Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107020689/dn3043sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107020689/dn3043Isup2.hkl |
CCDC reference: 652512
For related literature, see: Azarifar & Shaebanzadeh (2002); Bilgin et al. (1993); Cetin et al. (2003); Fahrni et al. (2003); Foster & Weinhold (1980); Frisch (1998); Glendening et al. (1993); Koóš et al. (1984, 1990); Korgaokar et al. (1996); Nauduri & Reddy (1998); Rurack et al. (2000); Udupi, Kushnoor & Bhat (1998); Udupi, Rao & Bhat (1998).
For the preparation of compound (I) (see scheme), 1-(4-bromophenyl)-3-(4-dimethylaminophenyl)prop-2-en-1-one (Koóš et al., 1984) and phenylhydrazine in glacial acetic acid were heated to reflux according to the previously described procedure of Koóš et al. (1990). Compound (I) (m.p. 459–460 K) crystallized from the solution during its cooling. 1H NMR (DMSO-d6, δ, p.p.m.): 6.62–7.68 (m, 13H, aromatic), 5.36 (dd, 1H, J = 6.2 and 12.2 Hz, 5-H), 3.81 (dd, 1H, J = 12.2 and 17.4 Hz, 4-Hcis), 3.02 (dd, 1H, J = 6.2 and 17.4 Hz, 4-Htrans), 2.81 (s, 6H, Me2N); 13C NMR (DMSO-d6, δ, p.p.m.): 149.8, 144.1, 131.8, 131.6, 129.6, 128.9, 127.5, 126.4, 121.6, 118.7, 113.2, 112.8 (aromatic), 146.1 (C-3), 63.1 (C-5), 42.8 (C-4), 39.7 (Me2N). Yellow single crystals of adequate quality for diffraction analysis were obtained by slow crystallization from ethanol.
H atoms were constrained to the ideal geometry using an appropriate riding model (C—H = 0.95–0.99 Å) and were refined isotropically. For the methyl groups, the C—H distances (0.98 Å) and N—C—H angles (109.5°) were kept fixed, while the torsion angles were allowed to refine with the starting position based on the threefold averaged circular Fourier synthesis.
NBO (natural bond orbital) calculations were carried out by means of the NBO program (Glendening et al., 1993) included in the GAUSSIAN98 package (Frisch et al., 1998), after full optimization of the geometric parameters of the isolated molecule at the B3LYP/6–31 G+ level of theory.
Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT and SADABS (Sheldrick, 2003); program(s) used to solve structure: SHELXTL (Bruker, 2003); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXTL.
C23H22BrN3 | F(000) = 3456 |
Mr = 420.35 | Dx = 1.429 Mg m−3 |
Orthorhombic, Fdd2 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: F 2 -2d | Cell parameters from 8192 reflections |
a = 32.3762 (4) Å | θ = 2.3–33.1° |
b = 43.4056 (2) Å | µ = 2.12 mm−1 |
c = 5.5618 (1) Å | T = 183 K |
V = 7816.04 (17) Å3 | Plate, yellow |
Z = 16 | 0.78 × 0.21 × 0.08 mm |
Siemens SMART CCD area-detector diffractometer | 6946 independent reflections |
Radiation source: fine-focus sealed tube | 5926 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
Detector resolution: 120 pixels mm-1 | θmax = 33.1°, θmin = 2.3° |
ω scans | h = −48→48 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −64→65 |
Tmin = 0.289, Tmax = 0.849 | l = −8→8 |
34545 measured reflections |
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)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.113 | w = 1/[σ2(Fo2) + (0.0626P)2 + 16.533P] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max = 0.001 |
6946 reflections | Δρmax = 0.41 e Å−3 |
268 parameters | Δρmin = −0.56 e Å−3 |
1 restraint | Absolute structure: Flack (1983), with 3062 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.003 (7) |
C23H22BrN3 | V = 7816.04 (17) Å3 |
Mr = 420.35 | Z = 16 |
Orthorhombic, Fdd2 | Mo Kα radiation |
a = 32.3762 (4) Å | µ = 2.12 mm−1 |
b = 43.4056 (2) Å | T = 183 K |
c = 5.5618 (1) Å | 0.78 × 0.21 × 0.08 mm |
Siemens SMART CCD area-detector diffractometer | 6946 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 5926 reflections with I > 2σ(I) |
Tmin = 0.289, Tmax = 0.849 | Rint = 0.034 |
34545 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.113 | w = 1/[σ2(Fo2) + (0.0626P)2 + 16.533P] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | Δρmax = 0.41 e Å−3 |
6946 reflections | Δρmin = −0.56 e Å−3 |
268 parameters | Absolute structure: Flack (1983), with 3062 Friedel pairs |
1 restraint | Absolute structure parameter: −0.003 (7) |
Experimental. Data were collected at 183 K using a Siemens SMART CCD diffractometer equipped with LT-2 A cooling device. A full sphere of reciprocal space was scanned by 0.3° steps in ω with a crystal-to-detector distance of 3.97 cm, 20 s per frame. Preliminary orientation matrix was obtained from the first 100 frames using SMART (Bruker, 2003). The collected frames were integrated using the preliminary orientation matrix, which was updated every 100 frames. Final cell parameters were obtained by refinement on the position of 8196 reflections with I>10σ(I) after integration of all the frames data using SAINT (Bruker, 2003). |
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 | ||
Br1 | 0.255810 (9) | 0.073372 (5) | 0.62951 (7) | 0.04393 (9) | |
N1 | 0.39126 (7) | −0.07600 (4) | 1.0749 (4) | 0.0307 (5) | |
N2 | 0.37467 (6) | −0.04680 (4) | 1.0627 (4) | 0.0254 (3) | |
N3 | 0.31998 (8) | −0.21392 (6) | 1.1861 (5) | 0.0466 (6) | |
C3 | 0.34988 (6) | −0.04541 (4) | 0.8798 (4) | 0.0241 (3) | |
C4 | 0.34736 (7) | −0.07504 (5) | 0.7382 (4) | 0.0277 (4) | |
H4A | 0.3551 | −0.0718 | 0.5679 | 0.036 (9)* | |
H4B | 0.3193 | −0.0840 | 0.7455 | 0.030 (8)* | |
C5 | 0.37926 (6) | −0.09584 (5) | 0.8690 (5) | 0.0259 (4) | |
H5 | 0.4037 | −0.0992 | 0.7625 | 0.040 (9)* | |
C6 | 0.28953 (13) | −0.21477 (9) | 1.3753 (7) | 0.0641 (10) | |
H6A | 0.2999 | −0.2034 | 1.5152 | 0.10 (2)* | |
H6B | 0.2842 | −0.2362 | 1.4207 | 0.074 (14)* | |
H6C | 0.2639 | −0.2053 | 1.3184 | 0.12 (2)* | |
C7 | 0.31722 (10) | −0.23924 (6) | 1.0176 (8) | 0.0505 (8) | |
H7A | 0.2936 | −0.2360 | 0.9101 | 0.055 (11)* | |
H7B | 0.3135 | −0.2586 | 1.1059 | 0.088 (15)* | |
H7C | 0.3427 | −0.2403 | 0.9227 | 0.050 (10)* | |
C11 | 0.42510 (7) | −0.08137 (5) | 1.2238 (4) | 0.0266 (4) | |
C12 | 0.44641 (7) | −0.10933 (6) | 1.2108 (5) | 0.0328 (5) | |
H12 | 0.4388 | −0.1243 | 1.0944 | 0.034 (8)* | |
C13 | 0.47883 (8) | −0.11524 (6) | 1.3686 (6) | 0.0391 (5) | |
H13 | 0.4932 | −0.1343 | 1.3579 | 0.050 (10)* | |
C14 | 0.49063 (9) | −0.09397 (7) | 1.5408 (6) | 0.0441 (7) | |
H14 | 0.5126 | −0.0983 | 1.6488 | 0.043 (9)* | |
C15 | 0.46954 (9) | −0.06604 (7) | 1.5519 (6) | 0.0418 (6) | |
H15 | 0.4774 | −0.0512 | 1.6686 | 0.051 (10)* | |
C16 | 0.43723 (7) | −0.05945 (5) | 1.3963 (5) | 0.0320 (5) | |
H16 | 0.4233 | −0.0402 | 1.4062 | 0.032 (7)* | |
C31 | 0.32751 (6) | −0.01695 (5) | 0.8225 (4) | 0.0241 (4) | |
C32 | 0.32899 (7) | 0.00873 (5) | 0.9758 (4) | 0.0278 (4) | |
H32 | 0.3446 | 0.0076 | 1.1203 | 0.035 (8)* | |
C33 | 0.30808 (7) | 0.03563 (5) | 0.9196 (4) | 0.0301 (5) | |
H33 | 0.3092 | 0.0530 | 1.0237 | 0.044 (9)* | |
C34 | 0.28540 (7) | 0.03670 (5) | 0.7074 (4) | 0.0274 (4) | |
C35 | 0.28335 (7) | 0.01208 (5) | 0.5512 (4) | 0.0287 (4) | |
H35 | 0.2678 | 0.0135 | 0.4068 | 0.046 (9)* | |
C36 | 0.30456 (7) | −0.01492 (5) | 0.6092 (4) | 0.0273 (4) | |
H36 | 0.3034 | −0.0321 | 0.5033 | 0.038 (9)* | |
C51 | 0.36262 (6) | −0.12667 (5) | 0.9509 (4) | 0.0247 (4) | |
C52 | 0.37140 (7) | −0.15325 (5) | 0.8205 (4) | 0.0294 (4) | |
H52 | 0.3877 | −0.1518 | 0.6788 | 0.049 (10)* | |
C53 | 0.35678 (8) | −0.18188 (5) | 0.8943 (6) | 0.0352 (5) | |
H53 | 0.3631 | −0.1996 | 0.8011 | 0.044 (9)* | |
C54 | 0.33300 (7) | −0.18512 (5) | 1.1028 (5) | 0.0314 (5) | |
C55 | 0.32390 (8) | −0.15801 (6) | 1.2318 (5) | 0.0341 (5) | |
H55 | 0.3075 | −0.1592 | 1.3729 | 0.050 (10)* | |
C56 | 0.33857 (7) | −0.12955 (5) | 1.1560 (5) | 0.0307 (4) | |
H56 | 0.3320 | −0.1117 | 1.2466 | 0.042 (9)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.05022 (15) | 0.02539 (10) | 0.05618 (17) | 0.00705 (10) | −0.01657 (14) | 0.00363 (12) |
N1 | 0.0330 (9) | 0.0216 (8) | 0.0376 (12) | 0.0034 (7) | −0.0149 (8) | −0.0049 (7) |
N2 | 0.0277 (8) | 0.0213 (7) | 0.0273 (9) | 0.0011 (6) | −0.0041 (7) | 0.0007 (6) |
N3 | 0.0434 (12) | 0.0365 (11) | 0.0601 (17) | −0.0112 (9) | −0.0144 (11) | 0.0136 (11) |
C3 | 0.0240 (8) | 0.0240 (8) | 0.0243 (9) | 0.0005 (6) | −0.0011 (8) | −0.0005 (8) |
C4 | 0.0296 (10) | 0.0262 (10) | 0.0274 (10) | 0.0034 (8) | −0.0073 (8) | −0.0032 (8) |
C5 | 0.0253 (9) | 0.0250 (8) | 0.0274 (9) | 0.0012 (7) | −0.0064 (8) | −0.0026 (8) |
C6 | 0.078 (2) | 0.068 (2) | 0.0466 (17) | −0.0377 (19) | −0.0115 (19) | 0.0176 (18) |
C7 | 0.0435 (15) | 0.0258 (11) | 0.082 (2) | −0.0029 (10) | −0.0160 (15) | 0.0085 (13) |
C11 | 0.0252 (9) | 0.0266 (9) | 0.0281 (10) | −0.0027 (7) | −0.0055 (8) | 0.0027 (8) |
C12 | 0.0298 (10) | 0.0297 (10) | 0.0389 (12) | 0.0024 (8) | −0.0111 (9) | −0.0011 (9) |
C13 | 0.0327 (11) | 0.0362 (11) | 0.0486 (14) | 0.0038 (9) | −0.0154 (12) | 0.0026 (12) |
C14 | 0.0380 (13) | 0.0452 (15) | 0.0491 (16) | −0.0018 (11) | −0.0217 (12) | 0.0052 (12) |
C15 | 0.0427 (14) | 0.0414 (13) | 0.0415 (14) | −0.0080 (11) | −0.0175 (11) | −0.0018 (11) |
C16 | 0.0336 (10) | 0.0272 (9) | 0.0354 (12) | −0.0041 (8) | −0.0087 (10) | −0.0009 (9) |
C31 | 0.0225 (8) | 0.0262 (9) | 0.0236 (10) | 0.0016 (7) | −0.0003 (7) | 0.0009 (7) |
C32 | 0.0274 (9) | 0.0295 (10) | 0.0265 (10) | 0.0006 (8) | −0.0045 (8) | −0.0005 (9) |
C33 | 0.0324 (10) | 0.0250 (9) | 0.0327 (13) | −0.0004 (8) | −0.0034 (9) | −0.0021 (8) |
C34 | 0.0260 (9) | 0.0238 (9) | 0.0324 (11) | 0.0006 (7) | −0.0009 (8) | 0.0052 (8) |
C35 | 0.0311 (10) | 0.0298 (10) | 0.0253 (10) | 0.0012 (8) | −0.0037 (8) | 0.0028 (8) |
C36 | 0.0299 (9) | 0.0268 (9) | 0.0250 (10) | 0.0026 (7) | −0.0028 (9) | −0.0005 (8) |
C51 | 0.0233 (9) | 0.0249 (9) | 0.0258 (10) | 0.0027 (7) | −0.0066 (7) | −0.0036 (7) |
C52 | 0.0292 (10) | 0.0288 (10) | 0.0301 (11) | 0.0028 (8) | −0.0009 (8) | −0.0054 (8) |
C53 | 0.0330 (10) | 0.0254 (10) | 0.0474 (14) | 0.0038 (8) | −0.0037 (12) | −0.0075 (11) |
C54 | 0.0272 (10) | 0.0293 (9) | 0.0377 (13) | −0.0014 (8) | −0.0104 (9) | 0.0036 (9) |
C55 | 0.0311 (11) | 0.0414 (13) | 0.0299 (11) | −0.0047 (9) | −0.0045 (9) | 0.0007 (10) |
C56 | 0.0314 (10) | 0.0312 (10) | 0.0293 (11) | −0.0004 (8) | −0.0026 (9) | −0.0077 (9) |
Br1—C34 | 1.908 (2) | C13—H13 | 0.9500 |
N1—N2 | 1.378 (3) | C14—C15 | 1.393 (4) |
N1—C11 | 1.393 (3) | C14—H14 | 0.9500 |
N1—C5 | 1.485 (3) | C15—C16 | 1.388 (4) |
N2—C3 | 1.297 (3) | C15—H15 | 0.9500 |
N3—C54 | 1.399 (3) | C16—H16 | 0.9500 |
N3—C6 | 1.442 (5) | C31—C36 | 1.402 (3) |
N3—C7 | 1.447 (4) | C31—C32 | 1.404 (3) |
C3—C31 | 1.467 (3) | C32—C33 | 1.386 (3) |
C3—C4 | 1.511 (3) | C32—H32 | 0.9500 |
C4—C5 | 1.553 (3) | C33—C34 | 1.391 (3) |
C4—H4A | 0.9900 | C33—H33 | 0.9500 |
C4—H4B | 0.9900 | C34—C35 | 1.379 (3) |
C5—C51 | 1.513 (3) | C35—C36 | 1.396 (3) |
C5—H5 | 1.0000 | C35—H35 | 0.9500 |
C6—H6A | 0.9800 | C36—H36 | 0.9500 |
C6—H6B | 0.9800 | C51—C52 | 1.392 (3) |
C6—H6C | 0.9800 | C51—C56 | 1.387 (3) |
C7—H7A | 0.9800 | C52—C53 | 1.391 (3) |
C7—H7B | 0.9800 | C52—H52 | 0.9500 |
C7—H7C | 0.9800 | C53—C54 | 1.399 (4) |
C11—C12 | 1.398 (3) | C53—H53 | 0.9500 |
C11—C16 | 1.407 (3) | C54—C55 | 1.409 (4) |
C12—C13 | 1.392 (3) | C55—C56 | 1.389 (4) |
C12—H12 | 0.9500 | C55—H55 | 0.9500 |
C13—C14 | 1.384 (4) | C56—H56 | 0.9500 |
N2—N1—C11 | 119.32 (18) | C15—C14—H14 | 120.8 |
N2—N1—C5 | 113.16 (17) | C13—C14—H14 | 120.8 |
C11—N1—C5 | 124.57 (19) | C16—C15—C14 | 121.4 (3) |
C3—N2—N1 | 108.82 (18) | C16—C15—H15 | 119.3 |
C54—N3—C6 | 118.1 (3) | C14—C15—H15 | 119.3 |
C54—N3—C7 | 118.9 (3) | C15—C16—C11 | 119.8 (2) |
C6—N3—C7 | 114.3 (3) | C15—C16—H16 | 120.1 |
N2—C3—C31 | 121.02 (19) | C11—C16—H16 | 120.1 |
N2—C3—C4 | 113.74 (18) | C36—C31—C32 | 118.8 (2) |
C31—C3—C4 | 125.2 (2) | C36—C31—C3 | 119.9 (2) |
C3—C4—C5 | 102.41 (18) | C32—C31—C3 | 121.3 (2) |
C3—C4—H4A | 111.3 | C33—C32—C31 | 121.0 (2) |
C5—C4—H4A | 111.3 | C33—C32—H32 | 119.5 |
C3—C4—H4B | 111.3 | C31—C32—H32 | 119.5 |
C5—C4—H4B | 111.3 | C32—C33—C34 | 118.5 (2) |
H4A—C4—H4B | 109.2 | C32—C33—H33 | 120.7 |
N1—C5—C51 | 112.0 (2) | C34—C33—H33 | 120.7 |
N1—C5—C4 | 101.44 (16) | C35—C34—C33 | 122.3 (2) |
C51—C5—C4 | 114.75 (17) | C35—C34—Br1 | 118.65 (18) |
N1—C5—H5 | 109.5 | C33—C34—Br1 | 119.06 (18) |
C51—C5—H5 | 109.5 | C34—C35—C36 | 118.8 (2) |
C4—C5—H5 | 109.5 | C34—C35—H35 | 120.6 |
N3—C6—H6A | 109.5 | C36—C35—H35 | 120.6 |
N3—C6—H6B | 109.5 | C35—C36—C31 | 120.6 (2) |
H6A—C6—H6B | 109.5 | C35—C36—H36 | 119.7 |
N3—C6—H6C | 109.5 | C31—C36—H36 | 119.7 |
H6A—C6—H6C | 109.5 | C52—C51—C56 | 117.9 (2) |
H6B—C6—H6C | 109.5 | C52—C51—C5 | 120.2 (2) |
N3—C7—H7A | 109.5 | C56—C51—C5 | 121.8 (2) |
N3—C7—H7B | 109.5 | C53—C52—C51 | 121.1 (2) |
H7A—C7—H7B | 109.5 | C53—C52—H52 | 119.4 |
N3—C7—H7C | 109.5 | C51—C52—H52 | 119.4 |
H7A—C7—H7C | 109.5 | C52—C53—C54 | 121.4 (2) |
H7B—C7—H7C | 109.5 | C52—C53—H53 | 119.3 |
N1—C11—C12 | 120.2 (2) | C54—C53—H53 | 119.3 |
N1—C11—C16 | 120.8 (2) | N3—C54—C53 | 122.0 (2) |
C12—C11—C16 | 119.0 (2) | N3—C54—C55 | 121.0 (3) |
C13—C12—C11 | 120.0 (2) | C53—C54—C55 | 116.9 (2) |
C13—C12—H12 | 120.0 | C56—C55—C54 | 121.1 (3) |
C11—C12—H12 | 120.0 | C56—C55—H55 | 119.4 |
C12—C13—C14 | 121.4 (2) | C54—C55—H55 | 119.4 |
C12—C13—H13 | 119.3 | C51—C56—C55 | 121.5 (2) |
C14—C13—H13 | 119.3 | C51—C56—H56 | 119.3 |
C15—C14—C13 | 118.4 (2) | C55—C56—H56 | 119.3 |
C11—N1—N2—C3 | 166.5 (2) | C36—C31—C32—C33 | 0.3 (3) |
C5—N1—N2—C3 | 5.1 (3) | C3—C31—C32—C33 | 179.4 (2) |
N1—N2—C3—C31 | 179.8 (2) | C31—C32—C33—C34 | 0.1 (4) |
N1—N2—C3—C4 | −0.9 (3) | C32—C33—C34—C35 | −0.5 (4) |
N2—C3—C4—C5 | −3.2 (3) | C32—C33—C34—Br1 | 179.14 (18) |
C31—C3—C4—C5 | 176.1 (2) | C33—C34—C35—C36 | 0.4 (4) |
N2—N1—C5—C51 | −129.50 (19) | Br1—C34—C35—C36 | −179.21 (17) |
C11—N1—C5—C51 | 70.2 (3) | C34—C35—C36—C31 | 0.0 (3) |
N2—N1—C5—C4 | −6.7 (3) | C32—C31—C36—C35 | −0.4 (3) |
C11—N1—C5—C4 | −167.0 (2) | C3—C31—C36—C35 | −179.5 (2) |
C3—C4—C5—N1 | 5.4 (2) | N1—C5—C51—C52 | −143.1 (2) |
C3—C4—C5—C51 | 126.3 (2) | C4—C5—C51—C52 | 102.0 (2) |
N2—N1—C11—C12 | −169.9 (2) | N1—C5—C51—C56 | 36.6 (3) |
C5—N1—C11—C12 | −10.7 (4) | C4—C5—C51—C56 | −78.3 (3) |
N2—N1—C11—C16 | 13.0 (4) | C56—C51—C52—C53 | −0.5 (3) |
C5—N1—C11—C16 | 172.2 (2) | C5—C51—C52—C53 | 179.3 (2) |
N1—C11—C12—C13 | −176.6 (3) | C51—C52—C53—C54 | −0.5 (4) |
C16—C11—C12—C13 | 0.6 (4) | C6—N3—C54—C53 | −168.8 (3) |
C11—C12—C13—C14 | 0.2 (5) | C7—N3—C54—C53 | −23.1 (4) |
C12—C13—C14—C15 | −0.7 (5) | C6—N3—C54—C55 | 13.6 (4) |
C13—C14—C15—C16 | 0.4 (5) | C7—N3—C54—C55 | 159.3 (3) |
C14—C15—C16—C11 | 0.4 (5) | C52—C53—C54—N3 | −176.5 (2) |
N1—C11—C16—C15 | 176.3 (3) | C52—C53—C54—C55 | 1.2 (4) |
C12—C11—C16—C15 | −0.8 (4) | N3—C54—C55—C56 | 176.7 (2) |
N2—C3—C31—C36 | 172.8 (2) | C53—C54—C55—C56 | −1.0 (4) |
C4—C3—C31—C36 | −6.4 (3) | C52—C51—C56—C55 | 0.7 (3) |
N2—C3—C31—C32 | −6.2 (3) | C5—C51—C56—C55 | −179.1 (2) |
C4—C3—C31—C32 | 174.5 (2) | C54—C55—C56—C51 | 0.1 (4) |
Experimental details
Crystal data | |
Chemical formula | C23H22BrN3 |
Mr | 420.35 |
Crystal system, space group | Orthorhombic, Fdd2 |
Temperature (K) | 183 |
a, b, c (Å) | 32.3762 (4), 43.4056 (2), 5.5618 (1) |
V (Å3) | 7816.04 (17) |
Z | 16 |
Radiation type | Mo Kα |
µ (mm−1) | 2.12 |
Crystal size (mm) | 0.78 × 0.21 × 0.08 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.289, 0.849 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 34545, 6946, 5926 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.769 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.113, 1.00 |
No. of reflections | 6946 |
No. of parameters | 268 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0626P)2 + 16.533P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.41, −0.56 |
Absolute structure | Flack (1983), with 3062 Friedel pairs |
Absolute structure parameter | −0.003 (7) |
Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SAINT and SADABS (Sheldrick, 2003), SHELXTL (Bruker, 2003), SHELXTL, DIAMOND (Brandenburg, 2006).
Br1—C34 | 1.908 (2) | N1—C5 | 1.485 (3) |
N1—N2 | 1.378 (3) | N2—C3 | 1.297 (3) |
N1—C11 | 1.393 (3) | N3—C54 | 1.399 (3) |
N2—N1—C5—C51 | −129.50 (19) | N2—C3—C31—C32 | −6.2 (3) |
N2—N1—C11—C16 | 13.0 (4) | N1—C5—C51—C56 | 36.6 (3) |
Planes defining the dihedral angle | Angle |
1,2 | 8.79 (13) |
1,3 | 5.75 (12) |
1,4 | 74.28 (12) |
2,3 | 13.83 (12) |
2,4 | 82.73 (12) |
3,4 | 68.90 (11) |
D—H···CgX | H···CgX | D—H···CgX |
C5—H5···Cg2i | 2.80 | 157 |
C14—H14···Cg4ii | 2.85 | 150 |
C35—H35···Cg3iii | 2.73 | 133 |
Symmetry codes: (i) x, y, z-1; (ii) x+1/4, -y-1/4, z-1/2; (iii) x-1/2, -y, z-1/2. |
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Pyrazolines have been reported to show a broad spectrum of biological activities including antibacterial (Nauduri & Reddy, 1998; Azarifar & Shaebanzadeh, 2002), antifungal (Korgaokar et al., 1996), antiprotozoal (Cetin et al., 2003), anti-inflammatory, analgesic (Udupi, Kushnoor et al., 1998; Udupi, Rao et al., 1998) and antidepressant (Bilgin et al., 1993) activities. Moreover, pyrazolines are useful synthons in organic synthesis. In this context, we have prepared several 1,3,5-triaryl-2-pyrazolines using the most straightforward method for the synthesis of 1,3,5-triphenyl-2-pyrazolines involving the one-pot condensation of chalcones with phenylhydrazine in glacial acetic acid. Here, we report the absolute structure determination of one of them, the title compound, (I), with a 4-bromophenyl moiety at position 3 of the pyrazoline ring (Fig. 1).
The values of relevant bond lengths (Table 1) in the C11/N1/N2/C3/C31 structural fragment indicate strong conjugation of the pyrazoline chromophore with the phenyl moieties at the N1 and C3 positions. These observations are in good agreement with those reported for 1,3-diphenyl-5-(4-dimethyaminophenyl)-2-pyrazoline (Rurack et al., 2000) with an unsubstituted phenyl moiety at C3 atom. Comparing this compound and (I), the Ar/C3/N2/N1 fragments are nearly planar in both cases, but in the case of compound (I), the phenyl ring at N1 is directed by ca 8° more to coplanarity with the Ar/C3/N2/N1 fragment. Additionally, although in both cases a synclinal orientation of the Ar/C5 moiety to the pyrazoline ring is observed, the values of the relevant dihedral angles [36.6° for N1—C5—C51—C56 in (I) versus 76.5° for the analogous dihedral angle in 1,3-diphenyl-5-(4-dimethyaminophenyl)-2-pyrazoline (Rurack et al., 2000)] indicate a significant shift in the synclinal→ synperiplanar direction for (I), in contrast with a synclinal→ anticlinal direction for 1,3-diphenyl-5-(4-dimethyaminophenyl)-2-pyrazoline. A similar orientation of the Ar/C5 moiety as demonstrated by the value of the relevant dihedral angle (-34.6°) observed for the (S) isomer of 1-(4-cyanophenyl)-3-phenyl-5-(4-diethyaminophenyl)-2-pyrazoline (Fahrni et al., 2003), while the values of the relevant dihedral angles for the other 5-(4-diethylaminophenyl)-2-pyrazolines of this series vary in the range from -47 to -63°.
The angles between the rings 1–4, defined in Fig. 1, are summarized in Table 2. In the absence of classical hydrogen-bond donors, the structure is stabilized by weak C—H···π interactions, two of them in an edge-to-face manner (Table 3 and Fig. 2).
Natural bond orbital (NBO) analysis (Foster & Weinhold, 1980) of the electronic structure of (I) shows that the bond orders (Wiberg indices) are very close to the expected values. The exceptions are the Br1—C34 (1.042), N2═C3 (1.679), N1—N2 (1.135), N1—C11 (1.072) and N3—C54 (1.123) bonds, where their bond orders are between a single and double bond and indicate electronic delocalization. A detailed analysis of the NBO results reveals that the electrons of the lone pair on atom Br1 contribute slightly to the Br1—C34 bond only, the electrons of the N2 lone pair are mainly delocalized on a double N2═C3 bond, and the electrons of the N1 lone pair contribute to the electronic density of the N1—C11 bond, lending it a partially double-bond character. The N1—N2 bond also has such double-bond character, as a consequence of the partial contributions of the two lone pairs on atoms N1 and N2 to this bond. The lone pair on atom N3 makes a dominant contribution to the N3—C54 bond. This electronic redistribution leads to a shortening of the N1—C11, N1—N2, N2═C3 and N3—C54 bonds.