0.45584 (12)0.0222 (4)
C230.90480 (9)0.27575 (15)0.50815 (12)0.0233 (4)
C240.89436 (9)0.30657 (15)0.57673 (11)0.0213 (3)
Cl240.93393 (2)0.43768 (4)0.63743 (3)0.02595 (14)
C250.85056 (10)0.23629 (16)0.59595 (12)0.0248 (4)
C260.81529 (10)0.13634 (15)0.54418 (12)0.0233 (4)
N30.73520 (7)0.06174 (11)0.42018 (9)0.0172 (3)
N40.69178 (7)0.12878 (12)0.34064 (9)0.0167 (3)
C50.66763 (9)0.24480 (14)0.35434 (11)0.0173 (3)
C510.60380 (8)0.29047 (15)0.26276 (11)0.0184 (3)
C520.55424 (9)0.21002 (16)0.19710 (12)0.0224 (4)
C530.49483 (9)0.25135 (17)0.11479 (12)0.0267 (4)
C540.48380 (10)0.37354 (18)0.09770 (13)0.0308 (4)
C550.53205 (10)0.45374 (18)0.16297 (14)0.0308 (4)
C560.59190 (9)0.41280 (16)0.24502 (12)0.0241 (4)
N60.72870 (7)0.32985 (12)0.39952 (9)0.0196 (3)
C6a0.78374 (8)0.32935 (14)0.37973 (10)0.0163 (3)
C70.83771 (9)0.42042 (15)0.41312 (11)0.0209 (3)
C80.89153 (9)0.42294 (16)0.39114 (12)0.0245 (4)
C90.89286 (9)0.33560 (16)0.33574 (13)0.0259 (4)
C100.84045 (9)0.24437 (15)0.30419 (11)0.0212 (3)
C10a0.78591 (8)0.23873 (14)0.32564 (10)0.0163 (3)
C10b0.73224 (8)0.13351 (14)0.29347 (11)0.0170 (3)
H1A0.74300.05130.27730.023*
H1B0.82240.01740.32900.023*
H220.87550.15440.40840.027*
H230.93640.32270.49700.028*
H250.84500.25690.64440.030*
H260.78570.08780.55770.028*
H50.64720.23190.39340.021*
H520.56100.12620.20860.027*
H530.46170.19560.07020.032*
H540.44340.40180.04150.037*
H550.52440.53760.15180.037*
H560.62490.46890.28930.029*
H60.73910.36240.45060.023*
H70.83750.48090.45110.025*
H80.92790.48510.41430.029*
H90.92910.33840.31980.031*
H100.84160.18390.26690.025*
H10B0.69640.13710.22680.020*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0210 (8)0.0177 (8)0.0219 (8)0.0003 (6)0.0139 (7)0.0006 (6)
C20.0154 (7)0.0152 (7)0.0197 (8)0.0050 (6)0.0105 (6)0.0032 (6)
C210.0158 (7)0.0176 (8)0.0191 (8)0.0041 (6)0.0088 (6)0.0028 (6)
C220.0229 (8)0.0228 (8)0.0263 (9)0.0001 (6)0.0167 (7)0.0023 (7)
C230.0207 (8)0.0236 (8)0.0285 (9)0.0025 (6)0.0150 (7)0.0023 (7)
C240.0153 (7)0.0246 (8)0.0193 (8)0.0036 (6)0.0062 (7)0.0019 (7)
Cl240.0197 (2)0.0276 (3)0.0255 (2)0.00038 (15)0.00878 (18)0.00796 (16)
C250.0266 (9)0.0304 (9)0.0197 (8)0.0014 (7)0.0139 (7)0.0018 (7)
C260.0260 (9)0.0246 (8)0.0237 (9)0.0006 (7)0.0162 (7)0.0025 (7)
N30.0160 (6)0.0177 (7)0.0185 (7)0.0026 (5)0.0096 (6)0.0003 (5)
N40.0167 (6)0.0182 (7)0.0187 (7)0.0007 (5)0.0119 (6)0.0002 (5)
C50.0171 (7)0.0188 (8)0.0214 (8)0.0021 (6)0.0139 (7)0.0035 (6)
C510.0144 (7)0.0233 (8)0.0228 (8)0.0003 (6)0.0135 (7)0.0020 (7)
C520.0172 (8)0.0260 (9)0.0273 (9)0.0028 (6)0.0142 (7)0.0039 (7)
C530.0159 (8)0.0403 (10)0.0242 (9)0.0018 (7)0.0109 (7)0.0049 (8)
C540.0176 (8)0.0449 (11)0.0282 (10)0.0073 (8)0.0112 (7)0.0053 (9)
C550.0265 (9)0.0296 (10)0.0352 (11)0.0073 (7)0.0159 (8)0.0065 (8)
C560.0207 (8)0.0248 (9)0.0279 (9)0.0006 (7)0.0138 (7)0.0015 (7)
N60.0186 (7)0.0229 (7)0.0197 (7)0.0037 (5)0.0119 (6)0.0072 (6)
C6a0.0141 (7)0.0174 (7)0.0158 (7)0.0011 (6)0.0070 (6)0.0017 (6)
C70.0186 (8)0.0195 (8)0.0190 (8)0.0021 (6)0.0063 (7)0.0002 (6)
C80.0164 (8)0.0248 (9)0.0263 (9)0.0053 (6)0.0075 (7)0.0048 (7)
C90.0175 (8)0.0315 (9)0.0326 (10)0.0004 (7)0.0161 (7)0.0078 (8)
C100.0220 (8)0.0221 (8)0.0252 (9)0.0022 (6)0.0165 (7)0.0029 (7)
C10a0.0141 (7)0.0182 (8)0.0162 (7)0.0004 (6)0.0080 (6)0.0026 (6)
C10b0.0179 (7)0.0185 (8)0.0184 (8)0.0004 (6)0.0124 (7)0.0016 (6)
Geometric parameters (Å, º) top
C1—C21.508 (2)C51—C521.393 (2)
C1—C10b1.531 (2)C52—C531.393 (2)
C1—H1A0.9900C52—H520.9500
C1—H1B0.9900C53—C541.386 (3)
C2—N31.294 (2)C53—H530.9500
C2—C211.463 (2)C54—C551.380 (3)
C21—C221.399 (2)C54—H540.9500
C21—C261.401 (2)C55—C561.392 (3)
C22—C231.387 (2)C55—H550.9500
C22—H220.9500C56—H560.9500
C23—C241.382 (2)N6—C6a1.3857 (19)
C23—H230.9500N6—H60.8800
C24—C251.388 (2)C6a—C71.401 (2)
C24—Cl241.7367 (17)C6a—C10a1.405 (2)
C25—C261.378 (2)C7—C81.388 (2)
C25—H250.9500C7—H70.9500
C26—H260.9500C8—C91.388 (3)
N3—N41.4079 (19)C8—H80.9500
N4—C51.457 (2)C9—C101.384 (2)
N4—C10b1.4804 (18)C9—H90.9500
C5—N61.450 (2)C10—C10a1.398 (2)
C5—C511.533 (2)C10—H100.9500
C5—H51.0000C10a—C10b1.516 (2)
C51—C561.390 (2)C10b—H10B1.0000
C2—C1—C10b100.69 (12)C53—C52—H52119.7
C2—C1—H1A111.6C51—C52—H52119.7
C10b—C1—H1A111.6C54—C53—C52120.22 (17)
C2—C1—H1B111.6C54—C53—H53119.9
C10b—C1—H1B111.6C52—C53—H53119.9
H1A—C1—H1B109.4C55—C54—C53119.44 (17)
N3—C2—C21123.42 (14)C55—C54—H54120.3
N3—C2—C1112.51 (14)C53—C54—H54120.3
C21—C2—C1123.58 (13)C54—C55—C56120.52 (18)
C22—C21—C26118.23 (15)C54—C55—H55119.7
C22—C21—C2119.60 (14)C56—C55—H55119.7
C26—C21—C2122.03 (14)C51—C56—C55120.57 (17)
C23—C22—C21120.97 (15)C51—C56—H56119.7
C23—C22—H22119.5C55—C56—H56119.7
C21—C22—H22119.5C6a—N6—C5119.01 (13)
C24—C23—C22119.29 (15)C6a—N6—H6118.3
C24—C23—H23120.4C5—N6—H6119.4
C22—C23—H23120.4N6—C6a—C7120.05 (14)
C23—C24—C25120.94 (16)N6—C6a—C10a120.74 (14)
C23—C24—Cl24119.66 (13)C7—C6a—C10a119.21 (14)
C25—C24—Cl24119.36 (13)C8—C7—C6a120.46 (15)
C26—C25—C24119.45 (15)C8—C7—H7119.8
C26—C25—H25120.3C6a—C7—H7119.8
C24—C25—H25120.3C9—C8—C7120.72 (16)
C25—C26—C21121.04 (15)C9—C8—H8119.6
C25—C26—H26119.5C7—C8—H8119.6
C21—C26—H26119.5C10—C9—C8118.82 (15)
C2—N3—N4108.33 (12)C10—C9—H9120.6
N3—N4—C5113.99 (12)C8—C9—H9120.6
N3—N4—C10b108.02 (11)C9—C10—C10a121.87 (16)
C5—N4—C10b114.96 (12)C9—C10—H10119.1
N6—C5—N4112.34 (12)C10a—C10—H10119.1
N6—C5—C51112.67 (13)C10—C10a—C6a118.90 (14)
N4—C5—C51108.13 (13)C10—C10a—C10b119.90 (14)
N6—C5—H5107.8C6a—C10a—C10b121.16 (13)
N4—C5—H5107.8N4—C10b—C10a111.29 (12)
C51—C5—H5107.8N4—C10b—C1100.57 (12)
C56—C51—C52118.61 (16)C10a—C10b—C1112.39 (12)
C56—C51—C5120.86 (15)N4—C10b—H10B110.7
C52—C51—C5120.46 (15)C10a—C10b—H10B110.7
C53—C52—C51120.62 (17)C1—C10b—H10B110.7
C10b—C1—C2—N315.76 (16)C52—C53—C54—C550.2 (3)
C10b—C1—C2—C21172.08 (14)C53—C54—C55—C560.7 (3)
N3—C2—C21—C22179.85 (15)C52—C51—C56—C550.6 (2)
C1—C2—C21—C228.8 (2)C5—C51—C56—C55177.46 (15)
N3—C2—C21—C264.5 (2)C54—C55—C56—C510.4 (3)
C1—C2—C21—C26166.82 (15)N4—C5—N6—C6a36.79 (19)
C26—C21—C22—C232.0 (2)C51—C5—N6—C6a85.64 (16)
C2—C21—C22—C23173.79 (15)C5—N6—C6a—C7171.52 (14)
C21—C22—C23—C240.4 (3)C5—N6—C6a—C10a8.0 (2)
C22—C23—C24—C252.4 (3)N6—C6a—C7—C8177.80 (15)
C22—C23—C24—Cl24175.44 (13)C10a—C6a—C7—C81.7 (2)
C23—C24—C25—C261.9 (3)C6a—C7—C8—C90.1 (3)
Cl24—C24—C25—C26175.94 (13)C7—C8—C9—C101.3 (3)
C24—C25—C26—C210.6 (3)C8—C9—C10—C10a0.8 (3)
C22—C21—C26—C252.5 (2)C9—C10—C10a—C6a0.9 (2)
C2—C21—C26—C25173.16 (15)C9—C10—C10a—C10b176.81 (15)
C21—C2—N3—N4168.43 (13)N6—C6a—C10a—C10177.33 (14)
C1—C2—N3—N43.74 (17)C7—C6a—C10a—C102.1 (2)
C2—N3—N4—C5152.17 (13)N6—C6a—C10a—C10b5.0 (2)
C2—N3—N4—C10b23.08 (15)C7—C6a—C10a—C10b175.56 (14)
N3—N4—C5—N671.45 (15)N3—N4—C10b—C10a87.84 (14)
C10b—N4—C5—N654.05 (17)C5—N4—C10b—C10a40.70 (17)
N3—N4—C5—C51163.59 (12)N3—N4—C10b—C131.41 (14)
C10b—N4—C5—C5170.92 (15)C5—N4—C10b—C1159.95 (13)
N6—C5—C51—C5625.73 (19)C10—C10a—C10b—N4166.26 (14)
N4—C5—C51—C56150.49 (14)C6a—C10a—C10b—N411.4 (2)
N6—C5—C51—C52157.43 (13)C10—C10a—C10b—C154.33 (19)
N4—C5—C51—C5232.66 (18)C6a—C10a—C10b—C1123.36 (15)
C56—C51—C52—C531.1 (2)C2—C1—C10b—N426.90 (14)
C5—C51—C52—C53178.05 (14)C2—C1—C10b—C10a91.55 (14)
C51—C52—C53—C540.8 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N6—H6···N3i0.882.203.083 (2)178
C1—H1A···Cg3ii0.992.443.407 (2)166
C22—H22···Cg5ii0.952.883.739 (2)152
Symmetry codes: (i) x+3/2, y+1/2, z+1; (ii) x+3/2, y1/2, z+1/2.
(IV) 5-(4-Bromophenyl)-2-(4-chlorophenyl)-1,5,6,10b-tetrahydropyrazolo[1,5-c] quinazoline top
Crystal data top
C22H17BrClN3Z = 2
Mr = 438.75F(000) = 444
Triclinic, P1Dx = 1.556 Mg m3
Hall symbol: -P_1Melting point: 487 K
a = 5.5560 (1) ÅMo Kα radiation, λ = 0.71073 Å
b = 12.2526 (2) ÅCell parameters from 4188 reflections
c = 14.0827 (3) Åθ = 3.0–27.4°
α = 77.9230 (9)°µ = 2.37 mm1
β = 83.0060 (8)°T = 120 K
γ = 87.814 (1)°Block, colourless
V = 930.41 (3) Å30.35 × 0.10 × 0.08 mm
Data collection top
Nonius KappaCCD area-detector
diffractometer
4188 independent reflections
Radiation source: fine-focus sealed X-ray tube3683 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.068
ϕ scans, and ω scans with κ offsetsθmax = 27.4°, θmin = 3.0°
Absorption correction: multi-scan
(DENZO-SMN; Otwinowski & Minor, 1997)
h = 77
Tmin = 0.492, Tmax = 0.843k = 1515
14350 measured reflectionsl = 1818
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034H-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 reflectionsΔρmax = 0.49 e Å3
269 parametersΔρmin = 0.68 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0130 (12)
Crystal data top
C22H17BrClN3γ = 87.814 (1)°
Mr = 438.75V = 930.41 (3) Å3
Triclinic, P1Z = 2
a = 5.5560 (1) ÅMo Kα radiation
b = 12.2526 (2) ŵ = 2.37 mm1
c = 14.0827 (3) ÅT = 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 = 0.843Rint = 0.068
14350 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.080H-atom parameters constrained
S = 1.05Δρmax = 0.49 e Å3
4188 reflectionsΔρmin = 0.68 e Å3
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
xyzUiso*/UeqOcc. (<1)
Cl240.57185 (14)1.26302 (5)1.00319 (4)0.04059 (18)
C10.0630 (4)0.8853 (2)0.78261 (17)0.0248 (5)
C20.2741 (4)0.96410 (17)0.75248 (16)0.0189 (4)
C21A0.3609 (9)1.0332 (4)0.8164 (2)0.0189 (4)0.50
C22A0.2721 (6)1.0162 (3)0.9149 (2)0.0191 (9)0.50
C23A0.3461 (6)1.0846 (3)0.9729 (2)0.0204 (9)0.50
C24A0.5088 (8)1.1699 (3)0.9324 (4)0.0139 (14)0.50
C25A0.5975 (9)1.1868 (5)0.8339 (4)0.0173 (17)0.50
C26A0.5235 (11)1.1185 (5)0.7758 (3)0.0130 (14)0.50
C21B0.3370 (8)1.0470 (4)0.8080 (2)0.0175 (11)0.50
C22B0.1737 (6)1.0680 (3)0.8853 (2)0.0201 (9)0.50
C23B0.2354 (7)1.1400 (3)0.9424 (2)0.0243 (10)0.50
C24B0.4603 (8)1.1911 (4)0.9224 (4)0.0225 (17)0.50
C25B0.6236 (7)1.1701 (6)0.8451 (5)0.025 (2)0.50
C26B0.5620 (8)1.0980 (6)0.7879 (4)0.0165 (17)0.50
N30.3764 (3)0.96414 (14)0.66559 (13)0.0171 (4)
N40.2497 (3)0.89011 (14)0.62532 (12)0.0161 (4)
C50.4110 (4)0.83725 (17)0.55841 (14)0.0158 (4)
C510.2592 (4)0.77798 (17)0.50144 (14)0.0152 (4)
C520.0743 (4)0.83624 (17)0.45246 (15)0.0178 (4)
C530.0574 (4)0.78592 (17)0.39556 (15)0.0185 (4)
C540.0027 (4)0.67636 (18)0.38782 (15)0.0180 (4)
Br540.17399 (4)0.608703 (18)0.306946 (16)0.02505 (9)
C550.1785 (4)0.61751 (19)0.43595 (17)0.0238 (5)
C560.3076 (4)0.66836 (18)0.49269 (16)0.0217 (5)
N60.5854 (3)0.76567 (15)0.61147 (13)0.0176 (4)
C6a0.4967 (4)0.68993 (17)0.69533 (16)0.0189 (4)
C70.6372 (4)0.59733 (19)0.73284 (18)0.0254 (5)
C80.5521 (5)0.5233 (2)0.81712 (19)0.0329 (6)
C90.3246 (5)0.5388 (2)0.86507 (18)0.0341 (6)
C100.1850 (4)0.6310 (2)0.82896 (17)0.0270 (5)
C10a0.2685 (4)0.70822 (17)0.74441 (15)0.0179 (4)
C10b0.1165 (4)0.81048 (18)0.70763 (15)0.0180 (4)
H1A0.09420.92540.77630.030*
H1B0.06440.84230.85040.030*
H22A0.16090.95790.94260.023*0.50
H23A0.28541.07301.04020.024*0.50
H25A0.70871.24510.80620.021*0.50
H26A0.58421.13010.70850.016*0.50
H22B0.02001.03310.89900.024*0.50
H23B0.12371.15440.99520.029*0.50
H25B0.77731.20490.83140.030*0.50
H26B0.67361.08370.73510.020*0.50
H50.50300.89760.51040.019*
H520.03780.91120.45800.021*
H530.18290.82600.36250.022*
H550.21470.54260.43030.029*
H560.43150.62740.52620.026*
H60.70870.74030.57650.021*
H70.79260.58540.70000.030*
H80.65010.46130.84240.039*
H90.26450.48670.92220.041*
H100.02970.64190.86230.032*
H10B0.03810.78780.68800.022*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl240.0711 (5)0.0325 (3)0.0238 (3)0.0193 (3)0.0073 (3)0.0143 (3)
C10.0207 (10)0.0305 (12)0.0271 (12)0.0071 (9)0.0047 (9)0.0178 (10)
C20.0191 (9)0.0196 (10)0.0200 (10)0.0022 (8)0.0000 (8)0.0097 (8)
C21A0.0191 (9)0.0196 (10)0.0200 (10)0.0022 (8)0.0000 (8)0.0097 (8)
C22A0.020 (2)0.021 (2)0.018 (2)0.0055 (18)0.0022 (17)0.0077 (18)
C23A0.023 (2)0.023 (2)0.015 (2)0.0009 (19)0.0007 (17)0.0057 (18)
C24A0.019 (2)0.009 (2)0.016 (3)0.002 (2)0.009 (2)0.004 (2)
C25A0.024 (3)0.015 (3)0.012 (3)0.003 (2)0.001 (2)0.004 (2)
C26A0.017 (2)0.010 (3)0.011 (3)0.006 (2)0.005 (2)0.001 (2)
C21B0.022 (2)0.019 (3)0.013 (2)0.0022 (19)0.0043 (17)0.0068 (18)
C22B0.021 (2)0.022 (2)0.018 (2)0.0008 (19)0.0010 (17)0.0074 (18)
C23B0.034 (3)0.028 (2)0.014 (2)0.002 (2)0.0012 (19)0.0110 (19)
C24B0.037 (3)0.018 (3)0.015 (3)0.007 (3)0.013 (2)0.007 (2)
C25B0.028 (4)0.016 (3)0.032 (4)0.005 (3)0.015 (3)0.002 (3)
C26B0.018 (3)0.016 (3)0.014 (3)0.007 (2)0.005 (2)0.001 (2)
N30.0204 (8)0.0162 (8)0.0174 (9)0.0012 (7)0.0039 (7)0.0086 (7)
N40.0181 (8)0.0165 (8)0.0159 (9)0.0003 (7)0.0024 (7)0.0084 (7)
C50.0177 (9)0.0159 (10)0.0144 (10)0.0004 (8)0.0007 (8)0.0053 (8)
C510.0166 (9)0.0175 (10)0.0123 (10)0.0015 (8)0.0011 (7)0.0061 (8)
C520.0213 (10)0.0154 (10)0.0178 (11)0.0011 (8)0.0031 (8)0.0058 (8)
C530.0193 (10)0.0200 (10)0.0165 (10)0.0009 (8)0.0037 (8)0.0038 (8)
C540.0187 (10)0.0216 (10)0.0155 (10)0.0021 (8)0.0016 (8)0.0081 (8)
Br540.02558 (13)0.02700 (14)0.02849 (15)0.00012 (9)0.01032 (9)0.01510 (10)
C550.0236 (11)0.0198 (11)0.0330 (13)0.0038 (9)0.0089 (9)0.0141 (9)
C560.0203 (10)0.0215 (11)0.0267 (12)0.0054 (9)0.0085 (9)0.0105 (9)
N60.0138 (8)0.0221 (9)0.0178 (9)0.0012 (7)0.0010 (7)0.0070 (7)
C6a0.0193 (10)0.0186 (10)0.0222 (11)0.0029 (8)0.0078 (8)0.0086 (8)
C70.0282 (11)0.0207 (11)0.0318 (13)0.0002 (9)0.0131 (10)0.0104 (9)
C80.0484 (15)0.0182 (11)0.0362 (14)0.0023 (11)0.0239 (12)0.0038 (10)
C90.0539 (16)0.0249 (12)0.0243 (13)0.0204 (12)0.0150 (11)0.0023 (10)
C100.0331 (12)0.0297 (12)0.0202 (12)0.0166 (10)0.0053 (9)0.0056 (9)
C10a0.0207 (10)0.0198 (10)0.0156 (10)0.0079 (8)0.0042 (8)0.0069 (8)
C10b0.0159 (9)0.0229 (11)0.0175 (11)0.0053 (8)0.0002 (8)0.0096 (8)
Geometric parameters (Å, º) top
Cl24—C24A1.735 (4)N4—C51.455 (3)
Cl24—C24B1.758 (4)N4—C10b1.488 (3)
C1—C21.510 (3)C5—N61.450 (3)
C1—C10b1.534 (3)C5—C511.529 (3)
C1—H1A0.9900C5—H51.0000
C1—H1B0.9900C51—C561.388 (3)
C2—N31.285 (3)C51—C521.397 (3)
C2—C21B1.480 (4)C52—C531.393 (3)
C2—C21A1.488 (4)C52—H520.9500
C21A—C22A1.3900C53—C541.389 (3)
C21A—C26A1.3900C53—H530.9500
C22A—C23A1.3900C54—C551.378 (3)
C22A—H22A0.9500C54—Br541.900 (2)
C23A—C24A1.3900C55—C561.387 (3)
C23A—H23A0.9500C55—H550.9500
C24A—C25A1.3900C56—H560.9500
C25A—C26A1.3900N6—C6a1.390 (3)
C25A—H25A0.9500N6—H60.8800
C26A—H26A0.9500C6a—C71.399 (3)
C21B—C22B1.3900C6a—C10a1.402 (3)
C21B—C26B1.3900C7—C81.378 (4)
C22B—C23B1.3900C7—H70.9500
C22B—H22B0.9500C8—C91.385 (4)
C23B—C24B1.3900C8—H80.9500
C23B—H23B0.9500C9—C101.387 (4)
C24B—C25B1.3900C9—H90.9500
C25B—C26B1.3900C10—C10a1.399 (3)
C25B—H25B0.9500C10—H100.9500
C26B—H26B0.9500C10a—C10b1.518 (3)
N3—N41.415 (2)C10b—H10B1.0000
C2—C1—C10b100.36 (16)N6—C5—N4109.97 (16)
C2—C1—H1A111.7N6—C5—C51114.40 (16)
C10b—C1—H1A111.7N4—C5—C51109.08 (16)
C2—C1—H1B111.7N6—C5—H5107.7
C10b—C1—H1B111.7N4—C5—H5107.7
H1A—C1—H1B109.5C51—C5—H5107.7
N3—C2—C21B121.5 (2)C56—C51—C52118.40 (19)
N3—C2—C21A122.8 (2)C56—C51—C5121.66 (18)
N3—C2—C1112.92 (18)C52—C51—C5119.86 (18)
C21B—C2—C1124.9 (2)C53—C52—C51120.89 (19)
C21A—C2—C1124.3 (2)C53—C52—H52119.6
C22A—C21A—C26A120.0C51—C52—H52119.6
C22A—C21A—C2120.5 (3)C54—C53—C52119.16 (19)
C26A—C21A—C2119.5 (3)C54—C53—H53120.4
C21A—C22A—C23A120.0C52—C53—H53120.4
C21A—C22A—H22A120.0C55—C54—C53120.72 (19)
C23A—C22A—H22A120.0C55—C54—Br54119.82 (16)
C24A—C23A—C22A120.0C53—C54—Br54119.44 (15)
C24A—C23A—H23A120.0C54—C55—C56119.6 (2)
C22A—C23A—H23A120.0C54—C55—H55120.2
C25A—C24A—C23A120.0C56—C55—H55120.2
C25A—C24A—Cl24120.8 (3)C55—C56—C51121.2 (2)
C23A—C24A—Cl24118.8 (3)C55—C56—H56119.4
C24A—C25A—C26A120.0C51—C56—H56119.4
C24A—C25A—H25A120.0C6a—N6—C5117.60 (16)
C26A—C25A—H25A120.0C6a—N6—H6114.3
C25A—C26A—C21A120.0C5—N6—H6117.0
C25A—C26A—H26A120.0N6—C6a—C7120.4 (2)
C21A—C26A—H26A120.0N6—C6a—C10a119.88 (19)
C22B—C21B—C26B120.0C7—C6a—C10a119.7 (2)
C22B—C21B—C2119.0 (3)C8—C7—C6a120.6 (2)
C26B—C21B—C2120.9 (3)C8—C7—H7119.7
C21B—C22B—C23B120.0C6a—C7—H7119.7
C21B—C22B—H22B120.0C7—C8—C9120.4 (2)
C23B—C22B—H22B120.0C7—C8—H8119.8
C22B—C23B—C24B120.0C9—C8—H8119.8
C22B—C23B—H23B120.0C8—C9—C10119.5 (2)
C24B—C23B—H23B120.0C8—C9—H9120.3
C25B—C24B—C23B120.0C10—C9—H9120.3
C25B—C24B—Cl24116.7 (3)C9—C10—C10a121.3 (2)
C23B—C24B—Cl24122.4 (3)C9—C10—H10119.3
C24B—C25B—C26B120.0C10a—C10—H10119.3
C24B—C25B—H25B120.0C10—C10a—C6a118.5 (2)
C26B—C25B—H25B120.0C10—C10a—C10b120.60 (19)
C25B—C26B—C21B120.0C6a—C10a—C10b120.85 (18)
C25B—C26B—H26B120.0N4—C10b—C10a112.50 (16)
C21B—C26B—H26B120.0N4—C10b—C1100.20 (16)
C2—N3—N4108.33 (16)C10a—C10b—C1112.66 (18)
N3—N4—C5111.42 (15)N4—C10b—H10B110.4
N3—N4—C10b107.92 (15)C10a—C10b—H10B110.4
C5—N4—C10b114.33 (16)C1—C10b—H10B110.4
C10b—C1—C2—N318.2 (2)N3—N4—C5—N665.5 (2)
C10b—C1—C2—C21B171.4 (3)C10b—N4—C5—N657.2 (2)
C10b—C1—C2—C21A160.5 (3)N3—N4—C5—C51168.29 (15)
N3—C2—C21A—C22A168.8 (3)C10b—N4—C5—C5169.0 (2)
C21B—C2—C21A—C22A106 (2)N6—C5—C51—C567.4 (3)
C1—C2—C21A—C22A9.8 (5)N4—C5—C51—C56131.0 (2)
N3—C2—C21A—C26A14.1 (4)N6—C5—C51—C52175.91 (17)
C21B—C2—C21A—C26A71 (2)N4—C5—C51—C5252.3 (2)
C1—C2—C21A—C26A167.3 (3)C56—C51—C52—C530.5 (3)
C26A—C21A—C22A—C23A0.0C5—C51—C52—C53176.34 (18)
C2—C21A—C22A—C23A177.1 (4)C51—C52—C53—C540.0 (3)
C21A—C22A—C23A—C24A0.0C52—C53—C54—C550.3 (3)
C22A—C23A—C24A—C25A0.0C52—C53—C54—Br54177.93 (15)
C22A—C23A—C24A—Cl24173.1 (4)C53—C54—C55—C560.0 (3)
C24B—Cl24—C24A—C25A78.7 (12)Br54—C54—C55—C56178.19 (17)
C24B—Cl24—C24A—C23A94.3 (13)C54—C55—C56—C510.5 (3)
C23A—C24A—C25A—C26A0.0C52—C51—C56—C550.8 (3)
Cl24—C24A—C25A—C26A172.9 (4)C5—C51—C56—C55176.0 (2)
C24A—C25A—C26A—C21A0.0N4—C5—N6—C6a49.9 (2)
C22A—C21A—C26A—C25A0.0C51—C5—N6—C6a73.2 (2)
C2—C21A—C26A—C25A177.1 (4)C5—N6—C6a—C7160.41 (18)
N3—C2—C21B—C22B159.1 (2)C5—N6—C6a—C10a21.6 (3)
C21A—C2—C21B—C22B100 (2)N6—C6a—C7—C8178.6 (2)
C1—C2—C21B—C22B10.5 (4)C10a—C6a—C7—C80.7 (3)
N3—C2—C21B—C26B25.1 (4)C6a—C7—C8—C90.9 (3)
C21A—C2—C21B—C26B76 (2)C7—C8—C9—C101.6 (4)
C1—C2—C21B—C26B165.3 (3)C8—C9—C10—C10a0.6 (3)
C26B—C21B—C22B—C23B0.0C9—C10—C10a—C6a0.9 (3)
C2—C21B—C22B—C23B175.8 (3)C9—C10—C10a—C10b178.2 (2)
C21B—C22B—C23B—C24B0.0N6—C6a—C10a—C10179.54 (19)
C22B—C23B—C24B—C25B0.0C7—C6a—C10a—C101.6 (3)
C22B—C23B—C24B—Cl24168.6 (4)N6—C6a—C10a—C10b0.5 (3)
C24A—Cl24—C24B—C25B62.5 (12)C7—C6a—C10a—C10b177.53 (18)
C24A—Cl24—C24B—C23B106.4 (13)N3—N4—C10b—C10a88.41 (19)
C23B—C24B—C25B—C26B0.0C5—N4—C10b—C10a36.2 (2)
Cl24—C24B—C25B—C26B169.2 (4)N3—N4—C10b—C131.47 (19)
C24B—C25B—C26B—C21B0.0C5—N4—C10b—C1156.04 (17)
C22B—C21B—C26B—C25B0.0C10—C10a—C10b—N4172.09 (18)
C2—C21B—C26B—C25B175.8 (3)C6a—C10a—C10b—N47.0 (3)
C21B—C2—N3—N4169.4 (2)C10—C10a—C10b—C159.7 (2)
C21A—C2—N3—N4179.9 (3)C6a—C10a—C10b—C1119.3 (2)
C1—C2—N3—N41.4 (2)C2—C1—C10b—N428.2 (2)
C2—N3—N4—C5147.98 (17)C2—C1—C10b—C10a91.6 (2)
C2—N3—N4—C10b21.7 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N6—H6···Cg5i0.882.823.666 (2)163
C10b—H10B···N6ii1.002.523.500 (3)168
Symmetry codes: (i) x+1, y, z; (ii) x1, y, z.

Experimental details

(I)(II)(III)(IV)
Crystal data
Chemical formulaC23H21N3C22H18BrN3C22H18ClN3C22H17BrClN3
Mr339.43404.30359.84438.75
Crystal system, space groupTriclinic, P1Triclinic, P1Monoclinic, C2/cTriclinic, P1
Temperature (K)120120120120
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), 9077.9230 (9), 83.0060 (8), 87.814 (1)
V3)878.1 (2)871.37 (4)3508.84 (11)930.41 (3)
Z2282
Radiation typeMo KαMo KαMo KαMo Kα
µ (mm1)0.082.370.232.37
Crystal size (mm)0.18 × 0.08 × 0.040.25 × 0.15 × 0.100.46 × 0.32 × 0.100.35 × 0.10 × 0.08
Data collection
DiffractometerBruker SMART1000 CCD area-detector
diffractometer
Nonius KappaCCD area-detector
diffractometer
Nonius KappaCCD area-detector
diffractometer
Nonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-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, Tmax0.986, 0.9970.719, 0.7890.902, 0.9780.492, 0.843
No. of measured, independent and
observed [I > 2σ(I)] reflections
5532, 3993, 3451 12439, 3775, 3235 15078, 4002, 3286 14350, 4188, 3683
Rint0.0140.0560.0850.068
(sin θ/λ)max1)0.6840.6500.6490.648
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 reflections3993377540024188
No. of parameters235235235269
H-atom treatmentH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.31, 0.270.46, 0.650.39, 0.540.49, 0.68

Computer programs: SMART (Bruker, 1997), KappaCCD Server Software (Nonius, 1997), SMART, DENZO-SMN (Otwinowski & Minor, 1997), SHELXTL (Bruker, 1997), DENZO-SMN, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976) and PLATON (Spek, 2002), SHELXL97 and PRPKAPPA (Ferguson, 1999).

Selected geometric parameters (Å, º) for (I) top
C1—C21.512 (2)N6—C6a1.374 (2)
C1—C10b1.539 (2)C6a—C71.406 (2)
C2—N31.288 (2)C6a—C10a1.408 (2)
C2—C211.470 (2)C7—C81.383 (2)
N3—N41.4147 (18)C8—C91.384 (3)
N4—C51.4620 (19)C9—C101.390 (3)
N4—C10b1.483 (2)C10—C10a1.392 (2)
C5—N61.445 (2)C10a—C10b1.522 (2)
C2—C1—C10b100.55 (12)C8—C7—C6a120.35 (16)
N3—C2—C1112.68 (14)C7—C8—C9120.78 (16)
C2—N3—N4108.49 (12)C8—C9—C10119.14 (16)
N3—N4—C5112.26 (12)C9—C10—C10a121.52 (16)
N3—N4—C10b107.96 (11)C10—C10a—C6a118.98 (15)
C5—N4—C10b114.03 (12)C10—C10a—C10b120.53 (14)
N6—C5—N4110.75 (12)C6a—C10a—C10b120.46 (13)
C6a—N6—C5118.73 (13)N4—C10b—C10a112.68 (12)
N6—C6a—C7120.66 (15)N4—C10b—C1100.43 (12)
N6—C6a—C10a120.15 (14)C10a—C10b—C1112.68 (13)
C7—C6a—C10a119.18 (15)
N3—C2—C21—C22177.79 (16)N6—C5—C51—C5624.1 (2)
C1—C2—C21—C225.8 (2)N4—C5—C51—C56147.76 (16)
N3—C2—C21—C263.1 (3)N6—C5—C51—C52158.96 (15)
C1—C2—C21—C26173.30 (16)N4—C5—C51—C5235.3 (2)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N6—H6···N3i0.882.263.122 (2)164
C53—H53···Cg4ii0.952.753.635 (3)156
Symmetry codes: (i) x, y+1, z+1; (ii) x, y+1, z.
Selected geometric parameters (Å, º) for (II) top
C1—C21.511 (3)C6a—C71.402 (3)
C1—C10b1.537 (3)C6a—C10a1.407 (3)
C2—N31.288 (3)C7—C81.389 (3)
N3—N41.416 (2)C8—C91.382 (4)
N4—C51.465 (3)C9—C101.388 (4)
N4—C10b1.490 (3)C10—C10a1.392 (3)
C5—N61.440 (3)C10a—C10b1.519 (3)
N6—C6a1.380 (3)
C2—C1—C10b101.04 (17)C8—C7—C6a120.0 (2)
N3—C2—C1112.81 (18)C9—C8—C7120.6 (2)
C2—N3—N4108.54 (17)C8—C9—C10119.4 (2)
N3—N4—C5111.94 (17)C9—C10—C10a121.5 (2)
N3—N4—C10b108.09 (16)C10—C10a—C6a118.7 (2)
C5—N4—C10b114.10 (17)C10—C10a—C10b120.1 (2)
N6—C5—N4111.18 (17)C6a—C10a—C10b121.17 (19)
C6a—N6—C5118.43 (18)N4—C10b—C10a112.59 (17)
N6—C6a—C7120.5 (2)N4—C10b—C1100.49 (16)
N6—C6a—C10a119.8 (2)C10a—C10b—C1113.07 (18)
C7—C6a—C10a119.7 (2)
N3—C2—C21—C22178.0 (2)N6—C5—C51—C5624.7 (3)
C1—C2—C21—C225.3 (3)N4—C5—C51—C56148.6 (2)
N3—C2—C21—C263.0 (3)N6—C5—C51—C52158.4 (2)
C1—C2—C21—C26173.7 (2)N4—C5—C51—C5234.4 (3)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N6—H6···N3i0.882.253.105 (3)162
C53—H53···Cg4ii0.952.713.588 (3)154
Symmetry codes: (i) x, y+1, z+1; (ii) x, y+1, z.
Selected geometric parameters (Å, º) for (III) top
C1—C21.508 (2)C6a—C71.401 (2)
C1—C10b1.531 (2)C6a—C10a1.405 (2)
C2—N31.294 (2)C7—C81.388 (2)
N3—N41.4079 (19)C8—C91.388 (3)
N4—C51.457 (2)C9—C101.384 (2)
N4—C10b1.4804 (18)C10—C10a1.398 (2)
C5—N61.450 (2)C10a—C10b1.516 (2)
N6—C6a1.3857 (19)
C2—C1—C10b100.69 (12)C8—C7—C6a120.46 (15)
N3—C2—C1112.51 (14)C9—C8—C7120.72 (16)
C2—N3—N4108.33 (12)C10—C9—C8118.82 (15)
N3—N4—C5113.99 (12)C9—C10—C10a121.87 (16)
N3—N4—C10b108.02 (11)C10—C10a—C6a118.90 (14)
C5—N4—C10b114.96 (12)C10—C10a—C10b119.90 (14)
N6—C5—N4112.34 (12)C6a—C10a—C10b121.16 (13)
C6a—N6—C5119.01 (13)N4—C10b—C10a111.29 (12)
N6—C6a—C7120.05 (14)N4—C10b—C1100.57 (12)
N6—C6a—C10a120.74 (14)C10a—C10b—C1112.39 (12)
C7—C6a—C10a119.21 (14)
N3—C2—C21—C22179.85 (15)N6—C5—C51—C5625.73 (19)
C1—C2—C21—C228.8 (2)N4—C5—C51—C56150.49 (14)
N3—C2—C21—C264.5 (2)N6—C5—C51—C52157.43 (13)
C1—C2—C21—C26166.82 (15)N4—C5—C51—C5232.66 (18)
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
N6—H6···N3i0.882.203.083 (2)178
C1—H1A···Cg3ii0.992.443.407 (2)166
C22—H22···Cg5ii0.952.883.739 (2)152
Symmetry codes: (i) x+3/2, y+1/2, z+1; (ii) x+3/2, y1/2, z+1/2.
Selected geometric parameters (Å, º) for (IV) top
C1—C21.510 (3)N6—C6a1.390 (3)
C1—C10b1.534 (3)C6a—C71.399 (3)
C2—N31.285 (3)C6a—C10a1.402 (3)
N3—N41.415 (2)C7—C81.378 (4)
N4—C51.455 (3)C8—C91.385 (4)
N4—C10b1.488 (3)C9—C101.387 (4)
C5—N61.450 (3)C10—C10a1.399 (3)
C5—C511.529 (3)C10a—C10b1.518 (3)
C2—C1—C10b100.36 (16)C8—C7—C6a120.6 (2)
N3—C2—C1112.92 (18)C7—C8—C9120.4 (2)
C2—N3—N4108.33 (16)C8—C9—C10119.5 (2)
N3—N4—C5111.42 (15)C9—C10—C10a121.3 (2)
N3—N4—C10b107.92 (15)C10—C10a—C6a118.5 (2)
C5—N4—C10b114.33 (16)C10—C10a—C10b120.60 (19)
N6—C5—N4109.97 (16)C6a—C10a—C10b120.85 (18)
C6a—N6—C5117.60 (16)N4—C10b—C10a112.50 (16)
N6—C6a—C7120.4 (2)N4—C10b—C1100.20 (16)
N6—C6a—C10a119.88 (19)C10a—C10b—C1112.66 (18)
C7—C6a—C10a119.7 (2)
N3—C2—C21A—C22A168.8 (3)N6—C5—C51—C567.4 (3)
N3—C2—C21A—C26A14.1 (4)N4—C5—C51—C56131.0 (2)
N3—C2—C21B—C22B159.1 (2)N6—C5—C51—C52175.91 (17)
N3—C2—C21B—C26B25.1 (4)N4—C5—C51—C5252.3 (2)
Hydrogen-bond geometry (Å, º) for (IV) top
D—H···AD—HH···AD···AD—H···A
N6—H6···Cg5i0.882.823.666 (2)163
C10b—H10B···N6ii1.002.523.500 (3)168
Symmetry codes: (i) x+1, y, z; (ii) x1, y, z.
 

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