Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104030392/fg1785sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104030392/fg1785Isup2.hkl |
CCDC reference: 263059
AZP was synthesized following the procedures described by Brown & Granneman (1975). AZP was cocrystallized with SA in a 1:1 molar ratio. In order to obtain high-quality crystals, they were mixed in a solution of acetone and ethanol (2:1, v/v), warmed until they dissolved completely and allowed to stand at room temperature for several days. After most of the solvent had evaporated, cocrystals of [AZP:SA] suitable for X-ray analysis were obtained.
H atoms were visible in difference maps and were subsequently allowed for as riding, with C—H distances of 0.93 Å for pyridyl H atoms and 0.97 Å for methylene H atoms, an O—H distance of 0.82 Å and Uiso(H) values of 1.2Ueq(C,O).
Data collection: R-AXIS RAPID Diffractometer Control Software (Rigaku, 2001); cell refinement: SHELXTL (Bruker, 2000); data reduction: R-AXIS RAPID Diffractometer Control Software; program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL.
C10H8N4·C4H6O4 | Z = 1 |
Mr = 302.29 | F(000) = 158 |
Triclinic, P1 | Dx = 1.404 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 4.738 (4) Å | Cell parameters from 2708 reflections |
b = 8.954 (9) Å | θ = 7.9–54.9° |
c = 9.073 (10) Å | µ = 0.11 mm−1 |
α = 108.33 (4)° | T = 298 K |
β = 92.84 (4)° | Block, red |
γ = 99.98 (4)° | 0.50 × 0.29 × 0.17 mm |
V = 357.6 (6) Å3 |
Rigaku R-AXIS RAPID diffractometer | 1601 independent reflections |
Radiation source: fine-focus sealed tube | 1290 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.011 |
ω scans | θmax = 27.5°, θmin = 3.9° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995). | h = −5→6 |
Tmin = 0.875, Tmax = 1.000 | k = −11→11 |
3428 measured reflections | l = −11→11 |
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.138 | H-atom parameters constrained |
S = 1.14 | w = 1/[σ2(Fo2) + (0.0778P)2 + 0.0314P] where P = (Fo2 + 2Fc2)/3 |
1601 reflections | (Δ/σ)max < 0.001 |
101 parameters | Δρmax = 0.17 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
C10H8N4·C4H6O4 | γ = 99.98 (4)° |
Mr = 302.29 | V = 357.6 (6) Å3 |
Triclinic, P1 | Z = 1 |
a = 4.738 (4) Å | Mo Kα radiation |
b = 8.954 (9) Å | µ = 0.11 mm−1 |
c = 9.073 (10) Å | T = 298 K |
α = 108.33 (4)° | 0.50 × 0.29 × 0.17 mm |
β = 92.84 (4)° |
Rigaku R-AXIS RAPID diffractometer | 1601 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995). | 1290 reflections with I > 2σ(I) |
Tmin = 0.875, Tmax = 1.000 | Rint = 0.011 |
3428 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.138 | H-atom parameters constrained |
S = 1.14 | Δρmax = 0.17 e Å−3 |
1601 reflections | Δρmin = −0.24 e Å−3 |
101 parameters |
Geometry. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 3.4683 (0.0099) x − 4.0540 (0.0103) y + 5.7530 (0.0202) z = 2.9148 (0.0199) * 0.0000 (0.0000) O1 * 0.0000 (0.0000) O2 * 0.0000 (0.0000) C8 − 0.0098 (0.0057) C9 Rms deviation of fitted atoms = 0.0000 3.3296 (0.0041) x − 5.2711 (0.0073) y + 5.6355 (0.0073) z = 1.8602 (0.0042) Angle to previous plane (with approximate e.s.d.) = 9.17 (0.26) * −0.0067 (0.0009) N1 * 0.0083 (0.0009) C2 * −0.0023 (0.0009) C3 * −0.0050 (0.0009) C4 * 0.0065 (0.0010) C5 * −0.0008 (0.0011) C6 0.0108 (0.0019) N7 − 0.0372 (0.0022) N7_$1 − 0.0196 (0.0036) N1_$1 − 0.0347 (0.0035) C2_$1 − 0.0241 (0.0036) C3_$1 − 0.0214 (0.0034) C4_$1 − 0.0328 (0.0037) C5_$1 − 0.0256 (0.0034) C6_$1 Rms deviation of fitted atoms = 0.0056 3.3297 (0.0041) x − 5.2708 (0.0073) y + 5.6355 (0.0073) z = 1.8604 (0.0042) Angle to previous plane (with approximate e.s.d.) = 0.00 (0.11) * −0.0067 (0.0009) N1 * 0.0083 (0.0010) C2 * −0.0023 (0.0009) C3 * −0.0050 (0.0009) C4 * 0.0065 (0.0010) C5 * −0.0009 (0.0011) C6 0.0109 (0.0019) N7 3.3406 (0.0039) N7_$3 3.2924 (0.0039) N7_$4 Rms deviation of fitted atoms = 0.0056 |
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 | ||
N1 | 1.2093 (2) | 0.67391 (14) | 0.24475 (14) | 0.0430 (3) | |
N7 | 0.5753 (2) | 0.56882 (13) | 0.52412 (13) | 0.0414 (3) | |
C2 | 1.0494 (3) | 0.52635 (17) | 0.20384 (16) | 0.0428 (3) | |
H2 | 1.0846 | 0.4493 | 0.1143 | 0.051* | |
C3 | 0.8336 (3) | 0.48203 (16) | 0.28805 (15) | 0.0405 (3) | |
H3 | 0.7236 | 0.3783 | 0.2551 | 0.049* | |
C4 | 0.7862 (3) | 0.59647 (15) | 0.42259 (14) | 0.0368 (3) | |
C5 | 0.9541 (3) | 0.74919 (17) | 0.46826 (17) | 0.0466 (4) | |
H5 | 0.9281 | 0.8276 | 0.5592 | 0.056* | |
C6 | 1.1621 (3) | 0.78213 (17) | 0.37486 (18) | 0.0488 (4) | |
H6 | 1.2744 | 0.8851 | 0.4047 | 0.059* | |
O1 | 1.5997 (2) | 0.73357 (11) | 0.05914 (13) | 0.0527 (3) | |
H1 | 1.4932 | 0.7224 | 0.1251 | 0.063* | |
O2 | 1.6630 (3) | 0.99119 (13) | 0.20257 (14) | 0.0694 (4) | |
C8 | 1.7197 (3) | 0.88604 (16) | 0.09423 (16) | 0.0401 (3) | |
C9 | 1.9323 (3) | 0.91278 (16) | −0.01677 (18) | 0.0459 (4) | |
H9A | 1.8351 | 0.8700 | −0.1224 | 0.055* | |
H9B | 2.0835 | 0.8536 | −0.0115 | 0.055* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0384 (6) | 0.0476 (6) | 0.0488 (7) | 0.0040 (5) | 0.0136 (5) | 0.0250 (5) |
N7 | 0.0405 (6) | 0.0459 (6) | 0.0393 (6) | 0.0050 (5) | 0.0134 (5) | 0.0164 (5) |
C2 | 0.0452 (7) | 0.0467 (7) | 0.0395 (7) | 0.0067 (6) | 0.0144 (5) | 0.0182 (6) |
C3 | 0.0400 (7) | 0.0412 (7) | 0.0391 (7) | −0.0014 (5) | 0.0090 (5) | 0.0158 (5) |
C4 | 0.0334 (6) | 0.0455 (7) | 0.0358 (7) | 0.0065 (5) | 0.0091 (5) | 0.0194 (5) |
C5 | 0.0490 (8) | 0.0422 (7) | 0.0450 (7) | 0.0042 (6) | 0.0134 (6) | 0.0109 (6) |
C6 | 0.0458 (8) | 0.0430 (7) | 0.0565 (9) | −0.0017 (6) | 0.0124 (6) | 0.0191 (6) |
O1 | 0.0557 (6) | 0.0424 (6) | 0.0610 (7) | −0.0001 (5) | 0.0292 (5) | 0.0200 (5) |
O2 | 0.0772 (8) | 0.0520 (7) | 0.0649 (8) | −0.0066 (6) | 0.0387 (6) | 0.0052 (5) |
C8 | 0.0366 (6) | 0.0414 (7) | 0.0428 (7) | 0.0018 (5) | 0.0098 (5) | 0.0167 (6) |
C9 | 0.0447 (8) | 0.0405 (7) | 0.0537 (8) | 0.0022 (6) | 0.0204 (6) | 0.0181 (6) |
N1—C6 | 1.328 (2) | C5—H5 | 0.9300 |
N1—C2 | 1.332 (2) | C6—H6 | 0.9300 |
N7—N7i | 1.243 (2) | O1—C8 | 1.315 (2) |
N7—C4 | 1.4342 (19) | O1—H1 | 0.8200 |
C2—C3 | 1.384 (2) | O2—C8 | 1.207 (2) |
C2—H2 | 0.9300 | C8—C9 | 1.501 (2) |
C3—C4 | 1.382 (2) | C9—C9ii | 1.509 (3) |
C3—H3 | 0.9300 | C9—H9A | 0.9700 |
C4—C5 | 1.381 (2) | C9—H9B | 0.9700 |
C5—C6 | 1.384 (2) | ||
C6—N1—C2 | 117.96 (12) | N1—C6—C5 | 123.22 (14) |
N7i—N7—C4 | 113.30 (15) | N1—C6—H6 | 118.4 |
N1—C2—C3 | 123.23 (13) | C5—C6—H6 | 118.4 |
N1—C2—H2 | 118.4 | C8—O1—H1 | 109.5 |
C3—C2—H2 | 118.4 | O2—C8—O1 | 123.53 (13) |
C4—C3—C2 | 118.01 (14) | O2—C8—C9 | 124.51 (14) |
C4—C3—H3 | 121.0 | O1—C8—C9 | 111.96 (12) |
C2—C3—H3 | 121.0 | C8—C9—C9ii | 113.49 (15) |
C5—C4—C3 | 119.43 (13) | C8—C9—H9A | 108.9 |
C5—C4—N7 | 115.74 (13) | C9ii—C9—H9A | 108.9 |
C3—C4—N7 | 124.81 (13) | C8—C9—H9B | 108.9 |
C4—C5—C6 | 118.12 (14) | C9ii—C9—H9B | 108.9 |
C4—C5—H5 | 120.9 | H9A—C9—H9B | 107.7 |
C6—C5—H5 | 120.9 | ||
C6—N1—C2—C3 | 1.6 (2) | C3—C4—C5—C6 | 1.0 (2) |
N1—C2—C3—C4 | −1.2 (2) | N7—C4—C5—C6 | 179.66 (13) |
C2—C3—C4—C5 | −0.18 (19) | C2—N1—C6—C5 | −0.7 (2) |
C2—C3—C4—N7 | −178.71 (12) | C4—C5—C6—N1 | −0.6 (2) |
N7i—N7—C4—C5 | 178.15 (13) | O2—C8—C9—C9ii | −1.4 (3) |
N7i—N7—C4—C3 | −3.3 (2) | O1—C8—C9—C9ii | 178.17 (15) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+4, −y+2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N1 | 0.82 | 1.85 | 2.660 (2) | 170 |
C2—H2···O1iii | 0.93 | 2.62 | 3.481 (3) | 155 |
Symmetry code: (iii) −x+3, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C10H8N4·C4H6O4 |
Mr | 302.29 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 4.738 (4), 8.954 (9), 9.073 (10) |
α, β, γ (°) | 108.33 (4), 92.84 (4), 99.98 (4) |
V (Å3) | 357.6 (6) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.50 × 0.29 × 0.17 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995). |
Tmin, Tmax | 0.875, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3428, 1601, 1290 |
Rint | 0.011 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.138, 1.14 |
No. of reflections | 1601 |
No. of parameters | 101 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.17, −0.24 |
Computer programs: R-AXIS RAPID Diffractometer Control Software (Rigaku, 2001), SHELXTL (Bruker, 2000), R-AXIS RAPID Diffractometer Control Software, SHELXTL, DIAMOND (Brandenburg, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N1 | 0.82 | 1.85 | 2.660 (2) | 170 |
C2—H2···O1i | 0.93 | 2.62 | 3.481 (3) | 155 |
Symmetry code: (i) −x+3, −y+1, −z. |
Crystal engineering makes controllable the stacking of molecules and molecular adducts by covalent and especially non-covalent interactions, such as hydrogen bonding or π–π interaction. This approach is attractive for the design and fabrication of functional materials (Aakeröy & Seddon, 1993; Aoyama et al., 1996; Kuduva et al., 1999; Kuduva et al., 2001; Muthuraman et al., 2001). Recently, much effort has been made in exploring the crystallization regularity of azaaromatic molecules with the presence of carboxylic acid as the supramolecular synthons (Bond, 2003; Bhogala & Nangia, 2003; Vishweshwar et al., 2002). The cocrystallization of 4,4'-bipyridyl in the presence of fumaric acid (FA) and adipic acid (AA), and the orderliness of 4,4'-bipyridyl and dicarboxylic acids around the aspect of odd and even –CH2– numbers, have been reported (Pedireddi et al., 1998; Chatterjee et al., 1998). In previous work, we have reported the preparation of a series of cocrystals of aromatic and azaaromatic molecules with dicarboxylic acids, viz. [BPE·SA], [AZP·FA], [BPE·AA], [AZP·AA], [AZP·SEA] and [AZP·OA] (BPE is 1,2-bis(4-pyridyl)ethylene, AZP is azopyridine, SA is succinic acid, SEA is sebacic acid and OA is oxalic acid), and revealed the regularity of their supramolecular alignments driven by hydrogen bonding (Zhang et al., 2003; Zhang et al., 2002; Wu et al., 2002).
As an extension of this previous work, we have prepared a new cocrystal, a 1:1 adduct, [AZP·SA], (I), of azopyridine and succinic acid, which should exhibit the stacking regularity noted previously (Zhang et al., 2003) and which we wish to compare with the structure of the [BPE·SA] 1:1 complex, (II).
Both AZP and SA components in (I) lie on independent inversion centres, as shown in Fig. 1, and are linked by O—H···N hydrogen bonds between alternating AZP and SA molecules. This configuration results in a linear chain of molecules extending in the [31–1] direction. The dihedral angle between the planes of the O1/O2/C8 SA carboxyl group and the N1/C2–C6 pyridyl ring is 9.2 (3)°. Compound (II) is isostructural with (I) and has an exactly analogous packing; the corresponding dihedral angle is larger [21.3 (3)°]. The two pyridyl rings in (I) are exactly parallel by symmetry but are slightly stepped [0.026 (4) Å]; the corresponding value for (II) is 0.097 (6) Å. The length of the AZP long axis in (I), between atoms N1 and N1B [at (1 − x,1 − y,1 − z)] (Fig. 1), is 9.013 (10) Å; for the SA molecule, the distance between the hydroxy H atom and the equivalent one at (4 − x, 2 − y, −z) is 7.27 Å. The corresponding data in (II) [9.407 (4) and 7.29 Å, respectively] show that the BPE molecule is slightly longer than the AZP molecule.
As illustrated in Figs. 2(a) and 2(b), the hydrogen-bonded chains in (I) are oriented so that there is an overlap between the pyridyl rings and azo groups in adjacent chains, consistent with strong pyridyl–azo π–π intrasheet interactions. The distance between the centre of the azo group [at (1/2,0.5, 1/2)] and the centroids of adjacent pyridyl rings [at (2 − x, 1 − y, 1 − z) and (x − 1, y, z)] is 3.340 Å.
In (II), as well as π–π interactions, there is a significant C—H···O interchain hydrogen bond between an aromatic CH group and an adjacent hydroxy O atom, with an H···O distance of 2.46 Å, a C···O distances of 3.376 (3) Å and a C—H···O angle of 160°. The small difference [0.394 Å] between the lengths of the AZP and BPE molecules as measured by the pyridyl N···N intramolecular separations in BPE and AZP preclude an exact match of the packing in (I) and (II). In the packing competition to link chains it is the drive to form sheets of molecules via π–π interactions that wins out over the drive to form sheets of molecules linked by C—H···O interactions; the result is a weaker C—H···O contact geometry in (I), with an H···O distance of 2.62 Å (Table 2 and Fig. 3).