Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110001952/gd3326sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110001952/gd3326Itsup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110001952/gd3326Imsup3.hkl |
CCDC references: 774038; 774039
For related literature, see: Armelin et al. (2001); Bernstein (2002); Dunitz & Bernstein (1995); Henschel et al. (2005); Jones & Kuś (2004); Jones & Mangalagiu (2009); Jones et al. (2002); Lozano et al. (2004); Ossowski et al. (2006); Zerbe et al. (2007).
The title compound was synthesized from terephthaloyl chloride and N,N-diethyl-1,4- diaminobenzene in benzene solution (standard procedure). The resulting golden yellow solid was washed with toluene and methanol and dried in air. Yield ca 40%, m.p. 544 K (uncorrected). Analysis: calculated for C28H34N4O2 C 73.33, H 7.47, N 12.22; found C 73.29, H 7.76, N 12.45. 1H NMR (DMSO-d6/TMS, 400 MHz): δ 10.07 (s, 2H, NH), 8.04 (s, 4H, ArH), 7.54, 6.66 (dd, 4H, J = 9.1 Hz, ArH), 3.30 (q, 4H, –CH2CH3), 1.07 (t, 6H, –CH2CH3). 13C NMR (DMSO-d6/TMS, 100 MHz): δ 164.07, 144.57, 137.46, 127.55, 127.50, 122.49, 111.80, 43.85, 12.48. IR (cm-1, KBr pellets): 3435, 3325, 3049, 2968, 2930, 2867, 2829, 1639, 1593, 1517, 1414, 1387, 1372, 1346, 1325, 1286, 1263, 1246, 1188, 1144, 1117, 1074, 1057, 1017, 1007, 930, 896, 866, 830, 811, 782, 686, 643. ESI MS (m/z, intensity): 230 (5) [M+2H]+2, 459.5 (100) [M+H]+, 916.8 (52) [2M]+; 457.3 (100) [M—H]-. Single crystals were obtained from DMSO-d6 solution (after NMR measurement). Both forms crystallized together in the NMR tube.
For polymorph (It) NH H atoms were refined freely. Methyl H atoms were located in difference syntheses, idealized to C—H 0.98 Å and H—C—H 109.5°, and refined as rigid groups allowed to rotate but not tip. Other H atoms were placed in calculated positions (C—H 0.95 Å for aromatic H and 0.99 Å for methylene H) and refined using a riding model. U(H) were set as 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms.
The initial R values were rather high and inspection showed that the crystal was non-merohedrally twinned by rotation of 180° about c*. For refinement, the HKLF 5 option was employed. Scale factors of five reflection batches, corresponding to different extents of twin overlap, indicated that the main component was occupied to the extent of 92%. The untwinning routines merge all equivalent reflections and thus no Rint value can be given. Data are only 93% complete to θ 67°, which may also be a consequence of the untwinning routines (rejection of poorly determined intensities).
For polymorph (Im) H atoms were refined as above, except that the N—H distances were restrained to be equal (SADI). The Flack parameter originally refined to 0.2 (4), which is essentially indeterminate (although successful determinations of absolute structure are, in principle, possible for Cu radiation and structures containing oxygen); for this reason, Friedel opposite reflections were merged and the resulting Flack parameter is meaningless. The necessarily poor data/parameter ratio was to some extent ameliorated by the use of restraints (SIMU, DELU) to the displacement parameters. Data are 98% complete to θ 67°.
For both compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
C28H34N4O2 | Z = 1 |
Mr = 458.59 | F(000) = 246 |
Triclinic, P1 | Dx = 1.303 Mg m−3 |
Hall symbol: -P 1 | Cu Kα radiation, λ = 1.54184 Å |
a = 5.1100 (9) Å | Cell parameters from 3618 reflections |
b = 9.946 (3) Å | θ = 3.7–71.0° |
c = 12.107 (3) Å | µ = 0.66 mm−1 |
α = 100.54 (2)° | T = 100 K |
β = 93.90 (2)° | Plate, yellow |
γ = 103.53 (2)° | 0.35 × 0.30 × 0.08 mm |
V = 584.2 (3) Å3 |
Oxford Diffraction Xcalibur Nova O diffractometer | 4870 independent reflections |
Radiation source: Nova (Cu) X-ray Source | 4407 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.000 |
Detector resolution: 8.3648 pixels mm-1 | θmax = 72.6°, θmin = 3.7° |
ω–scan | h = −6→6 |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008) | k = −11→11 |
Tmin = 0.647, Tmax = 1.000 | l = −14→14 |
4870 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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.162 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.12 | w = 1/[σ2(Fo2) + (0.1021P)2 + 0.1859P] where P = (Fo2 + 2Fc2)/3 |
4870 reflections | (Δ/σ)max < 0.001 |
164 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
C28H34N4O2 | γ = 103.53 (2)° |
Mr = 458.59 | V = 584.2 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 5.1100 (9) Å | Cu Kα radiation |
b = 9.946 (3) Å | µ = 0.66 mm−1 |
c = 12.107 (3) Å | T = 100 K |
α = 100.54 (2)° | 0.35 × 0.30 × 0.08 mm |
β = 93.90 (2)° |
Oxford Diffraction Xcalibur Nova O diffractometer | 4870 independent reflections |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008) | 4407 reflections with I > 2σ(I) |
Tmin = 0.647, Tmax = 1.000 | Rint = 0.000 |
4870 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.162 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.12 | Δρmax = 0.24 e Å−3 |
4870 reflections | Δρmin = −0.19 e Å−3 |
164 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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 2.7986 (0.0027) x + 2.6768 (0.0051) y + 7.1697 (0.0060) z = 7.0531 (0.0041) * 0.0030 (0.0009) C5 * -0.0047 (0.0009) C6 * 0.0023 (0.0009) C7 * 0.0018 (0.0009) C8 * -0.0035 (0.0009) C9 * 0.0011 (0.0010) C10 Rms deviation of fitted atoms = 0.0030 - 0.8095 (0.0030) x + 4.3296 (0.0048) y + 9.7377 (0.0049) z = 8.7574 (0.0033) Angle to previous plane (with approximate e.s.d.) = 42.56 (0.05) * 0.0105 (0.0005) C1 * -0.0060 (0.0010) C4 * -0.0012 (0.0004) O1 * -0.0164 (0.0008) N1 * 0.0131 (0.0006) C5 Rms deviation of fitted atoms = 0.0108 - 3.0039 (0.0029) x + 3.7214 (0.0060) y + 9.0024 (0.0061) z = 6.7207 (0.0056) Angle to previous plane (with approximate e.s.d.) = 27.63 (0.07) * 0.0002 (0.0006) C1 * -0.0002 (0.0006) C2 * -0.0002 (0.0006) C3 * -0.0002 (0.0006) C1_$2 * 0.0002 (0.0006) C2_$2 * 0.0002 (0.0006) C3_$2 Rms deviation of fitted atoms = 0.0002 |
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 | 0.5038 (2) | 0.88397 (12) | 0.54926 (10) | 0.0251 (3) | |
C2 | 0.2791 (2) | 0.88202 (13) | 0.47505 (10) | 0.0258 (3) | |
H2 | 0.1287 | 0.8017 | 0.4580 | 0.031* | |
C3 | 0.7222 (2) | 1.00224 (13) | 0.57320 (10) | 0.0268 (3) | |
H3 | 0.8746 | 1.0037 | 0.6234 | 0.032* | |
C4 | 0.5222 (2) | 0.76179 (12) | 0.60342 (10) | 0.0255 (3) | |
C5 | 0.2607 (2) | 0.56035 (12) | 0.67321 (10) | 0.0259 (3) | |
C6 | 0.4141 (2) | 0.46253 (12) | 0.64875 (10) | 0.0266 (3) | |
H6 | 0.5392 | 0.4733 | 0.5945 | 0.032* | |
C7 | 0.3865 (2) | 0.34990 (13) | 0.70258 (10) | 0.0267 (3) | |
H7 | 0.4953 | 0.2852 | 0.6850 | 0.032* | |
C8 | 0.2031 (2) | 0.32801 (12) | 0.78224 (10) | 0.0256 (3) | |
C9 | 0.0475 (3) | 0.42747 (13) | 0.80512 (11) | 0.0293 (3) | |
H9 | −0.0804 | 0.4164 | 0.8582 | 0.035* | |
C10 | 0.0773 (3) | 0.54081 (13) | 0.75183 (11) | 0.0295 (3) | |
H10 | −0.0297 | 0.6065 | 0.7693 | 0.035* | |
C11 | 0.3357 (3) | 0.11204 (13) | 0.80000 (11) | 0.0292 (3) | |
H11A | 0.5265 | 0.1602 | 0.8296 | 0.035* | |
H11B | 0.3242 | 0.0892 | 0.7164 | 0.035* | |
C12 | 0.2560 (3) | −0.02507 (14) | 0.84292 (12) | 0.0378 (3) | |
H12A | 0.2880 | −0.0044 | 0.9257 | 0.057* | |
H12B | 0.3651 | −0.0888 | 0.8120 | 0.057* | |
H12C | 0.0636 | −0.0701 | 0.8186 | 0.057* | |
C13 | 0.1203 (3) | 0.23087 (14) | 0.95289 (11) | 0.0324 (3) | |
H13A | 0.0311 | 0.1386 | 0.9700 | 0.039* | |
H13B | −0.0054 | 0.2928 | 0.9657 | 0.039* | |
C14 | 0.3763 (3) | 0.29584 (15) | 1.03466 (12) | 0.0375 (3) | |
H14A | 0.4973 | 0.2322 | 1.0265 | 0.056* | |
H14B | 0.3291 | 0.3104 | 1.1123 | 0.056* | |
H14C | 0.4679 | 0.3868 | 1.0180 | 0.056* | |
N1 | 0.2843 (2) | 0.67814 (11) | 0.61977 (9) | 0.0261 (3) | |
H01 | 0.139 (4) | 0.7019 (17) | 0.6137 (13) | 0.033 (4)* | |
N2 | 0.1648 (2) | 0.20924 (11) | 0.83312 (9) | 0.0273 (3) | |
O1 | 0.74457 (17) | 0.74183 (9) | 0.63127 (8) | 0.0296 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0222 (7) | 0.0273 (6) | 0.0302 (6) | 0.0123 (5) | 0.0071 (5) | 0.0075 (5) |
C2 | 0.0204 (7) | 0.0259 (6) | 0.0335 (7) | 0.0092 (5) | 0.0042 (5) | 0.0076 (5) |
C3 | 0.0200 (7) | 0.0319 (6) | 0.0316 (6) | 0.0117 (5) | 0.0024 (5) | 0.0080 (5) |
C4 | 0.0241 (7) | 0.0257 (6) | 0.0296 (6) | 0.0120 (5) | 0.0036 (5) | 0.0054 (5) |
C5 | 0.0206 (7) | 0.0264 (6) | 0.0320 (6) | 0.0074 (5) | 0.0000 (5) | 0.0084 (5) |
C6 | 0.0244 (7) | 0.0272 (6) | 0.0300 (6) | 0.0095 (5) | 0.0040 (5) | 0.0064 (5) |
C7 | 0.0235 (7) | 0.0261 (6) | 0.0330 (6) | 0.0116 (5) | 0.0019 (5) | 0.0055 (5) |
C8 | 0.0200 (7) | 0.0260 (6) | 0.0305 (6) | 0.0062 (5) | −0.0017 (5) | 0.0061 (5) |
C9 | 0.0227 (7) | 0.0326 (6) | 0.0361 (7) | 0.0099 (5) | 0.0074 (5) | 0.0105 (5) |
C10 | 0.0232 (7) | 0.0293 (6) | 0.0399 (7) | 0.0126 (5) | 0.0054 (5) | 0.0086 (5) |
C11 | 0.0302 (7) | 0.0256 (6) | 0.0332 (7) | 0.0101 (5) | 0.0019 (5) | 0.0065 (5) |
C12 | 0.0466 (9) | 0.0281 (6) | 0.0399 (8) | 0.0102 (6) | 0.0019 (6) | 0.0100 (5) |
C13 | 0.0293 (8) | 0.0372 (7) | 0.0392 (7) | 0.0158 (6) | 0.0107 (5) | 0.0172 (6) |
C14 | 0.0416 (9) | 0.0399 (7) | 0.0348 (7) | 0.0187 (6) | 0.0036 (6) | 0.0065 (6) |
N1 | 0.0194 (6) | 0.0274 (5) | 0.0367 (6) | 0.0120 (5) | 0.0037 (4) | 0.0115 (4) |
N2 | 0.0247 (6) | 0.0265 (5) | 0.0335 (6) | 0.0085 (4) | 0.0037 (4) | 0.0106 (4) |
O1 | 0.0207 (5) | 0.0307 (4) | 0.0428 (5) | 0.0122 (4) | 0.0041 (4) | 0.0136 (4) |
C1—C3 | 1.3894 (19) | C13—C14 | 1.518 (2) |
C1—C2 | 1.4030 (19) | C2—H2 | 0.9500 |
C1—C4 | 1.5008 (16) | C3—H3 | 0.9500 |
C2—C3i | 1.3841 (17) | C6—H6 | 0.9500 |
C3—C2i | 1.3841 (17) | C7—H7 | 0.9500 |
C4—O1 | 1.2336 (15) | C9—H9 | 0.9500 |
C4—N1 | 1.3527 (17) | C10—H10 | 0.9500 |
C5—C10 | 1.3878 (18) | C11—H11A | 0.9900 |
C5—C6 | 1.3901 (17) | C11—H11B | 0.9900 |
C5—N1 | 1.4239 (16) | C12—H12A | 0.9800 |
C6—C7 | 1.3803 (17) | C12—H12B | 0.9800 |
C7—C8 | 1.3999 (18) | C12—H12C | 0.9800 |
C8—C9 | 1.4091 (17) | C13—H13A | 0.9900 |
C8—N2 | 1.4098 (16) | C13—H13B | 0.9900 |
C9—C10 | 1.3818 (18) | C14—H14A | 0.9800 |
C11—N2 | 1.4693 (15) | C14—H14B | 0.9800 |
C11—C12 | 1.5245 (18) | C14—H14C | 0.9800 |
C13—N2 | 1.4676 (17) | N1—H01 | 0.832 (18) |
C3—C1—C2 | 119.45 (11) | C6—C7—H7 | 119.0 |
C3—C1—C4 | 117.76 (11) | C8—C7—H7 | 119.0 |
C2—C1—C4 | 122.78 (11) | C10—C9—H9 | 119.3 |
C3i—C2—C1 | 119.65 (12) | C8—C9—H9 | 119.3 |
C2i—C3—C1 | 120.90 (11) | C9—C10—H10 | 119.4 |
O1—C4—N1 | 123.20 (10) | C5—C10—H10 | 119.4 |
O1—C4—C1 | 120.61 (11) | N2—C11—H11A | 108.9 |
N1—C4—C1 | 116.19 (10) | C12—C11—H11A | 108.9 |
C10—C5—C6 | 118.36 (11) | N2—C11—H11B | 108.9 |
C10—C5—N1 | 119.41 (10) | C12—C11—H11B | 108.9 |
C6—C5—N1 | 122.24 (11) | H11A—C11—H11B | 107.7 |
C7—C6—C5 | 120.61 (11) | C11—C12—H12A | 109.5 |
C6—C7—C8 | 122.09 (10) | C11—C12—H12B | 109.5 |
C7—C8—C9 | 116.48 (11) | H12A—C12—H12B | 109.5 |
C7—C8—N2 | 122.18 (10) | C11—C12—H12C | 109.5 |
C9—C8—N2 | 121.26 (11) | H12A—C12—H12C | 109.5 |
C10—C9—C8 | 121.31 (11) | H12B—C12—H12C | 109.5 |
C9—C10—C5 | 121.15 (10) | N2—C13—H13A | 108.6 |
N2—C11—C12 | 113.44 (11) | C14—C13—H13A | 108.6 |
N2—C13—C14 | 114.45 (11) | N2—C13—H13B | 108.6 |
C4—N1—C5 | 124.43 (10) | C14—C13—H13B | 108.6 |
C8—N2—C13 | 117.29 (10) | H13A—C13—H13B | 107.6 |
C8—N2—C11 | 115.79 (10) | C13—C14—H14A | 109.5 |
C13—N2—C11 | 114.75 (9) | C13—C14—H14B | 109.5 |
C3i—C2—H2 | 120.2 | H14A—C14—H14B | 109.5 |
C1—C2—H2 | 120.2 | C13—C14—H14C | 109.5 |
C2i—C3—H3 | 119.5 | H14A—C14—H14C | 109.5 |
C1—C3—H3 | 119.5 | H14B—C14—H14C | 109.5 |
C7—C6—H6 | 119.7 | C4—N1—H01 | 122.0 (11) |
C5—C6—H6 | 119.7 | C5—N1—H01 | 112.0 (11) |
C3—C1—C2—C3i | −0.07 (18) | C8—C9—C10—C5 | 0.4 (2) |
C4—C1—C2—C3i | −179.00 (10) | C6—C5—C10—C9 | 0.2 (2) |
C2—C1—C3—C2i | 0.07 (18) | N1—C5—C10—C9 | 179.70 (12) |
C4—C1—C3—C2i | 179.06 (10) | O1—C4—N1—C5 | 1.76 (19) |
C3—C1—C4—O1 | −26.53 (16) | C1—C4—N1—C5 | −177.78 (10) |
C2—C1—C4—O1 | 152.42 (12) | C10—C5—N1—C4 | 136.23 (13) |
C3—C1—C4—N1 | 153.02 (11) | C6—C5—N1—C4 | −44.32 (18) |
C2—C1—C4—N1 | −28.03 (16) | C7—C8—N2—C13 | 142.46 (13) |
C10—C5—C6—C7 | −0.79 (19) | C9—C8—N2—C13 | −40.81 (17) |
N1—C5—C6—C7 | 179.76 (12) | C7—C8—N2—C11 | 1.87 (18) |
C5—C6—C7—C8 | 0.7 (2) | C9—C8—N2—C11 | 178.60 (11) |
C6—C7—C8—C9 | −0.13 (19) | C14—C13—N2—C8 | −79.16 (13) |
C6—C7—C8—N2 | 176.75 (12) | C14—C13—N2—C11 | 61.83 (14) |
C7—C8—C9—C10 | −0.44 (19) | C12—C11—N2—C8 | −171.05 (11) |
N2—C8—C9—C10 | −177.35 (12) | C12—C11—N2—C13 | 47.36 (15) |
Symmetry code: (i) −x+1, −y+2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H01···O1ii | 0.832 (18) | 2.161 (18) | 2.9773 (14) | 166.8 (14) |
Symmetry code: (ii) x−1, y, z. |
C28H34N4O2 | F(000) = 984 |
Mr = 458.59 | Dx = 1.278 Mg m−3 |
Monoclinic, Cc | Cu Kα radiation, λ = 1.54184 Å |
Hall symbol: C -2yc | Cell parameters from 11451 reflections |
a = 11.5899 (6) Å | θ = 3.6–70.8° |
b = 16.7899 (8) Å | µ = 0.64 mm−1 |
c = 13.4785 (8) Å | T = 100 K |
β = 114.667 (6)° | Plate, yellow |
V = 2383.5 (2) Å3 | 0.30 × 0.20 × 0.08 mm |
Z = 4 |
Oxford Diffraction Xcalibur Nova O diffractometer | 2182 independent reflections |
Radiation source: Nova (Cu) X-ray Source | 2167 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.022 |
Detector resolution: 8.3648 pixels mm-1 | θmax = 71.3°, θmin = 5.0° |
ω–scan | h = −13→14 |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008) | k = −19→19 |
Tmin = 0.810, Tmax = 1.000 | l = −16→15 |
12374 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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.153 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0495P)2 + 10.0008P] where P = (Fo2 + 2Fc2)/3 |
2182 reflections | (Δ/σ)max < 0.001 |
319 parameters | Δρmax = 0.34 e Å−3 |
303 restraints | Δρmin = −0.31 e Å−3 |
C28H34N4O2 | V = 2383.5 (2) Å3 |
Mr = 458.59 | Z = 4 |
Monoclinic, Cc | Cu Kα radiation |
a = 11.5899 (6) Å | µ = 0.64 mm−1 |
b = 16.7899 (8) Å | T = 100 K |
c = 13.4785 (8) Å | 0.30 × 0.20 × 0.08 mm |
β = 114.667 (6)° |
Oxford Diffraction Xcalibur Nova O diffractometer | 2182 independent reflections |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008) | 2167 reflections with I > 2σ(I) |
Tmin = 0.810, Tmax = 1.000 | Rint = 0.022 |
12374 measured reflections |
R[F2 > 2σ(F2)] = 0.055 | 303 restraints |
wR(F2) = 0.153 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0495P)2 + 10.0008P] where P = (Fo2 + 2Fc2)/3 |
2182 reflections | Δρmax = 0.34 e Å−3 |
319 parameters | Δρmin = −0.31 e Å−3 |
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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 4.5593 (0.0219) x + 15.2254 (0.0144) y - 4.0675 (0.0246) z = 7.0107 (0.0100) * -0.0065 (0.0034) C8 * 0.0009 (0.0035) C9 * 0.0099 (0.0036) C10 * -0.0151 (0.0035) C11 * 0.0101 (0.0036) C12 * 0.0008 (0.0035) C13 Rms deviation of fitted atoms = 0.0089 - 10.9233 (0.0095) x + 5.6010 (0.0381) y + 5.5585 (0.0218) z = 0.8202 (0.0139) Angle to previous plane (with approximate e.s.d.) = 85.90 (0.16) * 0.0122 (0.0022) C1 * -0.0163 (0.0038) C7 * 0.0030 (0.0014) O1 * -0.0100 (0.0036) N1 * 0.0111 (0.0026) C8 Rms deviation of fitted atoms = 0.0114 9.8492 (0.0116) x + 8.7212 (0.0272) y - 5.8768 (0.0225) z = 4.3542 (0.0094) Angle to previous plane (with approximate e.s.d.) = 50.98 (0.12) * -0.0338 (0.0033) C1 * 0.0254 (0.0034) C2 * 0.0065 (0.0034) C3 * -0.0294 (0.0033) C4 * 0.0209 (0.0032) C5 * 0.0105 (0.0032) C6 Rms deviation of fitted atoms = 0.0232 9.4236 (0.0162) x + 9.7655 (0.0325) y - 4.2751 (0.0258) z = 4.9220 (0.0152) Angle to previous plane (with approximate e.s.d.) = 7.73 (0.27) * -0.0104 (0.0022) C4 * 0.0121 (0.0041) C18 * -0.0019 (0.0016) O2 * 0.0103 (0.0033) N3 * -0.0102 (0.0024) C19 Rms deviation of fitted atoms = 0.0097 6.0442 (0.0200) x + 14.3167 (0.0177) y - 2.5573 (0.0263) z = 6.1798 (0.0144) Angle to previous plane (with approximate e.s.d.) = 22.97 (1/4) * 0.0123 (0.0035) C19 * -0.0030 (0.0036) C20 * -0.0078 (0.0036) C21 * 0.0094 (0.0034) C22 * -0.0003 (0.0035) C23 * -0.0105 (0.0036) C24 Rms deviation of fitted atoms = 0.0084 |
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. In the absence of significant anomalous dispersion effects, Friedel opposite reflections were merged and the Flack parameter is thus meaningless. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.0757 (5) | 0.3639 (3) | −0.0683 (4) | 0.0206 (9) | |
C2 | 0.0436 (5) | 0.4332 (3) | −0.0292 (4) | 0.0245 (10) | |
H2 | −0.0134 | 0.4704 | −0.0786 | 0.029* | |
C3 | 0.0953 (4) | 0.4478 (3) | 0.0823 (4) | 0.0225 (10) | |
H3 | 0.0708 | 0.4945 | 0.1084 | 0.027* | |
C4 | 0.1814 (4) | 0.3963 (3) | 0.1562 (4) | 0.0215 (9) | |
C5 | 0.2219 (4) | 0.3288 (3) | 0.1155 (4) | 0.0219 (10) | |
H5 | 0.2855 | 0.2944 | 0.1640 | 0.026* | |
C6 | 0.1679 (4) | 0.3141 (3) | 0.0049 (4) | 0.0229 (10) | |
H6 | 0.1943 | 0.2687 | −0.0222 | 0.028* | |
C7 | 0.0067 (4) | 0.3399 (3) | −0.1847 (4) | 0.0200 (9) | |
C8 | −0.0712 (5) | 0.3813 (3) | −0.3745 (4) | 0.0212 (9) | |
C9 | −0.1963 (5) | 0.4044 (3) | −0.4299 (4) | 0.0252 (10) | |
H9 | −0.2392 | 0.4277 | −0.3905 | 0.030* | |
C10 | −0.2601 (5) | 0.3944 (3) | −0.5412 (4) | 0.0263 (11) | |
H10 | −0.3456 | 0.4119 | −0.5774 | 0.032* | |
C11 | −0.2002 (5) | 0.3583 (3) | −0.6030 (4) | 0.0234 (10) | |
C12 | −0.0720 (5) | 0.3370 (3) | −0.5453 (4) | 0.0276 (11) | |
H12 | −0.0272 | 0.3149 | −0.5838 | 0.033* | |
C13 | −0.0096 (5) | 0.3476 (3) | −0.4334 (4) | 0.0244 (10) | |
H13 | 0.0766 | 0.3316 | −0.3963 | 0.029* | |
C14 | −0.3964 (5) | 0.3673 (4) | −0.7742 (4) | 0.0342 (12) | |
H14A | −0.4432 | 0.3588 | −0.7282 | 0.041* | |
H14B | −0.4358 | 0.3330 | −0.8396 | 0.041* | |
C15 | −0.4113 (6) | 0.4543 (4) | −0.8106 (5) | 0.0425 (14) | |
H15A | −0.3693 | 0.4887 | −0.7469 | 0.064* | |
H15B | −0.5017 | 0.4677 | −0.8465 | 0.064* | |
H15C | −0.3723 | 0.4622 | −0.8620 | 0.064* | |
C16 | −0.1987 (5) | 0.3107 (3) | −0.7754 (4) | 0.0324 (12) | |
H16A | −0.2626 | 0.2888 | −0.8448 | 0.039* | |
H16B | −0.1441 | 0.2661 | −0.7340 | 0.039* | |
C17 | −0.1164 (6) | 0.3711 (4) | −0.8018 (5) | 0.0420 (14) | |
H17A | −0.1694 | 0.4155 | −0.8433 | 0.063* | |
H17B | −0.0774 | 0.3451 | −0.8453 | 0.063* | |
H17C | −0.0498 | 0.3912 | −0.7337 | 0.063* | |
C18 | 0.2197 (5) | 0.4132 (3) | 0.2738 (4) | 0.0235 (10) | |
C19 | 0.3509 (5) | 0.3671 (3) | 0.4631 (4) | 0.0220 (10) | |
C20 | 0.2875 (5) | 0.4027 (3) | 0.5187 (4) | 0.0240 (10) | |
H20 | 0.2085 | 0.4285 | 0.4792 | 0.029* | |
C21 | 0.3391 (5) | 0.4008 (3) | 0.6318 (4) | 0.0237 (10) | |
H21 | 0.2939 | 0.4253 | 0.6685 | 0.028* | |
C22 | 0.4560 (5) | 0.3638 (3) | 0.6941 (4) | 0.0224 (10) | |
C23 | 0.5173 (4) | 0.3269 (3) | 0.6362 (4) | 0.0237 (10) | |
H23 | 0.5960 | 0.3007 | 0.6752 | 0.028* | |
C24 | 0.4654 (5) | 0.3279 (3) | 0.5233 (4) | 0.0249 (10) | |
H24 | 0.5083 | 0.3015 | 0.4861 | 0.030* | |
C25 | 0.4663 (5) | 0.4217 (3) | 0.8678 (4) | 0.0266 (11) | |
H25A | 0.4277 | 0.4688 | 0.8215 | 0.032* | |
H25B | 0.5409 | 0.4402 | 0.9328 | 0.032* | |
C26 | 0.3705 (5) | 0.3856 (3) | 0.9044 (4) | 0.0319 (12) | |
H26A | 0.2969 | 0.3663 | 0.8405 | 0.048* | |
H26B | 0.3430 | 0.4260 | 0.9423 | 0.048* | |
H26C | 0.4098 | 0.3410 | 0.9540 | 0.048* | |
C27 | 0.6219 (5) | 0.3190 (3) | 0.8716 (4) | 0.0246 (10) | |
H27A | 0.6181 | 0.2680 | 0.8336 | 0.030* | |
H27B | 0.6208 | 0.3066 | 0.9430 | 0.030* | |
C28 | 0.7460 (5) | 0.3603 (3) | 0.8914 (4) | 0.0320 (11) | |
H28A | 0.7484 | 0.3726 | 0.8212 | 0.048* | |
H28B | 0.8171 | 0.3252 | 0.9338 | 0.048* | |
H28C | 0.7526 | 0.4098 | 0.9320 | 0.048* | |
N1 | −0.0042 (4) | 0.3937 (3) | −0.2593 (3) | 0.0250 (9) | |
H01 | 0.049 (5) | 0.438 (3) | −0.237 (5) | 0.032 (16)* | |
N2 | −0.2643 (4) | 0.3425 (3) | −0.7129 (3) | 0.0286 (9) | |
N3 | 0.3054 (4) | 0.3625 (2) | 0.3474 (3) | 0.0229 (9) | |
H03 | 0.352 (4) | 0.328 (3) | 0.325 (4) | 0.012 (12)* | |
N4 | 0.5086 (4) | 0.3660 (3) | 0.8067 (3) | 0.0254 (9) | |
O1 | −0.0413 (3) | 0.27224 (19) | −0.2074 (3) | 0.0265 (7) | |
O2 | 0.1730 (4) | 0.4695 (2) | 0.3030 (3) | 0.0293 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.028 (2) | 0.015 (2) | 0.022 (2) | −0.0034 (18) | 0.0127 (19) | 0.0028 (17) |
C2 | 0.024 (2) | 0.024 (3) | 0.025 (2) | 0.0028 (19) | 0.0099 (19) | 0.0056 (19) |
C3 | 0.028 (2) | 0.016 (2) | 0.024 (2) | −0.0032 (18) | 0.0117 (19) | −0.0016 (18) |
C4 | 0.023 (2) | 0.017 (2) | 0.024 (2) | −0.0045 (18) | 0.0095 (18) | 0.0001 (17) |
C5 | 0.023 (2) | 0.019 (2) | 0.024 (2) | 0.0031 (18) | 0.0104 (19) | 0.0070 (19) |
C6 | 0.025 (2) | 0.015 (2) | 0.034 (2) | −0.0051 (17) | 0.0164 (19) | −0.0012 (19) |
C7 | 0.021 (2) | 0.014 (2) | 0.029 (2) | −0.0004 (18) | 0.0139 (18) | −0.0008 (18) |
C8 | 0.034 (3) | 0.007 (2) | 0.023 (2) | −0.0062 (18) | 0.0126 (19) | −0.0014 (17) |
C9 | 0.031 (3) | 0.022 (3) | 0.029 (2) | 0.001 (2) | 0.018 (2) | 0.000 (2) |
C10 | 0.027 (2) | 0.026 (3) | 0.027 (2) | 0.004 (2) | 0.011 (2) | 0.002 (2) |
C11 | 0.035 (3) | 0.013 (2) | 0.023 (2) | −0.0021 (19) | 0.0134 (19) | 0.0013 (18) |
C12 | 0.034 (3) | 0.024 (3) | 0.026 (2) | 0.001 (2) | 0.013 (2) | −0.004 (2) |
C13 | 0.028 (2) | 0.017 (2) | 0.028 (2) | 0.0026 (19) | 0.0109 (19) | 0.0011 (19) |
C14 | 0.038 (3) | 0.035 (3) | 0.028 (3) | 0.001 (2) | 0.011 (2) | 0.002 (2) |
C15 | 0.054 (4) | 0.031 (3) | 0.039 (3) | 0.007 (3) | 0.016 (3) | 0.000 (2) |
C16 | 0.043 (3) | 0.031 (3) | 0.023 (3) | 0.002 (2) | 0.013 (2) | −0.008 (2) |
C17 | 0.050 (4) | 0.041 (4) | 0.042 (3) | 0.000 (3) | 0.025 (3) | 0.001 (3) |
C18 | 0.028 (2) | 0.014 (2) | 0.027 (2) | −0.0005 (18) | 0.0100 (19) | 0.0019 (18) |
C19 | 0.025 (2) | 0.018 (2) | 0.023 (2) | −0.0012 (18) | 0.0100 (19) | 0.0000 (18) |
C20 | 0.025 (2) | 0.022 (3) | 0.024 (2) | 0.0014 (18) | 0.0085 (19) | 0.0038 (19) |
C21 | 0.024 (2) | 0.026 (3) | 0.023 (2) | 0.0018 (19) | 0.0117 (18) | −0.003 (2) |
C22 | 0.027 (2) | 0.019 (2) | 0.023 (2) | 0.0000 (18) | 0.0113 (19) | 0.0005 (19) |
C23 | 0.022 (2) | 0.023 (3) | 0.025 (2) | 0.0030 (18) | 0.0078 (19) | 0.0015 (19) |
C24 | 0.030 (3) | 0.021 (3) | 0.024 (2) | −0.0009 (19) | 0.013 (2) | −0.0030 (19) |
C25 | 0.031 (3) | 0.028 (3) | 0.021 (2) | 0.004 (2) | 0.0097 (19) | 0.002 (2) |
C26 | 0.035 (3) | 0.030 (3) | 0.034 (3) | 0.006 (2) | 0.019 (2) | 0.003 (2) |
C27 | 0.029 (2) | 0.024 (3) | 0.019 (2) | 0.0028 (19) | 0.0087 (19) | 0.0018 (18) |
C28 | 0.028 (3) | 0.037 (3) | 0.028 (3) | 0.002 (2) | 0.009 (2) | 0.001 (2) |
N1 | 0.034 (2) | 0.018 (2) | 0.0218 (19) | −0.0037 (18) | 0.0108 (17) | 0.0014 (17) |
N2 | 0.031 (2) | 0.029 (2) | 0.025 (2) | −0.0003 (18) | 0.0118 (18) | 0.0000 (18) |
N3 | 0.027 (2) | 0.019 (2) | 0.023 (2) | 0.0024 (16) | 0.0105 (17) | 0.0021 (16) |
N4 | 0.025 (2) | 0.032 (2) | 0.0186 (19) | 0.0046 (18) | 0.0081 (16) | 0.0002 (17) |
O1 | 0.0390 (19) | 0.0191 (17) | 0.0187 (15) | −0.0043 (15) | 0.0094 (14) | 0.0006 (13) |
O2 | 0.040 (2) | 0.0230 (18) | 0.0200 (16) | 0.0062 (16) | 0.0078 (14) | −0.0027 (14) |
C1—C2 | 1.390 (7) | C27—C28 | 1.517 (7) |
C1—C6 | 1.391 (7) | C2—H2 | 0.9500 |
C1—C7 | 1.490 (6) | C3—H3 | 0.9500 |
C2—C3 | 1.388 (7) | C5—H5 | 0.9500 |
C3—C4 | 1.380 (7) | C6—H6 | 0.9500 |
C4—C5 | 1.421 (7) | C9—H9 | 0.9500 |
C4—C18 | 1.485 (7) | C10—H10 | 0.9500 |
C5—C6 | 1.378 (7) | C12—H12 | 0.9500 |
C7—O1 | 1.245 (6) | C13—H13 | 0.9500 |
C7—N1 | 1.318 (6) | C14—H14A | 0.9900 |
C8—C9 | 1.382 (7) | C14—H14B | 0.9900 |
C8—C13 | 1.390 (7) | C15—H15A | 0.9800 |
C8—N1 | 1.432 (6) | C15—H15B | 0.9800 |
C9—C10 | 1.379 (7) | C15—H15C | 0.9800 |
C10—C11 | 1.423 (7) | C16—H16A | 0.9900 |
C11—N2 | 1.378 (6) | C16—H16B | 0.9900 |
C11—C12 | 1.406 (7) | C17—H17A | 0.9800 |
C12—C13 | 1.385 (7) | C17—H17B | 0.9800 |
C14—N2 | 1.465 (7) | C17—H17C | 0.9800 |
C14—C15 | 1.526 (8) | C20—H20 | 0.9500 |
C16—N2 | 1.452 (7) | C21—H21 | 0.9500 |
C16—C17 | 1.532 (8) | C23—H23 | 0.9500 |
C18—O2 | 1.232 (6) | C24—H24 | 0.9500 |
C18—N3 | 1.368 (6) | C25—H25A | 0.9900 |
C19—C20 | 1.386 (7) | C25—H25B | 0.9900 |
C19—C24 | 1.398 (7) | C26—H26A | 0.9800 |
C19—N3 | 1.425 (6) | C26—H26B | 0.9800 |
C20—C21 | 1.387 (7) | C26—H26C | 0.9800 |
C21—C22 | 1.406 (7) | C27—H27A | 0.9900 |
C22—N4 | 1.379 (6) | C27—H27B | 0.9900 |
C22—C23 | 1.401 (7) | C28—H28A | 0.9800 |
C23—C24 | 1.384 (7) | C28—H28B | 0.9800 |
C25—N4 | 1.460 (6) | C28—H28C | 0.9800 |
C25—C26 | 1.517 (7) | N1—H01 | 0.93 (4) |
C27—N4 | 1.467 (6) | N3—H03 | 0.92 (4) |
C2—C1—C6 | 118.9 (4) | C13—C12—H12 | 119.3 |
C2—C1—C7 | 121.0 (4) | C11—C12—H12 | 119.3 |
C6—C1—C7 | 120.0 (4) | C12—C13—H13 | 119.5 |
C3—C2—C1 | 119.7 (4) | C8—C13—H13 | 119.5 |
C4—C3—C2 | 121.7 (5) | N2—C14—H14A | 108.8 |
C3—C4—C5 | 118.5 (4) | C15—C14—H14A | 108.8 |
C3—C4—C18 | 117.1 (4) | N2—C14—H14B | 108.8 |
C5—C4—C18 | 124.4 (4) | C15—C14—H14B | 108.8 |
C6—C5—C4 | 119.1 (4) | H14A—C14—H14B | 107.7 |
C5—C6—C1 | 121.8 (4) | C14—C15—H15A | 109.5 |
O1—C7—N1 | 123.2 (4) | C14—C15—H15B | 109.5 |
O1—C7—C1 | 119.6 (4) | H15A—C15—H15B | 109.5 |
N1—C7—C1 | 117.1 (4) | C14—C15—H15C | 109.5 |
C9—C8—C13 | 118.7 (4) | H15A—C15—H15C | 109.5 |
C9—C8—N1 | 121.1 (4) | H15B—C15—H15C | 109.5 |
C13—C8—N1 | 120.2 (4) | N2—C16—H16A | 108.6 |
C10—C9—C8 | 121.3 (4) | C17—C16—H16A | 108.6 |
C9—C10—C11 | 121.1 (5) | N2—C16—H16B | 108.6 |
N2—C11—C12 | 121.1 (4) | C17—C16—H16B | 108.6 |
N2—C11—C10 | 122.3 (5) | H16A—C16—H16B | 107.5 |
C12—C11—C10 | 116.5 (4) | C16—C17—H17A | 109.5 |
C13—C12—C11 | 121.4 (5) | C16—C17—H17B | 109.5 |
C12—C13—C8 | 120.9 (5) | H17A—C17—H17B | 109.5 |
N2—C14—C15 | 113.9 (5) | C16—C17—H17C | 109.5 |
N2—C16—C17 | 114.8 (5) | H17A—C17—H17C | 109.5 |
O2—C18—N3 | 121.9 (5) | H17B—C17—H17C | 109.5 |
O2—C18—C4 | 120.8 (4) | C19—C20—H20 | 119.9 |
N3—C18—C4 | 117.3 (4) | C21—C20—H20 | 119.9 |
C20—C19—C24 | 118.6 (4) | C20—C21—H21 | 118.9 |
C20—C19—N3 | 125.3 (4) | C22—C21—H21 | 118.9 |
C24—C19—N3 | 116.0 (4) | C24—C23—H23 | 119.3 |
C19—C20—C21 | 120.1 (5) | C22—C23—H23 | 119.3 |
C20—C21—C22 | 122.2 (5) | C23—C24—H24 | 119.5 |
N4—C22—C23 | 122.1 (4) | C19—C24—H24 | 119.5 |
N4—C22—C21 | 121.2 (4) | N4—C25—H25A | 109.0 |
C23—C22—C21 | 116.7 (4) | C26—C25—H25A | 109.0 |
C24—C23—C22 | 121.3 (4) | N4—C25—H25B | 109.0 |
C23—C24—C19 | 121.0 (4) | C26—C25—H25B | 109.0 |
N4—C25—C26 | 112.9 (4) | H25A—C25—H25B | 107.8 |
N4—C27—C28 | 114.0 (4) | C25—C26—H26A | 109.5 |
C7—N1—C8 | 124.2 (4) | C25—C26—H26B | 109.5 |
C11—N2—C16 | 121.1 (4) | H26A—C26—H26B | 109.5 |
C11—N2—C14 | 121.3 (4) | C25—C26—H26C | 109.5 |
C16—N2—C14 | 117.0 (4) | H26A—C26—H26C | 109.5 |
C18—N3—C19 | 125.8 (4) | H26B—C26—H26C | 109.5 |
C22—N4—C25 | 122.6 (4) | N4—C27—H27A | 108.8 |
C22—N4—C27 | 121.1 (4) | C28—C27—H27A | 108.8 |
C25—N4—C27 | 115.8 (4) | N4—C27—H27B | 108.8 |
C3—C2—H2 | 120.1 | C28—C27—H27B | 108.8 |
C1—C2—H2 | 120.1 | H27A—C27—H27B | 107.6 |
C4—C3—H3 | 119.1 | C27—C28—H28A | 109.5 |
C2—C3—H3 | 119.1 | C27—C28—H28B | 109.5 |
C6—C5—H5 | 120.5 | H28A—C28—H28B | 109.5 |
C4—C5—H5 | 120.5 | C27—C28—H28C | 109.5 |
C5—C6—H6 | 119.1 | H28A—C28—H28C | 109.5 |
C1—C6—H6 | 119.1 | H28B—C28—H28C | 109.5 |
C10—C9—H9 | 119.3 | C7—N1—H01 | 117 (4) |
C8—C9—H9 | 119.3 | C8—N1—H01 | 117 (4) |
C9—C10—H10 | 119.4 | C18—N3—H03 | 120 (3) |
C11—C10—H10 | 119.4 | C19—N3—H03 | 113 (3) |
C6—C1—C2—C3 | −5.7 (7) | C20—C21—C22—N4 | 176.8 (5) |
C7—C1—C2—C3 | 169.9 (4) | C20—C21—C22—C23 | −1.5 (7) |
C1—C2—C3—C4 | 2.0 (7) | N4—C22—C23—C24 | −177.5 (5) |
C2—C3—C4—C5 | 3.1 (7) | C21—C22—C23—C24 | 0.7 (7) |
C2—C3—C4—C18 | −173.5 (4) | C22—C23—C24—C19 | 1.1 (8) |
C3—C4—C5—C6 | −4.4 (7) | C20—C19—C24—C23 | −2.3 (7) |
C18—C4—C5—C6 | 171.9 (4) | N3—C19—C24—C23 | −178.6 (4) |
C4—C5—C6—C1 | 0.7 (7) | O1—C7—N1—C8 | −0.4 (8) |
C2—C1—C6—C5 | 4.4 (7) | C1—C7—N1—C8 | −177.8 (4) |
C7—C1—C6—C5 | −171.3 (4) | C9—C8—N1—C7 | 94.8 (6) |
C2—C1—C7—O1 | −126.1 (5) | C13—C8—N1—C7 | −87.1 (6) |
C6—C1—C7—O1 | 49.5 (6) | C12—C11—N2—C16 | −6.3 (7) |
C2—C1—C7—N1 | 51.4 (6) | C10—C11—N2—C16 | 175.7 (5) |
C6—C1—C7—N1 | −133.0 (5) | C12—C11—N2—C14 | −177.6 (5) |
C13—C8—C9—C10 | 0.3 (7) | C10—C11—N2—C14 | 4.4 (7) |
N1—C8—C9—C10 | 178.4 (5) | C17—C16—N2—C11 | −74.9 (6) |
C8—C9—C10—C11 | 1.3 (8) | C17—C16—N2—C14 | 96.8 (6) |
C9—C10—C11—N2 | 175.4 (5) | C15—C14—N2—C11 | 81.9 (6) |
C9—C10—C11—C12 | −2.7 (7) | C15—C14—N2—C16 | −89.8 (6) |
N2—C11—C12—C13 | −175.4 (5) | O2—C18—N3—C19 | 0.1 (8) |
C10—C11—C12—C13 | 2.7 (7) | C4—C18—N3—C19 | −178.0 (4) |
C11—C12—C13—C8 | −1.3 (8) | C20—C19—N3—C18 | 24.4 (8) |
C9—C8—C13—C12 | −0.2 (7) | C24—C19—N3—C18 | −159.6 (5) |
N1—C8—C13—C12 | −178.4 (4) | C23—C22—N4—C25 | 162.3 (5) |
C3—C4—C18—O2 | 2.1 (7) | C21—C22—N4—C25 | −15.9 (7) |
C5—C4—C18—O2 | −174.3 (5) | C23—C22—N4—C27 | −9.7 (7) |
C3—C4—C18—N3 | −179.7 (4) | C21—C22—N4—C27 | 172.2 (5) |
C5—C4—C18—N3 | 3.9 (7) | C26—C25—N4—C22 | 96.6 (5) |
C24—C19—C20—C21 | 1.5 (7) | C26—C25—N4—C27 | −91.1 (5) |
N3—C19—C20—C21 | 177.5 (5) | C28—C27—N4—C22 | 86.1 (6) |
C19—C20—C21—C22 | 0.3 (8) | C28—C27—N4—C25 | −86.3 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H01···O2i | 0.93 (4) | 2.03 (4) | 2.960 (5) | 175 (6) |
N3—H03···O1ii | 0.92 (4) | 2.24 (4) | 3.149 (5) | 168 (4) |
C5—H5···O1ii | 0.95 | 2.32 | 3.262 (6) | 171 |
C14—H14A···O1iii | 0.99 | 2.55 | 3.223 (7) | 126 |
Symmetry codes: (i) x, −y+1, z−1/2; (ii) x+1/2, −y+1/2, z+1/2; (iii) x−1/2, −y+1/2, z−1/2. |
Experimental details
(It) | (Im) | |
Crystal data | ||
Chemical formula | C28H34N4O2 | C28H34N4O2 |
Mr | 458.59 | 458.59 |
Crystal system, space group | Triclinic, P1 | Monoclinic, Cc |
Temperature (K) | 100 | 100 |
a, b, c (Å) | 5.1100 (9), 9.946 (3), 12.107 (3) | 11.5899 (6), 16.7899 (8), 13.4785 (8) |
α, β, γ (°) | 100.54 (2), 93.90 (2), 103.53 (2) | 90, 114.667 (6), 90 |
V (Å3) | 584.2 (3) | 2383.5 (2) |
Z | 1 | 4 |
Radiation type | Cu Kα | Cu Kα |
µ (mm−1) | 0.66 | 0.64 |
Crystal size (mm) | 0.35 × 0.30 × 0.08 | 0.30 × 0.20 × 0.08 |
Data collection | ||
Diffractometer | Oxford Diffraction Xcalibur Nova O diffractometer | Oxford Diffraction Xcalibur Nova O diffractometer |
Absorption correction | Multi-scan (CrysAlis RED; Oxford Diffraction, 2008) | Multi-scan (CrysAlis RED; Oxford Diffraction, 2008) |
Tmin, Tmax | 0.647, 1.000 | 0.810, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4870, 4870, 4407 | 12374, 2182, 2167 |
Rint | 0.000 | 0.022 |
(sin θ/λ)max (Å−1) | 0.619 | 0.614 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.162, 1.12 | 0.055, 0.153, 1.10 |
No. of reflections | 4870 | 2182 |
No. of parameters | 164 | 319 |
No. of restraints | 0 | 303 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
w = 1/[σ2(Fo2) + (0.1021P)2 + 0.1859P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.0495P)2 + 10.0008P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.24, −0.19 | 0.34, −0.31 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2008), CrysAlis RED (Oxford Diffraction, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP (Siemens, 1994).
C2—C1—C4—N1 | −28.03 (16) | C6—C5—N1—C4 | −44.32 (18) |
C1—C4—N1—C5 | −177.78 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H01···O1i | 0.832 (18) | 2.161 (18) | 2.9773 (14) | 166.8 (14) |
Symmetry code: (i) x−1, y, z. |
C2—C1—C7—N1 | 51.4 (6) | C13—C8—N1—C7 | −87.1 (6) |
C5—C4—C18—N3 | 3.9 (7) | C4—C18—N3—C19 | −178.0 (4) |
C1—C7—N1—C8 | −177.8 (4) | C20—C19—N3—C18 | 24.4 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H01···O2i | 0.93 (4) | 2.03 (4) | 2.960 (5) | 175 (6) |
N3—H03···O1ii | 0.92 (4) | 2.24 (4) | 3.149 (5) | 168 (4) |
C5—H5···O1ii | 0.95 | 2.32 | 3.262 (6) | 171.2 |
C14—H14A···O1iii | 0.99 | 2.55 | 3.223 (7) | 125.5 |
Symmetry codes: (i) x, −y+1, z−1/2; (ii) x+1/2, −y+1/2, z+1/2; (iii) x−1/2, −y+1/2, z−1/2. |
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We are interested in the amides of terephthalic acid and have synthesized several such compounds from dimethyl terephthalate and published their structures (Jones et al., 2002). In six of the seven structures, the molecules crystallized with imposed inversion symmetry. Compounds with free NH functional groups formed ladder-like chains of molecules by translation via hydrogen bonding of the expected form N—H···O═C (two donors and two acceptors per molecule, but generally only one set per asymmetric unit), and a similar example, N,N'-bis(methoxycarbonylmethyl)terephthalamide, was presented by Armelin et al. (2001). A related single chain was observed in N-cyclohexyl-4-(methoxycarbonyl)benzamide, with only one O═CNH moiety per molecule (Jones & Kuś, 2004). We have also reported (Ossowski et al., 2006) the structures of two polymorphs of N,N'-diphenethylterephthalamide, one triclinic and one monoclinic, each of which crystallized with imposed inversion symmetry and the standard `ladder' structure, but with different C—H···O interactions; subsequently, all attempts to obtain the triclinic form failed and we thus regard it as a `disappearing polymorph' (Dunitz & Bernstein, 1995). Differential scanning calorimetry (DSC) measurements of this compound gave no indication of any phase change up to the melting point. We have now found two polymorphs of another related derivative, N,N'-bis[4-(diethylamino)phenyl]terephthaldiamide, (I), and report their structures here. For some of our other recent reports on polymorphism, see Jones & Mangalagiu (2009) and references therein; Lozano et al. (2004); Henschel et al. (2005), Zerbe et al. (2007).
Small amounts of crystalline material were available from an NMR tube containing a solution of (I) in d6-DMSO. Most of the sample consisted of poorly formed yellow prisms and plates, which were generally cracked and somewhat opaque. However, a usable single crystal was found and proved to be monoclinic [henceforth referred to as (Im)]. A few rather clearer plate-shaped crystals were identified optically and seemed to have a different cell, although they were invariably twinned. Eventually, an apparently untwinned triclinic crystal [form (It)] was found and measured, although this too proved to be twinned to a small extent.
The molecule of polymorph (It) is shown in Fig. 1; it displays inversion symmetry, so that there is one molecule per cell. The fragment C1—C4(═ O1)—N1—C5 is planar and subtends interplanar angles of 42.56 (5)° to the central and 27.63 (7)° to the outer rings; the rings themselves subtend an angle of 70.07 (5)°. The packing (Fig. 2) is of the established `ladder' type, with classical hydrogen bonds of the form N—H···O═C linking the molecules by translation parallel to the a axis. A precondition for this type of packing is that the N—H vectors should be antiparallel, and this is fulfilled exactly (angle between vectors 180°) for inversion-symmetric molecules.
The molecule of polymorph (Im) is shown in Fig. 3; there is, unusually for this type of molecule, no imposed molecular symmetry and indeed the molecule departs totally even from approximate inversion symmetry. The two central moieties C1—C7(═O1)—N1—C8 and C4—C18(═O2)—N3—C19 [chemically identical to the fragment discussed above for (It)] subtend different interplanar angles to their neighbouring rings; the former makes an angle of 85.9 (2)° to the outer ring and 60.0 (1)° to the central ring, whereas the latter makes corresponding angles of 23.0 (3) and 7.7 (3)° (for corresponding torsion angles, see the Tables). The angle between the N—H vectors is 79°, and the `ladder' packing is thus rendered impossible.
Fig. 4 shows the principal hydrogen bonds between the molecule and its four neighbouring molecules (two as acceptors, two as donors). N1—H01···O2 is a classical isolated hydrogen bond, whereas the hydrogen bond N3—H03···O1 is augmented by C5—H5···O1, forming a bifurcated system; we observed a similar system in N,N'-di(tert-butyl)-terephthaldiamide (Jones et al., 2002). At first sight, the `ladder' pattern seems to be upheld, but this is an artefact of projection in the view direction; in fact all hydrogen-bonded neighbour molecules are displaced in height with respect to the central molecule. The crosslinking leads to a three-dimensional pattern (Fig. 5).
Difficulties in recrystallizing the title compound (especially with regard to reproducibility) make it difficult to establish relationships between the phases. Powder investigations of the title compound were unsuccessful because of the very limited amount of compound available. Furthermore, this had been crystallized from methanol and was very probably a methanol solvate, although no single crystals could be obtained to confirm this. Nevertheless, it is reasonable to surmise that the monoclinic form is less stable; its density is 1.278 g cm-3 compared to 1.303 g cm-3 for the triclinic form (for a brief discussion of the `density rule', see e.g. Bernstein, 2002). The crosslinked packing pattern of the monoclinic form thus probably represents a kinetically stable island on the way to the simpler and presumably more efficient ladder pattern of the triclinic form. DSC measurements of (I) show a phase change at 407 K with ΔH = 21 J g-1. Thermogravimetric analysis at this point gave no indication of any mass change. The melting point determined by DSC for (I) is 547°C (3° higher than measured by standard methods).
It is not clear if terephthaldiamides, in view of their potentially different hydrogen-bonding patterns, have a generally high tendency to form polymorphs, and indeed this tendency can scarcely be quantified. However, our investigations at least show the value of a careful optical investigation of crystalline samples for revealing different crystal forms.