Acta Cryst. (2009). E65, o1223 [ doi:10.1107/S1600536809014858 ]
In the title compound, C28H18O4·2C3H7NO, the dihedral angle between the benzene rings and the anthracene system is 74.05 (12)°. A crystallographic inversion centre is located in the middle of the anthracene unit. The dimethylformamide solvent molecules are partially disordered over two positions of approximately equal occupancy [0.529 (6):0.471 (6)]. Intermolecular O-H
O hydrogen bonds with the major occupancy formamide O atom as acceptor result in the formation of 2:1 solvate-complex aggregates, which are alternately linked to shorter solvate units via weak intermolecular C-HO contacts generated from the rotational disorder of the formamide O atom (minor occupancy component). Weak C-H![[pi]](/logos/entities/pi_rmgif.gif)
interactions between the solvent molecules as the donor and the outer anthracene rings support these contacts in the crystal structure for both disorder components.
The title compound was obtained from the Suzuki coupling reaction of 9,10-dibromoanthracene and 4-carboxyphenylboronic acid as described in the literature (Li et al., 2008) and recrystallized from dimethylformamide at room temperature to give the desired crystals suitable for single-crystal X-ray diffraction.
H atoms attached to C atoms of the title compound were placed in geometrically idealized positions and treated as riding with C—H distances constrained to 0.93 (aromatic CH), or 0.96 Å (methyl CH3), and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C) (1.5Ueq for methyl H). The atom-site occupancies for the rotational disordered formamide oxygen atoms O3 and O3' refined to a ratio of 0.53/0.47.
Alert levels A and B for short intermolecular O1···O3' and H2D···H15' contacts with distances of2.50 Å and 2.01 Å may be explained by the difficulties to split the whole solvent molecule due to the pseudo two-fold rotation of the methyl groups around the N1—C15 axis. BUMP instruction or splitting of the whole solvent molecule resulted in unstable refinements. Introduction of shift-limiting restraints (DAMP instruction) resulted in larger R-values without improving the geometries. Therefore the partial disorder refinement (O3, O3', H15, H15') was preferred as a compromise.
Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
![[Figure 1]](./si2166fig1thm.gif)
| Fig. 1. The molecular structure of the title compound with displacement ellipsoids at the 30% probability level (suffix A denotes the symmetry code: -x + 1, -y + 1, -z). Weak C—H···π and C—H···O hydrogen bonding contacts are indicated with dashed lines. Cg1 is the centroid of the anthracene ring C8, C9, C10, C12A, C13A, C14A. |
![[Figure 2]](./si2166fig2thm.gif)
| Fig. 2. Partial view of the crystal packing showing the intermolecular O—H···O hydrogen bonds and weak C—H···π interactions. Cg1 is the centroid of the anthracene ring (C8, C9, C10, C12A, C13A, C14A). |
| C28H18O4·2C3H7NO | Z = 1 |
| Mr = 564.62 | F000 = 298 |
| Triclinic, P1 | Dx = 1.270 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation λ = 0.71073 Å |
| a = 7.3692 (15) Å | Cell parameters from 879 reflections |
| b = 8.9981 (18) Å | θ = 2.9–22.0º |
| c = 12.124 (2) Å | µ = 0.09 mm−1 |
| α = 71.157 (3)º | T = 295 K |
| β = 77.640 (3)º | Block, colourless |
| γ = 79.754 (3)º | 0.23 × 0.16 × 0.06 mm |
| V = 738.0 (3) Å3 |
| Bruker SMART APEX CCD area-detector diffractometer | 2721 independent reflections |
| Radiation source: fine-focus sealed tube | 1467 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.028 |
| T = 295 K | θmax = 25.5º |
| φ and ω scans | θmin = 2.4º |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→8 |
| Tmin = 0.980, Tmax = 0.994 | k = −10→9 |
| 5691 measured reflections | l = −14→14 |
| 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)] = 0.053 | H-atom parameters constrained |
| wR(F2) = 0.162 | w = 1/[σ2(Fo2) + (0.0732P)2 + 0.04P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.02 | (Δ/σ)max < 0.001 |
| 2721 reflections | Δρmax = 0.16 e Å−3 |
| 203 parameters | Δρmin = −0.20 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| C28H18O4·2C3H7NO | γ = 79.754 (3)º |
| Mr = 564.62 | V = 738.0 (3) Å3 |
| Triclinic, P1 | Z = 1 |
| a = 7.3692 (15) Å | Mo Kα |
| b = 8.9981 (18) Å | µ = 0.09 mm−1 |
| c = 12.124 (2) Å | T = 295 K |
| α = 71.157 (3)º | 0.23 × 0.16 × 0.06 mm |
| β = 77.640 (3)º |
| Bruker SMART APEX CCD area-detector diffractometer | 2721 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1467 reflections with I > 2σ(I) |
| Tmin = 0.980, Tmax = 0.994 | Rint = 0.028 |
| 5691 measured reflections |
| R[F2 > 2σ(F2)] = 0.053 | 203 parameters |
| wR(F2) = 0.162 | H-atom parameters constrained |
| S = 1.02 | Δρmax = 0.16 e Å−3 |
| 2721 reflections | Δρmin = −0.20 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 | Occ. (<1) | |
| C15 | 0.5707 (5) | 0.2790 (4) | 0.4860 (3) | 0.0742 (9) | 0.529 (6) |
| H15 | 0.4771 | 0.2595 | 0.4536 | 0.089* | 0.529 (6) |
| O3 | 0.5840 (5) | 0.2039 (5) | 0.5938 (4) | 0.0918 (18) | 0.529 (6) |
| C15' | 0.5707 (5) | 0.2790 (4) | 0.4860 (3) | 0.0742 (9) | 0.471 (6) |
| H15' | 0.5944 | 0.2141 | 0.5598 | 0.089* | 0.471 (6) |
| O3' | 0.4309 (7) | 0.2700 (6) | 0.4479 (4) | 0.096 (2) | 0.471 (6) |
| N1 | 0.6843 (3) | 0.3826 (3) | 0.41928 (19) | 0.0637 (6) | |
| C16 | 0.6620 (5) | 0.4705 (4) | 0.2994 (3) | 0.0999 (12) | |
| H16A | 0.5498 | 0.4476 | 0.2831 | 0.150* | |
| H16B | 0.7677 | 0.4407 | 0.2459 | 0.150* | |
| H16C | 0.6535 | 0.5816 | 0.2895 | 0.150* | |
| C17 | 0.8377 (4) | 0.4104 (5) | 0.4627 (3) | 0.0945 (11) | |
| H17A | 0.8375 | 0.3450 | 0.5429 | 0.142* | |
| H17B | 0.8249 | 0.5196 | 0.4598 | 0.142* | |
| H17C | 0.9532 | 0.3852 | 0.4146 | 0.142* | |
| O1 | −0.1924 (3) | −0.0937 (3) | 0.42504 (19) | 0.1024 (9) | |
| O2 | −0.3377 (3) | −0.0181 (3) | 0.2730 (2) | 0.1090 (9) | |
| H2D | −0.4140 | −0.0728 | 0.3213 | 0.163* | |
| C1 | −0.0616 (3) | 0.0915 (3) | 0.2520 (2) | 0.0496 (6) | |
| C2 | −0.0651 (4) | 0.1757 (3) | 0.1348 (2) | 0.0638 (8) | |
| H2 | −0.1589 | 0.1662 | 0.0978 | 0.077* | |
| C3 | 0.0713 (4) | 0.2746 (3) | 0.0719 (2) | 0.0594 (7) | |
| H3 | 0.0669 | 0.3313 | −0.0068 | 0.071* | |
| C4 | 0.2133 (3) | 0.2901 (3) | 0.1243 (2) | 0.0445 (6) | |
| C5 | 0.2169 (3) | 0.2037 (3) | 0.2414 (2) | 0.0525 (7) | |
| H5 | 0.3117 | 0.2117 | 0.2783 | 0.063* | |
| C6 | 0.0805 (3) | 0.1053 (3) | 0.3045 (2) | 0.0537 (7) | |
| H6 | 0.0852 | 0.0480 | 0.3831 | 0.064* | |
| C7 | −0.2053 (4) | −0.0146 (3) | 0.3219 (3) | 0.0643 (8) | |
| C8 | 0.6573 (4) | 0.1754 (3) | −0.1369 (2) | 0.0640 (8) | |
| H8 | 0.6611 | 0.0821 | −0.1552 | 0.077* | |
| C9 | 0.5159 (4) | 0.2148 (3) | −0.0568 (2) | 0.0549 (7) | |
| H9 | 0.4239 | 0.1477 | −0.0204 | 0.066* | |
| C10 | 0.5040 (3) | 0.3575 (3) | −0.02629 (19) | 0.0432 (6) | |
| C11 | 0.3592 (3) | 0.3985 (3) | 0.05850 (19) | 0.0419 (6) | |
| C12 | 0.3533 (3) | 0.5398 (3) | 0.08512 (19) | 0.0419 (6) | |
| C13 | 0.2061 (3) | 0.5896 (3) | 0.1681 (2) | 0.0514 (7) | |
| H13 | 0.1110 | 0.5259 | 0.2059 | 0.062* | |
| C14 | 0.2008 (4) | 0.7263 (3) | 0.1932 (2) | 0.0620 (8) | |
| H14 | 0.1031 | 0.7554 | 0.2478 | 0.074* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C15 | 0.066 (2) | 0.089 (2) | 0.066 (2) | −0.0197 (18) | −0.0072 (17) | −0.0164 (19) |
| O3 | 0.082 (3) | 0.114 (4) | 0.071 (3) | −0.054 (3) | −0.012 (2) | 0.006 (3) |
| C15' | 0.066 (2) | 0.089 (2) | 0.066 (2) | −0.0197 (18) | −0.0072 (17) | −0.0164 (19) |
| O3' | 0.087 (4) | 0.120 (4) | 0.079 (3) | −0.060 (3) | −0.015 (3) | 0.000 (3) |
| N1 | 0.0574 (14) | 0.0753 (17) | 0.0547 (14) | −0.0202 (12) | −0.0040 (11) | −0.0113 (12) |
| C16 | 0.088 (2) | 0.119 (3) | 0.071 (2) | −0.022 (2) | −0.0099 (18) | 0.004 (2) |
| C17 | 0.079 (2) | 0.125 (3) | 0.086 (2) | −0.045 (2) | −0.0063 (19) | −0.028 (2) |
| O1 | 0.0933 (16) | 0.128 (2) | 0.0722 (15) | −0.0639 (15) | −0.0176 (13) | 0.0188 (14) |
| O2 | 0.0826 (16) | 0.137 (2) | 0.0938 (17) | −0.0672 (15) | −0.0245 (14) | 0.0188 (15) |
| C1 | 0.0454 (14) | 0.0470 (15) | 0.0548 (16) | −0.0134 (12) | −0.0041 (12) | −0.0114 (12) |
| C2 | 0.0535 (16) | 0.0701 (19) | 0.0652 (18) | −0.0227 (14) | −0.0159 (14) | −0.0045 (15) |
| C3 | 0.0605 (16) | 0.0624 (18) | 0.0512 (15) | −0.0233 (14) | −0.0133 (13) | −0.0001 (13) |
| C4 | 0.0460 (14) | 0.0408 (14) | 0.0468 (14) | −0.0098 (11) | −0.0061 (11) | −0.0115 (12) |
| C5 | 0.0541 (15) | 0.0553 (16) | 0.0474 (15) | −0.0189 (13) | −0.0085 (12) | −0.0077 (13) |
| C6 | 0.0593 (16) | 0.0519 (16) | 0.0453 (14) | −0.0170 (13) | −0.0041 (12) | −0.0058 (12) |
| C7 | 0.0506 (17) | 0.0634 (19) | 0.074 (2) | −0.0191 (14) | −0.0030 (15) | −0.0121 (16) |
| C8 | 0.085 (2) | 0.0442 (16) | 0.0605 (17) | −0.0144 (14) | 0.0043 (15) | −0.0192 (14) |
| C9 | 0.0667 (17) | 0.0400 (15) | 0.0549 (16) | −0.0186 (12) | 0.0012 (13) | −0.0107 (12) |
| C10 | 0.0494 (14) | 0.0359 (14) | 0.0416 (13) | −0.0110 (11) | −0.0061 (11) | −0.0054 (11) |
| C11 | 0.0453 (13) | 0.0386 (14) | 0.0391 (13) | −0.0119 (10) | −0.0083 (11) | −0.0034 (11) |
| C12 | 0.0426 (13) | 0.0404 (14) | 0.0404 (13) | −0.0080 (10) | −0.0063 (10) | −0.0074 (11) |
| C13 | 0.0485 (14) | 0.0494 (16) | 0.0499 (15) | −0.0125 (12) | 0.0041 (12) | −0.0104 (12) |
| C14 | 0.0724 (18) | 0.0492 (17) | 0.0573 (17) | −0.0080 (14) | 0.0079 (14) | −0.0178 (14) |
| C15—O3 | 1.279 (4) | C3—H3 | 0.9300 |
| C15—N1 | 1.314 (4) | C4—C5 | 1.385 (3) |
| C15—H15 | 0.9300 | C4—C11 | 1.499 (3) |
| N1—C17 | 1.434 (4) | C5—C6 | 1.389 (3) |
| N1—C16 | 1.441 (3) | C5—H5 | 0.9300 |
| C16—H16A | 0.9600 | C6—H6 | 0.9300 |
| C16—H16B | 0.9600 | C8—C9 | 1.346 (3) |
| C16—H16C | 0.9600 | C8—C14i | 1.406 (4) |
| C17—H17A | 0.9600 | C8—H8 | 0.9300 |
| C17—H17B | 0.9600 | C9—C10 | 1.430 (3) |
| C17—H17C | 0.9600 | C9—H9 | 0.9300 |
| O1—C7 | 1.238 (3) | C10—C11 | 1.403 (3) |
| O2—C7 | 1.255 (3) | C10—C12i | 1.438 (3) |
| O2—H2D | 0.8200 | C11—C12 | 1.401 (3) |
| C1—C6 | 1.378 (3) | C12—C13 | 1.428 (3) |
| C1—C2 | 1.381 (3) | C12—C10i | 1.438 (3) |
| C1—C7 | 1.485 (3) | C13—C14 | 1.353 (3) |
| C2—C3 | 1.392 (3) | C13—H13 | 0.9300 |
| C2—H2 | 0.9300 | C14—C8i | 1.406 (4) |
| C3—C4 | 1.382 (3) | C14—H14 | 0.9300 |
| O3—C15—N1 | 122.5 (4) | C4—C5—C6 | 120.7 (2) |
| O3—C15—H15 | 118.8 | C4—C5—H5 | 119.6 |
| N1—C15—H15 | 118.8 | C6—C5—H5 | 119.6 |
| C15—N1—C17 | 121.0 (3) | C1—C6—C5 | 120.8 (2) |
| C15—N1—C16 | 121.5 (3) | C1—C6—H6 | 119.6 |
| C17—N1—C16 | 117.5 (2) | C5—C6—H6 | 119.6 |
| N1—C16—H16A | 109.5 | O1—C7—O2 | 122.7 (3) |
| N1—C16—H16B | 109.5 | O1—C7—C1 | 119.7 (3) |
| H16A—C16—H16B | 109.5 | O2—C7—C1 | 117.6 (3) |
| N1—C16—H16C | 109.5 | C9—C8—C14i | 120.8 (3) |
| H16A—C16—H16C | 109.5 | C9—C8—H8 | 119.6 |
| H16B—C16—H16C | 109.5 | C14i—C8—H8 | 119.6 |
| N1—C17—H17A | 109.5 | C8—C9—C10 | 121.5 (2) |
| N1—C17—H17B | 109.5 | C8—C9—H9 | 119.2 |
| H17A—C17—H17B | 109.5 | C10—C9—H9 | 119.2 |
| N1—C17—H17C | 109.5 | C11—C10—C9 | 122.0 (2) |
| H17A—C17—H17C | 109.5 | C11—C10—C12i | 119.9 (2) |
| H17B—C17—H17C | 109.5 | C9—C10—C12i | 118.1 (2) |
| C7—O2—H2D | 109.5 | C12—C11—C10 | 119.9 (2) |
| C6—C1—C2 | 118.9 (2) | C12—C11—C4 | 119.3 (2) |
| C6—C1—C7 | 119.4 (2) | C10—C11—C4 | 120.8 (2) |
| C2—C1—C7 | 121.6 (2) | C11—C12—C13 | 122.3 (2) |
| C1—C2—C3 | 120.2 (2) | C11—C12—C10i | 120.2 (2) |
| C1—C2—H2 | 119.9 | C13—C12—C10i | 117.5 (2) |
| C3—C2—H2 | 119.9 | C14—C13—C12 | 122.0 (2) |
| C4—C3—C2 | 121.2 (2) | C14—C13—H13 | 119.0 |
| C4—C3—H3 | 119.4 | C12—C13—H13 | 119.0 |
| C2—C3—H3 | 119.4 | C13—C14—C8i | 120.0 (2) |
| C3—C4—C5 | 118.1 (2) | C13—C14—H14 | 120.0 |
| C3—C4—C11 | 121.9 (2) | C8i—C14—H14 | 120.0 |
| C5—C4—C11 | 119.9 (2) | ||
| O3—C15—N1—C17 | 3.6 (5) | C8—C9—C10—C11 | −178.9 (2) |
| O3—C15—N1—C16 | −177.4 (4) | C8—C9—C10—C12i | 0.9 (4) |
| C6—C1—C2—C3 | −1.1 (4) | C9—C10—C11—C12 | −179.8 (2) |
| C7—C1—C2—C3 | 179.7 (2) | C12i—C10—C11—C12 | 0.4 (4) |
| C1—C2—C3—C4 | 0.5 (4) | C9—C10—C11—C4 | 2.2 (3) |
| C2—C3—C4—C5 | 0.3 (4) | C12i—C10—C11—C4 | −177.6 (2) |
| C2—C3—C4—C11 | −178.8 (2) | C3—C4—C11—C12 | 106.8 (3) |
| C3—C4—C5—C6 | −0.5 (4) | C5—C4—C11—C12 | −72.3 (3) |
| C11—C4—C5—C6 | 178.6 (2) | C3—C4—C11—C10 | −75.2 (3) |
| C2—C1—C6—C5 | 0.9 (4) | C5—C4—C11—C10 | 105.7 (3) |
| C7—C1—C6—C5 | −179.9 (2) | C10—C11—C12—C13 | 178.1 (2) |
| C4—C5—C6—C1 | −0.1 (4) | C4—C11—C12—C13 | −3.9 (3) |
| C6—C1—C7—O1 | −2.6 (4) | C10—C11—C12—C10i | −0.4 (4) |
| C2—C1—C7—O1 | 176.6 (3) | C4—C11—C12—C10i | 177.6 (2) |
| C6—C1—C7—O2 | 176.5 (3) | C11—C12—C13—C14 | −179.8 (2) |
| C2—C1—C7—O2 | −4.3 (4) | C10i—C12—C13—C14 | −1.3 (4) |
| C14i—C8—C9—C10 | 0.3 (4) | C12—C13—C14—C8i | 0.1 (4) |
| Symmetry codes: (i) −x+1, −y+1, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H2D···O3ii | 0.82 | 1.79 | 2.603 (4) | 170 |
| C5—H5···O3' | 0.93 | 2.63 | 3.478 (5) | 152 |
| C16—H16A···Cg1 | 0.96 | 2.91 | 3.485 (3) | 120 |
| Symmetry codes: (ii) −x, −y, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H2D···O3i | 0.82 | 1.79 | 2.603 (4) | 170 |
| C5—H5···O3' | 0.93 | 2.63 | 3.478 (5) | 152 |
| C16—H16A···Cg1 | 0.96 | 2.91 | 3.485 (3) | 120 |
| Symmetry codes: (i) −x, −y, −z+1. |
This work was supported by the Doctoral Foundation of Zhengzhou University of Light Industry (000420).
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Cyclopalladated ferrocenylimine complexs with monophosphino ligands were successfully used as catalysts for Suzuki reactions (Xu et al. 2006; Li et al., 2006; Xu et al. 2008). We have recently reported that the structure of 4-(2,5-dihexyloxyphenyl)benzoic acid was obtained from the Suzuki coupling reaction (Li et al., 2008). The title compound was derived from the Suzuki reaction of 9,10-dibromoanthracene and 4-carboxyphenylboronic acid.
In the title compound (Fig.1), the dihedral angle between benzene rings and anthracene rings is 74.05 (12)°. A crystallographic inversion centre is in the middle of the anthracene unit, and an approximate two-fold pseudo rotation axis is running along the plane of the anthracene unit. The dimethylformamide solvent molecules are partially disordered over two positions, O3 and O3', of approximately equal occupancy, (0.529 (6) and 0.471 (6), respectively. The different intermolecular hydrogen bonding contacts are shown in Fig. 1 (O3' is the acceptor) and Fig. 2 (with O3 as acceptor). The intermolecular O—H···O hydrogen bonds result in the formation of long 2:1 solvate:complex aggregates, (Table 1) which are alternately linked via weak intermolecular C—H···O contacts generated from the rotational disorder of the formamide oxygen atom (0.471 (6) site occupancy). C—H···π interactions support these contacts in the crystal structure foming a one-dimensional supramolecular architecture (Fig. 1 and Fig. 2).