The title compound, C28H20N2O2, forms two conformational polymorphs, (I) and (II), where the molecular structures are similar except for the orientation of the two hydroxy groups. In (I), which was obtained by slow evaporation from chloroform, the two hydroxy groups have an anti conformation. The molecules form a sheet structure within the ac plane, where the hydroxy groups form zigzag hydrogen bonds. In (II), which was obtained by slow evaporation from acetonitrile, the two hydroxy groups have a syn conformation. The molecules form a double-sheet structure within the ab plane, where the hydroxy groups form 4-helix hydrogen bonds.
Supporting information
CCDC references: 862235; 862236
The title compound was prepared according to the method of Tabata et al.
(2011). A suspension of copper(I) chloride (0.81 g, 7.8 mmol) in
acetone (15 ml) was degassed by argon bubbling for 30 min, and then TMEDA [Please
define] (400 µl, 2.6 mmol) was added and the suspension stirred for 30 min. The supernatant solution containing the CuCl–TMEDA catalyst was
transferred to a mixture of
N1,N4-diethynyl-N1,N4-diphenylbenzene-1,4-diamine (1.00 g, 3.24 mmol) and 2-propyn-1-ol (2.7 ml, 45 mmol) in acetone
(63 ml) at 253 K. The solution was stirred for 2 d under an oxygen atmosphere.
The solvent was evaporated and the residue extracted with dichloromethane (200 ml). The solution was washed with 5% ammonium hydroxide (300 ml) and the water
layer was extracted twice with dichloromethane (200 ml). The combined organic
layer was washed with water (300 ml) and dried over anhydrous sodium sulfate.
After the solvent had evaporated, the residue was purified by gas-phase
chromatography to give the title compound as a white powder (yield 0.68 g,
yield 50%). Slow evaporation from solutions in chloroform or acetonitrile gave
polymorphs (I) and (II), respectively.
In polymorph (I), the C-bound H atoms, except for those on atoms C23 and C28,
were obtained from a difference Fourier map and refined isotropically. The H
atoms on C23 and C28 were placed in idealized locations (C—H = 0.99 Å) and
were refined as riding on their parent C atoms, with Uiso(H) =
1.2Ueq(C). The O-bound H atoms were obtained from a difference
Fourier map and found to be disordered. The occupancies of these H atoms were
fixed at 0.5. The O-bound H-atom positions were refined with the restraint
O—H = 0.84 (2) Å (DFIX instruction in SHELXL97; Sheldrick,
2008)
with Uiso(H) = 1.2Ueq(O1 and O2). Similar U
restraints (SIMU instruction in SHELXL97) and approximately isotropic
restraints (ISOR instruction in SHELXL97) were applied to atoms C22,
C23, C27, C28, O1 and O2, with an effective s.u. of 0.005 Å2. Restraints
(SADI instruction in SHELXL97) were applied to the C···H distances
C23···H1A/H1B and C28···H2A/H2B, the O—H lengths
O1—H1A/H1B and O2—H2A/H2B, and the C—O
lengths C23—O1 and C28—O2, with an effective s.u. of 0.004 Å. A
planarity restraint (FLAT instruction in SHELXL97) was applied to the
groups C17/O1/H1A/O1i [symmetry code: (i) -x + 1, -y +
1, -z + 1], C17/O1/H1B/O2ii [symmetry code: (ii) -x +
??, y - 1/2, -z + 1/2], C28/O2/H2A/O1iii
[symmetry code: (iii) -x + 2, y + 1/2, -z + 1/2] and
C28/O2/H2B/O2iv [symmetry code: (iv) -x + 2, -y + 2,
-z].
In polymorph (II), the H atoms were obtained from a difference Fourier map. All
H atoms, except H4, H6 and H14, were refined isotropically. The positions of
H4, H6 and H14 were refined, although their Uiso(H) values were fixed
at 1.2Ueq(C).
For both compounds, data collection: APEX2 (Bruker, 2010); cell refinement: APEX2 (Bruker, 2010); 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: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: enCIFer (Allen et al., 2004).
(I)
N1,
N4-bis(5-hydroxypenta-1,3-diynyl)-
N1,
N4-diphenylbenzene-1,4-diamine
top
Crystal data top
C28H20N2O2 | F(000) = 872 |
Mr = 416.46 | Dx = 1.304 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 9.0669 (18) Å | Cell parameters from 2923 reflections |
b = 7.7778 (16) Å | θ = 2.3–27.4° |
c = 30.135 (6) Å | µ = 0.08 mm−1 |
β = 93.148 (2)° | T = 100 K |
V = 2121.9 (7) Å3 | Plate, pale yellow |
Z = 4 | 0.49 × 0.16 × 0.05 mm |
Data collection top
Bruker APEXII CCD area-detector diffractometer | 4842 independent reflections |
Radiation source: Bruker TXS fine-focus rotating anode | 3703 reflections with I > 2σ(I) |
Bruker Helios multilayer confocal mirror monochromator | Rint = 0.030 |
Detector resolution: 8.333 pixels mm-1 | θmax = 27.5°, θmin = 1.4° |
ϕ and ω scans | h = −9→11 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −9→10 |
Tmin = 0.961, Tmax = 0.996 | l = −30→39 |
11823 measured reflections | |
Refinement top
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)] = 0.051 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.133 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0512P)2 + 1.2491P] where P = (Fo2 + 2Fc2)/3 |
4842 reflections | (Δ/σ)max < 0.001 |
358 parameters | Δρmax = 0.65 e Å−3 |
81 restraints | Δρmin = −0.53 e Å−3 |
Crystal data top
C28H20N2O2 | V = 2121.9 (7) Å3 |
Mr = 416.46 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.0669 (18) Å | µ = 0.08 mm−1 |
b = 7.7778 (16) Å | T = 100 K |
c = 30.135 (6) Å | 0.49 × 0.16 × 0.05 mm |
β = 93.148 (2)° | |
Data collection top
Bruker APEXII CCD area-detector diffractometer | 4842 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 3703 reflections with I > 2σ(I) |
Tmin = 0.961, Tmax = 0.996 | Rint = 0.030 |
11823 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.051 | 81 restraints |
wR(F2) = 0.133 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.65 e Å−3 |
4842 reflections | Δρmin = −0.53 e Å−3 |
358 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
C1 | 0.97406 (18) | 0.9263 (2) | 0.32887 (5) | 0.0186 (4) | |
C2 | 1.0220 (2) | 0.8268 (2) | 0.29412 (6) | 0.0203 (4) | |
C3 | 0.94556 (19) | 0.8304 (2) | 0.25305 (6) | 0.0196 (4) | |
C4 | 0.82030 (18) | 0.9331 (2) | 0.24653 (5) | 0.0172 (4) | |
C5 | 0.77410 (19) | 1.0344 (2) | 0.28120 (6) | 0.0184 (4) | |
C6 | 0.85049 (19) | 1.0309 (2) | 0.32224 (6) | 0.0190 (4) | |
C7 | 1.20500 (19) | 0.9286 (2) | 0.37841 (6) | 0.0201 (4) | |
C8 | 1.2746 (2) | 0.8571 (3) | 0.41628 (6) | 0.0229 (4) | |
C9 | 1.4265 (2) | 0.8739 (3) | 0.42327 (6) | 0.0256 (4) | |
C10 | 1.5094 (2) | 0.9603 (3) | 0.39305 (6) | 0.0256 (4) | |
C11 | 1.4390 (2) | 1.0305 (3) | 0.35527 (6) | 0.0243 (4) | |
C12 | 1.2876 (2) | 1.0151 (2) | 0.34770 (6) | 0.0214 (4) | |
C13 | 0.58928 (19) | 0.9688 (2) | 0.19674 (6) | 0.0199 (4) | |
C14 | 0.5351 (2) | 1.0377 (3) | 0.15658 (7) | 0.0287 (4) | |
C15 | 0.3841 (2) | 1.0636 (3) | 0.14915 (8) | 0.0361 (5) | |
C16 | 0.2876 (2) | 1.0264 (3) | 0.18203 (8) | 0.0343 (5) | |
C17 | 0.3431 (2) | 0.9579 (3) | 0.22186 (7) | 0.0289 (5) | |
C18 | 0.4929 (2) | 0.9256 (2) | 0.22940 (6) | 0.0226 (4) | |
C19 | 0.96509 (19) | 0.8878 (3) | 0.40665 (6) | 0.0224 (4) | |
C20 | 0.88956 (19) | 0.8610 (3) | 0.43739 (6) | 0.0247 (4) | |
C21 | 0.80320 (19) | 0.8218 (3) | 0.47201 (6) | 0.0220 (4) | |
C22 | 0.72713 (19) | 0.7873 (3) | 0.50211 (6) | 0.0221 (4) | |
C23 | 0.6372 (2) | 0.7159 (2) | 0.53664 (6) | 0.0246 (4) | |
H17 | 0.6871 | 0.7372 | 0.5662 | 0.030* | |
H18 | 0.5405 | 0.7753 | 0.5357 | 0.030* | |
C24 | 0.82673 (19) | 0.9179 (2) | 0.16790 (6) | 0.0196 (4) | |
C25 | 0.90268 (19) | 0.8987 (3) | 0.13693 (6) | 0.0221 (4) | |
C26 | 0.9874 (2) | 0.8637 (3) | 0.10157 (6) | 0.0268 (4) | |
C27 | 1.0611 (2) | 0.8295 (3) | 0.07110 (7) | 0.0382 (5) | |
C28 | 1.1467 (3) | 0.7863 (4) | 0.03282 (7) | 0.0561 (7) | |
H19 | 1.2528 | 0.7805 | 0.0425 | 0.067* | |
H20 | 1.1164 | 0.6713 | 0.0216 | 0.067* | |
H3 | 1.111 (2) | 0.751 (3) | 0.2995 (6) | 0.025 (5)* | |
H4 | 0.977 (2) | 0.761 (3) | 0.2290 (6) | 0.015 (5)* | |
H5 | 0.690 (2) | 1.107 (3) | 0.2763 (6) | 0.023 (5)* | |
H6 | 0.820 (2) | 1.104 (3) | 0.3469 (6) | 0.018 (5)* | |
H7 | 1.214 (2) | 0.793 (3) | 0.4377 (7) | 0.027 (5)* | |
H8 | 1.474 (2) | 0.821 (3) | 0.4497 (7) | 0.033 (6)* | |
H9 | 1.617 (3) | 0.975 (3) | 0.3985 (7) | 0.034 (6)* | |
H10 | 1.495 (2) | 1.092 (3) | 0.3343 (6) | 0.022 (5)* | |
H11 | 1.237 (2) | 1.068 (3) | 0.3218 (7) | 0.033 (6)* | |
H12 | 0.603 (2) | 1.067 (3) | 0.1343 (7) | 0.032 (6)* | |
H13 | 0.348 (3) | 1.110 (3) | 0.1200 (8) | 0.045 (7)* | |
H14 | 0.178 (2) | 1.046 (3) | 0.1750 (7) | 0.029 (6)* | |
H15 | 0.277 (2) | 0.929 (3) | 0.2454 (7) | 0.034 (6)* | |
H16 | 0.530 (2) | 0.871 (3) | 0.2569 (7) | 0.025 (5)* | |
H1A | 0.5522 (13) | 0.5249 (15) | 0.5106 (5) | 0.075 (12)* | 0.50 |
H2A | 1.2080 (13) | 0.939 (3) | −0.0086 (7) | 0.075 (12)* | 0.50 |
H1B | 0.6920 (16) | 0.495 (2) | 0.5242 (18) | 0.075 (12)* | 0.50 |
H2B | 1.053 (2) | 0.961 (3) | 0.0017 (7) | 0.075 (12)* | 0.50 |
N1 | 1.04834 (16) | 0.9169 (2) | 0.37201 (5) | 0.0210 (3) | |
N2 | 0.74536 (16) | 0.9391 (2) | 0.20355 (5) | 0.0192 (3) | |
O1 | 0.6139 (2) | 0.5375 (2) | 0.53103 (8) | 0.0620 (6) | |
O2 | 1.1279 (2) | 0.9048 (2) | −0.00128 (5) | 0.0452 (5) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0176 (8) | 0.0224 (9) | 0.0161 (8) | −0.0009 (7) | 0.0033 (6) | 0.0038 (7) |
C2 | 0.0195 (9) | 0.0214 (9) | 0.0205 (9) | 0.0035 (7) | 0.0053 (7) | 0.0023 (7) |
C3 | 0.0201 (8) | 0.0202 (9) | 0.0190 (8) | 0.0019 (7) | 0.0059 (7) | −0.0011 (7) |
C4 | 0.0174 (8) | 0.0190 (9) | 0.0156 (8) | −0.0029 (6) | 0.0039 (6) | 0.0011 (6) |
C5 | 0.0157 (8) | 0.0190 (9) | 0.0207 (8) | 0.0014 (7) | 0.0039 (7) | 0.0008 (7) |
C6 | 0.0198 (8) | 0.0204 (9) | 0.0171 (8) | −0.0001 (7) | 0.0054 (7) | −0.0013 (7) |
C7 | 0.0197 (8) | 0.0225 (9) | 0.0183 (8) | 0.0030 (7) | 0.0036 (7) | −0.0015 (7) |
C8 | 0.0242 (9) | 0.0281 (10) | 0.0167 (8) | 0.0015 (8) | 0.0042 (7) | 0.0031 (7) |
C9 | 0.0259 (10) | 0.0305 (11) | 0.0202 (9) | 0.0044 (8) | −0.0020 (7) | 0.0019 (8) |
C10 | 0.0195 (9) | 0.0302 (11) | 0.0271 (10) | 0.0012 (8) | 0.0005 (7) | −0.0022 (8) |
C11 | 0.0242 (9) | 0.0244 (10) | 0.0249 (9) | 0.0007 (7) | 0.0080 (7) | 0.0002 (8) |
C12 | 0.0236 (9) | 0.0224 (10) | 0.0185 (9) | 0.0041 (7) | 0.0035 (7) | 0.0019 (7) |
C13 | 0.0178 (8) | 0.0189 (9) | 0.0230 (9) | −0.0015 (7) | 0.0013 (7) | −0.0019 (7) |
C14 | 0.0230 (10) | 0.0318 (11) | 0.0312 (11) | −0.0024 (8) | −0.0002 (8) | 0.0095 (9) |
C15 | 0.0267 (10) | 0.0378 (13) | 0.0428 (13) | 0.0002 (9) | −0.0067 (9) | 0.0115 (10) |
C16 | 0.0172 (9) | 0.0321 (12) | 0.0531 (14) | 0.0015 (8) | −0.0021 (9) | −0.0045 (10) |
C17 | 0.0210 (9) | 0.0280 (11) | 0.0387 (11) | −0.0058 (8) | 0.0090 (8) | −0.0094 (9) |
C18 | 0.0230 (9) | 0.0215 (9) | 0.0234 (9) | −0.0047 (7) | 0.0038 (7) | −0.0039 (7) |
C19 | 0.0197 (9) | 0.0282 (10) | 0.0193 (9) | 0.0041 (7) | 0.0016 (7) | 0.0029 (7) |
C20 | 0.0186 (9) | 0.0347 (11) | 0.0208 (9) | 0.0040 (8) | 0.0012 (7) | 0.0050 (8) |
C21 | 0.0189 (8) | 0.0287 (10) | 0.0184 (9) | 0.0031 (7) | 0.0012 (7) | 0.0032 (7) |
C22 | 0.0205 (9) | 0.0265 (10) | 0.0193 (8) | 0.0003 (7) | 0.0007 (7) | −0.0002 (7) |
C23 | 0.0254 (9) | 0.0260 (10) | 0.0232 (9) | −0.0011 (7) | 0.0091 (7) | 0.0007 (7) |
C24 | 0.0184 (8) | 0.0224 (9) | 0.0180 (8) | −0.0017 (7) | −0.0006 (7) | 0.0011 (7) |
C25 | 0.0193 (9) | 0.0296 (10) | 0.0173 (8) | −0.0010 (7) | 0.0007 (7) | 0.0017 (7) |
C26 | 0.0224 (9) | 0.0405 (12) | 0.0175 (9) | 0.0036 (8) | 0.0012 (7) | 0.0049 (8) |
C27 | 0.0292 (10) | 0.0646 (15) | 0.0211 (10) | 0.0144 (10) | 0.0045 (8) | 0.0105 (10) |
C28 | 0.0497 (14) | 0.0916 (19) | 0.0288 (11) | 0.0365 (13) | 0.0195 (10) | 0.0200 (12) |
N1 | 0.0173 (7) | 0.0315 (9) | 0.0145 (7) | 0.0023 (6) | 0.0042 (6) | 0.0034 (6) |
N2 | 0.0178 (7) | 0.0246 (8) | 0.0154 (7) | 0.0001 (6) | 0.0039 (6) | 0.0000 (6) |
O1 | 0.0711 (13) | 0.0280 (9) | 0.0931 (14) | −0.0128 (8) | 0.0612 (11) | −0.0114 (9) |
O2 | 0.0815 (13) | 0.0280 (8) | 0.0289 (8) | −0.0082 (8) | 0.0286 (8) | −0.0006 (6) |
Geometric parameters (Å, º) top
N1—C19 | 1.341 (2) | C9—H8 | 0.98 (2) |
C19—C20 | 1.200 (2) | C10—C11 | 1.387 (3) |
C20—C21 | 1.373 (2) | C10—H9 | 0.98 (2) |
C21—C22 | 1.200 (2) | C11—C12 | 1.384 (3) |
C22—C23 | 1.466 (2) | C11—H10 | 0.96 (2) |
N2—C24 | 1.346 (2) | C12—H11 | 0.97 (2) |
C24—C25 | 1.199 (2) | C13—C14 | 1.388 (3) |
C25—C26 | 1.375 (2) | C13—C18 | 1.393 (2) |
C26—C27 | 1.195 (3) | C13—N2 | 1.437 (2) |
C27—C28 | 1.465 (3) | C14—C15 | 1.390 (3) |
C1—C6 | 1.390 (2) | C14—H12 | 0.96 (2) |
C1—C2 | 1.391 (2) | C15—C16 | 1.388 (3) |
C1—N1 | 1.433 (2) | C15—H13 | 0.99 (2) |
C2—C3 | 1.385 (2) | C16—C17 | 1.383 (3) |
C2—H3 | 1.00 (2) | C16—H14 | 1.02 (2) |
C3—C4 | 1.394 (2) | C17—C18 | 1.387 (3) |
C3—H4 | 0.960 (19) | C17—H15 | 0.98 (2) |
C4—C5 | 1.391 (2) | C18—H16 | 0.98 (2) |
C4—N2 | 1.430 (2) | C23—O1 | 1.412 (2) |
C5—C6 | 1.384 (2) | C23—H17 | 0.9900 |
C5—H5 | 0.95 (2) | C23—H18 | 0.9900 |
C6—H6 | 0.989 (19) | C28—O2 | 1.384 (3) |
C7—C8 | 1.389 (2) | C28—H19 | 0.9900 |
C7—C12 | 1.395 (2) | C28—H20 | 0.9900 |
C7—N1 | 1.426 (2) | O1—H1A | 0.816 (11) |
C8—C9 | 1.387 (3) | O1—H1B | 0.817 (11) |
C8—H7 | 1.00 (2) | O2—H2A | 0.816 (11) |
C9—C10 | 1.386 (3) | O2—H2B | 0.816 (11) |
| | | |
C6—C1—C2 | 120.01 (16) | C16—C15—H13 | 121.5 (14) |
C6—C1—N1 | 119.69 (15) | C14—C15—H13 | 117.9 (14) |
C2—C1—N1 | 120.26 (16) | C17—C16—C15 | 119.07 (19) |
C3—C2—C1 | 119.98 (16) | C17—C16—H14 | 123.0 (12) |
C3—C2—H3 | 120.9 (11) | C15—C16—H14 | 117.9 (12) |
C1—C2—H3 | 119.1 (11) | C16—C17—C18 | 121.26 (19) |
C2—C3—C4 | 120.09 (16) | C16—C17—H15 | 120.5 (13) |
C2—C3—H4 | 120.5 (11) | C18—C17—H15 | 118.3 (13) |
C4—C3—H4 | 119.4 (11) | C17—C18—C13 | 119.15 (19) |
C5—C4—C3 | 119.69 (16) | C17—C18—H16 | 120.6 (12) |
C5—C4—N2 | 120.95 (16) | C13—C18—H16 | 120.2 (12) |
C3—C4—N2 | 119.29 (15) | N1—C19—C20 | 179.4 (2) |
C6—C5—C4 | 120.23 (16) | C19—C20—C21 | 177.1 (2) |
C6—C5—H5 | 120.4 (12) | C22—C21—C20 | 179.7 (2) |
C4—C5—H5 | 119.4 (12) | C21—C22—C23 | 170.6 (2) |
C5—C6—C1 | 119.98 (16) | O1—C23—C22 | 111.87 (16) |
C5—C6—H6 | 120.8 (11) | O1—C23—H17 | 109.2 |
C1—C6—H6 | 119.2 (11) | C22—C23—H17 | 109.2 |
C8—C7—C12 | 120.10 (17) | O1—C23—H18 | 109.2 |
C8—C7—N1 | 119.34 (16) | C22—C23—H18 | 109.2 |
C12—C7—N1 | 120.53 (16) | H17—C23—H18 | 107.9 |
C9—C8—C7 | 119.31 (17) | N2—C24—C25 | 178.16 (18) |
C9—C8—H7 | 121.4 (12) | C24—C25—C26 | 175.7 (2) |
C7—C8—H7 | 119.3 (12) | C27—C26—C25 | 178.5 (2) |
C10—C9—C8 | 121.04 (18) | C26—C27—C28 | 178.0 (2) |
C10—C9—H8 | 120.8 (13) | O2—C28—C27 | 112.5 (2) |
C8—C9—H8 | 118.1 (13) | O2—C28—H19 | 109.1 |
C9—C10—C11 | 119.23 (17) | C27—C28—H19 | 109.1 |
C9—C10—H9 | 120.8 (13) | O2—C28—H20 | 109.1 |
C11—C10—H9 | 119.9 (13) | C27—C28—H20 | 109.1 |
C12—C11—C10 | 120.58 (17) | H19—C28—H20 | 107.8 |
C12—C11—H10 | 119.2 (12) | C19—N1—C7 | 120.31 (14) |
C10—C11—H10 | 120.2 (12) | C19—N1—C1 | 117.29 (14) |
C11—C12—C7 | 119.74 (17) | C7—N1—C1 | 122.33 (13) |
C11—C12—H11 | 120.9 (13) | C24—N2—C4 | 117.70 (14) |
C7—C12—H11 | 119.3 (13) | C24—N2—C13 | 118.95 (14) |
C14—C13—C18 | 120.20 (17) | C4—N2—C13 | 123.34 (14) |
C14—C13—N2 | 119.02 (16) | C23—O1—H1A | 107.5 (9) |
C18—C13—N2 | 120.76 (16) | C23—O1—H1B | 107.3 (7) |
C13—C14—C15 | 119.67 (19) | H1A—O1—H1B | 109 (4) |
C13—C14—H12 | 119.0 (13) | C28—O2—H2A | 110.1 (10) |
C15—C14—H12 | 121.3 (13) | C28—O2—H2B | 110.0 (10) |
C16—C15—C14 | 120.6 (2) | H2A—O2—H2B | 128 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O1i | 0.82 (1) | 1.97 (2) | 2.771 (3) | 169 (1) |
O1—H1B···O2ii | 0.82 (3) | 1.94 (3) | 2.753 (3) | 173 (5) |
O2—H2A···O1iii | 0.82 (2) | 1.94 (2) | 2.753 (3) | 173 (2) |
O2—H2B···O2iv | 0.82 (2) | 1.94 (2) | 2.756 (3) | 173 (2) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, y−1/2, −z+1/2; (iii) −x+2, y+1/2, −z+1/2; (iv) −x+2, −y+2, −z. |
(II)
N1,
N4-bis(5-hydroxypenta-1,3-diynyl)-
N1,
N4-diphenylbenzene-1,4-diamine
top
Crystal data top
C28H20N2O2 | F(000) = 872.00 |
Mr = 416.46 | Dx = 1.309 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 15.530 (4) Å | Cell parameters from 1658 reflections |
b = 8.831 (2) Å | θ = 2.7–24.4° |
c = 17.108 (4) Å | µ = 0.08 mm−1 |
β = 115.766 (3)° | T = 100 K |
V = 2113.0 (9) Å3 | Plate, pale yellow |
Z = 4 | 0.22 × 0.18 × 0.05 mm |
Data collection top
Bruker APEXII CCD area-detector diffractometer | 4826 independent reflections |
Radiation source: Bruker TXS fine-focus rotating anode | 3150 reflections with F2 > 2σ(F2) |
Bruker Helios multilayer confocal mirror monochromator | Rint = 0.046 |
Detector resolution: 8.333 pixels mm-1 | θmax = 27.5°, θmin = 1.5° |
ϕ and ω scans | h = −20→17 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −11→11 |
Tmin = 0.982, Tmax = 0.996 | l = −10→22 |
11897 measured reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.048 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.111 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0376P)2 + 0.2149P] where P = (Fo2 + 2Fc2)/3 |
4826 reflections | (Δ/σ)max = 0.001 |
366 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
Primary atom site location: structure-invariant direct methods | |
Crystal data top
C28H20N2O2 | V = 2113.0 (9) Å3 |
Mr = 416.46 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 15.530 (4) Å | µ = 0.08 mm−1 |
b = 8.831 (2) Å | T = 100 K |
c = 17.108 (4) Å | 0.22 × 0.18 × 0.05 mm |
β = 115.766 (3)° | |
Data collection top
Bruker APEXII CCD area-detector diffractometer | 4826 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 3150 reflections with F2 > 2σ(F2) |
Tmin = 0.982, Tmax = 0.996 | Rint = 0.046 |
11897 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.111 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.24 e Å−3 |
4826 reflections | Δρmin = −0.24 e Å−3 |
366 parameters | |
Special details top
Refinement. Refinement was performed using all reflections. The weighted R-factor
(wR) and goodness of fit (S) are based on F2.
R-factor (gt) are based on F. The threshold expression of
F2 > 2.0 σ(F2) is used only for calculating R-factor
(gt). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 1.03768 (11) | 0.3145 (2) | 0.11216 (11) | 0.0209 (4) | |
C2 | 0.94865 (12) | 0.2728 (2) | 0.04859 (11) | 0.0229 (4) | |
C3 | 0.86699 (12) | 0.3425 (2) | 0.04507 (11) | 0.0225 (4) | |
C4 | 0.87482 (11) | 0.45533 (19) | 0.10439 (11) | 0.0206 (4) | |
C5 | 0.96434 (12) | 0.4980 (2) | 0.16704 (11) | 0.0232 (4) | |
C6 | 1.04539 (12) | 0.4265 (2) | 0.17084 (11) | 0.0234 (4) | |
C7 | 1.14378 (12) | 0.0863 (2) | 0.13764 (11) | 0.0217 (4) | |
C8 | 1.23015 (12) | 0.0255 (2) | 0.14516 (11) | 0.0255 (5) | |
C9 | 1.25180 (13) | −0.1247 (3) | 0.16747 (12) | 0.0278 (5) | |
C10 | 1.18896 (13) | −0.2173 (3) | 0.18286 (12) | 0.0279 (5) | |
C11 | 1.10368 (13) | −0.1573 (3) | 0.17540 (12) | 0.0283 (5) | |
C12 | 1.08064 (12) | −0.0063 (2) | 0.15286 (11) | 0.0241 (4) | |
C13 | 0.78335 (11) | 0.68605 (19) | 0.11052 (10) | 0.0206 (4) | |
C14 | 0.72482 (12) | 0.7443 (2) | 0.14613 (11) | 0.0231 (4) | |
C15 | 0.71310 (12) | 0.8996 (2) | 0.14847 (11) | 0.0258 (5) | |
C16 | 0.76090 (12) | 0.9980 (3) | 0.11736 (12) | 0.0269 (5) | |
C17 | 0.81998 (12) | 0.9385 (3) | 0.08321 (11) | 0.0259 (5) | |
C18 | 0.83178 (12) | 0.7839 (2) | 0.07967 (11) | 0.0229 (4) | |
C19 | 1.19491 (12) | 0.3343 (2) | 0.12125 (11) | 0.0223 (4) | |
C20 | 1.26101 (12) | 0.4081 (2) | 0.12431 (11) | 0.0234 (4) | |
C21 | 1.33644 (12) | 0.4927 (2) | 0.12635 (11) | 0.0224 (4) | |
C22 | 1.40161 (12) | 0.5654 (2) | 0.12702 (11) | 0.0237 (4) | |
C23 | 1.48274 (14) | 0.6529 (3) | 0.12949 (13) | 0.0300 (5) | |
C24 | 0.71811 (12) | 0.4367 (2) | 0.09782 (11) | 0.0221 (4) | |
C25 | 0.65215 (12) | 0.3618 (2) | 0.09357 (11) | 0.0229 (4) | |
C26 | 0.57875 (12) | 0.2715 (2) | 0.09088 (11) | 0.0225 (4) | |
C27 | 0.51492 (12) | 0.1910 (2) | 0.08721 (11) | 0.0244 (4) | |
C28 | 0.43735 (13) | 0.0928 (3) | 0.08334 (12) | 0.0259 (5) | |
H1 | 1.5138 (17) | 0.822 (3) | 0.2045 (15) | 0.064 (8)* | |
H2 | 0.4596 (16) | 0.095 (3) | 0.2016 (15) | 0.063 (8)* | |
H3 | 0.9435 (12) | 0.197 (2) | 0.0060 (11) | 0.025 (5)* | |
H4 | 0.8029 (13) | 0.3123 (19) | −0.0001 (11) | 0.0270* | |
H5 | 0.9680 (12) | 0.575 (2) | 0.2093 (12) | 0.028 (5)* | |
H6 | 1.1084 (13) | 0.453 (2) | 0.2153 (11) | 0.0281* | |
H7 | 1.2757 (14) | 0.095 (3) | 0.1354 (12) | 0.037 (6)* | |
H8 | 1.3132 (13) | −0.164 (2) | 0.1723 (11) | 0.032 (5)* | |
H9 | 1.2080 (12) | −0.324 (2) | 0.2000 (11) | 0.029 (5)* | |
H10 | 1.0567 (13) | −0.221 (2) | 0.1860 (12) | 0.033 (6)* | |
H11 | 1.0215 (13) | 0.034 (2) | 0.1467 (11) | 0.028 (5)* | |
H12 | 0.6919 (13) | 0.671 (3) | 0.1683 (11) | 0.032 (6)* | |
H13 | 0.6709 (13) | 0.939 (2) | 0.1730 (11) | 0.027 (5)* | |
H14 | 0.7526 (13) | 1.108 (3) | 0.1198 (11) | 0.0323* | |
H15 | 0.8509 (12) | 1.007 (2) | 0.0585 (11) | 0.027 (5)* | |
H16 | 0.8696 (13) | 0.741 (2) | 0.0538 (11) | 0.025 (5)* | |
H17 | 1.4598 (15) | 0.733 (3) | 0.0800 (14) | 0.052 (7)* | |
H18 | 1.5277 (14) | 0.585 (3) | 0.1198 (12) | 0.040 (6)* | |
H19 | 0.4259 (13) | 0.013 (3) | 0.0386 (13) | 0.037 (6)* | |
H20 | 0.3759 (14) | 0.158 (3) | 0.0639 (12) | 0.040 (6)* | |
N1 | 1.12345 (9) | 0.24282 (16) | 0.11683 (9) | 0.0225 (4) | |
N2 | 0.79082 (9) | 0.52556 (16) | 0.10306 (9) | 0.0221 (4) | |
O1 | 1.53518 (9) | 0.72606 (16) | 0.21136 (8) | 0.0279 (3) | |
O2 | 0.45732 (9) | 0.01895 (15) | 0.16366 (8) | 0.0278 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0161 (9) | 0.0249 (10) | 0.0239 (10) | 0.0001 (7) | 0.0107 (8) | 0.0020 (8) |
C2 | 0.0236 (10) | 0.0234 (10) | 0.0225 (10) | −0.0024 (8) | 0.0106 (8) | −0.0003 (8) |
C3 | 0.0166 (9) | 0.0255 (10) | 0.0231 (10) | −0.0030 (8) | 0.0066 (8) | −0.0000 (8) |
C4 | 0.0161 (9) | 0.0225 (10) | 0.0246 (10) | −0.0012 (7) | 0.0101 (8) | 0.0016 (8) |
C5 | 0.0224 (9) | 0.0263 (11) | 0.0214 (10) | −0.0027 (8) | 0.0098 (8) | −0.0019 (8) |
C6 | 0.0170 (9) | 0.0278 (11) | 0.0236 (10) | −0.0045 (8) | 0.0070 (8) | −0.0004 (8) |
C7 | 0.0194 (9) | 0.0251 (10) | 0.0207 (10) | −0.0009 (8) | 0.0087 (8) | −0.0014 (8) |
C8 | 0.0204 (9) | 0.0286 (11) | 0.0302 (11) | −0.0005 (8) | 0.0136 (8) | −0.0003 (8) |
C9 | 0.0231 (10) | 0.0316 (11) | 0.0295 (11) | 0.0029 (9) | 0.0124 (8) | −0.0014 (8) |
C10 | 0.0295 (11) | 0.0259 (11) | 0.0263 (11) | 0.0010 (9) | 0.0103 (9) | −0.0006 (9) |
C11 | 0.0277 (10) | 0.0280 (11) | 0.0314 (11) | −0.0053 (9) | 0.0149 (9) | 0.0008 (9) |
C12 | 0.0188 (9) | 0.0287 (11) | 0.0265 (11) | −0.0018 (8) | 0.0113 (8) | −0.0016 (8) |
C13 | 0.0141 (9) | 0.0233 (10) | 0.0191 (9) | −0.0018 (7) | 0.0023 (7) | −0.0008 (8) |
C14 | 0.0155 (9) | 0.0282 (11) | 0.0233 (10) | −0.0020 (8) | 0.0062 (8) | −0.0016 (8) |
C15 | 0.0197 (9) | 0.0307 (11) | 0.0241 (10) | 0.0019 (8) | 0.0068 (8) | −0.0046 (8) |
C16 | 0.0220 (10) | 0.0233 (11) | 0.0271 (11) | 0.0001 (8) | 0.0029 (8) | −0.0028 (8) |
C17 | 0.0205 (9) | 0.0269 (11) | 0.0250 (10) | −0.0045 (8) | 0.0050 (8) | 0.0036 (8) |
C18 | 0.0172 (9) | 0.0280 (11) | 0.0223 (10) | 0.0011 (8) | 0.0074 (8) | −0.0011 (8) |
C19 | 0.0188 (9) | 0.0266 (10) | 0.0229 (10) | 0.0031 (8) | 0.0103 (8) | 0.0011 (8) |
C20 | 0.0188 (9) | 0.0260 (10) | 0.0254 (10) | 0.0024 (8) | 0.0096 (8) | 0.0013 (8) |
C21 | 0.0207 (9) | 0.0253 (10) | 0.0203 (10) | 0.0002 (8) | 0.0080 (8) | −0.0003 (8) |
C22 | 0.0214 (9) | 0.0240 (10) | 0.0264 (10) | −0.0010 (8) | 0.0111 (8) | 0.0001 (8) |
C23 | 0.0294 (11) | 0.0325 (12) | 0.0319 (12) | −0.0118 (9) | 0.0168 (9) | −0.0077 (10) |
C24 | 0.0176 (9) | 0.0244 (10) | 0.0244 (10) | −0.0002 (8) | 0.0093 (8) | −0.0005 (8) |
C25 | 0.0201 (9) | 0.0236 (10) | 0.0258 (10) | 0.0016 (8) | 0.0108 (8) | −0.0009 (8) |
C26 | 0.0186 (9) | 0.0252 (10) | 0.0236 (10) | 0.0018 (8) | 0.0091 (8) | 0.0002 (8) |
C27 | 0.0216 (9) | 0.0268 (11) | 0.0242 (10) | 0.0011 (8) | 0.0092 (8) | 0.0003 (8) |
C28 | 0.0210 (10) | 0.0304 (11) | 0.0245 (11) | −0.0063 (9) | 0.0083 (8) | 0.0016 (9) |
N1 | 0.0171 (7) | 0.0228 (8) | 0.0308 (9) | −0.0010 (7) | 0.0133 (7) | 0.0009 (7) |
N2 | 0.0156 (7) | 0.0220 (9) | 0.0291 (9) | −0.0020 (6) | 0.0101 (7) | −0.0009 (7) |
O1 | 0.0264 (7) | 0.0279 (8) | 0.0279 (8) | −0.0057 (6) | 0.0103 (6) | −0.0033 (6) |
O2 | 0.0305 (7) | 0.0279 (8) | 0.0261 (8) | −0.0048 (6) | 0.0134 (6) | 0.0007 (6) |
Geometric parameters (Å, º) top
N1—C19 | 1.348 (3) | C9—C10 | 1.383 (4) |
C19—C20 | 1.198 (3) | C9—H8 | 0.98 (2) |
C20—C21 | 1.377 (3) | C10—C11 | 1.380 (3) |
C21—C22 | 1.194 (3) | C10—H9 | 0.996 (18) |
C22—C23 | 1.463 (3) | C11—C12 | 1.391 (3) |
N2—C24 | 1.346 (3) | C11—H10 | 1.00 (3) |
C24—C25 | 1.195 (3) | C12—H11 | 0.95 (2) |
C25—C26 | 1.375 (3) | C13—C14 | 1.394 (3) |
C26—C27 | 1.199 (3) | C13—C18 | 1.391 (3) |
C27—C28 | 1.462 (3) | C13—N2 | 1.432 (3) |
C1—C2 | 1.386 (2) | C14—C15 | 1.387 (3) |
C1—C6 | 1.378 (3) | C14—H12 | 1.00 (3) |
C1—N1 | 1.445 (3) | C15—C16 | 1.390 (3) |
C2—C3 | 1.387 (3) | C15—H13 | 0.98 (3) |
C2—H3 | 0.968 (19) | C16—C17 | 1.387 (4) |
C3—C4 | 1.389 (3) | C16—H14 | 0.98 (2) |
C3—H4 | 0.995 (16) | C17—C18 | 1.383 (3) |
C4—C5 | 1.389 (2) | C17—H15 | 0.98 (2) |
C4—N2 | 1.436 (3) | C18—H16 | 0.96 (3) |
C5—C6 | 1.384 (3) | C23—O1 | 1.432 (3) |
C5—H5 | 0.98 (2) | C23—H17 | 1.04 (3) |
C6—H6 | 0.971 (16) | C23—H18 | 0.99 (3) |
C7—C8 | 1.398 (3) | C28—O2 | 1.428 (3) |
C7—C12 | 1.386 (3) | C28—H19 | 1.00 (2) |
C7—N1 | 1.428 (3) | C28—H20 | 1.04 (2) |
C8—C9 | 1.381 (3) | O1—H1 | 0.90 (3) |
C8—H7 | 1.01 (3) | O2—H2 | 0.92 (3) |
| | | |
N1—C1—C2 | 120.55 (17) | C15—C14—H12 | 122.4 (12) |
N1—C1—C6 | 119.23 (13) | C14—C15—C16 | 120.6 (2) |
C2—C1—C6 | 120.22 (18) | C14—C15—H13 | 119.0 (11) |
C1—C2—C3 | 119.84 (17) | C16—C15—H13 | 120.5 (11) |
C1—C2—H3 | 120.2 (10) | C15—C16—C17 | 119.05 (19) |
C3—C2—H3 | 120.0 (10) | C15—C16—H14 | 120.0 (14) |
C2—C3—C4 | 119.89 (14) | C17—C16—H14 | 121.0 (14) |
C2—C3—H4 | 120.1 (12) | C16—C17—C18 | 121.1 (2) |
C4—C3—H4 | 120.0 (12) | C16—C17—H15 | 119.1 (12) |
N2—C4—C3 | 120.52 (13) | C18—C17—H15 | 119.7 (12) |
N2—C4—C5 | 119.54 (17) | C13—C18—C17 | 119.5 (2) |
C3—C4—C5 | 119.92 (18) | C13—C18—H16 | 118.0 (12) |
C4—C5—C6 | 119.83 (18) | C17—C18—H16 | 122.4 (12) |
C4—C5—H5 | 118.5 (10) | N1—C19—C20 | 176.1 (2) |
C6—C5—H5 | 121.6 (10) | C19—C20—C21 | 179.0 (2) |
C1—C6—C5 | 120.28 (14) | C20—C21—C22 | 179.1 (2) |
C1—C6—H6 | 118.8 (13) | C21—C22—C23 | 178.83 (17) |
C5—C6—H6 | 121.0 (13) | O1—C23—C22 | 112.5 (2) |
N1—C7—C8 | 119.61 (18) | O1—C23—H17 | 109.7 (12) |
N1—C7—C12 | 121.35 (18) | O1—C23—H18 | 107.2 (10) |
C8—C7—C12 | 119.02 (17) | C22—C23—H17 | 110.5 (12) |
C7—C8—C9 | 120.20 (19) | C22—C23—H18 | 109.6 (13) |
C7—C8—H7 | 117.7 (12) | H17—C23—H18 | 107.1 (19) |
C9—C8—H7 | 122.1 (12) | N2—C24—C25 | 177.9 (2) |
C8—C9—C10 | 120.9 (2) | C24—C25—C26 | 177.73 (18) |
C8—C9—H8 | 118.2 (12) | C25—C26—C27 | 178.6 (3) |
C10—C9—H8 | 120.9 (12) | C26—C27—C28 | 179.63 (19) |
C9—C10—C11 | 118.93 (18) | O2—C28—C27 | 113.40 (13) |
C9—C10—H9 | 118.3 (13) | O2—C28—H19 | 107.9 (12) |
C11—C10—H9 | 122.8 (13) | O2—C28—H20 | 110.3 (13) |
C10—C11—C12 | 121.0 (2) | C27—C28—H19 | 108.8 (14) |
C10—C11—H10 | 120.9 (11) | C27—C28—H20 | 108.0 (12) |
C12—C11—H10 | 118.2 (11) | H19—C28—H20 | 108.3 (15) |
C7—C12—C11 | 120.01 (19) | C1—N1—C7 | 122.42 (16) |
C7—C12—H11 | 119.2 (12) | C1—N1—C19 | 117.21 (15) |
C11—C12—H11 | 120.8 (12) | C7—N1—C19 | 118.60 (15) |
N2—C13—C14 | 119.83 (17) | C4—N2—C13 | 122.30 (15) |
N2—C13—C18 | 120.17 (18) | C4—N2—C24 | 118.64 (15) |
C14—C13—C18 | 119.96 (17) | C13—N2—C24 | 119.01 (16) |
C13—C14—C15 | 119.75 (19) | C23—O1—H1 | 106.1 (13) |
C13—C14—H12 | 117.8 (12) | C28—O2—H2 | 105.7 (16) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2i | 0.90 (3) | 1.93 (3) | 2.821 (2) | 168 (3) |
O2—H2···O1ii | 0.92 (3) | 1.86 (3) | 2.777 (2) | 172 (3) |
Symmetry codes: (i) x+1, y+1, z; (ii) −x+2, y−1/2, −z+1/2. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C28H20N2O2 | C28H20N2O2 |
Mr | 416.46 | 416.46 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 100 | 100 |
a, b, c (Å) | 9.0669 (18), 7.7778 (16), 30.135 (6) | 15.530 (4), 8.831 (2), 17.108 (4) |
β (°) | 93.148 (2) | 115.766 (3) |
V (Å3) | 2121.9 (7) | 2113.0 (9) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.08 | 0.08 |
Crystal size (mm) | 0.49 × 0.16 × 0.05 | 0.22 × 0.18 × 0.05 |
|
Data collection |
Diffractometer | Bruker APEXII CCD area-detector diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.961, 0.996 | 0.982, 0.996 |
No. of measured, independent and observed reflections | 11823, 4842, 3703 [I > 2σ(I)] | 11897, 4826, 3150 [F2 > 2σ(F2)] |
Rint | 0.030 | 0.046 |
(sin θ/λ)max (Å−1) | 0.649 | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.133, 1.06 | 0.048, 0.111, 1.05 |
No. of reflections | 4842 | 4826 |
No. of parameters | 358 | 366 |
No. of restraints | 81 | 0 |
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 |
Δρmax, Δρmin (e Å−3) | 0.65, −0.53 | 0.24, −0.24 |
Selected geometric parameters (Å, º) for (I) topN1—C19 | 1.341 (2) | N2—C24 | 1.346 (2) |
C19—C20 | 1.200 (2) | C24—C25 | 1.199 (2) |
C20—C21 | 1.373 (2) | C25—C26 | 1.375 (2) |
C21—C22 | 1.200 (2) | C26—C27 | 1.195 (3) |
C22—C23 | 1.466 (2) | C27—C28 | 1.465 (3) |
| | | |
N1—C19—C20 | 179.4 (2) | N2—C24—C25 | 178.16 (18) |
C19—C20—C21 | 177.1 (2) | C24—C25—C26 | 175.7 (2) |
C22—C21—C20 | 179.7 (2) | C27—C26—C25 | 178.5 (2) |
C21—C22—C23 | 170.6 (2) | C26—C27—C28 | 178.0 (2) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O1i | 0.815 (14) | 1.97 (2) | 2.771 (3) | 168.9 (14) |
O1—H1B···O2ii | 0.82 (3) | 1.94 (3) | 2.753 (3) | 173 (5) |
O2—H2A···O1iii | 0.815 (15) | 1.94 (2) | 2.753 (3) | 173 (2) |
O2—H2B···O2iv | 0.82 (2) | 1.94 (2) | 2.756 (3) | 173 (2) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, y−1/2, −z+1/2; (iii) −x+2, y+1/2, −z+1/2; (iv) −x+2, −y+2, −z. |
Selected geometric parameters (Å, º) for (II) topN1—C19 | 1.348 (3) | N2—C24 | 1.346 (3) |
C19—C20 | 1.198 (3) | C24—C25 | 1.195 (3) |
C20—C21 | 1.377 (3) | C25—C26 | 1.375 (3) |
C21—C22 | 1.194 (3) | C26—C27 | 1.199 (3) |
C22—C23 | 1.463 (3) | C27—C28 | 1.462 (3) |
| | | |
N1—C19—C20 | 176.1 (2) | N2—C24—C25 | 177.9 (2) |
C19—C20—C21 | 179.0 (2) | C24—C25—C26 | 177.73 (18) |
C20—C21—C22 | 179.1 (2) | C25—C26—C27 | 178.6 (3) |
C21—C22—C23 | 178.83 (17) | C26—C27—C28 | 179.63 (19) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2i | 0.90 (3) | 1.93 (3) | 2.821 (2) | 168 (3) |
O2—H2···O1ii | 0.92 (3) | 1.86 (3) | 2.777 (2) | 172 (3) |
Symmetry codes: (i) x+1, y+1, z; (ii) −x+2, y−1/2, −z+1/2. |
Benzene-1,4-diamines show electron-donating ability and are able to act as π-conjugated linkers. Acetylene derivatives which have amino groups as substituents are named ynamines, and they are known to be unstable because of their high reactivity. In the course of our research into ynamine compounds (Okuno et al., 2006), we succeeded in the preparation and characterization of the title compound, which incorporates an N,N'-diethynylbenzene-1,4-diamine skeleton. The molecule is a key unit to form two-leg ladder polydiacetylenes by solid-state polymerization. We also found conformational polymorphism (Bernstein, 2002) depending on the recrystallization solvent of the title compound, shown in the orientation of the hydroxy groups. Either crystal could be obtained independently, as judged by powder X-ray diffraction. In order to clarify the difference in the hydrogen-bonding patterns and crystal packings caused by the different hydroxy-group orientations, the crystal structures of the two polymorphs, (I) and (II), were determined.
Displacement ellipsoid plots of the two polymorphs are shown in Fig. 1. The bond lengths and angles of both polymorphs are almost similar (Tables 1 and 3). These structural geometries are consistent with those of the reported ynamines (Galli et al., 1988, 1989; Mayerle & Flandera, 1978; Okuno et al., 2006).
In (I), the structures around the N atoms, viz. the N1/C1/C7/C19 plane (r.m.s. deviation = 0.010 Å) and the N2/C4/C13/C24 plane (r.m.s. deviation = 0.003 Å), are planar. The dihedral angles between the C1–C6 ring and the N1/C1/C7/C19 and N2/C4/C13/C24 planes are 49.15 (8) and 31.92 (8)°, respectively. A large residual density of 0.65 e Å-3 is located near atom C28, which has rather elongated displacement ellipsoids. This is presumably due to thermal motion of the hydroxymethyl group.
In (II), the structures around the N atoms, viz. the N1/C1/C7/C19 plane (r.m.s. deviation = 0.045 Å) and the N2/C4/C13/C24 plane (r.m.s. deviation = 0.007 Å), are planar. The dihedral angles between the C1–C6 ring and the N1/C1/C7/C19 and N2/C4/C13/C24 planes are 57.36 (8) and 46.98 (8)°, respectively.
In both polymorphs, intramolecular conjugation between the two diacetylene units, i.e. overlap of p- or π-orbitals, is estimated by the value of cos2θ, where θ is the torsion angle between the two orbitals. Even in the case of the smallest cos2θ with θ = 57.36° in (II), the value is 0.29, suggesting the two diacetylene units are conjugated effectively.
We now discuss the differences between the molecular structures in the two polymorphs. A significant difference between the structures of (I) and (II) is the orientation of the hydroxy groups to the C23/N1/N2/C28 planes. The hydroxy groups in (I) have an anti conformation, while those in (II) make a syn conformation (Fig. 2), affording different types of intermolecular hydrogen bonds and different molecular packing structures. There are no significant π–π and C—H···π interactions.
The molecules in (I) and (II) form similar sheet structures, which are parallel to the ac and ab planes, respectively. In (I), the hydrogen bonds connect two sheets above and below (Fig. 3) to give zigzag intermolecular hydrogen bonds. The H atoms of both hydroxy groups are disordered and there are four types of O—H···O hydrogen bonds (Table 2). Therefore, two kinds of zigzag intermolecular hydrogen bonds are observed, which are distinguished by black and grey lines in Fig. 4. When the structure of (I) was solved in the P21/c space group without disorder, the distances between the O-bound H atoms became too close, because the hydrogen-bonded pair of molecules are related by inversion symmetry. The remaining peaks around the O atoms were also high, indicating the existence of disorder. The possibility of solving the structure in space group P21 was examined carefully, but the disorder was still present, as indicated by large peaks around the O atoms.
In (II), intermolecular hydrogen bonds are limited within two sheets (Table 4), giving double-sheet structures (Fig. 5). The hydrogen-bonding pattern was classified as a 4-helix (Fig. 4) (Taylor & Macrae, 2001).
In spite of the difference in sheet packing, (I) and (II) have almost the same unit-cell volume and calculated densities of 1.304 and 1.309 Mg m-3, respectively.