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In the 1:1 supramolecular adduct of azo­pyridine (AZP) and succinic acid (SA) [systematic name: di-4-pyridyl­diazene–succinic acid (1/1)], C10H8N4·C4H6O4 or AZP·SA, both components lie on inversion centers. Alternating AZP and SA mol­ecules are linked by O—H...N hydrogen bonds to form a linear chain extending in the [31\overline1] direction. Between chains there is a strong pyridyl–azo π–π interaction, with a 3.340 Å separation between the inversion center at the mid-point of the azo bond and the centroid of the pyridine ring; this interaction results in the formation of sheets.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104030392/fg1785sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104030392/fg1785Isup2.hkl
Contains datablock I

CCDC reference: 263059

Comment top

Crystal engineering makes controllable the stacking of molecules and molecular adducts by covalent and especially non-covalent interactions, such as hydrogen bonding or ππ 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 ππ 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 ππ 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 ππ 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).

Experimental top

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.

Refinement top

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).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. A 50% displacement ellipsoid diagram of the [AZP·SA] complex. Atoms labeled with the suffixes A and B are at (4 − x,2 − y,-z) and (1 − x,1 − y,1 − z), respectively.
[Figure 2] Fig. 2. (a) A stereoview of the AZP overlap, showing the pyridyl–azo ππ intrasheet interaction. (b) A view showing details of the ππ interactions; atoms labeled with an asterisk (*), a dollar sign () or a hash (#) are at equivalent positions (1 − x,1 − y,1 − z), (2 − x,1 − y,1 − z) and (x − 1,y,z), respectively.
[Figure 3] Fig. 3. A packing diagram showing the general chain arrangement and the weak C—H···O interactions between chains; atom O1& is at equivalent position (3 − x,1 − y,-z), and atoms marked with an asterisk (*) are at (1 − x,1 − y,1 − z).
di-4-pyridyldiazene–succinic acid (1/1) top
Crystal data top
C10H8N4·C4H6O4Z = 1
Mr = 302.29F(000) = 158
Triclinic, P1Dx = 1.404 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 4.738 (4) ÅCell parameters from 2708 reflections
b = 8.954 (9) Åθ = 7.9–54.9°
c = 9.073 (10) ŵ = 0.11 mm1
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
Data collection top
Rigaku R-AXIS RAPID
diffractometer
1601 independent reflections
Radiation source: fine-focus sealed tube1290 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.011
ω scansθmax = 27.5°, θmin = 3.9°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995).
h = 56
Tmin = 0.875, Tmax = 1.000k = 1111
3428 measured reflectionsl = 1111
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)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.138H-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 parametersΔρmax = 0.17 e Å3
0 restraintsΔρmin = 0.24 e Å3
Crystal data top
C10H8N4·C4H6O4γ = 99.98 (4)°
Mr = 302.29V = 357.6 (6) Å3
Triclinic, P1Z = 1
a = 4.738 (4) ÅMo Kα radiation
b = 8.954 (9) ŵ = 0.11 mm1
c = 9.073 (10) ÅT = 298 K
α = 108.33 (4)°0.50 × 0.29 × 0.17 mm
β = 92.84 (4)°
Data collection top
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 = 1.000Rint = 0.011
3428 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.138H-atom parameters constrained
S = 1.14Δρmax = 0.17 e Å3
1601 reflectionsΔρmin = 0.24 e Å3
101 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N11.2093 (2)0.67391 (14)0.24475 (14)0.0430 (3)
N70.5753 (2)0.56882 (13)0.52412 (13)0.0414 (3)
C21.0494 (3)0.52635 (17)0.20384 (16)0.0428 (3)
H21.08460.44930.11430.051*
C30.8336 (3)0.48203 (16)0.28805 (15)0.0405 (3)
H30.72360.37830.25510.049*
C40.7862 (3)0.59647 (15)0.42259 (14)0.0368 (3)
C50.9541 (3)0.74919 (17)0.46826 (17)0.0466 (4)
H50.92810.82760.55920.056*
C61.1621 (3)0.78213 (17)0.37486 (18)0.0488 (4)
H61.27440.88510.40470.059*
O11.5997 (2)0.73357 (11)0.05914 (13)0.0527 (3)
H11.49320.72240.12510.063*
O21.6630 (3)0.99119 (13)0.20257 (14)0.0694 (4)
C81.7197 (3)0.88604 (16)0.09423 (16)0.0401 (3)
C91.9323 (3)0.91278 (16)0.01677 (18)0.0459 (4)
H9A1.83510.87000.12240.055*
H9B2.08350.85360.01150.055*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0384 (6)0.0476 (6)0.0488 (7)0.0040 (5)0.0136 (5)0.0250 (5)
N70.0405 (6)0.0459 (6)0.0393 (6)0.0050 (5)0.0134 (5)0.0164 (5)
C20.0452 (7)0.0467 (7)0.0395 (7)0.0067 (6)0.0144 (5)0.0182 (6)
C30.0400 (7)0.0412 (7)0.0391 (7)0.0014 (5)0.0090 (5)0.0158 (5)
C40.0334 (6)0.0455 (7)0.0358 (7)0.0065 (5)0.0091 (5)0.0194 (5)
C50.0490 (8)0.0422 (7)0.0450 (7)0.0042 (6)0.0134 (6)0.0109 (6)
C60.0458 (8)0.0430 (7)0.0565 (9)0.0017 (6)0.0124 (6)0.0191 (6)
O10.0557 (6)0.0424 (6)0.0610 (7)0.0001 (5)0.0292 (5)0.0200 (5)
O20.0772 (8)0.0520 (7)0.0649 (8)0.0066 (6)0.0387 (6)0.0052 (5)
C80.0366 (6)0.0414 (7)0.0428 (7)0.0018 (5)0.0098 (5)0.0167 (6)
C90.0447 (8)0.0405 (7)0.0537 (8)0.0022 (6)0.0204 (6)0.0181 (6)
Geometric parameters (Å, º) top
N1—C61.328 (2)C5—H50.9300
N1—C21.332 (2)C6—H60.9300
N7—N7i1.243 (2)O1—C81.315 (2)
N7—C41.4342 (19)O1—H10.8200
C2—C31.384 (2)O2—C81.207 (2)
C2—H20.9300C8—C91.501 (2)
C3—C41.382 (2)C9—C9ii1.509 (3)
C3—H30.9300C9—H9A0.9700
C4—C51.381 (2)C9—H9B0.9700
C5—C61.384 (2)
C6—N1—C2117.96 (12)N1—C6—C5123.22 (14)
N7i—N7—C4113.30 (15)N1—C6—H6118.4
N1—C2—C3123.23 (13)C5—C6—H6118.4
N1—C2—H2118.4C8—O1—H1109.5
C3—C2—H2118.4O2—C8—O1123.53 (13)
C4—C3—C2118.01 (14)O2—C8—C9124.51 (14)
C4—C3—H3121.0O1—C8—C9111.96 (12)
C2—C3—H3121.0C8—C9—C9ii113.49 (15)
C5—C4—C3119.43 (13)C8—C9—H9A108.9
C5—C4—N7115.74 (13)C9ii—C9—H9A108.9
C3—C4—N7124.81 (13)C8—C9—H9B108.9
C4—C5—C6118.12 (14)C9ii—C9—H9B108.9
C4—C5—H5120.9H9A—C9—H9B107.7
C6—C5—H5120.9
C6—N1—C2—C31.6 (2)C3—C4—C5—C61.0 (2)
N1—C2—C3—C41.2 (2)N7—C4—C5—C6179.66 (13)
C2—C3—C4—C50.18 (19)C2—N1—C6—C50.7 (2)
C2—C3—C4—N7178.71 (12)C4—C5—C6—N10.6 (2)
N7i—N7—C4—C5178.15 (13)O2—C8—C9—C9ii1.4 (3)
N7i—N7—C4—C33.3 (2)O1—C8—C9—C9ii178.17 (15)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+4, y+2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N10.821.852.660 (2)170
C2—H2···O1iii0.932.623.481 (3)155
Symmetry code: (iii) x+3, y+1, z.

Experimental details

Crystal data
Chemical formulaC10H8N4·C4H6O4
Mr302.29
Crystal system, space groupTriclinic, 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)
V3)357.6 (6)
Z1
Radiation typeMo Kα
µ (mm1)0.11
Crystal size (mm)0.50 × 0.29 × 0.17
Data collection
DiffractometerRigaku R-AXIS RAPID
diffractometer
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995).
Tmin, Tmax0.875, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
3428, 1601, 1290
Rint0.011
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.138, 1.14
No. of reflections1601
No. of parameters101
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N10.821.852.660 (2)170
C2—H2···O1i0.932.623.481 (3)155
Symmetry code: (i) x+3, y+1, z.
 

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