Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807024336/fb2051sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807024336/fb2051Isup2.hkl |
CCDC reference: 651500
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.002 Å
- R factor = 0.035
- wR factor = 0.095
- Data-to-parameter ratio = 15.6
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ?
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For related literature, see: Allen (2002); Brown & Kee (1993); Elguero (1996); Esquius et al. (2000).
A solution of triphenylchloromethane (2.9 g, 10.4 mmol) in toluene (20 ml) was added to a solution of 3,5-dimethylpyrazole (1.0 g, 10.4 mmol) in toluene (20 ml). Triethylammine (2 ml) was added and the solution stirred at 80° C for 15 h. The resultant Et3NH+Cl- salt was removed by filtration and the solution was evaporated to dryness. A brown solid was obtained. The product was purified by chromatography using silica gel and CH2Cl2:hexane (5:1) as eluent. Compound (I) crystallized upon slow evaporation of the solvent to give X-ray quality crystals. Yield = 2.57 g (73%). 1H NMR (CDCl3): δ 7.45, 7.14 (15 H, (C6H5)3); 6.03 (s, 1H, 4-pz); 2.23 (s, 3H, 5-Me); 1.46 (s, 3H, 3-Me). 13C{1H} NMR (CDCl3): δ 146.0 (C (5-pz)); 144.1 (phenyl); 142.0 (C(3-pz)); 128.0, 127.5 (phenyl); 127.3 (phenyl); 108.1 (C (4-pz)); 82.0 (C (C(Ph)3)); 15.2 (C(CH3, 5-pz)); 14.6 (C(CH3, 3-pz)). IR (Nujol): 1701 cm-1(υC=C,pz); 1571 cm-1 (υC=N).
Although all the hydrogen atoms were discernible in the difference Fourier map, they were placed in idealized locations and refined as riding with appropriate thermal displacement coefficients Uiso(H) = 1.2 or 1.5 (methyl H atoms) times Ueq of the parent atom. The C—H distances were set to 0.98 Å for the hydrogen atoms attached to methyl-carbon atoms C1 and C5 and 0.95 Å for all other hydrogen atoms.
Water-soluble substituted pyrazoles constitute an important family of heterocyclic compounds that have found use in drug development and in catalysis (Elguero et al. 1996, Brown et al., 1993). In attempts to prepare water soluble palladium and platinum complexes with potential anti-cancer properties, we set out to prepare 4-alkylaminopyrazoles using a route reported by Esquius et al. (2000). The route involves protection of the position 1 of the 3,5-dimethylpyrazole, followed by aminoalkylation of the position 4. This offers a more efficient route to making water soluble 4-alkylaminopyrazoles (Esquius et al. 2000). When we used this route with a trityl group to protect the position 1 of the pyrazole, we could not alkylate position 4 of the pyrazole efficiently and isolated compound (I) instead.
Within (I) the bond distances and angles are typical. Carbon atom C6 exhibits a distorted tetrahedral geometry with the average X—C6—C angles being 109 (2)°. The six X—C6—C angles range from 106.17 (8)° to 113.01 (9)°. The torsion angles N—C—C(ipso)-C(ortho) involving the phenyl rings are very different at 5.20 (14), 46.68 (12), and 69.65 (12)°. A quality-restrictive search (R-factor <0.05, not disordered, no errors, and no powder structures) of the Cambridge Structural Database (Version 5.28, January 2007 update, Allen, 2002) for organic compounds with N-CPh3 fragments returned 34 hits and revealed that the N—C—C(ipso)-C(ortho) angles vary to a large extent but are usually different at 13 (9), 36 (10), and 73 (13)°. The trend is in agreement with that of the corresponding parameters in (I).
For related literature, see: Allen (2002); Brown & Kee (1993); Elguero (1996); Esquius et al. (2000).
Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2003); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, publCIF (Westrip, 2007) and modiCIFer (Guzei, 1995).
Fig. 1. Molecular structure of (I). The thermal ellipsoids are shown at 50% probability level. All hydrogen atoms were omitted for clarity. |
C24H22N2 | F(000) = 720 |
Mr = 338.44 | Dx = 1.238 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 7180 reflections |
a = 9.5264 (5) Å | θ = 2.1–26.4° |
b = 8.6992 (4) Å | µ = 0.07 mm−1 |
c = 21.9714 (11) Å | T = 100 K |
β = 93.961 (1)° | Block, colorless |
V = 1816.47 (16) Å3 | 0.41 × 0.27 × 0.19 mm |
Z = 4 |
Bruker SMART 1000 CCD area-detector diffractometer | 3708 independent reflections |
Radiation source: fine-focus sealed tube | 3141 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.039 |
0.30° ω scans | θmax = 26.4°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | h = −11→11 |
Tmin = 0.971, Tmax = 0.986 | k = −10→10 |
14683 measured reflections | l = −27→27 |
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)] = 0.035 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.095 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.048P)2 + 0.4396P] where P = (Fo2 + 2Fc2)/3 |
3708 reflections | (Δ/σ)max = 0.001 |
237 parameters | Δρmax = 0.29 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
86 constraints |
C24H22N2 | V = 1816.47 (16) Å3 |
Mr = 338.44 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.5264 (5) Å | µ = 0.07 mm−1 |
b = 8.6992 (4) Å | T = 100 K |
c = 21.9714 (11) Å | 0.41 × 0.27 × 0.19 mm |
β = 93.961 (1)° |
Bruker SMART 1000 CCD area-detector diffractometer | 3708 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | 3141 reflections with I > 2σ(I) |
Tmin = 0.971, Tmax = 0.986 | Rint = 0.039 |
14683 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.095 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.29 e Å−3 |
3708 reflections | Δρmin = −0.24 e Å−3 |
237 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.19656 (9) | 0.32354 (10) | 0.32906 (4) | 0.0180 (2) | |
N2 | 0.31711 (9) | 0.23745 (11) | 0.33155 (4) | 0.0208 (2) | |
C1 | 0.01024 (13) | 0.42816 (15) | 0.25096 (5) | 0.0284 (3) | |
H1A | 0.0001 | 0.4333 | 0.2063 | 0.043* | |
H1B | 0.0164 | 0.5325 | 0.2677 | 0.043* | |
H1C | −0.0715 | 0.3756 | 0.2660 | 0.043* | |
C2 | 0.14076 (12) | 0.34152 (13) | 0.27048 (5) | 0.0217 (2) | |
C3 | 0.22915 (13) | 0.26332 (14) | 0.23435 (5) | 0.0252 (3) | |
H3 | 0.2197 | 0.2537 | 0.1912 | 0.030* | |
C4 | 0.33584 (12) | 0.20082 (13) | 0.27390 (5) | 0.0236 (3) | |
C5 | 0.45955 (14) | 0.10514 (16) | 0.25862 (7) | 0.0344 (3) | |
H5A | 0.4290 | 0.0280 | 0.2280 | 0.052* | |
H5B | 0.4992 | 0.0535 | 0.2955 | 0.052* | |
H5C | 0.5312 | 0.1714 | 0.2423 | 0.052* | |
C6 | 0.14571 (11) | 0.39237 (12) | 0.38588 (5) | 0.0171 (2) | |
C7 | 0.18242 (11) | 0.56500 (12) | 0.38913 (5) | 0.0179 (2) | |
C8 | 0.24280 (12) | 0.64229 (13) | 0.34215 (5) | 0.0224 (2) | |
H8 | 0.2611 | 0.5888 | 0.3058 | 0.027* | |
C9 | 0.27665 (12) | 0.79768 (14) | 0.34788 (6) | 0.0258 (3) | |
H9 | 0.3174 | 0.8491 | 0.3153 | 0.031* | |
C10 | 0.25182 (12) | 0.87807 (13) | 0.40039 (6) | 0.0242 (3) | |
H10 | 0.2743 | 0.9842 | 0.4039 | 0.029* | |
C11 | 0.19341 (12) | 0.80087 (13) | 0.44779 (6) | 0.0231 (3) | |
H11 | 0.1763 | 0.8544 | 0.4842 | 0.028* | |
C12 | 0.15986 (11) | 0.64602 (13) | 0.44236 (5) | 0.0202 (2) | |
H12 | 0.1209 | 0.5944 | 0.4754 | 0.024* | |
C13 | −0.01407 (11) | 0.36151 (12) | 0.38356 (5) | 0.0169 (2) | |
C14 | −0.11368 (11) | 0.47309 (13) | 0.39443 (5) | 0.0200 (2) | |
H14 | −0.0840 | 0.5746 | 0.4048 | 0.024* | |
C15 | −0.25684 (12) | 0.43740 (14) | 0.39027 (5) | 0.0238 (3) | |
H15 | −0.3236 | 0.5145 | 0.3984 | 0.029* | |
C16 | −0.30255 (12) | 0.29088 (14) | 0.37438 (5) | 0.0248 (3) | |
H16 | −0.4001 | 0.2672 | 0.3713 | 0.030* | |
C17 | −0.20363 (12) | 0.17872 (13) | 0.36297 (5) | 0.0233 (3) | |
H17 | −0.2338 | 0.0781 | 0.3515 | 0.028* | |
C18 | −0.06131 (12) | 0.21310 (13) | 0.36831 (5) | 0.0202 (2) | |
H18 | 0.0053 | 0.1347 | 0.3615 | 0.024* | |
C19 | 0.22179 (11) | 0.31466 (12) | 0.44228 (5) | 0.0177 (2) | |
C20 | 0.15200 (12) | 0.22381 (12) | 0.48246 (5) | 0.0197 (2) | |
H20 | 0.0540 | 0.2055 | 0.4750 | 0.024* | |
C21 | 0.22369 (13) | 0.15898 (13) | 0.53369 (5) | 0.0251 (3) | |
H21 | 0.1740 | 0.0980 | 0.5609 | 0.030* | |
C22 | 0.36624 (14) | 0.18284 (14) | 0.54502 (6) | 0.0291 (3) | |
H22 | 0.4156 | 0.1359 | 0.5792 | 0.035* | |
C23 | 0.43700 (13) | 0.27640 (15) | 0.50588 (6) | 0.0286 (3) | |
H23 | 0.5349 | 0.2948 | 0.5137 | 0.034* | |
C24 | 0.36525 (12) | 0.34268 (13) | 0.45559 (5) | 0.0230 (3) | |
H24 | 0.4142 | 0.4082 | 0.4297 | 0.028* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0187 (5) | 0.0169 (5) | 0.0186 (5) | 0.0002 (4) | 0.0037 (4) | −0.0016 (4) |
N2 | 0.0178 (5) | 0.0179 (5) | 0.0275 (5) | 0.0001 (4) | 0.0063 (4) | −0.0023 (4) |
C1 | 0.0327 (7) | 0.0326 (7) | 0.0194 (6) | 0.0023 (5) | −0.0014 (5) | 0.0034 (5) |
C2 | 0.0268 (6) | 0.0193 (6) | 0.0192 (6) | −0.0044 (5) | 0.0033 (4) | −0.0002 (4) |
C3 | 0.0315 (6) | 0.0239 (6) | 0.0210 (6) | −0.0073 (5) | 0.0075 (5) | −0.0030 (5) |
C4 | 0.0240 (6) | 0.0201 (6) | 0.0281 (6) | −0.0047 (5) | 0.0103 (5) | −0.0044 (5) |
C5 | 0.0331 (7) | 0.0316 (7) | 0.0407 (8) | 0.0005 (6) | 0.0171 (6) | −0.0078 (6) |
C6 | 0.0181 (5) | 0.0168 (5) | 0.0168 (5) | 0.0001 (4) | 0.0038 (4) | −0.0012 (4) |
C7 | 0.0143 (5) | 0.0174 (5) | 0.0220 (6) | 0.0007 (4) | 0.0000 (4) | 0.0002 (4) |
C8 | 0.0234 (6) | 0.0217 (6) | 0.0225 (6) | −0.0015 (4) | 0.0049 (4) | −0.0006 (4) |
C9 | 0.0254 (6) | 0.0229 (6) | 0.0296 (7) | −0.0036 (5) | 0.0053 (5) | 0.0046 (5) |
C10 | 0.0207 (6) | 0.0157 (5) | 0.0358 (7) | −0.0008 (4) | −0.0007 (5) | −0.0003 (5) |
C11 | 0.0217 (6) | 0.0204 (6) | 0.0270 (6) | 0.0007 (4) | 0.0009 (5) | −0.0051 (5) |
C12 | 0.0190 (5) | 0.0207 (6) | 0.0211 (6) | −0.0003 (4) | 0.0026 (4) | −0.0001 (4) |
C13 | 0.0181 (5) | 0.0190 (5) | 0.0134 (5) | −0.0005 (4) | 0.0008 (4) | 0.0018 (4) |
C14 | 0.0214 (6) | 0.0198 (5) | 0.0187 (5) | −0.0002 (4) | 0.0014 (4) | −0.0008 (4) |
C15 | 0.0203 (6) | 0.0277 (6) | 0.0237 (6) | 0.0043 (5) | 0.0023 (4) | −0.0011 (5) |
C16 | 0.0176 (5) | 0.0313 (7) | 0.0254 (6) | −0.0030 (5) | 0.0003 (4) | 0.0015 (5) |
C17 | 0.0242 (6) | 0.0217 (6) | 0.0234 (6) | −0.0047 (5) | −0.0015 (5) | 0.0016 (5) |
C18 | 0.0217 (6) | 0.0189 (5) | 0.0199 (6) | 0.0012 (4) | 0.0009 (4) | 0.0017 (4) |
C19 | 0.0197 (5) | 0.0153 (5) | 0.0180 (5) | 0.0027 (4) | 0.0012 (4) | −0.0031 (4) |
C20 | 0.0220 (6) | 0.0165 (5) | 0.0208 (6) | 0.0004 (4) | 0.0021 (4) | −0.0029 (4) |
C21 | 0.0340 (7) | 0.0193 (6) | 0.0219 (6) | 0.0012 (5) | 0.0011 (5) | −0.0005 (4) |
C22 | 0.0355 (7) | 0.0264 (6) | 0.0241 (6) | 0.0073 (5) | −0.0070 (5) | 0.0009 (5) |
C23 | 0.0220 (6) | 0.0305 (7) | 0.0323 (7) | 0.0029 (5) | −0.0050 (5) | −0.0041 (5) |
C24 | 0.0213 (6) | 0.0227 (6) | 0.0252 (6) | −0.0004 (5) | 0.0020 (5) | −0.0011 (5) |
N1—C2 | 1.3673 (14) | C11—C12 | 1.3876 (16) |
N1—N2 | 1.3690 (13) | C11—H11 | 0.9500 |
N1—C6 | 1.4950 (13) | C12—H12 | 0.9500 |
N2—C4 | 1.3299 (15) | C13—C14 | 1.3896 (15) |
C1—C2 | 1.4914 (17) | C13—C18 | 1.4003 (15) |
C1—H1A | 0.9800 | C14—C15 | 1.3955 (16) |
C1—H1B | 0.9800 | C14—H14 | 0.9500 |
C1—H1C | 0.9800 | C15—C16 | 1.3839 (17) |
C2—C3 | 1.3762 (16) | C15—H15 | 0.9500 |
C3—C4 | 1.4005 (18) | C16—C17 | 1.3912 (17) |
C3—H3 | 0.9500 | C16—H16 | 0.9500 |
C4—C5 | 1.4997 (17) | C17—C18 | 1.3854 (16) |
C5—H5A | 0.9800 | C17—H17 | 0.9500 |
C5—H5B | 0.9800 | C18—H18 | 0.9500 |
C5—H5C | 0.9800 | C19—C20 | 1.3882 (15) |
C6—C7 | 1.5425 (15) | C19—C24 | 1.3991 (15) |
C6—C13 | 1.5430 (14) | C20—C21 | 1.3948 (16) |
C6—C19 | 1.5472 (15) | C20—H20 | 0.9500 |
C7—C8 | 1.3894 (16) | C21—C22 | 1.3792 (18) |
C7—C12 | 1.3948 (16) | C21—H21 | 0.9500 |
C8—C9 | 1.3934 (17) | C22—C23 | 1.3916 (19) |
C8—H8 | 0.9500 | C22—H22 | 0.9500 |
C9—C10 | 1.3834 (17) | C23—C24 | 1.3842 (17) |
C9—H9 | 0.9500 | C23—H23 | 0.9500 |
C10—C11 | 1.3876 (17) | C24—H24 | 0.9500 |
C10—H10 | 0.9500 | ||
C2—N1—N2 | 111.75 (9) | C10—C11—C12 | 120.48 (11) |
C2—N1—C6 | 127.80 (9) | C10—C11—H11 | 119.8 |
N2—N1—C6 | 120.34 (9) | C12—C11—H11 | 119.8 |
C4—N2—N1 | 105.10 (9) | C11—C12—C7 | 120.98 (11) |
C2—C1—H1A | 109.5 | C11—C12—H12 | 119.5 |
C2—C1—H1B | 109.5 | C7—C12—H12 | 119.5 |
H1A—C1—H1B | 109.5 | C14—C13—C18 | 118.24 (10) |
C2—C1—H1C | 109.5 | C14—C13—C6 | 123.82 (10) |
H1A—C1—H1C | 109.5 | C18—C13—C6 | 117.92 (9) |
H1B—C1—H1C | 109.5 | C13—C14—C15 | 120.61 (10) |
N1—C2—C3 | 105.83 (10) | C13—C14—H14 | 119.7 |
N1—C2—C1 | 126.20 (10) | C15—C14—H14 | 119.7 |
C3—C2—C1 | 127.97 (11) | C16—C15—C14 | 120.70 (11) |
C2—C3—C4 | 106.31 (10) | C16—C15—H15 | 119.7 |
C2—C3—H3 | 126.8 | C14—C15—H15 | 119.7 |
C4—C3—H3 | 126.8 | C15—C16—C17 | 119.09 (10) |
N2—C4—C3 | 111.00 (10) | C15—C16—H16 | 120.5 |
N2—C4—C5 | 120.36 (11) | C17—C16—H16 | 120.5 |
C3—C4—C5 | 128.64 (11) | C18—C17—C16 | 120.30 (11) |
C4—C5—H5A | 109.5 | C18—C17—H17 | 119.9 |
C4—C5—H5B | 109.5 | C16—C17—H17 | 119.9 |
H5A—C5—H5B | 109.5 | C17—C18—C13 | 121.04 (10) |
C4—C5—H5C | 109.5 | C17—C18—H18 | 119.5 |
H5A—C5—H5C | 109.5 | C13—C18—H18 | 119.5 |
H5B—C5—H5C | 109.5 | C20—C19—C24 | 118.04 (10) |
N1—C6—C7 | 110.07 (8) | C20—C19—C6 | 122.66 (10) |
N1—C6—C13 | 106.17 (8) | C24—C19—C6 | 119.22 (10) |
C7—C6—C13 | 113.01 (9) | C19—C20—C21 | 120.94 (11) |
N1—C6—C19 | 109.44 (8) | C19—C20—H20 | 119.5 |
C7—C6—C19 | 107.23 (8) | C21—C20—H20 | 119.5 |
C13—C6—C19 | 110.91 (8) | C22—C21—C20 | 120.39 (11) |
C8—C7—C12 | 118.30 (10) | C22—C21—H21 | 119.8 |
C8—C7—C6 | 122.74 (10) | C20—C21—H21 | 119.8 |
C12—C7—C6 | 118.89 (9) | C21—C22—C23 | 119.30 (11) |
C7—C8—C9 | 120.48 (11) | C21—C22—H22 | 120.4 |
C7—C8—H8 | 119.8 | C23—C22—H22 | 120.4 |
C9—C8—H8 | 119.8 | C24—C23—C22 | 120.23 (11) |
C10—C9—C8 | 120.93 (11) | C24—C23—H23 | 119.9 |
C10—C9—H9 | 119.5 | C22—C23—H23 | 119.9 |
C8—C9—H9 | 119.5 | C23—C24—C19 | 121.04 (11) |
C9—C10—C11 | 118.80 (11) | C23—C24—H24 | 119.5 |
C9—C10—H10 | 120.6 | C19—C24—H24 | 119.5 |
C11—C10—H10 | 120.6 | ||
C2—N1—N2—C4 | −0.38 (12) | C8—C7—C12—C11 | 1.63 (16) |
C6—N1—N2—C4 | −177.00 (9) | C6—C7—C12—C11 | 178.94 (10) |
N2—N1—C2—C3 | 0.20 (12) | N1—C6—C13—C14 | −131.89 (10) |
C6—N1—C2—C3 | 176.51 (10) | C7—C6—C13—C14 | −11.14 (14) |
N2—N1—C2—C1 | 179.95 (11) | C19—C6—C13—C14 | 109.30 (11) |
C6—N1—C2—C1 | −3.74 (18) | N1—C6—C13—C18 | 46.68 (12) |
N1—C2—C3—C4 | 0.05 (12) | C7—C6—C13—C18 | 167.43 (9) |
C1—C2—C3—C4 | −179.69 (11) | C19—C6—C13—C18 | −72.12 (12) |
N1—N2—C4—C3 | 0.41 (12) | C18—C13—C14—C15 | 0.08 (16) |
N1—N2—C4—C5 | −179.94 (10) | C6—C13—C14—C15 | 178.65 (10) |
C2—C3—C4—N2 | −0.30 (13) | C13—C14—C15—C16 | −0.94 (17) |
C2—C3—C4—C5 | −179.92 (12) | C14—C15—C16—C17 | 0.46 (17) |
C2—N1—C6—C7 | −73.89 (13) | C15—C16—C17—C18 | 0.88 (17) |
N2—N1—C6—C7 | 102.14 (10) | C16—C17—C18—C13 | −1.77 (17) |
C2—N1—C6—C13 | 48.74 (13) | C14—C13—C18—C17 | 1.27 (16) |
N2—N1—C6—C13 | −135.22 (9) | C6—C13—C18—C17 | −177.39 (10) |
C2—N1—C6—C19 | 168.51 (10) | N1—C6—C19—C20 | −113.81 (11) |
N2—N1—C6—C19 | −15.46 (13) | C7—C6—C19—C20 | 126.83 (10) |
N1—C6—C7—C8 | 5.20 (14) | C13—C6—C19—C20 | 3.00 (14) |
C13—C6—C7—C8 | −113.30 (11) | N1—C6—C19—C24 | 69.65 (12) |
C19—C6—C7—C8 | 124.17 (11) | C7—C6—C19—C24 | −49.72 (12) |
N1—C6—C7—C12 | −171.98 (9) | C13—C6—C19—C24 | −173.54 (9) |
C13—C6—C7—C12 | 69.51 (12) | C24—C19—C20—C21 | −1.72 (16) |
C19—C6—C7—C12 | −53.02 (12) | C6—C19—C20—C21 | −178.31 (10) |
C12—C7—C8—C9 | −1.45 (16) | C19—C20—C21—C22 | −0.68 (17) |
C6—C7—C8—C9 | −178.65 (10) | C20—C21—C22—C23 | 2.07 (18) |
C7—C8—C9—C10 | 0.38 (18) | C21—C22—C23—C24 | −1.02 (18) |
C8—C9—C10—C11 | 0.54 (17) | C22—C23—C24—C19 | −1.43 (18) |
C9—C10—C11—C12 | −0.37 (17) | C20—C19—C24—C23 | 2.78 (16) |
C10—C11—C12—C7 | −0.73 (17) | C6—C19—C24—C23 | 179.48 (10) |
Experimental details
Crystal data | |
Chemical formula | C24H22N2 |
Mr | 338.44 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 9.5264 (5), 8.6992 (4), 21.9714 (11) |
β (°) | 93.961 (1) |
V (Å3) | 1816.47 (16) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.07 |
Crystal size (mm) | 0.41 × 0.27 × 0.19 |
Data collection | |
Diffractometer | Bruker SMART 1000 CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2003) |
Tmin, Tmax | 0.971, 0.986 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14683, 3708, 3141 |
Rint | 0.039 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.095, 1.03 |
No. of reflections | 3708 |
No. of parameters | 237 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.29, −0.24 |
Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SAINT, SHELXTL (Bruker, 2003), SHELXTL, publCIF (Westrip, 2007) and modiCIFer (Guzei, 1995).
N1—C6—C7 | 110.07 (8) | N1—C6—C19 | 109.44 (8) |
N1—C6—C13 | 106.17 (8) | C7—C6—C19 | 107.23 (8) |
C7—C6—C13 | 113.01 (9) | C13—C6—C19 | 110.91 (8) |
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Water-soluble substituted pyrazoles constitute an important family of heterocyclic compounds that have found use in drug development and in catalysis (Elguero et al. 1996, Brown et al., 1993). In attempts to prepare water soluble palladium and platinum complexes with potential anti-cancer properties, we set out to prepare 4-alkylaminopyrazoles using a route reported by Esquius et al. (2000). The route involves protection of the position 1 of the 3,5-dimethylpyrazole, followed by aminoalkylation of the position 4. This offers a more efficient route to making water soluble 4-alkylaminopyrazoles (Esquius et al. 2000). When we used this route with a trityl group to protect the position 1 of the pyrazole, we could not alkylate position 4 of the pyrazole efficiently and isolated compound (I) instead.
Within (I) the bond distances and angles are typical. Carbon atom C6 exhibits a distorted tetrahedral geometry with the average X—C6—C angles being 109 (2)°. The six X—C6—C angles range from 106.17 (8)° to 113.01 (9)°. The torsion angles N—C—C(ipso)-C(ortho) involving the phenyl rings are very different at 5.20 (14), 46.68 (12), and 69.65 (12)°. A quality-restrictive search (R-factor <0.05, not disordered, no errors, and no powder structures) of the Cambridge Structural Database (Version 5.28, January 2007 update, Allen, 2002) for organic compounds with N-CPh3 fragments returned 34 hits and revealed that the N—C—C(ipso)-C(ortho) angles vary to a large extent but are usually different at 13 (9), 36 (10), and 73 (13)°. The trend is in agreement with that of the corresponding parameters in (I).