Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106046452/gz3032sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106046452/gz3032IIsup2.hkl |
CCDC reference: 634881
Hexakis(4-cyanophenyl)benzene, (I), was synthesized by the reported method of Maly et al. (2006). Crystals were grown by placing a solution of compound (I) in CH2Cl2 (0.1 M, 2 ml) at the bottom of a test tube, then carefully covering it with successive layers composed of pure CH2Cl2 (1 ml), a 1:1 mixture of CH2Cl2 and CH3OH (1 ml), and finally pure CH3OH (2 ml). The test tube was sealed tightly and left undisturbed. Crystals of (II) appeared after how long?
H atoms were placed in idealized positions, with C—H distances in the range 0.95–0.99 Å, and refined using a riding model, with Uiso(H) = 1.2Ueq(C).
The dichloromethane molecule was found to be disordered over two sites. The first molecule (C29, Cl1 and Cl2) was refined with restraints on the C—Cl distances and atomic displacement parameters by the use of SADI and DELU instructions in SHELXL97 (Sheldrick, 1997). The second part of the disordered dichloromethane molecule (C30, Cl3 and Cl4) was refined to be similar to the first one by use of SAME and EADP instructions in SHELXL97. With these restraints, the occupancy factors converged to 0.5312 (11) and 0.4688 (11).
Data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: enCIFer (Allen et al., 2004) and publCIF (Westrip, 2006).
C48H24N6·2CH2Cl2 | F(000) = 1752 |
Mr = 854.58 | Dx = 1.311 Mg m−3 |
Orthorhombic, Pbcn | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: -P 2n 2ab | Cell parameters from 17112 reflections |
a = 11.0921 (3) Å | θ = 4.4–67.2° |
b = 19.3442 (3) Å | µ = 2.82 mm−1 |
c = 20.1742 (4) Å | T = 150 K |
V = 4328.73 (16) Å3 | Block, colorless |
Z = 4 | 0.15 × 0.08 × 0.07 mm |
Bruker SMART 6000 diffractometer | 3865 independent reflections |
Radiation source: Rotating Anode | 3494 reflections with I > 2σ(I) |
Montel 200 optics monochromator | Rint = 0.051 |
Detector resolution: 5.5 pixels mm-1 | θmax = 68.2°, θmin = 4.4° |
ω scans | h = −13→13 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | k = −23→23 |
Tmin = 0.700, Tmax = 0.850 | l = −23→23 |
57445 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)] = 0.058 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.138 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.119P)2] where P = (Fo2 + 2Fc2)/3 |
3865 reflections | (Δ/σ)max < 0.001 |
286 parameters | Δρmax = 0.27 e Å−3 |
11 restraints | Δρmin = −0.28 e Å−3 |
C48H24N6·2CH2Cl2 | V = 4328.73 (16) Å3 |
Mr = 854.58 | Z = 4 |
Orthorhombic, Pbcn | Cu Kα radiation |
a = 11.0921 (3) Å | µ = 2.82 mm−1 |
b = 19.3442 (3) Å | T = 150 K |
c = 20.1742 (4) Å | 0.15 × 0.08 × 0.07 mm |
Bruker SMART 6000 diffractometer | 3865 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | 3494 reflections with I > 2σ(I) |
Tmin = 0.700, Tmax = 0.850 | Rint = 0.051 |
57445 measured reflections |
R[F2 > 2σ(F2)] = 0.058 | 11 restraints |
wR(F2) = 0.138 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.27 e Å−3 |
3865 reflections | Δρmin = −0.28 e Å−3 |
286 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 | Occ. (<1) | |
C1 | 0.0000 | 0.54553 (6) | 0.2500 | 0.0295 (3) | |
N1 | 0.0000 | 0.88565 (7) | 0.2500 | 0.0705 (5) | |
C2 | 0.06316 (8) | 0.51073 (5) | 0.19855 (4) | 0.0289 (2) | |
N2 | 0.37714 (12) | 0.67215 (6) | −0.05659 (6) | 0.0651 (4) | |
C3 | 0.06362 (8) | 0.44098 (5) | 0.19866 (5) | 0.0307 (2) | |
N3 | 0.38402 (16) | 0.26434 (11) | −0.04262 (11) | 0.1071 (7) | |
C4 | 0.0000 | 0.40677 (7) | 0.2500 | 0.0312 (3) | |
N4 | 0.0000 | 0.06745 (7) | 0.2500 | 0.0586 (4) | |
C5 | 0.0000 | 0.61995 (6) | 0.2500 | 0.0309 (3) | |
C6 | −0.05247 (10) | 0.65481 (5) | 0.19553 (5) | 0.0372 (3) | |
H6 | −0.0871 | 0.6296 | 0.1599 | 0.045* | |
C7 | −0.05239 (11) | 0.72363 (5) | 0.19524 (6) | 0.0434 (3) | |
H7 | −0.0864 | 0.7489 | 0.1594 | 0.052* | |
C8 | 0.0000 | 0.75784 (7) | 0.2500 | 0.0431 (4) | |
C9 | 0.0000 | 0.82943 (8) | 0.2500 | 0.0509 (4) | |
C10 | 0.12990 (9) | 0.54787 (5) | 0.14348 (5) | 0.0316 (2) | |
C11 | 0.23002 (10) | 0.58647 (5) | 0.15963 (5) | 0.0398 (3) | |
H11 | 0.2560 | 0.5903 | 0.2044 | 0.048* | |
C12 | 0.29244 (11) | 0.61985 (6) | 0.10888 (6) | 0.0454 (3) | |
H12 | 0.3608 | 0.6471 | 0.1200 | 0.054* | |
C13 | 0.25731 (10) | 0.61477 (5) | 0.03955 (6) | 0.0412 (3) | |
C14 | 0.15595 (11) | 0.57602 (6) | 0.02361 (5) | 0.0424 (3) | |
H14 | 0.1298 | 0.5720 | −0.0211 | 0.051* | |
C15 | 0.09324 (10) | 0.54306 (6) | 0.07492 (5) | 0.0390 (3) | |
H15 | 0.0239 | 0.5165 | 0.0642 | 0.047* | |
C16 | 0.32203 (12) | 0.64664 (6) | −0.01203 (6) | 0.0493 (3) | |
C17 | 0.13343 (9) | 0.40327 (5) | 0.14529 (5) | 0.0333 (2) | |
C18 | 0.25865 (10) | 0.40777 (5) | 0.14290 (6) | 0.0396 (3) | |
H18 | 0.3001 | 0.4358 | 0.1742 | 0.048* | |
C19 | 0.32396 (10) | 0.37149 (6) | 0.09494 (6) | 0.0495 (3) | |
H19 | 0.4094 | 0.3746 | 0.0942 | 0.059* | |
C20 | 0.26421 (12) | 0.33033 (7) | 0.04765 (7) | 0.0535 (3) | |
C21 | 0.13814 (12) | 0.32596 (6) | 0.05053 (6) | 0.0493 (3) | |
H21 | 0.0961 | 0.2986 | 0.0190 | 0.059* | |
C22 | 0.07419 (10) | 0.36141 (5) | 0.09914 (6) | 0.0392 (3) | |
H22 | −0.0111 | 0.3571 | 0.1010 | 0.047* | |
C23 | 0.32914 (15) | 0.29406 (8) | −0.00100 (9) | 0.0743 (5) | |
C24 | 0.0000 | 0.33275 (7) | 0.2500 | 0.0334 (3) | |
C25 | −0.10428 (10) | 0.29803 (5) | 0.23224 (6) | 0.0409 (3) | |
H25 | −0.1750 | 0.3230 | 0.2207 | 0.049* | |
C26 | −0.10419 (10) | 0.22943 (5) | 0.23159 (7) | 0.0446 (3) | |
H26 | −0.1741 | 0.2044 | 0.2188 | 0.054* | |
C27 | 0.0000 | 0.19525 (7) | 0.2500 | 0.0403 (4) | |
C28 | 0.0000 | 0.12432 (8) | 0.2500 | 0.0442 (4) | |
C29 | 0.6145 (6) | 0.4921 (2) | 0.1182 (4) | 0.0666 (7) | 0.5312 (11) |
H29A | 0.6001 | 0.4598 | 0.0810 | 0.080* | 0.5312 (11) |
H29B | 0.5464 | 0.4881 | 0.1497 | 0.080* | 0.5312 (11) |
Cl1 | 0.7509 (7) | 0.4705 (3) | 0.1586 (4) | 0.0848 (8) | 0.5312 (11) |
Cl2 | 0.62378 (12) | 0.57770 (7) | 0.08797 (6) | 0.1118 (3) | 0.5312 (11) |
C30 | 0.6042 (7) | 0.4850 (4) | 0.1294 (3) | 0.0666 (7) | 0.4688 (11) |
H30A | 0.5789 | 0.4362 | 0.1252 | 0.080* | 0.4688 (11) |
H30B | 0.5519 | 0.5076 | 0.1627 | 0.080* | 0.4688 (11) |
Cl3 | 0.7561 (8) | 0.4891 (3) | 0.1554 (5) | 0.0848 (8) | 0.4688 (11) |
Cl4 | 0.58793 (15) | 0.52710 (7) | 0.05219 (7) | 0.1118 (3) | 0.4688 (11) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0315 (7) | 0.0264 (6) | 0.0306 (7) | 0.000 | −0.0028 (5) | 0.000 |
N1 | 0.0845 (12) | 0.0302 (7) | 0.0967 (14) | 0.000 | 0.0255 (10) | 0.000 |
C2 | 0.0324 (5) | 0.0258 (4) | 0.0285 (5) | −0.0015 (3) | −0.0026 (4) | 0.0002 (3) |
N2 | 0.0811 (8) | 0.0476 (6) | 0.0668 (8) | −0.0113 (6) | 0.0285 (6) | 0.0048 (5) |
C3 | 0.0307 (5) | 0.0276 (5) | 0.0337 (6) | −0.0004 (3) | −0.0019 (4) | −0.0026 (3) |
N3 | 0.0891 (11) | 0.1170 (13) | 0.1150 (16) | 0.0123 (10) | 0.0248 (10) | −0.0638 (12) |
C4 | 0.0292 (6) | 0.0277 (6) | 0.0367 (7) | 0.000 | −0.0035 (5) | 0.000 |
N4 | 0.0661 (10) | 0.0337 (7) | 0.0759 (11) | 0.000 | 0.0046 (8) | 0.000 |
C5 | 0.0355 (7) | 0.0261 (6) | 0.0312 (7) | 0.000 | 0.0039 (5) | 0.000 |
C6 | 0.0448 (6) | 0.0317 (5) | 0.0350 (6) | 0.0020 (4) | 0.0007 (4) | 0.0013 (4) |
C7 | 0.0516 (7) | 0.0333 (5) | 0.0452 (7) | 0.0046 (4) | 0.0049 (5) | 0.0095 (4) |
C8 | 0.0500 (9) | 0.0251 (6) | 0.0542 (10) | 0.000 | 0.0171 (7) | 0.000 |
C9 | 0.0579 (10) | 0.0328 (8) | 0.0622 (11) | 0.000 | 0.0231 (8) | 0.000 |
C10 | 0.0352 (5) | 0.0270 (4) | 0.0325 (5) | −0.0007 (4) | 0.0010 (4) | −0.0017 (3) |
C11 | 0.0429 (6) | 0.0440 (5) | 0.0327 (6) | −0.0096 (4) | −0.0015 (4) | −0.0022 (4) |
C12 | 0.0448 (6) | 0.0435 (6) | 0.0478 (7) | −0.0139 (5) | 0.0036 (5) | −0.0046 (5) |
C13 | 0.0459 (6) | 0.0329 (5) | 0.0447 (7) | 0.0001 (4) | 0.0097 (4) | 0.0019 (4) |
C14 | 0.0522 (6) | 0.0426 (5) | 0.0324 (6) | −0.0061 (5) | −0.0017 (5) | 0.0023 (4) |
C15 | 0.0431 (6) | 0.0396 (5) | 0.0343 (6) | −0.0079 (4) | −0.0021 (4) | −0.0014 (4) |
C16 | 0.0571 (7) | 0.0374 (5) | 0.0534 (7) | −0.0044 (5) | 0.0115 (6) | −0.0018 (5) |
C17 | 0.0369 (5) | 0.0283 (4) | 0.0348 (5) | 0.0020 (4) | 0.0007 (4) | −0.0010 (4) |
C18 | 0.0393 (6) | 0.0365 (5) | 0.0429 (6) | −0.0002 (4) | 0.0030 (4) | −0.0068 (4) |
C19 | 0.0388 (6) | 0.0522 (6) | 0.0575 (8) | 0.0003 (5) | 0.0090 (5) | −0.0120 (5) |
C20 | 0.0547 (7) | 0.0478 (6) | 0.0581 (8) | 0.0035 (5) | 0.0100 (6) | −0.0177 (5) |
C21 | 0.0550 (7) | 0.0431 (6) | 0.0499 (7) | 0.0013 (5) | −0.0027 (5) | −0.0170 (5) |
C22 | 0.0415 (5) | 0.0318 (5) | 0.0442 (6) | −0.0002 (4) | −0.0017 (4) | −0.0059 (4) |
C23 | 0.0641 (9) | 0.0734 (9) | 0.0855 (11) | 0.0025 (7) | 0.0102 (8) | −0.0363 (9) |
C24 | 0.0360 (7) | 0.0294 (7) | 0.0347 (7) | 0.000 | 0.0024 (6) | 0.000 |
C25 | 0.0395 (6) | 0.0298 (5) | 0.0534 (7) | −0.0013 (4) | −0.0027 (5) | 0.0039 (4) |
C26 | 0.0442 (6) | 0.0322 (5) | 0.0574 (8) | −0.0083 (4) | −0.0030 (5) | 0.0005 (4) |
C27 | 0.0493 (9) | 0.0277 (6) | 0.0438 (8) | 0.000 | 0.0076 (6) | 0.000 |
C28 | 0.0472 (9) | 0.0334 (8) | 0.0522 (10) | 0.000 | 0.0086 (7) | 0.000 |
C29 | 0.0634 (13) | 0.0775 (13) | 0.0591 (19) | 0.0014 (10) | 0.0024 (14) | −0.0105 (9) |
Cl1 | 0.0630 (6) | 0.120 (3) | 0.0714 (8) | −0.0069 (16) | −0.0152 (5) | −0.0179 (17) |
Cl2 | 0.1311 (7) | 0.1109 (6) | 0.0935 (6) | 0.0271 (5) | 0.0168 (5) | 0.0294 (4) |
C30 | 0.0634 (13) | 0.0775 (13) | 0.0591 (19) | 0.0014 (10) | 0.0024 (14) | −0.0105 (9) |
Cl3 | 0.0630 (6) | 0.120 (3) | 0.0714 (8) | −0.0069 (16) | −0.0152 (5) | −0.0179 (17) |
Cl4 | 0.1311 (7) | 0.1109 (6) | 0.0935 (6) | 0.0271 (5) | 0.0168 (5) | 0.0294 (4) |
C1—C2i | 1.4217 (11) | C14—H14 | 0.9500 |
C1—C2 | 1.4217 (11) | C15—H15 | 0.9500 |
C1—C5 | 1.4397 (17) | C17—C18 | 1.3925 (15) |
N1—C9 | 1.088 (2) | C17—C22 | 1.3980 (14) |
C2—C3 | 1.3493 (13) | C18—C19 | 1.3977 (15) |
C2—C10 | 1.5161 (13) | C18—H18 | 0.9500 |
N2—C16 | 1.1939 (17) | C19—C20 | 1.4083 (18) |
C3—C4 | 1.4173 (11) | C19—H19 | 0.9500 |
C3—C17 | 1.5136 (13) | C20—C21 | 1.4021 (19) |
N3—C23 | 1.186 (2) | C20—C23 | 1.4051 (19) |
C4—C3i | 1.4173 (11) | C21—C22 | 1.3910 (16) |
C4—C24 | 1.4318 (18) | C21—H21 | 0.9500 |
N4—C28 | 1.100 (2) | C22—H22 | 0.9500 |
C5—C6i | 1.4144 (12) | C24—C25i | 1.3847 (12) |
C5—C6 | 1.4145 (12) | C24—C25 | 1.3848 (12) |
C6—C7 | 1.3314 (14) | C25—C26 | 1.3271 (14) |
C6—H6 | 0.9500 | C25—H25 | 0.9500 |
C7—C8 | 1.4128 (14) | C26—C27 | 1.3823 (13) |
C7—H7 | 0.9500 | C26—H26 | 0.9500 |
C8—C9 | 1.385 (2) | C27—C28 | 1.3721 (19) |
C8—C7i | 1.4128 (14) | C27—C26i | 1.3824 (14) |
C10—C11 | 1.3773 (15) | C29—Cl2 | 1.768 (3) |
C10—C15 | 1.4447 (15) | C29—Cl1 | 1.768 (2) |
C11—C12 | 1.3945 (16) | C29—H29A | 0.9900 |
C11—H11 | 0.9500 | C29—H29B | 0.9900 |
C12—C13 | 1.4553 (18) | C30—Cl4 | 1.766 (3) |
C12—H12 | 0.9500 | C30—Cl3 | 1.767 (3) |
C13—C14 | 1.3891 (16) | C30—H30A | 0.9900 |
C13—C16 | 1.4065 (17) | C30—H30B | 0.9900 |
C14—C15 | 1.4007 (16) | ||
C2i—C1—C2 | 123.49 (11) | C18—C17—C22 | 118.81 (10) |
C2i—C1—C5 | 118.25 (6) | C18—C17—C3 | 120.32 (9) |
C2—C1—C5 | 118.26 (6) | C22—C17—C3 | 120.83 (9) |
C3—C2—C1 | 118.30 (8) | C17—C18—C19 | 120.64 (10) |
C3—C2—C10 | 118.24 (8) | C17—C18—H18 | 119.7 |
C1—C2—C10 | 123.46 (8) | C19—C18—H18 | 119.7 |
C2—C3—C4 | 117.79 (9) | C18—C19—C20 | 120.59 (11) |
C2—C3—C17 | 118.87 (8) | C18—C19—H19 | 119.7 |
C4—C3—C17 | 123.33 (8) | C20—C19—H19 | 119.7 |
C3i—C4—C3 | 124.32 (12) | C21—C20—C23 | 120.66 (13) |
C3i—C4—C24 | 117.84 (6) | C21—C20—C19 | 118.39 (11) |
C3—C4—C24 | 117.84 (6) | C23—C20—C19 | 120.95 (12) |
C6i—C5—C6 | 123.06 (12) | C22—C21—C20 | 120.53 (11) |
C6i—C5—C1 | 118.47 (6) | C22—C21—H21 | 119.7 |
C6—C5—C1 | 118.47 (6) | C20—C21—H21 | 119.7 |
C7—C6—C5 | 118.67 (10) | C21—C22—C17 | 121.03 (10) |
C7—C6—H6 | 120.7 | C21—C22—H22 | 119.5 |
C5—C6—H6 | 120.7 | C17—C22—H22 | 119.5 |
C6—C7—C8 | 117.73 (10) | N3—C23—C20 | 179.0 (2) |
C6—C7—H7 | 121.1 | C25i—C24—C25 | 121.97 (13) |
C8—C7—H7 | 121.1 | C25i—C24—C4 | 119.02 (6) |
C9—C8—C7i | 117.94 (6) | C25—C24—C4 | 119.02 (6) |
C9—C8—C7 | 117.93 (6) | C26—C25—C24 | 119.14 (10) |
C7i—C8—C7 | 124.13 (13) | C26—C25—H25 | 120.4 |
N1—C9—C8 | 180.000 (1) | C24—C25—H25 | 120.4 |
C11—C10—C15 | 119.24 (9) | C25—C26—C27 | 118.44 (10) |
C11—C10—C2 | 118.50 (9) | C25—C26—H26 | 120.8 |
C15—C10—C2 | 122.25 (8) | C27—C26—H26 | 120.8 |
C10—C11—C12 | 118.53 (10) | C28—C27—C26 | 118.57 (7) |
C10—C11—H11 | 120.7 | C28—C27—C26i | 118.57 (7) |
C12—C11—H11 | 120.7 | C26—C27—C26i | 122.86 (13) |
C11—C12—C13 | 122.78 (10) | N4—C28—C27 | 180.0 |
C11—C12—H12 | 118.6 | Cl2—C29—Cl1 | 109.3 (3) |
C13—C12—H12 | 118.6 | Cl2—C29—H29A | 109.8 |
C14—C13—C16 | 118.58 (11) | Cl1—C29—H29A | 109.8 |
C14—C13—C12 | 118.41 (10) | Cl2—C29—H29B | 109.8 |
C16—C13—C12 | 123.01 (10) | Cl1—C29—H29B | 109.8 |
C13—C14—C15 | 118.45 (10) | H29A—C29—H29B | 108.3 |
C13—C14—H14 | 120.8 | Cl4—C30—Cl3 | 109.8 (4) |
C15—C14—H14 | 120.8 | Cl4—C30—H30A | 109.7 |
C14—C15—C10 | 122.58 (10) | Cl3—C30—H30A | 109.7 |
C14—C15—H15 | 118.7 | Cl4—C30—H30B | 109.7 |
C10—C15—H15 | 118.7 | Cl3—C30—H30B | 109.7 |
N2—C16—C13 | 178.37 (12) | H30A—C30—H30B | 108.2 |
Symmetry code: (i) −x, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C19—H19···N2ii | 0.95 | 2.65 | 3.5076 (17) | 151 |
C7—H7···N2iii | 0.95 | 2.61 | 3.5355 (16) | 165 |
C21—H21···N3iv | 0.95 | 2.69 | 3.320 (2) | 124 |
C29—H29B···N4v | 0.99 | 2.59 | 3.288 (9) | 127 |
Symmetry codes: (ii) −x+1, −y+1, −z; (iii) x−1/2, −y+3/2, −z; (iv) x−1/2, −y+1/2, −z; (v) x+1/2, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C48H24N6·2CH2Cl2 |
Mr | 854.58 |
Crystal system, space group | Orthorhombic, Pbcn |
Temperature (K) | 150 |
a, b, c (Å) | 11.0921 (3), 19.3442 (3), 20.1742 (4) |
V (Å3) | 4328.73 (16) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 2.82 |
Crystal size (mm) | 0.15 × 0.08 × 0.07 |
Data collection | |
Diffractometer | Bruker SMART 6000 diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2001) |
Tmin, Tmax | 0.700, 0.850 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 57445, 3865, 3494 |
Rint | 0.051 |
(sin θ/λ)max (Å−1) | 0.602 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.138, 1.02 |
No. of reflections | 3865 |
No. of parameters | 286 |
No. of restraints | 11 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.27, −0.28 |
Computer programs: SMART (Bruker, 2001), SMART, SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000), enCIFer (Allen et al., 2004) and publCIF (Westrip, 2006).
D—H···A | D—H | H···A | D···A | D—H···A |
C19—H19···N2i | 0.95 | 2.65 | 3.5076 (17) | 151 |
C7—H7···N2ii | 0.95 | 2.61 | 3.5355 (16) | 165 |
C21—H21···N3iii | 0.95 | 2.69 | 3.320 (2) | 124 |
C29—H29B···N4iv | 0.99 | 2.59 | 3.288 (9) | 127 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x−1/2, −y+3/2, −z; (iii) x−1/2, −y+1/2, −z; (iv) x+1/2, y+1/2, −z+1/2. |
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Networks of hydrogen bonds continue to be used extensively by crystal engineers to help maintain the integrity of crystals and to position their constituent molecules predictably (Wuest, 2005). Hydrogen bonds offer the advantages of strength and directionality, leading to the formation of robust networks that frequently define cavities or channels for the inclusion of guests. Crystal engineers have also explored the potential of weaker intermolecular interactions, which can exhibit some of the geometric, structural and spectroscopic characteristics of hydrogen bonds (Desiraju, 2002). For example, we recently reported a study of structures maintained in part by weak C—H···N interactions involving the nitrile groups of hexakis(4-cyanophenyl)benzene, (I) (Maly et al., 2006). Despite having a well defined molecular geometry imposed by the hexaphenylbenzene core, compound (I) crystallized under seven different sets of conditions to give inclusion compounds with widely different structures. Although networks maintained by C—H···N interactions were observed in all of these pseudopolymorphs, the particular geometries of the interactions varied widely and the overall structures proved to depend critically on the choice of solvent. These observations underscore the difficulty of using C—H···N interactions to engineer crystals with predictable structural features.
This conclusion has now been reinforced by the analysis of the structure of a new pseudopolymorph obtained by crystallizing compound (I) from CH3OH–CH2Cl2 as the dichloromethane disolvate, (II). In this structure, the molecule of (I) lies on an axis of twofold rotation directed through atoms C1 and C4 in the plane of the inner benzene ring composed of atoms C1–C4/C3i/C2i [symmetry code: (i) −x, y, −z + 1/2]. The hexaphenylbenzene core of compound (II) has a chiral propeller conformation, with torsion angles in the range 61.97 (4)–73.37 (4)° (Fig. 1). Similar conformations have been noted in other pseudopolymorphs of compound (I) (Maly et al., 2006).
The observed structure contains equal numbers of each enantiomer. The disc-like shape of hexaphenylbenzene and its derivatives normally favors structures in which the molecules lie parallel and define distinct layers. For example, hexaphenylbenzene itself (Bart, 1968), its inclusion compound with anisole (Larson et al., 1990), and its derivatives substituted in the para position by 4-(carboxyphenyl)ethynyl (Kobayashi et al., 2005), iodo (Kobayashi et al., 2005), –COOH (Kobayashi et al., 2000), trifluorovinyloxy (Spraul et al., 2004), hydroxyl (Kobayashi et al., 1999), ethynyl (Constable et al., 2000), –CONH2 (Kobayashi et al., 2003) and –CN (Maly et al., 2006), all have crystal structures in which the molecules are roughly coplanar. In contrast, the new polymorph of (I) crystallizes to form a structure in which the molecules occupy two sets of planes, which intersect along the b axis at an angle of 68.29 (3)°. The only previously reported non-coplanar architecture was obtained when hexakis(4-carbamoylphenyl)benzene was crystallized under hydrothermal conditions (Kobayashi et al., 2003).
Each molecule of (I) is surrounded by 14 neighbors, with ten neighbors linked to the central molecule by a total of 12 C—H···N interactions involving H···N distances less than 2.80 Å and C—H···N angles greater than 90° (Fig. 2). Four additional neighbors have C—H···N interactions that are only slightly longer [H···N distances of 2.85 (1) Å] (Fig. 2). The resulting network defines spaces for including partially disordered molecules of CH2Cl2, which engage in van der Waals interactions and C—H···N interactions with nearby molecules of compound (I). Specifically, atom Cl1 is in close contact [3.324 (8) Å] with the centroid (Cg1) of the inner benzene ring of the molecule at (x + 1, y, z), with a C29—Cl1···Cg1 angle of 163.6 (3)°. Approximately 21% of the volume of the crystal is accessible to guests, as measured by standard methods (Spek, 2003). This value falls within the wide range of percentages (15–58%) found in the other seven known pseudopolymorphs of (I). It is interesting to note that compound (I) crystallizes from pure CH3OH as an inclusion compound of composition (I)·2CH3OH (Maly et al., 2006), whereas crystallization from CH3OH–CH2Cl2 produces an inclusion compound containing only CH2Cl2, which is presumably a preferred guest.
Together, these observations confirm that nitrile groups tend to engage in C—H···N interactions and can help direct the construction of open molecular networks. However, the use of these interactions in crystal engineering is limited by their weakness and lack of clear directional preferences, which lead, in the case of (II), to crystallization as multiple pseudopolymorphs with very diverse structures.