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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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270111045951/uk3036sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270111045951/uk3036Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270111045951/uk3036IIsup3.hkl
Contains datablock II

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270111045951/uk3036Isup4.cml
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270111045951/uk3036IIsup5.cml
Supplementary material

CCDC references: 862235; 862236

Comment top

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 ππ 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.

Related literature top

For related literature, see: Bernstein (2002); Galli et al. (1988, 1989); Mayerle & Flandera (1978); Okuno et al. (2006); Sheldrick (2008); Tabata et al. (2011); Taylor & Macrae (2001).

Experimental top

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.

Refinement top

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).

Computing details top

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).

Figures top
[Figure 1] Fig. 1. The asymmetric units of (a) polymorph (I) and (b) polymorph (II) of the title compound, showing the atom-numbering schemes. Displacement ellipsoids are drawn at the 50% probability level. The disordered H atoms in polymorph (I) are identified by subscripts.
[Figure 2] Fig. 2. Views of (a) polymorph (I) and (b) polymorph (II), projected along the N1···N2 direction, with the benzene rings horizontal.
[Figure 3] Fig. 3. A view of the hydrogen-bonding interactions in (I) (dashed lines). [Symmetry codes: (i) -x + 1, -y + 1, -z + 1; (ii) x - 1, -y + 3/2, z + 1/2; (iii) -x + 1, y - 1/2, -z + 1/2; (iv) x - 1, y, z.]
[Figure 4] Fig. 4. Schematic presentations of (a) the zigzag hydrogen-bonding network of (I) and (b) the 4-helix hydrogen-bonding network of (II). The disordered hydrogen bonds of (I) are identified by black and grey lines. [Symmetry codes: (i) -x + 1, -y + 1, -z + 1; (ii) x - 1, -y + 3/2, z + 1/2; (iii) -x + 1, y - 1/2, -z + 1/2; (iv) x - 1, y, z; (v) x + 1, y + 1, z; (vi) -x + 3, y + 1/2, -z + 1/2; (vii) -x + 2, y + 3/2, -z + 1/2; (viii) x, y + 1, z].
[Figure 5] Fig. 5. A view of the hydrogen-bonding interactions in (II) (dashed lines). [Symmetry codes: (i) x + 1, y + 1, z; (ii) -x + 3, y + 1/2, -z + 1/2; (iii) -x + 2, y + 3/2, -z + 1/2; (iv) x, y + 1, z.]
(I) N1,N4-bis(5-hydroxypenta-1,3-diynyl)- N1,N4-diphenylbenzene-1,4-diamine top
Crystal data top
C28H20N2O2F(000) = 872
Mr = 416.46Dx = 1.304 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 9.0669 (18) ÅCell parameters from 2923 reflections
b = 7.7778 (16) Åθ = 2.3–27.4°
c = 30.135 (6) ŵ = 0.08 mm1
β = 93.148 (2)°T = 100 K
V = 2121.9 (7) Å3Plate, pale yellow
Z = 40.49 × 0.16 × 0.05 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer
4842 independent reflections
Radiation source: Bruker TXS fine-focus rotating anode3703 reflections with I > 2σ(I)
Bruker Helios multilayer confocal mirror monochromatorRint = 0.030
Detector resolution: 8.333 pixels mm-1θmax = 27.5°, θmin = 1.4°
ϕ and ω scansh = 911
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
k = 910
Tmin = 0.961, Tmax = 0.996l = 3039
11823 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.051Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.133H 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 parametersΔρmax = 0.65 e Å3
81 restraintsΔρmin = 0.53 e Å3
Crystal data top
C28H20N2O2V = 2121.9 (7) Å3
Mr = 416.46Z = 4
Monoclinic, P21/cMo Kα radiation
a = 9.0669 (18) ŵ = 0.08 mm1
b = 7.7778 (16) ÅT = 100 K
c = 30.135 (6) Å0.49 × 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 = 0.996Rint = 0.030
11823 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.05181 restraints
wR(F2) = 0.133H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.65 e Å3
4842 reflectionsΔρmin = 0.53 e Å3
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
xyzUiso*/UeqOcc. (<1)
C10.97406 (18)0.9263 (2)0.32887 (5)0.0186 (4)
C21.0220 (2)0.8268 (2)0.29412 (6)0.0203 (4)
C30.94556 (19)0.8304 (2)0.25305 (6)0.0196 (4)
C40.82030 (18)0.9331 (2)0.24653 (5)0.0172 (4)
C50.77410 (19)1.0344 (2)0.28120 (6)0.0184 (4)
C60.85049 (19)1.0309 (2)0.32224 (6)0.0190 (4)
C71.20500 (19)0.9286 (2)0.37841 (6)0.0201 (4)
C81.2746 (2)0.8571 (3)0.41628 (6)0.0229 (4)
C91.4265 (2)0.8739 (3)0.42327 (6)0.0256 (4)
C101.5094 (2)0.9603 (3)0.39305 (6)0.0256 (4)
C111.4390 (2)1.0305 (3)0.35527 (6)0.0243 (4)
C121.2876 (2)1.0151 (2)0.34770 (6)0.0214 (4)
C130.58928 (19)0.9688 (2)0.19674 (6)0.0199 (4)
C140.5351 (2)1.0377 (3)0.15658 (7)0.0287 (4)
C150.3841 (2)1.0636 (3)0.14915 (8)0.0361 (5)
C160.2876 (2)1.0264 (3)0.18203 (8)0.0343 (5)
C170.3431 (2)0.9579 (3)0.22186 (7)0.0289 (5)
C180.4929 (2)0.9256 (2)0.22940 (6)0.0226 (4)
C190.96509 (19)0.8878 (3)0.40665 (6)0.0224 (4)
C200.88956 (19)0.8610 (3)0.43739 (6)0.0247 (4)
C210.80320 (19)0.8218 (3)0.47201 (6)0.0220 (4)
C220.72713 (19)0.7873 (3)0.50211 (6)0.0221 (4)
C230.6372 (2)0.7159 (2)0.53664 (6)0.0246 (4)
H170.68710.73720.56620.030*
H180.54050.77530.53570.030*
C240.82673 (19)0.9179 (2)0.16790 (6)0.0196 (4)
C250.90268 (19)0.8987 (3)0.13693 (6)0.0221 (4)
C260.9874 (2)0.8637 (3)0.10157 (6)0.0268 (4)
C271.0611 (2)0.8295 (3)0.07110 (7)0.0382 (5)
C281.1467 (3)0.7863 (4)0.03282 (7)0.0561 (7)
H191.25280.78050.04250.067*
H201.11640.67130.02160.067*
H31.111 (2)0.751 (3)0.2995 (6)0.025 (5)*
H40.977 (2)0.761 (3)0.2290 (6)0.015 (5)*
H50.690 (2)1.107 (3)0.2763 (6)0.023 (5)*
H60.820 (2)1.104 (3)0.3469 (6)0.018 (5)*
H71.214 (2)0.793 (3)0.4377 (7)0.027 (5)*
H81.474 (2)0.821 (3)0.4497 (7)0.033 (6)*
H91.617 (3)0.975 (3)0.3985 (7)0.034 (6)*
H101.495 (2)1.092 (3)0.3343 (6)0.022 (5)*
H111.237 (2)1.068 (3)0.3218 (7)0.033 (6)*
H120.603 (2)1.067 (3)0.1343 (7)0.032 (6)*
H130.348 (3)1.110 (3)0.1200 (8)0.045 (7)*
H140.178 (2)1.046 (3)0.1750 (7)0.029 (6)*
H150.277 (2)0.929 (3)0.2454 (7)0.034 (6)*
H160.530 (2)0.871 (3)0.2569 (7)0.025 (5)*
H1A0.5522 (13)0.5249 (15)0.5106 (5)0.075 (12)*0.50
H2A1.2080 (13)0.939 (3)0.0086 (7)0.075 (12)*0.50
H1B0.6920 (16)0.495 (2)0.5242 (18)0.075 (12)*0.50
H2B1.053 (2)0.961 (3)0.0017 (7)0.075 (12)*0.50
N11.04834 (16)0.9169 (2)0.37201 (5)0.0210 (3)
N20.74536 (16)0.9391 (2)0.20355 (5)0.0192 (3)
O10.6139 (2)0.5375 (2)0.53103 (8)0.0620 (6)
O21.1279 (2)0.9048 (2)0.00128 (5)0.0452 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0176 (8)0.0224 (9)0.0161 (8)0.0009 (7)0.0033 (6)0.0038 (7)
C20.0195 (9)0.0214 (9)0.0205 (9)0.0035 (7)0.0053 (7)0.0023 (7)
C30.0201 (8)0.0202 (9)0.0190 (8)0.0019 (7)0.0059 (7)0.0011 (7)
C40.0174 (8)0.0190 (9)0.0156 (8)0.0029 (6)0.0039 (6)0.0011 (6)
C50.0157 (8)0.0190 (9)0.0207 (8)0.0014 (7)0.0039 (7)0.0008 (7)
C60.0198 (8)0.0204 (9)0.0171 (8)0.0001 (7)0.0054 (7)0.0013 (7)
C70.0197 (8)0.0225 (9)0.0183 (8)0.0030 (7)0.0036 (7)0.0015 (7)
C80.0242 (9)0.0281 (10)0.0167 (8)0.0015 (8)0.0042 (7)0.0031 (7)
C90.0259 (10)0.0305 (11)0.0202 (9)0.0044 (8)0.0020 (7)0.0019 (8)
C100.0195 (9)0.0302 (11)0.0271 (10)0.0012 (8)0.0005 (7)0.0022 (8)
C110.0242 (9)0.0244 (10)0.0249 (9)0.0007 (7)0.0080 (7)0.0002 (8)
C120.0236 (9)0.0224 (10)0.0185 (9)0.0041 (7)0.0035 (7)0.0019 (7)
C130.0178 (8)0.0189 (9)0.0230 (9)0.0015 (7)0.0013 (7)0.0019 (7)
C140.0230 (10)0.0318 (11)0.0312 (11)0.0024 (8)0.0002 (8)0.0095 (9)
C150.0267 (10)0.0378 (13)0.0428 (13)0.0002 (9)0.0067 (9)0.0115 (10)
C160.0172 (9)0.0321 (12)0.0531 (14)0.0015 (8)0.0021 (9)0.0045 (10)
C170.0210 (9)0.0280 (11)0.0387 (11)0.0058 (8)0.0090 (8)0.0094 (9)
C180.0230 (9)0.0215 (9)0.0234 (9)0.0047 (7)0.0038 (7)0.0039 (7)
C190.0197 (9)0.0282 (10)0.0193 (9)0.0041 (7)0.0016 (7)0.0029 (7)
C200.0186 (9)0.0347 (11)0.0208 (9)0.0040 (8)0.0012 (7)0.0050 (8)
C210.0189 (8)0.0287 (10)0.0184 (9)0.0031 (7)0.0012 (7)0.0032 (7)
C220.0205 (9)0.0265 (10)0.0193 (8)0.0003 (7)0.0007 (7)0.0002 (7)
C230.0254 (9)0.0260 (10)0.0232 (9)0.0011 (7)0.0091 (7)0.0007 (7)
C240.0184 (8)0.0224 (9)0.0180 (8)0.0017 (7)0.0006 (7)0.0011 (7)
C250.0193 (9)0.0296 (10)0.0173 (8)0.0010 (7)0.0007 (7)0.0017 (7)
C260.0224 (9)0.0405 (12)0.0175 (9)0.0036 (8)0.0012 (7)0.0049 (8)
C270.0292 (10)0.0646 (15)0.0211 (10)0.0144 (10)0.0045 (8)0.0105 (10)
C280.0497 (14)0.0916 (19)0.0288 (11)0.0365 (13)0.0195 (10)0.0200 (12)
N10.0173 (7)0.0315 (9)0.0145 (7)0.0023 (6)0.0042 (6)0.0034 (6)
N20.0178 (7)0.0246 (8)0.0154 (7)0.0001 (6)0.0039 (6)0.0000 (6)
O10.0711 (13)0.0280 (9)0.0931 (14)0.0128 (8)0.0612 (11)0.0114 (9)
O20.0815 (13)0.0280 (8)0.0289 (8)0.0082 (8)0.0286 (8)0.0006 (6)
Geometric parameters (Å, º) top
N1—C191.341 (2)C9—H80.98 (2)
C19—C201.200 (2)C10—C111.387 (3)
C20—C211.373 (2)C10—H90.98 (2)
C21—C221.200 (2)C11—C121.384 (3)
C22—C231.466 (2)C11—H100.96 (2)
N2—C241.346 (2)C12—H110.97 (2)
C24—C251.199 (2)C13—C141.388 (3)
C25—C261.375 (2)C13—C181.393 (2)
C26—C271.195 (3)C13—N21.437 (2)
C27—C281.465 (3)C14—C151.390 (3)
C1—C61.390 (2)C14—H120.96 (2)
C1—C21.391 (2)C15—C161.388 (3)
C1—N11.433 (2)C15—H130.99 (2)
C2—C31.385 (2)C16—C171.383 (3)
C2—H31.00 (2)C16—H141.02 (2)
C3—C41.394 (2)C17—C181.387 (3)
C3—H40.960 (19)C17—H150.98 (2)
C4—C51.391 (2)C18—H160.98 (2)
C4—N21.430 (2)C23—O11.412 (2)
C5—C61.384 (2)C23—H170.9900
C5—H50.95 (2)C23—H180.9900
C6—H60.989 (19)C28—O21.384 (3)
C7—C81.389 (2)C28—H190.9900
C7—C121.395 (2)C28—H200.9900
C7—N11.426 (2)O1—H1A0.816 (11)
C8—C91.387 (3)O1—H1B0.817 (11)
C8—H71.00 (2)O2—H2A0.816 (11)
C9—C101.386 (3)O2—H2B0.816 (11)
C6—C1—C2120.01 (16)C16—C15—H13121.5 (14)
C6—C1—N1119.69 (15)C14—C15—H13117.9 (14)
C2—C1—N1120.26 (16)C17—C16—C15119.07 (19)
C3—C2—C1119.98 (16)C17—C16—H14123.0 (12)
C3—C2—H3120.9 (11)C15—C16—H14117.9 (12)
C1—C2—H3119.1 (11)C16—C17—C18121.26 (19)
C2—C3—C4120.09 (16)C16—C17—H15120.5 (13)
C2—C3—H4120.5 (11)C18—C17—H15118.3 (13)
C4—C3—H4119.4 (11)C17—C18—C13119.15 (19)
C5—C4—C3119.69 (16)C17—C18—H16120.6 (12)
C5—C4—N2120.95 (16)C13—C18—H16120.2 (12)
C3—C4—N2119.29 (15)N1—C19—C20179.4 (2)
C6—C5—C4120.23 (16)C19—C20—C21177.1 (2)
C6—C5—H5120.4 (12)C22—C21—C20179.7 (2)
C4—C5—H5119.4 (12)C21—C22—C23170.6 (2)
C5—C6—C1119.98 (16)O1—C23—C22111.87 (16)
C5—C6—H6120.8 (11)O1—C23—H17109.2
C1—C6—H6119.2 (11)C22—C23—H17109.2
C8—C7—C12120.10 (17)O1—C23—H18109.2
C8—C7—N1119.34 (16)C22—C23—H18109.2
C12—C7—N1120.53 (16)H17—C23—H18107.9
C9—C8—C7119.31 (17)N2—C24—C25178.16 (18)
C9—C8—H7121.4 (12)C24—C25—C26175.7 (2)
C7—C8—H7119.3 (12)C27—C26—C25178.5 (2)
C10—C9—C8121.04 (18)C26—C27—C28178.0 (2)
C10—C9—H8120.8 (13)O2—C28—C27112.5 (2)
C8—C9—H8118.1 (13)O2—C28—H19109.1
C9—C10—C11119.23 (17)C27—C28—H19109.1
C9—C10—H9120.8 (13)O2—C28—H20109.1
C11—C10—H9119.9 (13)C27—C28—H20109.1
C12—C11—C10120.58 (17)H19—C28—H20107.8
C12—C11—H10119.2 (12)C19—N1—C7120.31 (14)
C10—C11—H10120.2 (12)C19—N1—C1117.29 (14)
C11—C12—C7119.74 (17)C7—N1—C1122.33 (13)
C11—C12—H11120.9 (13)C24—N2—C4117.70 (14)
C7—C12—H11119.3 (13)C24—N2—C13118.95 (14)
C14—C13—C18120.20 (17)C4—N2—C13123.34 (14)
C14—C13—N2119.02 (16)C23—O1—H1A107.5 (9)
C18—C13—N2120.76 (16)C23—O1—H1B107.3 (7)
C13—C14—C15119.67 (19)H1A—O1—H1B109 (4)
C13—C14—H12119.0 (13)C28—O2—H2A110.1 (10)
C15—C14—H12121.3 (13)C28—O2—H2B110.0 (10)
C16—C15—C14120.6 (2)H2A—O2—H2B128 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···O1i0.82 (1)1.97 (2)2.771 (3)169 (1)
O1—H1B···O2ii0.82 (3)1.94 (3)2.753 (3)173 (5)
O2—H2A···O1iii0.82 (2)1.94 (2)2.753 (3)173 (2)
O2—H2B···O2iv0.82 (2)1.94 (2)2.756 (3)173 (2)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+2, y1/2, 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
C28H20N2O2F(000) = 872.00
Mr = 416.46Dx = 1.309 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 15.530 (4) ÅCell parameters from 1658 reflections
b = 8.831 (2) Åθ = 2.7–24.4°
c = 17.108 (4) ŵ = 0.08 mm1
β = 115.766 (3)°T = 100 K
V = 2113.0 (9) Å3Plate, pale yellow
Z = 40.22 × 0.18 × 0.05 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer
4826 independent reflections
Radiation source: Bruker TXS fine-focus rotating anode3150 reflections with F2 > 2σ(F2)
Bruker Helios multilayer confocal mirror monochromatorRint = 0.046
Detector resolution: 8.333 pixels mm-1θmax = 27.5°, θmin = 1.5°
ϕ and ω scansh = 2017
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
k = 1111
Tmin = 0.982, Tmax = 0.996l = 1022
11897 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048Hydrogen site location: difference Fourier map
wR(F2) = 0.111H 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 parametersΔρmax = 0.24 e Å3
0 restraintsΔρmin = 0.24 e Å3
Primary atom site location: structure-invariant direct methods
Crystal data top
C28H20N2O2V = 2113.0 (9) Å3
Mr = 416.46Z = 4
Monoclinic, P21/cMo Kα radiation
a = 15.530 (4) ŵ = 0.08 mm1
b = 8.831 (2) ÅT = 100 K
c = 17.108 (4) Å0.22 × 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 = 0.996Rint = 0.046
11897 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0480 restraints
wR(F2) = 0.111H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.24 e Å3
4826 reflectionsΔρmin = 0.24 e Å3
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
xyzUiso*/Ueq
C11.03768 (11)0.3145 (2)0.11216 (11)0.0209 (4)
C20.94865 (12)0.2728 (2)0.04859 (11)0.0229 (4)
C30.86699 (12)0.3425 (2)0.04507 (11)0.0225 (4)
C40.87482 (11)0.45533 (19)0.10439 (11)0.0206 (4)
C50.96434 (12)0.4980 (2)0.16704 (11)0.0232 (4)
C61.04539 (12)0.4265 (2)0.17084 (11)0.0234 (4)
C71.14378 (12)0.0863 (2)0.13764 (11)0.0217 (4)
C81.23015 (12)0.0255 (2)0.14516 (11)0.0255 (5)
C91.25180 (13)0.1247 (3)0.16747 (12)0.0278 (5)
C101.18896 (13)0.2173 (3)0.18286 (12)0.0279 (5)
C111.10368 (13)0.1573 (3)0.17540 (12)0.0283 (5)
C121.08064 (12)0.0063 (2)0.15286 (11)0.0241 (4)
C130.78335 (11)0.68605 (19)0.11052 (10)0.0206 (4)
C140.72482 (12)0.7443 (2)0.14613 (11)0.0231 (4)
C150.71310 (12)0.8996 (2)0.14847 (11)0.0258 (5)
C160.76090 (12)0.9980 (3)0.11736 (12)0.0269 (5)
C170.81998 (12)0.9385 (3)0.08321 (11)0.0259 (5)
C180.83178 (12)0.7839 (2)0.07967 (11)0.0229 (4)
C191.19491 (12)0.3343 (2)0.12125 (11)0.0223 (4)
C201.26101 (12)0.4081 (2)0.12431 (11)0.0234 (4)
C211.33644 (12)0.4927 (2)0.12635 (11)0.0224 (4)
C221.40161 (12)0.5654 (2)0.12702 (11)0.0237 (4)
C231.48274 (14)0.6529 (3)0.12949 (13)0.0300 (5)
C240.71811 (12)0.4367 (2)0.09782 (11)0.0221 (4)
C250.65215 (12)0.3618 (2)0.09357 (11)0.0229 (4)
C260.57875 (12)0.2715 (2)0.09088 (11)0.0225 (4)
C270.51492 (12)0.1910 (2)0.08721 (11)0.0244 (4)
C280.43735 (13)0.0928 (3)0.08334 (12)0.0259 (5)
H11.5138 (17)0.822 (3)0.2045 (15)0.064 (8)*
H20.4596 (16)0.095 (3)0.2016 (15)0.063 (8)*
H30.9435 (12)0.197 (2)0.0060 (11)0.025 (5)*
H40.8029 (13)0.3123 (19)0.0001 (11)0.0270*
H50.9680 (12)0.575 (2)0.2093 (12)0.028 (5)*
H61.1084 (13)0.453 (2)0.2153 (11)0.0281*
H71.2757 (14)0.095 (3)0.1354 (12)0.037 (6)*
H81.3132 (13)0.164 (2)0.1723 (11)0.032 (5)*
H91.2080 (12)0.324 (2)0.2000 (11)0.029 (5)*
H101.0567 (13)0.221 (2)0.1860 (12)0.033 (6)*
H111.0215 (13)0.034 (2)0.1467 (11)0.028 (5)*
H120.6919 (13)0.671 (3)0.1683 (11)0.032 (6)*
H130.6709 (13)0.939 (2)0.1730 (11)0.027 (5)*
H140.7526 (13)1.108 (3)0.1198 (11)0.0323*
H150.8509 (12)1.007 (2)0.0585 (11)0.027 (5)*
H160.8696 (13)0.741 (2)0.0538 (11)0.025 (5)*
H171.4598 (15)0.733 (3)0.0800 (14)0.052 (7)*
H181.5277 (14)0.585 (3)0.1198 (12)0.040 (6)*
H190.4259 (13)0.013 (3)0.0386 (13)0.037 (6)*
H200.3759 (14)0.158 (3)0.0639 (12)0.040 (6)*
N11.12345 (9)0.24282 (16)0.11683 (9)0.0225 (4)
N20.79082 (9)0.52556 (16)0.10306 (9)0.0221 (4)
O11.53518 (9)0.72606 (16)0.21136 (8)0.0279 (3)
O20.45732 (9)0.01895 (15)0.16366 (8)0.0278 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0161 (9)0.0249 (10)0.0239 (10)0.0001 (7)0.0107 (8)0.0020 (8)
C20.0236 (10)0.0234 (10)0.0225 (10)0.0024 (8)0.0106 (8)0.0003 (8)
C30.0166 (9)0.0255 (10)0.0231 (10)0.0030 (8)0.0066 (8)0.0000 (8)
C40.0161 (9)0.0225 (10)0.0246 (10)0.0012 (7)0.0101 (8)0.0016 (8)
C50.0224 (9)0.0263 (11)0.0214 (10)0.0027 (8)0.0098 (8)0.0019 (8)
C60.0170 (9)0.0278 (11)0.0236 (10)0.0045 (8)0.0070 (8)0.0004 (8)
C70.0194 (9)0.0251 (10)0.0207 (10)0.0009 (8)0.0087 (8)0.0014 (8)
C80.0204 (9)0.0286 (11)0.0302 (11)0.0005 (8)0.0136 (8)0.0003 (8)
C90.0231 (10)0.0316 (11)0.0295 (11)0.0029 (9)0.0124 (8)0.0014 (8)
C100.0295 (11)0.0259 (11)0.0263 (11)0.0010 (9)0.0103 (9)0.0006 (9)
C110.0277 (10)0.0280 (11)0.0314 (11)0.0053 (9)0.0149 (9)0.0008 (9)
C120.0188 (9)0.0287 (11)0.0265 (11)0.0018 (8)0.0113 (8)0.0016 (8)
C130.0141 (9)0.0233 (10)0.0191 (9)0.0018 (7)0.0023 (7)0.0008 (8)
C140.0155 (9)0.0282 (11)0.0233 (10)0.0020 (8)0.0062 (8)0.0016 (8)
C150.0197 (9)0.0307 (11)0.0241 (10)0.0019 (8)0.0068 (8)0.0046 (8)
C160.0220 (10)0.0233 (11)0.0271 (11)0.0001 (8)0.0029 (8)0.0028 (8)
C170.0205 (9)0.0269 (11)0.0250 (10)0.0045 (8)0.0050 (8)0.0036 (8)
C180.0172 (9)0.0280 (11)0.0223 (10)0.0011 (8)0.0074 (8)0.0011 (8)
C190.0188 (9)0.0266 (10)0.0229 (10)0.0031 (8)0.0103 (8)0.0011 (8)
C200.0188 (9)0.0260 (10)0.0254 (10)0.0024 (8)0.0096 (8)0.0013 (8)
C210.0207 (9)0.0253 (10)0.0203 (10)0.0002 (8)0.0080 (8)0.0003 (8)
C220.0214 (9)0.0240 (10)0.0264 (10)0.0010 (8)0.0111 (8)0.0001 (8)
C230.0294 (11)0.0325 (12)0.0319 (12)0.0118 (9)0.0168 (9)0.0077 (10)
C240.0176 (9)0.0244 (10)0.0244 (10)0.0002 (8)0.0093 (8)0.0005 (8)
C250.0201 (9)0.0236 (10)0.0258 (10)0.0016 (8)0.0108 (8)0.0009 (8)
C260.0186 (9)0.0252 (10)0.0236 (10)0.0018 (8)0.0091 (8)0.0002 (8)
C270.0216 (9)0.0268 (11)0.0242 (10)0.0011 (8)0.0092 (8)0.0003 (8)
C280.0210 (10)0.0304 (11)0.0245 (11)0.0063 (9)0.0083 (8)0.0016 (9)
N10.0171 (7)0.0228 (8)0.0308 (9)0.0010 (7)0.0133 (7)0.0009 (7)
N20.0156 (7)0.0220 (9)0.0291 (9)0.0020 (6)0.0101 (7)0.0009 (7)
O10.0264 (7)0.0279 (8)0.0279 (8)0.0057 (6)0.0103 (6)0.0033 (6)
O20.0305 (7)0.0279 (8)0.0261 (8)0.0048 (6)0.0134 (6)0.0007 (6)
Geometric parameters (Å, º) top
N1—C191.348 (3)C9—C101.383 (4)
C19—C201.198 (3)C9—H80.98 (2)
C20—C211.377 (3)C10—C111.380 (3)
C21—C221.194 (3)C10—H90.996 (18)
C22—C231.463 (3)C11—C121.391 (3)
N2—C241.346 (3)C11—H101.00 (3)
C24—C251.195 (3)C12—H110.95 (2)
C25—C261.375 (3)C13—C141.394 (3)
C26—C271.199 (3)C13—C181.391 (3)
C27—C281.462 (3)C13—N21.432 (3)
C1—C21.386 (2)C14—C151.387 (3)
C1—C61.378 (3)C14—H121.00 (3)
C1—N11.445 (3)C15—C161.390 (3)
C2—C31.387 (3)C15—H130.98 (3)
C2—H30.968 (19)C16—C171.387 (4)
C3—C41.389 (3)C16—H140.98 (2)
C3—H40.995 (16)C17—C181.383 (3)
C4—C51.389 (2)C17—H150.98 (2)
C4—N21.436 (3)C18—H160.96 (3)
C5—C61.384 (3)C23—O11.432 (3)
C5—H50.98 (2)C23—H171.04 (3)
C6—H60.971 (16)C23—H180.99 (3)
C7—C81.398 (3)C28—O21.428 (3)
C7—C121.386 (3)C28—H191.00 (2)
C7—N11.428 (3)C28—H201.04 (2)
C8—C91.381 (3)O1—H10.90 (3)
C8—H71.01 (3)O2—H20.92 (3)
N1—C1—C2120.55 (17)C15—C14—H12122.4 (12)
N1—C1—C6119.23 (13)C14—C15—C16120.6 (2)
C2—C1—C6120.22 (18)C14—C15—H13119.0 (11)
C1—C2—C3119.84 (17)C16—C15—H13120.5 (11)
C1—C2—H3120.2 (10)C15—C16—C17119.05 (19)
C3—C2—H3120.0 (10)C15—C16—H14120.0 (14)
C2—C3—C4119.89 (14)C17—C16—H14121.0 (14)
C2—C3—H4120.1 (12)C16—C17—C18121.1 (2)
C4—C3—H4120.0 (12)C16—C17—H15119.1 (12)
N2—C4—C3120.52 (13)C18—C17—H15119.7 (12)
N2—C4—C5119.54 (17)C13—C18—C17119.5 (2)
C3—C4—C5119.92 (18)C13—C18—H16118.0 (12)
C4—C5—C6119.83 (18)C17—C18—H16122.4 (12)
C4—C5—H5118.5 (10)N1—C19—C20176.1 (2)
C6—C5—H5121.6 (10)C19—C20—C21179.0 (2)
C1—C6—C5120.28 (14)C20—C21—C22179.1 (2)
C1—C6—H6118.8 (13)C21—C22—C23178.83 (17)
C5—C6—H6121.0 (13)O1—C23—C22112.5 (2)
N1—C7—C8119.61 (18)O1—C23—H17109.7 (12)
N1—C7—C12121.35 (18)O1—C23—H18107.2 (10)
C8—C7—C12119.02 (17)C22—C23—H17110.5 (12)
C7—C8—C9120.20 (19)C22—C23—H18109.6 (13)
C7—C8—H7117.7 (12)H17—C23—H18107.1 (19)
C9—C8—H7122.1 (12)N2—C24—C25177.9 (2)
C8—C9—C10120.9 (2)C24—C25—C26177.73 (18)
C8—C9—H8118.2 (12)C25—C26—C27178.6 (3)
C10—C9—H8120.9 (12)C26—C27—C28179.63 (19)
C9—C10—C11118.93 (18)O2—C28—C27113.40 (13)
C9—C10—H9118.3 (13)O2—C28—H19107.9 (12)
C11—C10—H9122.8 (13)O2—C28—H20110.3 (13)
C10—C11—C12121.0 (2)C27—C28—H19108.8 (14)
C10—C11—H10120.9 (11)C27—C28—H20108.0 (12)
C12—C11—H10118.2 (11)H19—C28—H20108.3 (15)
C7—C12—C11120.01 (19)C1—N1—C7122.42 (16)
C7—C12—H11119.2 (12)C1—N1—C19117.21 (15)
C11—C12—H11120.8 (12)C7—N1—C19118.60 (15)
N2—C13—C14119.83 (17)C4—N2—C13122.30 (15)
N2—C13—C18120.17 (18)C4—N2—C24118.64 (15)
C14—C13—C18119.96 (17)C13—N2—C24119.01 (16)
C13—C14—C15119.75 (19)C23—O1—H1106.1 (13)
C13—C14—H12117.8 (12)C28—O2—H2105.7 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O2i0.90 (3)1.93 (3)2.821 (2)168 (3)
O2—H2···O1ii0.92 (3)1.86 (3)2.777 (2)172 (3)
Symmetry codes: (i) x+1, y+1, z; (ii) x+2, y1/2, z+1/2.

Experimental details

(I)(II)
Crystal data
Chemical formulaC28H20N2O2C28H20N2O2
Mr416.46416.46
Crystal system, space groupMonoclinic, P21/cMonoclinic, P21/c
Temperature (K)100100
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)
V3)2121.9 (7)2113.0 (9)
Z44
Radiation typeMo KαMo Kα
µ (mm1)0.080.08
Crystal size (mm)0.49 × 0.16 × 0.050.22 × 0.18 × 0.05
Data collection
DiffractometerBruker APEXII CCD area-detector
diffractometer
Bruker APEXII CCD area-detector
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.961, 0.9960.982, 0.996
No. of measured, independent and
observed reflections
11823, 4842, 3703 [I > 2σ(I)]11897, 4826, 3150 [F2 > 2σ(F2)]
Rint0.0300.046
(sin θ/λ)max1)0.6490.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.051, 0.133, 1.06 0.048, 0.111, 1.05
No. of reflections48424826
No. of parameters358366
No. of restraints810
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.65, 0.530.24, 0.24

Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), enCIFer (Allen et al., 2004).

Selected geometric parameters (Å, º) for (I) top
N1—C191.341 (2)N2—C241.346 (2)
C19—C201.200 (2)C24—C251.199 (2)
C20—C211.373 (2)C25—C261.375 (2)
C21—C221.200 (2)C26—C271.195 (3)
C22—C231.466 (2)C27—C281.465 (3)
N1—C19—C20179.4 (2)N2—C24—C25178.16 (18)
C19—C20—C21177.1 (2)C24—C25—C26175.7 (2)
C22—C21—C20179.7 (2)C27—C26—C25178.5 (2)
C21—C22—C23170.6 (2)C26—C27—C28178.0 (2)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···O1i0.815 (14)1.97 (2)2.771 (3)168.9 (14)
O1—H1B···O2ii0.82 (3)1.94 (3)2.753 (3)173 (5)
O2—H2A···O1iii0.815 (15)1.94 (2)2.753 (3)173 (2)
O2—H2B···O2iv0.82 (2)1.94 (2)2.756 (3)173 (2)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+2, y1/2, 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) top
N1—C191.348 (3)N2—C241.346 (3)
C19—C201.198 (3)C24—C251.195 (3)
C20—C211.377 (3)C25—C261.375 (3)
C21—C221.194 (3)C26—C271.199 (3)
C22—C231.463 (3)C27—C281.462 (3)
N1—C19—C20176.1 (2)N2—C24—C25177.9 (2)
C19—C20—C21179.0 (2)C24—C25—C26177.73 (18)
C20—C21—C22179.1 (2)C25—C26—C27178.6 (3)
C21—C22—C23178.83 (17)C26—C27—C28179.63 (19)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O2i0.90 (3)1.93 (3)2.821 (2)168 (3)
O2—H2···O1ii0.92 (3)1.86 (3)2.777 (2)172 (3)
Symmetry codes: (i) x+1, y+1, z; (ii) x+2, y1/2, z+1/2.
 

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