Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104034079/fr1518sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104034079/fr1518Isup2.hkl |
CCDC reference: 264813
The title compound was synthesized by the condensation reaction of 4-benzoylpyridine with hydrazine. An ethanol solution (10 ml) of 4-benzoylpyridine (Acros; 10 mmol) was mixed with hydrazine hydrate (Acros; 5 mmol) and two drops of formic acid. The mixture was refluxed for 12 h, resulting in a clear yellow solution. The solvent was removed under reduced pressure to obtain a yellow residue, which was crystallized from ethanol to obtain a yellow microcrystalline product. Single crystals of (I) were obtained by slow evaporation of a methanol solution of the product. Analysis calculated for C24H18N4: C 79.54, H 5.01, N 15.46%; found: C 79.28, H 5.05, N 15.65%. Main IR bands (cm−1): 3099 (w), 3055 (m), 3032 (m), 3016 (w), 2984 (w), 1601 (m), 1588 (s), 1568 (m), 1543 (m), 1489 (m), 1444 (m), 1410 (m), 1328 (m), 1317 (m), 1307 (m), 1218 (m), 992 (m), 819 (s), 777 (s), 691 (s).
All H atoms were located from the difference Fourier map and refined isotropically. The refined C—H distances fall in the range 0.939 (16)–0.994 (18) Å.
Data collection: COLLECT (Nonius, 1998); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and maXus (Mackay et al., 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXL97.
C24H18N4 | Z = 1 |
Mr = 362.42 | F(000) = 190 |
Triclinic, P1 | Dx = 1.293 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.1251 (12) Å | Cell parameters from 6326 reflections |
b = 7.3258 (15) Å | θ = 3.4–27.5° |
c = 10.456 (2) Å | µ = 0.08 mm−1 |
α = 93.35 (3)° | T = 293 K |
β = 91.28 (3)° | Rod, yellow |
γ = 96.00 (3)° | 0.4 × 0.15 × 0.15 mm |
V = 465.62 (16) Å3 |
Nonius KappaCCD area-detector diffractometer | 2101 independent reflections |
Radiation source: fine-focus sealed tube | 1637 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
Detector resolution: 0.76 pixels mm-1 | θmax = 27.5°, θmin = 3.5° |
ϕ and ω scans | h = −7→7 |
Absorption correction: empirical (using intensity measurements) (Blessing, 1995, 1997) | k = −9→9 |
Tmin = 0.969, Tmax = 0.998 | l = −13→13 |
10946 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.041 | All H-atom parameters refined |
wR(F2) = 0.110 | w = 1/[σ2(Fo2) + (0.0535P)2 + 0.0573P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
2101 reflections | Δρmax = 0.19 e Å−3 |
164 parameters | Δρmin = −0.15 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997a), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.080 (13) |
C24H18N4 | γ = 96.00 (3)° |
Mr = 362.42 | V = 465.62 (16) Å3 |
Triclinic, P1 | Z = 1 |
a = 6.1251 (12) Å | Mo Kα radiation |
b = 7.3258 (15) Å | µ = 0.08 mm−1 |
c = 10.456 (2) Å | T = 293 K |
α = 93.35 (3)° | 0.4 × 0.15 × 0.15 mm |
β = 91.28 (3)° |
Nonius KappaCCD area-detector diffractometer | 2101 independent reflections |
Absorption correction: empirical (using intensity measurements) (Blessing, 1995, 1997) | 1637 reflections with I > 2σ(I) |
Tmin = 0.969, Tmax = 0.998 | Rint = 0.036 |
10946 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.110 | All H-atom parameters refined |
S = 1.05 | Δρmax = 0.19 e Å−3 |
2101 reflections | Δρmin = −0.15 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. |
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 > 2σ(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 | 0.14151 (19) | 0.29594 (16) | 0.13918 (11) | 0.0344 (3) | |
C2 | 0.1134 (2) | 0.21261 (19) | 0.25500 (13) | 0.0444 (3) | |
H2 | 0.224 (3) | 0.242 (2) | 0.3250 (16) | 0.059 (4)* | |
C3 | −0.0681 (3) | 0.0872 (2) | 0.27047 (16) | 0.0551 (4) | |
H3 | −0.085 (3) | 0.028 (3) | 0.3513 (19) | 0.079 (6)* | |
C4 | −0.2246 (3) | 0.0470 (2) | 0.17276 (16) | 0.0563 (4) | |
H4 | −0.348 (3) | −0.038 (2) | 0.1856 (17) | 0.070 (5)* | |
C5 | −0.1993 (2) | 0.1312 (2) | 0.05942 (15) | 0.0499 (4) | |
H5 | −0.312 (3) | 0.103 (2) | −0.0108 (17) | 0.063 (5)* | |
C6 | −0.0172 (2) | 0.25409 (18) | 0.04132 (13) | 0.0402 (3) | |
H6 | 0.005 (2) | 0.315 (2) | −0.0395 (16) | 0.054 (4)* | |
C7 | 0.43509 (19) | 0.54309 (16) | 0.23360 (11) | 0.0339 (3) | |
C8 | 0.3185 (2) | 0.6749 (2) | 0.29159 (13) | 0.0476 (3) | |
H8 | 0.173 (3) | 0.695 (2) | 0.2589 (15) | 0.058 (4)* | |
C9 | 0.4109 (3) | 0.7808 (2) | 0.39721 (14) | 0.0570 (4) | |
H9 | 0.329 (3) | 0.878 (3) | 0.4368 (18) | 0.080 (6)* | |
C10 | 0.7139 (2) | 0.6298 (2) | 0.39438 (13) | 0.0511 (4) | |
H10 | 0.859 (3) | 0.616 (2) | 0.4341 (17) | 0.065 (5)* | |
C11 | 0.6387 (2) | 0.5212 (2) | 0.28614 (13) | 0.0450 (3) | |
H11 | 0.726 (3) | 0.434 (2) | 0.2508 (15) | 0.056 (4)* | |
C12 | 0.33808 (18) | 0.42629 (16) | 0.11961 (11) | 0.0328 (3) | |
N1 | 0.6060 (2) | 0.75934 (18) | 0.44989 (11) | 0.0547 (3) | |
N2 | 0.40933 (16) | 0.43361 (14) | 0.00485 (9) | 0.0375 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0346 (6) | 0.0335 (6) | 0.0343 (6) | 0.0020 (5) | 0.0014 (5) | −0.0020 (5) |
C2 | 0.0470 (7) | 0.0465 (7) | 0.0386 (7) | −0.0013 (6) | 0.0025 (6) | 0.0042 (6) |
C3 | 0.0609 (9) | 0.0494 (8) | 0.0538 (9) | −0.0057 (7) | 0.0116 (7) | 0.0099 (7) |
C4 | 0.0481 (8) | 0.0451 (8) | 0.0720 (10) | −0.0118 (6) | 0.0110 (7) | −0.0007 (7) |
C5 | 0.0401 (7) | 0.0467 (8) | 0.0596 (9) | −0.0038 (6) | −0.0052 (6) | −0.0079 (7) |
C6 | 0.0392 (7) | 0.0392 (7) | 0.0410 (7) | 0.0020 (5) | −0.0032 (5) | −0.0020 (5) |
C7 | 0.0358 (6) | 0.0358 (6) | 0.0287 (6) | −0.0028 (5) | 0.0025 (4) | 0.0010 (4) |
C8 | 0.0445 (7) | 0.0551 (8) | 0.0421 (7) | 0.0081 (6) | −0.0007 (6) | −0.0093 (6) |
C9 | 0.0662 (10) | 0.0565 (9) | 0.0464 (8) | 0.0080 (7) | 0.0024 (7) | −0.0157 (7) |
C10 | 0.0478 (8) | 0.0608 (9) | 0.0420 (7) | −0.0024 (7) | −0.0102 (6) | −0.0007 (6) |
C11 | 0.0426 (7) | 0.0505 (8) | 0.0412 (7) | 0.0061 (6) | −0.0038 (5) | −0.0040 (6) |
C12 | 0.0325 (6) | 0.0350 (6) | 0.0305 (6) | 0.0032 (5) | −0.0004 (4) | −0.0008 (4) |
N1 | 0.0647 (8) | 0.0570 (8) | 0.0383 (6) | −0.0064 (6) | −0.0042 (5) | −0.0073 (5) |
N2 | 0.0368 (5) | 0.0413 (6) | 0.0324 (5) | −0.0042 (4) | 0.0017 (4) | −0.0017 (4) |
C1—C2 | 1.3938 (18) | C7—C8 | 1.3803 (18) |
C1—C6 | 1.3938 (17) | C7—C12 | 1.4996 (16) |
C1—C12 | 1.4821 (17) | C8—C9 | 1.386 (2) |
C2—C3 | 1.385 (2) | C8—H8 | 0.978 (16) |
C2—H2 | 0.986 (16) | C9—N1 | 1.333 (2) |
C3—C4 | 1.382 (2) | C9—H9 | 0.994 (18) |
C3—H3 | 0.98 (2) | C10—N1 | 1.3262 (19) |
C4—C5 | 1.372 (2) | C10—C11 | 1.3861 (19) |
C4—H4 | 0.944 (18) | C10—H10 | 0.989 (17) |
C5—C6 | 1.3818 (19) | C11—H11 | 0.939 (16) |
C5—H5 | 0.994 (17) | C12—N2 | 1.2882 (15) |
C6—H6 | 0.985 (17) | N2—N2i | 1.4074 (19) |
C7—C11 | 1.3799 (18) | ||
C2—C1—C6 | 119.09 (12) | C11—C7—C12 | 122.11 (11) |
C2—C1—C12 | 120.62 (11) | C8—C7—C12 | 120.22 (11) |
C6—C1—C12 | 120.29 (11) | C7—C8—C9 | 119.26 (13) |
C3—C2—C1 | 119.90 (13) | C7—C8—H8 | 120.9 (10) |
C3—C2—H2 | 120.5 (9) | C9—C8—H8 | 119.9 (10) |
C1—C2—H2 | 119.6 (9) | N1—C9—C8 | 123.67 (14) |
C4—C3—C2 | 120.44 (14) | N1—C9—H9 | 117.4 (11) |
C4—C3—H3 | 120.3 (11) | C8—C9—H9 | 119.0 (11) |
C2—C3—H3 | 119.2 (11) | N1—C10—C11 | 124.37 (14) |
C5—C4—C3 | 119.80 (13) | N1—C10—H10 | 115.3 (10) |
C5—C4—H4 | 121.1 (11) | C11—C10—H10 | 120.3 (10) |
C3—C4—H4 | 119.1 (11) | C7—C11—C10 | 118.77 (13) |
C4—C5—C6 | 120.59 (14) | C7—C11—H11 | 121.7 (9) |
C4—C5—H5 | 119.9 (10) | C10—C11—H11 | 119.5 (9) |
C6—C5—H5 | 119.5 (10) | N2—C12—C1 | 117.23 (10) |
C5—C6—C1 | 120.16 (13) | N2—C12—C7 | 124.96 (11) |
C5—C6—H6 | 121.9 (9) | C1—C12—C7 | 117.79 (10) |
C1—C6—H6 | 118.0 (9) | C10—N1—C9 | 116.24 (12) |
C11—C7—C8 | 117.65 (12) | C12—N2—N2i | 112.96 (12) |
C6—C1—C2—C3 | 1.38 (19) | N1—C10—C11—C7 | −2.2 (2) |
C12—C1—C2—C3 | −178.17 (12) | C2—C1—C12—N2 | 148.94 (12) |
C1—C2—C3—C4 | −1.5 (2) | C6—C1—C12—N2 | −30.60 (16) |
C2—C3—C4—C5 | 0.4 (2) | C2—C1—C12—C7 | −32.72 (16) |
C3—C4—C5—C6 | 0.9 (2) | C6—C1—C12—C7 | 147.74 (11) |
C4—C5—C6—C1 | −1.0 (2) | C11—C7—C12—N2 | −69.45 (17) |
C2—C1—C6—C5 | −0.15 (18) | C8—C7—C12—N2 | 112.11 (15) |
C12—C1—C6—C5 | 179.40 (11) | C11—C7—C12—C1 | 112.35 (13) |
C11—C7—C8—C9 | 1.2 (2) | C8—C7—C12—C1 | −66.09 (16) |
C12—C7—C8—C9 | 179.71 (13) | C11—C10—N1—C9 | 1.3 (2) |
C7—C8—C9—N1 | −2.2 (2) | C8—C9—N1—C10 | 0.9 (2) |
C8—C7—C11—C10 | 0.83 (19) | C1—C12—N2—N2i | 177.58 (11) |
C12—C7—C11—C10 | −177.65 (12) | C7—C12—N2—N2i | −0.63 (19) |
Symmetry code: (i) −x+1, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···N1ii | 0.986 (16) | 2.553 (17) | 3.483 (2) | 157.2 (12) |
Symmetry code: (ii) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C24H18N4 |
Mr | 362.42 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 6.1251 (12), 7.3258 (15), 10.456 (2) |
α, β, γ (°) | 93.35 (3), 91.28 (3), 96.00 (3) |
V (Å3) | 465.62 (16) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.4 × 0.15 × 0.15 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (Blessing, 1995, 1997) |
Tmin, Tmax | 0.969, 0.998 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10946, 2101, 1637 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.110, 1.05 |
No. of reflections | 2101 |
No. of parameters | 164 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.19, −0.15 |
Computer programs: COLLECT (Nonius, 1998), HKL SCALEPACK (Otwinowski & Minor, 1997), HKL DENZO (Otwinowski & Minor, 1997) and maXus (Mackay et al., 1998), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···N1i | 0.986 (16) | 2.553 (17) | 3.483 (2) | 157.2 (12) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
The hydrogen bond is a subject that has attracted intense attention, due to its great importance in a vast number of chemical, biological and materials systems (Steiner, 2002). The weak hydrogen bond of the C—H···X type (X = O, N, and π acceptors) has been well established in structural, supramolecular and biological chemistry, and it has been widely used as a tool for crystal engineering of organic and organometallic solids (Desiraju & Steiner, 1999; Desiraju, 1996; Braga & Grepioni, 2000; Braga et al., 1998). In this paper, we report the synthesis and crystal structure of a Schiff base compound, 1,4-tris(4-pyridyl)-1,4-diphenyl-2,3-diaza-1,3-butadiene, (I), in which the C—H···N and C—H···π hydrogen bonds act as the dominant forces to organize the molecules into an interesting two-dimensional supramolecular layer architecture.
A perspective view of the molecule of (I), with the atom-labelling scheme, is depicted in Fig. 1. Each molecule is centrosymmetric, with the inversion centre at the mid-point of the N—N bond. The aromatic C—C bond lengths in the pyridyl and phenyl rings fall in the narrow range of 1.372 (2)–1.3938 (18) Å, and the two C—N bonds of the pyridyl rings are 1.333 (2) and 1.3262 (19) Å. The C═N bond length (C12—N2) is 1.2882 (15) Å, and the central N—N bond (N2—N2A) is 1.4074 (19) Å. All the data are in good agreement with the chemical structure of the Schiff base, shown in the scheme.
The molecule is distorted severely from planarity. Neither the pyridyl nor the phenyl ring is coplanar with the central C═N—N═C planar spacer, the dihedral angles being 69.54 (9) and 32.25 (12)°, respectively, while the dihedral angle between the pyridyl and phenyl rings is 85.07 (5)°.
Of particular interest are the intermolecular C—H···N and C—H···π hydrogen bonds organizing the molecules of (I) into a supramolecular architecture. The molecule contains two equivalent phenyl rings and two equivalent pyridyl rings, and all these aromatic groups are involved in intermolecular C—H···N and C—H···π hydrogen bonding. In the c direction, each pyridyl N atom of one molecule forms a hydrogen bond with a phenyl C—H group from a neighbouring molecule (C2—H···N1B; Fig. 2). Thus, each molecule interacts with two neighbours via four equivalent C—H···N hydrogen bonds, generating infinite hydrogen-bonded chains parallel to the c direction. The relevant geometrical parameters are 3.483 (2) Å for the C···N distance, 2.553 (17) Å for the H···N distance and 157.2 (12)° for the C—H···N angle.
In the a direction, each pyridyl C11—H group from one molecule points to the centre of the neighbouring phenyl ring from another molecule, suggesting the formation of C—H···π hydrogen bonds (Fig. 2). Consequently, each molecule interacts with two neighbours via four equivalent C—H···π hydrogen bonds, generating infinite hydrogen-bonded chains parallel to the a direction. In this hydrogen-bonding motif, the distances of the H and C atoms to the centroid (Cg) of the phenyl ring, H···Cg and C···Cg, are 2.66 and 3.60 Å, respectively, within the literature range for the C—H···Ph interaction (Braga et al., 1998). The ω(H) angle defined by Desiraju & Steiner (1999), between the H···Cg line and the normal axis of the phenyl ring, is only 2.5°, and the C—H···Cg angle is 176.5°, very close to 180°, suggesting an almost linear and centred C—H···Ph hydrogen bond (Desiraju & Steiner, 1999).
As can be seen from Fig. 2, these two different types of weak hydrogen bonds, which propagate along different directions (the c and a directions), operate concurrently to organize the molecules into an interesting two-dimensional hydrogen-bonded layer extending parallel to the ac plane, in which each molecule interacts with four neighbours via a total of eight hydrogen bonds. The layers are stacked down the b direction in a parallel and featureless fashion, without evident indications of hydrogen bonding or π—π interactions.
To summarize, we have synthesized and characterized a new symmetric Schiff base bearing two pyridyl and two phenyl groups. All these groups are involved in intermolecular C—H···N and C—H···π hydrogen bonds, which serve as the dominant and concurrent forces to organize the molecules into an interesting two-dimensional hydrogen-bonded layer architecture.