Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106054369/gd3067sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106054369/gd3067Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106054369/gd3067IIsup3.hkl |
CCDC references: 638326; 638327
For the syntheses of azo-ester compounds containing an acryloyloxy group, first the derivatives of 4-hydroxyazobenzene dyes are prepared by the usual azo-coupling reaction of 2,6-dimethylphenol with substituted aryldiazonium salts, and then their acryloyloxy derivatives are synthesized in a Schottene–Bauman-type reaction similar to the following procedure and by the method described previously (Kocaokutgen et al., 2005). To a stirred tetrahydrofuran (20 ml) solution of substituted 4-hydroxyazobenzene dye (2.48 mmol) and sodium metal (2.48 mmol), acryloyl chloride (2.48 mmol) were directly added dropwise in an atmosphere of dry nitrogen. After 2 h of stirring, the mixture was filtered and the desired product was precipitated out by adding water. The solid was filtered off, washed several times with water and then dried. The products were crystallized from an ethanol/water mixture to give related compounds. The products were crystallized from dimethyl sulfoxide to produce crystals of suitable quality for X-ray difraction analysis.
Crystals of (II) gave a low mean data intensity, so the proportion of the data labelled `observed' is rather low (49%). In both compounds, all H atoms attached to C atoms were refined using a riding model [C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for aromatic H atoms, and C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C) for methyl H atoms], except for atom H10 in compound (II), which was located from a difference map after the other H atoms were refined using a riding model.
For both compounds, data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
C17H15BrN2O2 | Z = 2 |
Mr = 359.21 | F(000) = 364 |
Triclinic, P1 | Dx = 1.443 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.2168 (10) Å | Cell parameters from 1578 reflections |
b = 9.7823 (10) Å | θ = 1.9–25.1° |
c = 14.0973 (7) Å | µ = 2.49 mm−1 |
α = 98.977 (3)° | T = 297 K |
β = 101.160 (2)° | Prism, orange |
γ = 93.697 (7)° | 0.4 × 0.3 × 0.2 mm |
V = 826.83 (16) Å3 |
STOE IPDS-2 diffractometer | 3931 independent reflections |
Radiation source: fine-focus sealed tube | 2667 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.056 |
Detector resolution: 6.67 pixels mm-1 | θmax = 27.9°, θmin = 2.1° |
ω scans | h = −8→7 |
Absorption correction: integration X-RED32 (Stoe & Cie, 2002) | k = −12→12 |
Tmin = 0.975, Tmax = 0.987 | l = −18→18 |
14480 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.109 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0493P)2 + 0.2083P] where P = (Fo2 + 2Fc2)/3 |
3931 reflections | (Δ/σ)max < 0.001 |
201 parameters | Δρmax = 0.36 e Å−3 |
0 restraints | Δρmin = −0.41 e Å−3 |
C17H15BrN2O2 | γ = 93.697 (7)° |
Mr = 359.21 | V = 826.83 (16) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.2168 (10) Å | Mo Kα radiation |
b = 9.7823 (10) Å | µ = 2.49 mm−1 |
c = 14.0973 (7) Å | T = 297 K |
α = 98.977 (3)° | 0.4 × 0.3 × 0.2 mm |
β = 101.160 (2)° |
STOE IPDS-2 diffractometer | 3931 independent reflections |
Absorption correction: integration X-RED32 (Stoe & Cie, 2002) | 2667 reflections with I > 2σ(I) |
Tmin = 0.975, Tmax = 0.987 | Rint = 0.056 |
14480 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.109 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.36 e Å−3 |
3931 reflections | Δρmin = −0.41 e Å−3 |
201 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 | ||
C1 | 0.4818 (4) | 0.0587 (3) | 0.28362 (19) | 0.0541 (6) | |
C2 | 0.5385 (4) | 0.0053 (3) | 0.1958 (2) | 0.0588 (6) | |
H2 | 0.4523 | −0.0701 | 0.1545 | 0.071* | |
C3 | 0.7219 (4) | 0.0631 (3) | 0.1690 (2) | 0.0603 (6) | |
C4 | 0.8443 (4) | 0.1764 (3) | 0.2336 (2) | 0.0575 (6) | |
C5 | 0.7935 (4) | 0.2320 (3) | 0.3219 (2) | 0.0573 (6) | |
C6 | 0.6083 (4) | 0.1715 (3) | 0.3457 (2) | 0.0573 (6) | |
H6 | 0.5681 | 0.2070 | 0.4042 | 0.069* | |
C7 | 0.9386 (5) | 0.3508 (3) | 0.3909 (2) | 0.0773 (9) | |
H7A | 1.0861 | 0.3252 | 0.4067 | 0.116* | |
H7B | 0.8829 | 0.3713 | 0.4500 | 0.116* | |
H7C | 0.9390 | 0.4316 | 0.3600 | 0.116* | |
C8 | 0.7915 (5) | 0.0026 (4) | 0.0766 (2) | 0.0813 (9) | |
H8A | 0.6961 | −0.0797 | 0.0452 | 0.122* | |
H8B | 0.9404 | −0.0207 | 0.0922 | 0.122* | |
H8C | 0.7826 | 0.0694 | 0.0332 | 0.122* | |
C9 | 1.0380 (5) | 0.3145 (3) | 0.1479 (2) | 0.0660 (7) | |
C10 | 1.2619 (6) | 0.3389 (4) | 0.1273 (3) | 0.0808 (9) | |
H10 | 1.3780 | 0.3008 | 0.1628 | 0.097* | |
C11 | 1.3009 (7) | 0.4093 (5) | 0.0634 (3) | 0.1158 (15) | |
H11A | 1.1871 | 0.4483 | 0.0270 | 0.139* | |
H11B | 1.4434 | 0.4220 | 0.0529 | 0.139* | |
C12 | 0.0179 (4) | −0.1648 (3) | 0.29502 (19) | 0.0569 (6) | |
C13 | −0.0854 (5) | −0.2872 (3) | 0.2380 (2) | 0.0746 (8) | |
H13 | −0.0381 | −0.3231 | 0.1813 | 0.090* | |
C14 | −0.2589 (5) | −0.3571 (3) | 0.2642 (2) | 0.0775 (9) | |
H14 | −0.3278 | −0.4403 | 0.2260 | 0.093* | |
C15 | −0.3275 (4) | −0.3024 (3) | 0.3470 (2) | 0.0621 (7) | |
C16 | −0.2303 (5) | −0.1789 (3) | 0.4039 (2) | 0.0668 (7) | |
H16 | −0.2813 | −0.1421 | 0.4594 | 0.080* | |
C17 | −0.0556 (5) | −0.1099 (3) | 0.3776 (2) | 0.0634 (7) | |
H17 | 0.0122 | −0.0264 | 0.4157 | 0.076* | |
N2 | 0.1971 (4) | −0.1040 (2) | 0.26148 (17) | 0.0618 (6) | |
N1 | 0.3006 (3) | 0.0010 (2) | 0.31815 (16) | 0.0579 (5) | |
O1 | 1.0427 (3) | 0.2272 (2) | 0.21223 (15) | 0.0696 (5) | |
O2 | 0.8742 (4) | 0.3615 (3) | 0.11343 (19) | 0.0906 (7) | |
Br1 | −0.56024 (5) | −0.40066 (4) | 0.38566 (3) | 0.08644 (16) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0475 (12) | 0.0578 (14) | 0.0608 (15) | −0.0005 (11) | 0.0188 (11) | 0.0141 (11) |
C2 | 0.0515 (13) | 0.0651 (15) | 0.0595 (15) | −0.0030 (12) | 0.0159 (11) | 0.0077 (12) |
C3 | 0.0543 (13) | 0.0727 (16) | 0.0590 (15) | 0.0025 (12) | 0.0221 (11) | 0.0152 (12) |
C4 | 0.0442 (12) | 0.0660 (15) | 0.0699 (16) | 0.0031 (11) | 0.0209 (11) | 0.0238 (13) |
C5 | 0.0513 (13) | 0.0550 (14) | 0.0678 (16) | 0.0000 (11) | 0.0164 (12) | 0.0144 (12) |
C6 | 0.0548 (13) | 0.0584 (14) | 0.0618 (15) | −0.0006 (11) | 0.0224 (11) | 0.0093 (12) |
C7 | 0.0679 (17) | 0.0718 (18) | 0.088 (2) | −0.0163 (15) | 0.0176 (15) | 0.0073 (16) |
C8 | 0.0730 (18) | 0.105 (2) | 0.0699 (19) | −0.0011 (18) | 0.0320 (15) | 0.0087 (17) |
C9 | 0.0669 (17) | 0.0674 (17) | 0.0669 (17) | −0.0038 (14) | 0.0223 (14) | 0.0152 (14) |
C10 | 0.0801 (19) | 0.082 (2) | 0.083 (2) | −0.0169 (16) | 0.0316 (16) | 0.0155 (16) |
C11 | 0.089 (2) | 0.149 (4) | 0.120 (3) | −0.018 (3) | 0.038 (2) | 0.050 (3) |
C12 | 0.0503 (13) | 0.0567 (14) | 0.0640 (15) | −0.0047 (11) | 0.0153 (11) | 0.0115 (12) |
C13 | 0.0744 (18) | 0.0730 (18) | 0.0745 (19) | −0.0162 (15) | 0.0287 (15) | −0.0005 (15) |
C14 | 0.0707 (18) | 0.0680 (17) | 0.087 (2) | −0.0228 (15) | 0.0201 (16) | −0.0004 (15) |
C15 | 0.0536 (13) | 0.0636 (15) | 0.0726 (17) | −0.0057 (12) | 0.0186 (12) | 0.0201 (13) |
C16 | 0.0657 (16) | 0.0690 (17) | 0.0686 (17) | −0.0079 (14) | 0.0264 (13) | 0.0113 (14) |
C17 | 0.0619 (14) | 0.0630 (15) | 0.0642 (16) | −0.0115 (12) | 0.0211 (12) | 0.0050 (13) |
N2 | 0.0565 (12) | 0.0657 (13) | 0.0651 (13) | −0.0063 (10) | 0.0221 (10) | 0.0102 (10) |
N1 | 0.0525 (11) | 0.0589 (12) | 0.0635 (13) | −0.0078 (10) | 0.0201 (10) | 0.0093 (10) |
O1 | 0.0486 (9) | 0.0850 (13) | 0.0852 (13) | −0.0002 (9) | 0.0261 (9) | 0.0326 (11) |
O2 | 0.0823 (15) | 0.0970 (17) | 0.1064 (18) | 0.0075 (13) | 0.0275 (13) | 0.0499 (14) |
Br1 | 0.0725 (2) | 0.0857 (2) | 0.1061 (3) | −0.02050 (16) | 0.03389 (17) | 0.02399 (18) |
C1—C2 | 1.385 (4) | C9—O1 | 1.337 (4) |
C1—C6 | 1.387 (3) | C9—C10 | 1.488 (4) |
C1—N1 | 1.428 (3) | C10—C11 | 1.264 (5) |
C2—C3 | 1.383 (3) | C10—H10 | 0.9300 |
C2—H2 | 0.9300 | C11—H11A | 0.9300 |
C3—C4 | 1.394 (4) | C11—H11B | 0.9300 |
C3—C8 | 1.499 (4) | C12—C13 | 1.376 (4) |
C4—C5 | 1.381 (4) | C12—C17 | 1.377 (4) |
C4—O1 | 1.404 (3) | C12—N2 | 1.423 (3) |
C5—C6 | 1.383 (3) | C13—C14 | 1.381 (4) |
C5—C7 | 1.511 (4) | C13—H13 | 0.9300 |
C6—H6 | 0.9300 | C14—C15 | 1.363 (4) |
C7—H7A | 0.9600 | C14—H14 | 0.9300 |
C7—H7B | 0.9600 | C15—C16 | 1.372 (4) |
C7—H7C | 0.9600 | C15—Br1 | 1.899 (2) |
C8—H8A | 0.9600 | C16—C17 | 1.383 (3) |
C8—H8B | 0.9600 | C16—H16 | 0.9300 |
C8—H8C | 0.9600 | C17—H17 | 0.9300 |
C9—O2 | 1.193 (4) | N2—N1 | 1.252 (3) |
C2—C1—C6 | 120.2 (2) | O2—C9—O1 | 123.0 (3) |
C2—C1—N1 | 123.9 (2) | O2—C9—C10 | 127.5 (3) |
C6—C1—N1 | 115.8 (2) | O1—C9—C10 | 109.6 (3) |
C3—C2—C1 | 120.7 (2) | C11—C10—C9 | 122.8 (4) |
C3—C2—H2 | 119.7 | C11—C10—H10 | 118.6 |
C1—C2—H2 | 119.7 | C9—C10—H10 | 118.6 |
C2—C3—C4 | 117.1 (2) | C10—C11—H11A | 120.0 |
C2—C3—C8 | 121.3 (3) | C10—C11—H11B | 120.0 |
C4—C3—C8 | 121.5 (2) | H11A—C11—H11B | 120.0 |
C5—C4—C3 | 123.8 (2) | C13—C12—C17 | 119.7 (2) |
C5—C4—O1 | 118.1 (2) | C13—C12—N2 | 115.3 (2) |
C3—C4—O1 | 117.7 (2) | C17—C12—N2 | 125.0 (2) |
C4—C5—C6 | 117.2 (2) | C12—C13—C14 | 120.5 (3) |
C4—C5—C7 | 121.3 (2) | C12—C13—H13 | 119.7 |
C6—C5—C7 | 121.5 (3) | C14—C13—H13 | 119.7 |
C5—C6—C1 | 120.9 (2) | C15—C14—C13 | 119.0 (3) |
C5—C6—H6 | 119.5 | C15—C14—H14 | 120.5 |
C1—C6—H6 | 119.5 | C13—C14—H14 | 120.5 |
C5—C7—H7A | 109.5 | C14—C15—C16 | 121.6 (2) |
C5—C7—H7B | 109.5 | C14—C15—Br1 | 119.2 (2) |
H7A—C7—H7B | 109.5 | C16—C15—Br1 | 119.2 (2) |
C5—C7—H7C | 109.5 | C15—C16—C17 | 119.1 (3) |
H7A—C7—H7C | 109.5 | C15—C16—H16 | 120.4 |
H7B—C7—H7C | 109.5 | C17—C16—H16 | 120.4 |
C3—C8—H8A | 109.5 | C12—C17—C16 | 120.0 (2) |
C3—C8—H8B | 109.5 | C12—C17—H17 | 120.0 |
H8A—C8—H8B | 109.5 | C16—C17—H17 | 120.0 |
C3—C8—H8C | 109.5 | N1—N2—C12 | 114.5 (2) |
H8A—C8—H8C | 109.5 | N2—N1—C1 | 113.4 (2) |
H8B—C8—H8C | 109.5 | C9—O1—C4 | 119.4 (2) |
C6—C1—C2—C3 | 0.3 (4) | N2—C12—C13—C14 | 178.8 (3) |
N1—C1—C2—C3 | −177.3 (3) | C12—C13—C14—C15 | 0.6 (5) |
C1—C2—C3—C4 | −0.3 (4) | C13—C14—C15—C16 | 0.9 (5) |
C1—C2—C3—C8 | 177.1 (3) | C13—C14—C15—Br1 | −178.2 (3) |
C2—C3—C4—C5 | 0.6 (4) | C14—C15—C16—C17 | −1.3 (5) |
C8—C3—C4—C5 | −176.8 (3) | Br1—C15—C16—C17 | 177.7 (2) |
C2—C3—C4—O1 | 173.7 (2) | C13—C12—C17—C16 | 1.1 (5) |
C8—C3—C4—O1 | −3.6 (4) | N2—C12—C17—C16 | −179.3 (3) |
C3—C4—C5—C6 | −0.8 (4) | C15—C16—C17—C12 | 0.3 (5) |
O1—C4—C5—C6 | −173.9 (2) | C13—C12—N2—N1 | −174.5 (3) |
C3—C4—C5—C7 | 177.2 (3) | C17—C12—N2—N1 | 5.9 (4) |
O1—C4—C5—C7 | 4.0 (4) | C12—N2—N1—C1 | 179.0 (2) |
C4—C5—C6—C1 | 0.7 (4) | C2—C1—N1—N2 | 0.5 (4) |
C7—C5—C6—C1 | −177.2 (3) | C6—C1—N1—N2 | −177.2 (2) |
C2—C1—C6—C5 | −0.5 (4) | O2—C9—O1—C4 | 6.6 (4) |
N1—C1—C6—C5 | 177.2 (2) | C10—C9—O1—C4 | −172.5 (2) |
O2—C9—C10—C11 | −4.4 (6) | C5—C4—O1—C9 | −104.1 (3) |
O1—C9—C10—C11 | 174.6 (4) | C3—C4—O1—C9 | 82.3 (3) |
C17—C12—C13—C14 | −1.6 (5) |
C18H18N2O2 | Z = 2 |
Mr = 294.34 | F(000) = 312 |
Triclinic, P1 | Dx = 1.171 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.1589 (8) Å | Cell parameters from 1385 reflections |
b = 11.2603 (15) Å | θ = 2.8–27.6° |
c = 12.3461 (16) Å | µ = 0.08 mm−1 |
α = 82.780 (11)° | T = 297 K |
β = 80.070 (11)° | Prism, orange |
γ = 85.321 (11)° | 0.23 × 0.21 × 0.16 mm |
V = 835.13 (19) Å3 |
STOE IPDS-2 diffractometer | 3298 independent reflections |
Radiation source: fine-focus sealed tube | 1615 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.144 |
Detector resolution: 6.67 pixels mm-1 | θmax = 26.0°, θmin = 2.3° |
ω scans | h = −7→7 |
Absorption correction: integration X-RED32 (Stoe & Cie, 2002) | k = −13→13 |
Tmin = 0.980, Tmax = 0.985 | l = −15→15 |
10895 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)] = 0.084 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.216 | w = 1/[σ2(Fo2) + (0.0544P)2 + 0.315P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max < 0.001 |
3298 reflections | Δρmax = 0.13 e Å−3 |
206 parameters | Δρmin = −0.16 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.018 (5) |
C18H18N2O2 | γ = 85.321 (11)° |
Mr = 294.34 | V = 835.13 (19) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.1589 (8) Å | Mo Kα radiation |
b = 11.2603 (15) Å | µ = 0.08 mm−1 |
c = 12.3461 (16) Å | T = 297 K |
α = 82.780 (11)° | 0.23 × 0.21 × 0.16 mm |
β = 80.070 (11)° |
STOE IPDS-2 diffractometer | 3298 independent reflections |
Absorption correction: integration X-RED32 (Stoe & Cie, 2002) | 1615 reflections with I > 2σ(I) |
Tmin = 0.980, Tmax = 0.985 | Rint = 0.144 |
10895 measured reflections |
R[F2 > 2σ(F2)] = 0.084 | 0 restraints |
wR(F2) = 0.216 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.13 e Å−3 |
3298 reflections | Δρmin = −0.16 e Å−3 |
206 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 | ||
C1 | 0.3100 (5) | 0.2166 (4) | 0.2333 (3) | 0.0657 (10) | |
C2 | 0.3576 (6) | 0.3300 (4) | 0.2507 (3) | 0.0737 (11) | |
H2 | 0.2788 | 0.3970 | 0.2218 | 0.088* | |
C3 | 0.5225 (6) | 0.3445 (4) | 0.3112 (3) | 0.0717 (11) | |
C4 | 0.6375 (5) | 0.2413 (4) | 0.3502 (3) | 0.0658 (10) | |
C5 | 0.5950 (6) | 0.1274 (4) | 0.3356 (3) | 0.0689 (10) | |
C6 | 0.4257 (6) | 0.1172 (4) | 0.2757 (3) | 0.0732 (11) | |
H6 | 0.3905 | 0.0414 | 0.2644 | 0.088* | |
C7 | 0.5839 (9) | 0.4655 (4) | 0.3277 (4) | 0.1147 (19) | |
H7A | 0.5733 | 0.4711 | 0.4054 | 0.172* | |
H7B | 0.4852 | 0.5258 | 0.2969 | 0.172* | |
H7C | 0.7326 | 0.4777 | 0.2914 | 0.172* | |
C8 | 0.7305 (7) | 0.0185 (4) | 0.3765 (4) | 0.0989 (15) | |
H8A | 0.8760 | 0.0177 | 0.3334 | 0.148* | |
H8B | 0.6611 | −0.0527 | 0.3693 | 0.148* | |
H8C | 0.7407 | 0.0213 | 0.4528 | 0.148* | |
C12 | −0.1025 (6) | 0.2579 (4) | 0.0598 (3) | 0.0680 (10) | |
C13 | −0.2171 (7) | 0.3575 (4) | 0.0150 (3) | 0.0858 (13) | |
H13 | −0.1907 | 0.4342 | 0.0282 | 0.103* | |
C14 | −0.3732 (7) | 0.3408 (4) | −0.0505 (3) | 0.0826 (12) | |
H14 | −0.4506 | 0.4076 | −0.0806 | 0.099* | |
C15 | −0.4163 (6) | 0.2292 (4) | −0.0718 (3) | 0.0696 (11) | |
C16 | −0.2977 (6) | 0.1325 (4) | −0.0265 (3) | 0.0790 (12) | |
H16 | −0.3216 | 0.0559 | −0.0409 | 0.095* | |
C17 | −0.1439 (6) | 0.1458 (4) | 0.0399 (3) | 0.0769 (11) | |
H17 | −0.0686 | 0.0786 | 0.0709 | 0.092* | |
C18 | −0.5889 (6) | 0.2139 (5) | −0.1422 (3) | 0.0916 (14) | |
H18A | −0.5217 | 0.2191 | −0.2187 | 0.137* | |
H18B | −0.7047 | 0.2759 | −0.1323 | 0.137* | |
H18C | −0.6494 | 0.1370 | −0.1203 | 0.137* | |
C9 | 0.7864 (7) | 0.2610 (4) | 0.5110 (3) | 0.0741 (11) | |
C10 | 0.9968 (8) | 0.2759 (5) | 0.5478 (4) | 0.0929 (16) | |
C11 | 1.0081 (9) | 0.2886 (5) | 0.6475 (5) | 0.122 (2) | |
H11A | 0.8806 | 0.2886 | 0.7003 | 0.146* | |
H11B | 1.1440 | 0.2978 | 0.6677 | 0.146* | |
N1 | 0.1474 (5) | 0.1919 (3) | 0.1691 (3) | 0.0730 (9) | |
N2 | 0.0549 (5) | 0.2839 (3) | 0.1267 (3) | 0.0741 (9) | |
O1 | 0.8204 (4) | 0.2556 (3) | 0.4017 (2) | 0.0781 (8) | |
O2 | 0.6091 (5) | 0.2529 (3) | 0.5670 (2) | 0.1019 (11) | |
H10 | 1.122 (8) | 0.300 (5) | 0.511 (4) | 0.122* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0543 (19) | 0.091 (3) | 0.056 (2) | −0.011 (2) | −0.0129 (16) | −0.016 (2) |
C2 | 0.070 (2) | 0.093 (3) | 0.063 (2) | −0.002 (2) | −0.0251 (18) | −0.011 (2) |
C3 | 0.078 (2) | 0.078 (3) | 0.064 (2) | −0.008 (2) | −0.0182 (19) | −0.014 (2) |
C4 | 0.055 (2) | 0.091 (3) | 0.055 (2) | −0.014 (2) | −0.0162 (16) | −0.007 (2) |
C5 | 0.059 (2) | 0.084 (3) | 0.065 (2) | −0.005 (2) | −0.0148 (17) | −0.006 (2) |
C6 | 0.065 (2) | 0.083 (3) | 0.077 (3) | −0.009 (2) | −0.0183 (19) | −0.019 (2) |
C7 | 0.152 (5) | 0.088 (4) | 0.127 (4) | −0.015 (3) | −0.079 (4) | −0.014 (3) |
C8 | 0.084 (3) | 0.099 (4) | 0.119 (4) | 0.005 (3) | −0.037 (3) | −0.013 (3) |
C12 | 0.054 (2) | 0.094 (3) | 0.059 (2) | −0.003 (2) | −0.0126 (16) | −0.016 (2) |
C13 | 0.084 (3) | 0.100 (4) | 0.084 (3) | 0.007 (3) | −0.034 (2) | −0.026 (3) |
C14 | 0.079 (3) | 0.098 (4) | 0.074 (3) | 0.012 (2) | −0.028 (2) | −0.013 (2) |
C15 | 0.059 (2) | 0.098 (3) | 0.054 (2) | −0.010 (2) | −0.0120 (16) | −0.008 (2) |
C16 | 0.073 (2) | 0.094 (3) | 0.076 (3) | −0.018 (2) | −0.028 (2) | −0.005 (2) |
C17 | 0.069 (2) | 0.085 (3) | 0.080 (3) | −0.005 (2) | −0.025 (2) | −0.006 (2) |
C18 | 0.076 (3) | 0.131 (4) | 0.075 (3) | −0.019 (3) | −0.031 (2) | −0.007 (3) |
C9 | 0.077 (3) | 0.084 (3) | 0.067 (2) | −0.009 (2) | −0.024 (2) | −0.009 (2) |
C10 | 0.104 (3) | 0.102 (4) | 0.088 (3) | −0.017 (3) | −0.059 (3) | −0.003 (3) |
C11 | 0.103 (4) | 0.162 (6) | 0.117 (4) | −0.010 (4) | −0.052 (3) | −0.025 (4) |
N1 | 0.0617 (18) | 0.091 (3) | 0.0691 (19) | −0.0069 (17) | −0.0175 (15) | −0.0099 (18) |
N2 | 0.0606 (18) | 0.096 (3) | 0.070 (2) | −0.0003 (18) | −0.0196 (16) | −0.0179 (19) |
O1 | 0.0604 (15) | 0.115 (2) | 0.0652 (16) | −0.0124 (15) | −0.0219 (12) | −0.0137 (15) |
O2 | 0.083 (2) | 0.168 (3) | 0.0619 (17) | −0.023 (2) | −0.0165 (15) | −0.0231 (19) |
C1—C6 | 1.373 (5) | C13—C14 | 1.396 (5) |
C1—C2 | 1.384 (5) | C13—H13 | 0.9300 |
C1—N1 | 1.443 (4) | C14—C15 | 1.372 (6) |
C2—C3 | 1.391 (5) | C14—H14 | 0.9300 |
C2—H2 | 0.9300 | C15—C16 | 1.374 (5) |
C3—C4 | 1.388 (5) | C15—C18 | 1.517 (5) |
C3—C7 | 1.490 (6) | C16—C17 | 1.383 (5) |
C4—C5 | 1.369 (5) | C16—H16 | 0.9300 |
C4—O1 | 1.414 (4) | C17—H17 | 0.9300 |
C5—C6 | 1.398 (5) | C18—H18A | 0.9600 |
C5—C8 | 1.509 (5) | C18—H18B | 0.9600 |
C6—H6 | 0.9300 | C18—H18C | 0.9600 |
C7—H7A | 0.9600 | C9—O2 | 1.191 (5) |
C7—H7B | 0.9600 | C9—O1 | 1.338 (4) |
C7—H7C | 0.9600 | C9—C10 | 1.474 (5) |
C8—H8A | 0.9600 | C10—C11 | 1.270 (6) |
C8—H8B | 0.9600 | C10—H10 | 0.87 (5) |
C8—H8C | 0.9600 | C11—H11A | 0.9300 |
C12—C17 | 1.368 (6) | C11—H11B | 0.9300 |
C12—C13 | 1.383 (5) | N1—N2 | 1.241 (4) |
C12—N2 | 1.446 (4) | ||
C6—C1—C2 | 120.1 (3) | C12—C13—C14 | 118.6 (4) |
C6—C1—N1 | 115.0 (4) | C12—C13—H13 | 120.7 |
C2—C1—N1 | 124.9 (4) | C14—C13—H13 | 120.7 |
C1—C2—C3 | 120.5 (4) | C15—C14—C13 | 122.3 (4) |
C1—C2—H2 | 119.8 | C15—C14—H14 | 118.9 |
C3—C2—H2 | 119.8 | C13—C14—H14 | 118.9 |
C4—C3—C2 | 117.1 (4) | C14—C15—C16 | 117.3 (3) |
C4—C3—C7 | 121.0 (3) | C14—C15—C18 | 121.0 (4) |
C2—C3—C7 | 121.8 (4) | C16—C15—C18 | 121.7 (4) |
C5—C4—C3 | 124.4 (3) | C15—C16—C17 | 121.9 (4) |
C5—C4—O1 | 117.9 (4) | C15—C16—H16 | 119.0 |
C3—C4—O1 | 117.5 (4) | C17—C16—H16 | 119.0 |
C4—C5—C6 | 116.5 (4) | C12—C17—C16 | 119.9 (4) |
C4—C5—C8 | 122.1 (3) | C12—C17—H17 | 120.0 |
C6—C5—C8 | 121.3 (4) | C16—C17—H17 | 120.0 |
C1—C6—C5 | 121.5 (4) | C15—C18—H18A | 109.5 |
C1—C6—H6 | 119.3 | C15—C18—H18B | 109.5 |
C5—C6—H6 | 119.3 | H18A—C18—H18B | 109.5 |
C3—C7—H7A | 109.5 | C15—C18—H18C | 109.5 |
C3—C7—H7B | 109.5 | H18A—C18—H18C | 109.5 |
H7A—C7—H7B | 109.5 | H18B—C18—H18C | 109.5 |
C3—C7—H7C | 109.5 | O2—C9—O1 | 122.8 (3) |
H7A—C7—H7C | 109.5 | O2—C9—C10 | 127.2 (4) |
H7B—C7—H7C | 109.5 | O1—C9—C10 | 110.0 (4) |
C5—C8—H8A | 109.5 | C11—C10—C9 | 122.4 (5) |
C5—C8—H8B | 109.5 | C11—C10—H10 | 104 (4) |
H8A—C8—H8B | 109.5 | C9—C10—H10 | 131 (4) |
C5—C8—H8C | 109.5 | C10—C11—H11A | 120.0 |
H8A—C8—H8C | 109.5 | C10—C11—H11B | 120.0 |
H8B—C8—H8C | 109.5 | H11A—C11—H11B | 120.0 |
C17—C12—C13 | 119.9 (3) | N2—N1—C1 | 113.3 (4) |
C17—C12—N2 | 125.4 (4) | N1—N2—C12 | 112.7 (4) |
C13—C12—N2 | 114.7 (4) | C9—O1—C4 | 118.6 (3) |
C6—C1—C2—C3 | 0.0 (6) | C13—C14—C15—C16 | −0.5 (6) |
N1—C1—C2—C3 | −178.0 (4) | C13—C14—C15—C18 | 179.3 (4) |
C1—C2—C3—C4 | 1.3 (6) | C14—C15—C16—C17 | 1.3 (6) |
C1—C2—C3—C7 | 177.6 (4) | C18—C15—C16—C17 | −178.5 (4) |
C2—C3—C4—C5 | −1.9 (6) | C13—C12—C17—C16 | 1.0 (6) |
C7—C3—C4—C5 | −178.1 (4) | N2—C12—C17—C16 | −179.5 (4) |
C2—C3—C4—O1 | 173.6 (3) | C15—C16—C17—C12 | −1.6 (6) |
C7—C3—C4—O1 | −2.7 (6) | O2—C9—C10—C11 | −4.0 (9) |
C3—C4—C5—C6 | 1.0 (6) | O1—C9—C10—C11 | 177.0 (5) |
O1—C4—C5—C6 | −174.4 (3) | C6—C1—N1—N2 | −176.1 (3) |
C3—C4—C5—C8 | 177.8 (4) | C2—C1—N1—N2 | 2.0 (5) |
O1—C4—C5—C8 | 2.5 (6) | C1—N1—N2—C12 | 178.2 (3) |
C2—C1—C6—C5 | −1.0 (6) | C17—C12—N2—N1 | −2.4 (5) |
N1—C1—C6—C5 | 177.2 (3) | C13—C12—N2—N1 | 177.2 (4) |
C4—C5—C6—C1 | 0.5 (6) | O2—C9—O1—C4 | 0.9 (6) |
C8—C5—C6—C1 | −176.4 (4) | C10—C9—O1—C4 | 180.0 (4) |
C17—C12—C13—C14 | −0.2 (6) | C5—C4—O1—C9 | −94.4 (4) |
N2—C12—C13—C14 | −179.8 (4) | C3—C4—O1—C9 | 89.9 (4) |
C12—C13—C14—C15 | −0.1 (6) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C17H15BrN2O2 | C18H18N2O2 |
Mr | 359.21 | 294.34 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 297 | 297 |
a, b, c (Å) | 6.2168 (10), 9.7823 (10), 14.0973 (7) | 6.1589 (8), 11.2603 (15), 12.3461 (16) |
α, β, γ (°) | 98.977 (3), 101.160 (2), 93.697 (7) | 82.780 (11), 80.070 (11), 85.321 (11) |
V (Å3) | 826.83 (16) | 835.13 (19) |
Z | 2 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 2.49 | 0.08 |
Crystal size (mm) | 0.4 × 0.3 × 0.2 | 0.23 × 0.21 × 0.16 |
Data collection | ||
Diffractometer | STOE IPDS2 diffractometer | STOE IPDS2 diffractometer |
Absorption correction | Integration X-RED32 (Stoe & Cie, 2002) | Integration X-RED32 (Stoe & Cie, 2002) |
Tmin, Tmax | 0.975, 0.987 | 0.980, 0.985 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14480, 3931, 2667 | 10895, 3298, 1615 |
Rint | 0.056 | 0.144 |
(sin θ/λ)max (Å−1) | 0.658 | 0.617 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.109, 1.02 | 0.084, 0.216, 1.08 |
No. of reflections | 3931 | 3298 |
No. of parameters | 201 | 206 |
H-atom treatment | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.36, −0.41 | 0.13, −0.16 |
Computer programs: X-AREA (Stoe & Cie, 2002), X-AREA, X-RED32 (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).
Aromatic azo compounds represent the dominant class of synthetic colorant (Peter & Freeman, 1991); they are the most widely used class of dyes because of their versatile application in various fields, such as the dyeing of textiles and fibres, colorants in printing, and high-technology areas, such as ink-jet printers (Catino & Farris, 1985). The reversible inter-conversion between the cis and trans isomers of azo compound facilities the use of these compounds in optical data storage and switching devices (Jeon et al., 2002; Tian et al., 2004). Such optical properties depend on not only the spectroscopic properties of the molecules but also their crystallographic arrangement (Biswas & Umapathy, 2000). There is also interest in their biochemical applications due to their ability to bind to proteins (Ojala et al., 1996). In our ongoing research on azo compounds, in order to provide templates for molecular modeling studies, we have synthesized some diazene derivative compounds and the crystal structures of the title compounds, (I) and (II) (Figs. 1 and 2), have been determined. Both compounds crystallize in the centrosymmetric space group P1; therefore the optical frequency-doubling (or second-harmonic generation) in nonlinear optics does not occur in the solid state. This process can occur only in non-centrosymmetric crystals.
The bond lengths and angles in both structures are within the normally expected ranges. Both structures have a trans configuration about the azo linkage with a nearly planar geometry [the torsion angle of the central –C—N═N—C– unit is 179.0 (2)° for (I) and 178.2 (3)° for (II)] and with C2—C1—N1═N2 and C13—C12—N2═N1 torsion angles of 0.5 (4) and -174.5 (3)°, respectively, in (I), and 2.0 (5) and 177.2 (4)° in (II). These torsion angles suggest delocalization of electron density between the aromatic rings and the azo group. However, the ester and 2,6-dimethyl groups will probably cause the acryloyloxy group to rotate out conjugation with the benzene ring, thus leading to a loss of planarity. The dihedral angle between the aromatic rings is 8.31 (2)° in (I) and 3.74 (2)° in (II).
The ester mean planes of (I) and (II) are approximately planar, with r.m.s. deviations of 0.0240 and 0.0148 Å; the largest deviations from the mean planes are 0.037 (3) and 0.025 (4) Å for atom C10, respectively. The mean planes of the ester groups are nearly perpendicular with the aromatic rings, as indicated by the dihedral angle of 89.6 (1) and 82.7 (1)° in (I), and 88.1 (2) and 87.8 (2)° in (II). The N1—C1 and N2—C12 bond lengths are 1.428 (3) and 1.423 (3) Å for (I), and 1.443 (4) and 1.446 (4) Å for (II), respectively, consistent with that of the conventional single C—N bond length (1.450 Å). Comparing the N2—C12 bond distances in both compounds, we find that the N2—C12 bond length in (I) is slightly shorter than that of compound (II), as a result of the presence of the Br atom in a para position with respect to the azo linkage. This result can be attributed to the electron-withdrawing groups attached to the benzene ring.
The N═N bond lengths [N1═N2 = 1.252 (3) Å for (I) and 1.241 (4) Å for (II)] in both compounds are indicative of significant double-bond character, as has been observed in other trans-azo compound (Kocaokutgen et al., 2003; Soylu et al., 2004). The C—Br bond distance in (I) is consistent with that in 2-{(E)-3-[(E)-4-bromophenyliminomethyl]-4-hydroxyphenyldiazenyl}benzoic acid toluene hemisolvate (Linden et al., 2006) and in (E)-5-(4-bromophenyldiazenyl) salicylaldehyde (Şahin et al., 2005). The O2═C9 bond distance in both compounds is consistent with the value of the C═O double bond in other ester compounds (Kocaokutgen et al., 2005).
In the extended structure of (I) and (II), there are no intra- or intermolecular hydrogen-bonding interactions. The crystal packing of (I) features π–π and π-ring interactions, which form supramolecular motifs extending along the crystallographic a axis (Fig. 3), while in (II), the crystal packing comprises only π–π interactions (Fig. 4). An intermolecular π–π contact occurs between the two symmetry-related aromatic rings (C1–C6: ring A; C12–C17: ring B) of neighbouring azo molecules. Rings A and B are oriented in such a way that the perpendicular distance from A to Bi is 3.310 Å for (I) and 3.529 Å for (II), the closest interatomic distance is C3···C12i [3.466 (4) Å; symmetry code (i): 1 + x, y, z] for (I) and C2···C13i [3.564 (5) Å; symmetry code (i): 1 + x, y, z] for (II), and the dihedral angles between the planes of the rings are 8.31 (2)° for (I) and 3.74 (2)° for (II). The distance between the ring centroids is 3.857 (2) Å for (I) and 3.756 (2) Å for (II). Ring A is also involved in an intermolecular C—H···π interaction with atom C10 of the ester group in (I). The distance between atom H10 and the centre of ring A (CgA) is 2.902 Å, the distance between atom H10 and the plane of ring A is 2.900 Å, and the C10—H10···CgAi angle is 165.4°. A three-dimensional network in the crystal structure of both complexes is constructed from van der Waals forces between parallel associations formed by π–π and π-ring interactions. There is strong short contact between atoms C17 and C17ii [symmetry code: (ii) -x, -y, 1 - z] [C17···C17ii = 3.685 (4) Å] for I and O2 and C18iii [symmetry code (iii): x + 1, y, z + 1] atoms [O2···C18iii = 3.570 (5) Å] for (I)I.