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The 1:1 complexes N,N'-bis(2-pyridyl)­benzene-1,4-di­amine-anilic acid (2,5-di­hydroxy-1,4-benzo­quinone) (1/1), C16H14N4·C6H4O4, (I), and N,N'-bis(2-pyridyl)­bi­phenyl-4,4'-di­amine-anilic acid (1/1), C22H18N4·C6H4O4, (II), have been prepared and their solid-state structures investigated. The component mol­ecules of these complexes are connected via conventional N-H...O and O-H...N hydrogen bonds, leading to the formation of an infinite one-dimensional network generated by the cyclic motif R{_2^2}(9). The anilic acid molecules in both crystal structures lie around inversion centres and the observed bond lengths are typical for the neutral mol­ecule. Nevertheless, the pyridine C-N-C angles [120.9 (2) and 120.13 (17)° for complexes (I) and (II), respectively] point to a partial H-atom transfer from anilic aicd to the bispyridyl­amine, and hence to H-atom disorder in the OHN bridge. The bispyridyl­amine mol­ecules of (I) and (II) also lie around inversion centres and exhibit disorder of their central phenyl rings over two positions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102020644/sk1587sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102020644/sk1587Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102020644/sk1587IIsup3.hkl
Contains datablock II

CCDC references: 201285; 201286

Comment top

N,N'-Bis(2-pyridyl)aryldiamines (Bensemann et al., 2002), bearing two H-atom donor and two H-atom acceptor sites, can be used as versatile substrates in the synthesis of extended supramolecular arrays, as we have shown recently (Bensemann et al., 2003). For example, co-crystallization of these compounds with dicarboxylic acids or with squaric acid yields 1:1 complexes of predictable structures, involving infinite chains of the alternating components joined by the cyclic hydrogen-bond motifs R22(8) and R22(9), respectively [for graph-set notation, see Etter (1990) and Bernstein et al. (1995)]. In addition, further assembly of these one-dimensional networks into two-dimensional structures via weaker C—H···O and C—H···π interactions occurs in a predictable way, since the acid-base infinite chains are always related by a characteristic unit translation of ca 9 Å, forming densely packed layers (Bensemann et al., 2003).

Anilic acid, (3), being a weak dibasic acid structurally related to squaric acid (Karle et al., 1996), has frequently been used in the preparation of transition metal coordination polymers [for a review, see Kitagawa & Kawata (2002)], and only recently has found broader application as a potential structural element in the construction of organic supramolecular networks (Zaman et al., 2001, and references therein; Cowan, Howard & Leech, 2001; Cowan, Howard et al. 2001). We expected that the 2-aminopyridine unit should be capable of forming cyclic R22(9) hydrogen-bond motifs with the α-hydroxycarbonyl functions of (3), which may generate well defined extended one-dimensional supramolecular frameworks. Indeed, co-crystallization of equimolar amounts of N,N'-bis(2-pyridyl)benzene-1,4-diamine, (1), and N,N'-bis(2-pyridyl)biphenyl-4,4'-diamine, (2), with (3) from acetonitrile gave the 1:1 complexes (I) and (II), respectively, the crystals of which were suitable for X-ray analysis. The structures of these two 1:1 complexes are presented here. \sch

As expected, the bispyridylamine and (3) in complexes (I) and (II) are assembled into infinite one-dimensional networks analogous to those observed earlier in the squaric acid complex of (1) (Bensemann et al., 2003). The component molecules alternating along the chain are connected via hydrogen bonds to form heterodimeric R22(9) motifs. The hydrogen-bonded 2-aminopyridine units and the molecules of (3) are nearly coplanar, as shown by the corresponding dihedral angles of 7.0 (2) and 6.5 (1)° for (I) and (II), respectively. Diagrams of the one-dimensional networks and the atom-labelling schemes in (I) and (II) are shown in Figs. 1 and 2, respectively. The asymmetric units of (I) and (II) contain one half-molecule of bispyridylamine and one half-molecule of (3). All molecules are situated around inversion centres.

The anilic acid molecule (3) in both complexes exhibits a pronounced quinoid character, with a bond-length pattern (Tables 1 and 3) similar to that observed for the neutral molecule (Cowan, Howard & Leech, 2001; Jene et al., 2001; Semmingsen, 1977]. Nevertheless, we observed a systematic shortening of the C—O bonds to the hydroxyl groups [1.292 (2) and 1.307 (2) Å in (I) and (II), respectively] and the partially double C2A—C3A bonds [1.410 (3) and 1.422 (3) Å in (I) and (II), respectively], compared with the neutral molecule of (3), with C—O and C—C bond lengths falling in the ranges 1.328–1.333 Å and 1.438–1.450 Å, respectively (Cowan, Howard & Leech, 2001; Jene et al., 2001; Semmingsen, 1977)

The above geometric parameters point either to a strong polarization of the O—H bond of (3), or to a partial deprotonation of (3) with the H atom transferred from the hydroxy group to the pyridine N atom (Tables 2 and 4). This is supported by the values of the pyridine C—N—C angles [120.9 (2) and 120.13 (17)° in (I) and (II), respectively], which indicate that the pyridine moiety is in a state intermediate between neutral and fully protonated (Cowan, Howard & Leech, 2001; Dega-Szafran et al., 1992).

Because the electron-density difference map showed a broad peak with an unequal intensity double maximum close to the middle of the O—N vector, H-atom disorder in the NHO bridge was assumed. However, subsequent refinement of the occupancy factors for the two H-atom positions in the NHO bridge gave equal occupancies for the two positions, indicating that, in complexes (I) and (II), the molecule of (3) exists as a monoanion.

The hydrogen-bonded one-dimensional networks in (I) run in two directions, [120] and [120]. They are arranged into layers parallel to (001) by forming stacks along the y axis (translation parameter 5.03 Å). No close-packed chains of (1), analogous to those observed in the 1:1 complexes of (1) with dicarboxylic acids, were found here.

The central phenyl ring of bispyridylamine (1) in (I) is disordered over two perpendicular orientations related by rotation around the C8—C8' vector. The phenyl ring is twisted relative to the aminopyridine unit about the C—N bond, by -43.2 (4)° for the primed orientation and 50.0 (4)° for the unprimed one. As can be seen from Fig. 3, the phenyl ring is parallel to the y axis in one orientation and nearly perpendicular to it in the second. The observed disorder can be explained if we assume that adjacent phenyl rings packed along the y axis are mutually perpendicular, which actually means that a single stack is ordered. However, there are two types of stacks, namely that with a primed ring located around the inversion centre at y = 0, and the other with the primed ring at y = 1/2. We observe superposition of these two stacks due to their random distribution in the crystal.

The one-dimensional networks in complex (II) run in the directions [210] and [210] and, as in (I), they stack along the y axis (translation parameter 5.08 Å) and form layers parallel to (001).

The biphenyl unit of (II), with the phenyl rings found in two positions and forming a dihedral angle of 36.5 (7)°, is disordered. Because a centrosymmetric biphenyl fragment has to be planar, the observed disorder reflects one of two possible situations: superposition of two flat but differently oriented biphenyl units or, more probably, superposition of two oppositely twisted biphenyl fragments. The hydrogen-bonded one-dimensional networks adjacent to the [001] direction show edge-to-face aromatic-aromatic interactions between the phenyl and pyridine rings.

Experimental top

The N,N'-bis(2-pyridyl)aryldiamines, (1) and (2), were prepared as described by Bensemann et al. (2002). Complex (I) was prepared by dissolving (1) and anilic acid, (3), in an equimolar ratio in boiling acetonitrile and allowing the solution to crystallize slowly at room temperature. In the case of (II), a hot solution of anilic acid, (3), in acetonitrile was added to (2) dissolved in a small amount of N,N'-dimethylformamide and the mixture was allowed to stand at room temperature.

Refinement top

In both complexes, the central aryl moieties of the bispyridylamines are disordered over two positions. During refinement, the sum of the occupancy factors for the two orientations was kept fixed at 1.0, and the occupancy factors for the primed orientations were refined to 0.493 (4) and 0.453 (11) for (I) and (II), respectively. No restraints were imposed on the geometry of the phenyl rings during refinement. All H atoms were located in electron-density difference maps. The H atom in the N1···H···O2A bridge appeared as a broad peak and H-atom disorder over two positions was assumed. Atoms H1 and H2O were placed in calculated positions (N—H = 0.90 and O—H = 0.85 Å) and were refined as riding, with a common isotropic displacement parameter. The sum of their occupancy factors was kept fixed at 1.0 and the occupancy factors for H2O refined to 0.51 (4) [Uiso = 0.044 (6) Å2] and 0.49 (3) [Uiso = 0.076 (11) Å2] for (I) and (II), respectively. H atoms from C—H groups were placed in calculated positions (C—H = 0.96 Å) and were allowed to refine as riding models, with displacement parameters fixed at 120% of those of their attached C atoms.

Computing details top

For both compounds, data collection: CrysAlis (Oxford Diffraction, 2000); cell refinement: CrysAlis; data reduction: CrysAlis; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Stereochemical Workstation Operation Manual (Siemens, 1989); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. A view of the hydrogen-bonded one-dimensional network in (I), with 50% probability displacement ellipsoids.
[Figure 2] Fig. 2. A view of the hydrogen-bonded one-dimensional network in (II), with 50% probability displacement ellipsoids.
[Figure 3] Fig. 3. A projection of the crystal packing of (I) along the y axis.
[Figure 4] Fig. 4. A projection of the crystal packing of (II) along the y axis.
(I) N,N'-bis(2-pyridyl)benzene-1,4-diamine 2,5-dihydroxy-1,4-benzoquinone (1/1) top
Crystal data top
C16H14N4·C6H4O4F(000) = 840
Mr = 402.40Dx = 1.406 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2140 reflections
a = 25.166 (3) Åθ = 4–25°
b = 5.0290 (5) ŵ = 0.10 mm1
c = 15.1590 (16) ÅT = 296 K
β = 97.648 (9)°Plate, colourless
V = 1901.5 (4) Å30.20 × 0.10 × 0.02 mm
Z = 4
Data collection top
Kuma KM-4 CCD κ geometry
diffractometer
909 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.043
Graphite monochromatorθmax = 25.0°, θmin = 4.0°
ω scansh = 2929
4700 measured reflectionsk = 55
1665 independent reflectionsl = 1518
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difmap, geom
R[F2 > 2σ(F2)] = 0.045H-atom parameters constrained
wR(F2) = 0.088 w = 1/[σ2(Fo2) + (0.0338P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.94(Δ/σ)max < 0.001
1665 reflectionsΔρmax = 0.13 e Å3
160 parametersΔρmin = 0.13 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0034 (5)
Crystal data top
C16H14N4·C6H4O4V = 1901.5 (4) Å3
Mr = 402.40Z = 4
Monoclinic, C2/cMo Kα radiation
a = 25.166 (3) ŵ = 0.10 mm1
b = 5.0290 (5) ÅT = 296 K
c = 15.1590 (16) Å0.20 × 0.10 × 0.02 mm
β = 97.648 (9)°
Data collection top
Kuma KM-4 CCD κ geometry
diffractometer
909 reflections with I > 2σ(I)
4700 measured reflectionsRint = 0.043
1665 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.088H-atom parameters constrained
S = 0.94Δρmax = 0.13 e Å3
1665 reflectionsΔρmin = 0.13 e Å3
160 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
O1A0.34204 (6)0.0212 (3)0.01558 (10)0.0527 (5)
O2A0.26456 (7)0.1714 (3)0.11315 (10)0.0504 (5)
H2O0.29390.25640.11850.044 (6)*0.51 (4)
C1A0.25571 (9)0.0302 (4)0.06047 (14)0.0385 (6)
C2A0.29976 (9)0.1110 (4)0.00622 (14)0.0379 (6)
C3A0.29090 (9)0.3299 (4)0.05197 (14)0.0410 (6)
H3A0.31840.37920.08710.044 (6)*
N10.34334 (7)0.5014 (4)0.17280 (12)0.0456 (5)
H10.32510.37140.14120.034 (16)*0.49 (4)
C20.39184 (9)0.5683 (5)0.15232 (16)0.0460 (6)
C30.42112 (10)0.7691 (5)0.20047 (17)0.0604 (8)
H30.45500.82130.18350.073*
C40.39899 (12)0.8947 (6)0.26767 (18)0.0749 (9)
H40.41791.04430.29600.090*
C50.34919 (12)0.8199 (6)0.28783 (17)0.0667 (8)
H50.33360.90000.33580.080*
C60.32271 (10)0.6240 (5)0.23897 (16)0.0541 (7)
H60.28860.56270.25270.065*
N70.40808 (8)0.4291 (4)0.08444 (13)0.0542 (6)
H70.38600.30500.05700.065 (8)*
C80.45470 (9)0.4710 (5)0.04335 (16)0.0441 (6)
C90.4830 (2)0.2510 (10)0.0200 (3)0.0618 (18)0.507 (4)
H90.47180.07540.03430.074*0.507 (4)
C100.4717 (2)0.7171 (10)0.0217 (3)0.0602 (18)0.507 (4)
H100.45000.87200.02710.072*0.507 (4)
C9'0.5061 (2)0.4976 (9)0.0917 (3)0.0507 (16)0.493 (4)
H9'0.50900.48220.15530.061*0.493 (4)
C10'0.44960 (18)0.4733 (10)0.0468 (3)0.0531 (17)0.493 (4)
H10'0.41360.45410.07610.064*0.493 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O1A0.0404 (10)0.0535 (11)0.0653 (12)0.0136 (8)0.0105 (8)0.0072 (9)
O2A0.0494 (11)0.0478 (10)0.0559 (11)0.0106 (9)0.0141 (8)0.0145 (9)
C1A0.0429 (15)0.0353 (14)0.0372 (14)0.0011 (13)0.0053 (11)0.0020 (12)
C2A0.0373 (15)0.0391 (14)0.0372 (14)0.0004 (12)0.0046 (11)0.0071 (11)
C3A0.0387 (15)0.0420 (15)0.0450 (15)0.0027 (12)0.0151 (12)0.0047 (12)
N10.0429 (12)0.0498 (13)0.0452 (12)0.0062 (11)0.0103 (10)0.0023 (11)
C20.0433 (16)0.0508 (17)0.0452 (15)0.0058 (13)0.0109 (13)0.0020 (13)
C30.0543 (18)0.073 (2)0.0553 (18)0.0166 (15)0.0109 (14)0.0092 (15)
C40.083 (2)0.081 (2)0.0612 (19)0.0233 (18)0.0124 (17)0.0226 (16)
C50.077 (2)0.075 (2)0.0518 (18)0.0026 (17)0.0220 (16)0.0107 (15)
C60.0578 (17)0.0606 (18)0.0454 (16)0.0007 (14)0.0130 (14)0.0012 (14)
N70.0458 (13)0.0588 (14)0.0622 (14)0.0166 (11)0.0224 (11)0.0187 (12)
C80.0370 (15)0.0431 (17)0.0542 (18)0.0099 (13)0.0131 (13)0.0075 (13)
C90.070 (4)0.040 (4)0.082 (4)0.006 (3)0.034 (3)0.003 (3)
C100.064 (4)0.042 (4)0.082 (4)0.002 (3)0.037 (3)0.004 (3)
C9'0.047 (3)0.065 (4)0.040 (3)0.008 (3)0.007 (2)0.008 (3)
C10'0.031 (3)0.075 (4)0.054 (4)0.003 (3)0.007 (2)0.012 (3)
Geometric parameters (Å, º) top
O1A—C2A1.247 (2)C5—C61.354 (3)
O2A—C1A1.292 (2)C5—H50.9600
O2A—H2O0.8483C6—H60.9600
C1A—C3Ai1.359 (3)N7—C81.415 (3)
C1A—C2A1.521 (3)N7—H70.8999
C2A—C3A1.410 (3)C8—C10'1.356 (5)
C3A—C1Ai1.359 (3)C8—C101.364 (5)
C3A—H3A0.9600C8—C91.387 (5)
N1—C61.339 (3)C8—C9'1.406 (5)
N1—C21.342 (3)C9—C10ii1.386 (6)
N1—H10.8999C9—H90.9600
C2—N71.352 (3)C10—C9ii1.386 (6)
C2—C31.397 (3)C10—H100.9599
C3—C41.378 (3)C9'—C10'ii1.388 (6)
C3—H30.9599C9'—H9'0.9601
C4—C51.381 (3)C10'—C9'ii1.388 (6)
C4—H40.9601C10'—H10'0.9601
C1A—O2A—H2O122.0N1—C6—C5122.2 (3)
O2A—C1A—C3Ai122.7 (2)N1—C6—H6117.5
O2A—C1A—C2A117.75 (19)C5—C6—H6120.2
C3Ai—C1A—C2A119.51 (19)C2—N7—C8127.6 (2)
O1A—C2A—C3A123.3 (2)C2—N7—H7118.7
O1A—C2A—C1A117.9 (2)C8—N7—H7113.4
C3A—C2A—C1A118.73 (19)C10—C8—C9118.4 (3)
C1Ai—C3A—C2A121.8 (2)C10'—C8—C9'118.8 (3)
C1Ai—C3A—H3A119.4C10'—C8—N7118.2 (3)
C2A—C3A—H3A118.9C10—C8—N7123.0 (3)
C6—N1—C2120.9 (2)C9—C8—N7118.5 (3)
C6—N1—H1120.8C9'—C8—N7123.0 (3)
C2—N1—H1118.3C10ii—C9—C8120.4 (4)
N1—C2—N7115.0 (2)C10ii—C9—H9119.6
N1—C2—C3119.5 (2)C8—C9—H9120.0
N7—C2—C3125.4 (2)C8—C10—C9ii121.2 (4)
C4—C3—C2118.7 (2)C8—C10—H10121.1
C4—C3—H3122.3C9ii—C10—H10117.1
C2—C3—H3118.9C10'ii—C9'—C8119.9 (4)
C3—C4—C5120.4 (2)C10'ii—C9'—H9'122.8
C3—C4—H4117.7C8—C9'—H9'117.2
C5—C4—H4121.6C8—C10'—C9'ii121.3 (4)
C6—C5—C4118.2 (3)C8—C10'—H10'115.0
C6—C5—H5119.9C9'ii—C10'—H10'123.7
C4—C5—H5121.9
C3—C2—N7—C86.0 (4)C2—N7—C8—C1043.2 (4)
N1—C2—N7—C8174.0 (2)C2—N7—C8—C9'50.0 (4)
C2—N7—C8—C9140.0 (3)C2—N7—C8—C10'133.1 (3)
Symmetry codes: (i) x+1/2, y1/2, z; (ii) x+1, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2A—H2O···N10.851.862.650 (3)154
N1—H1···O2A0.901.832.650 (3)151
N7—H7···O1A0.901.862.756 (3)172
(II) N,N'-bis(2-pyridyl)biphenyl-4,4'-diamine 2,5-dihydroxy-1,4-benzoquinone (1/1) top
Crystal data top
C22H18N4·C6H4O4F(000) = 500
Mr = 478.50Dx = 1.442 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2223 reflections
a = 14.8368 (18) Åθ = 4–25°
b = 5.0801 (6) ŵ = 0.10 mm1
c = 16.0207 (16) ÅT = 294 K
β = 114.106 (11)°Plate, colourless
V = 1102.2 (2) Å30.20 × 0.15 × 0.02 mm
Z = 2
Data collection top
Kuma KM-4 CCD κ geometry
diffractometer
1195 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.024
Graphite monochromatorθmax = 25.0°, θmin = 3.7°
ω scansh = 1717
5270 measured reflectionsk = 46
1919 independent reflectionsl = 1819
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difmap, geom
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.100 w = 1/[σ2(Fo2) + (0.0597P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.93(Δ/σ)max < 0.001
1919 reflectionsΔρmax = 0.12 e Å3
204 parametersΔρmin = 0.12 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.007 (2)
Crystal data top
C22H18N4·C6H4O4V = 1102.2 (2) Å3
Mr = 478.50Z = 2
Monoclinic, P21/cMo Kα radiation
a = 14.8368 (18) ŵ = 0.10 mm1
b = 5.0801 (6) ÅT = 294 K
c = 16.0207 (16) Å0.20 × 0.15 × 0.02 mm
β = 114.106 (11)°
Data collection top
Kuma KM-4 CCD κ geometry
diffractometer
1195 reflections with I > 2σ(I)
5270 measured reflectionsRint = 0.024
1919 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.100H-atom parameters constrained
S = 0.93Δρmax = 0.12 e Å3
1919 reflectionsΔρmin = 0.12 e Å3
204 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)
C1A0.49051 (13)0.2086 (3)0.43750 (12)0.0438 (5)
C2A0.41278 (13)0.1563 (3)0.47334 (12)0.0434 (5)
C3A0.42749 (13)0.0562 (3)0.53531 (12)0.0478 (5)
H3A0.37830.09340.55830.057*
O1A0.33929 (9)0.3020 (2)0.44704 (9)0.0580 (4)
O2A0.47505 (10)0.4045 (3)0.38035 (9)0.0585 (4)
H2O0.42280.49610.36500.076 (11)*0.49 (3)
N10.33350 (11)0.7538 (3)0.28757 (11)0.0497 (4)
H10.36220.61600.32410.076 (11)*0.51 (3)
C20.25055 (13)0.8597 (4)0.28804 (12)0.0462 (5)
C30.20587 (15)1.0736 (4)0.23149 (14)0.0577 (5)
H30.14491.14540.22890.069*
C40.24929 (16)1.1710 (4)0.17666 (14)0.0675 (6)
H40.21981.32230.13960.081*
C50.33389 (16)1.0603 (4)0.17637 (13)0.0634 (6)
H50.36131.13660.13710.076*
C60.37350 (14)0.8534 (4)0.23270 (13)0.0564 (5)
H60.43220.76140.23840.068*
N70.21666 (12)0.7336 (3)0.34516 (11)0.0544 (5)
H70.25600.60460.37930.083 (7)*
C80.15151 (13)0.8188 (4)0.38358 (13)0.0467 (5)
C90.0654 (4)0.9652 (16)0.3388 (4)0.0532 (16)0.547 (12)
H90.04991.04600.28040.064*0.547 (12)
C100.0079 (5)1.0344 (16)0.3846 (4)0.0537 (17)0.547 (12)
H100.04431.15840.35510.064*0.547 (12)
C110.03057 (13)0.9605 (3)0.47512 (12)0.0446 (5)
C120.1116 (6)0.7986 (16)0.5125 (5)0.0489 (17)0.547 (12)
H120.12530.73410.57280.059*0.547 (12)
C130.1690 (6)0.7306 (16)0.4689 (6)0.0505 (17)0.547 (12)
H130.22300.61010.49610.061*0.547 (12)
C9'0.1080 (9)1.0679 (16)0.3729 (8)0.073 (3)0.453 (12)
H9'0.11951.19170.33300.088*0.453 (12)
C10'0.0486 (9)1.1307 (16)0.4176 (8)0.069 (3)0.453 (12)
H10'0.02231.30620.40780.083*0.453 (12)
C12'0.0764 (9)0.716 (2)0.4884 (8)0.074 (3)0.453 (12)
H12'0.05700.58510.52110.089*0.453 (12)
C13'0.1349 (9)0.646 (2)0.4428 (9)0.070 (3)0.453 (12)
H13'0.16690.47770.45180.084*0.453 (12)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C1A0.0499 (11)0.0396 (10)0.0426 (11)0.0034 (9)0.0196 (9)0.0041 (9)
C2A0.0442 (11)0.0411 (10)0.0459 (11)0.0002 (9)0.0193 (9)0.0061 (8)
C3A0.0497 (12)0.0473 (11)0.0539 (12)0.0026 (9)0.0287 (10)0.0024 (9)
O1A0.0523 (8)0.0550 (8)0.0699 (9)0.0136 (7)0.0281 (7)0.0073 (7)
O2A0.0598 (9)0.0572 (8)0.0666 (9)0.0107 (7)0.0342 (7)0.0168 (7)
N10.0527 (10)0.0521 (10)0.0520 (10)0.0056 (8)0.0291 (8)0.0003 (8)
C20.0503 (11)0.0474 (11)0.0442 (11)0.0015 (9)0.0225 (9)0.0074 (9)
C30.0567 (12)0.0647 (13)0.0548 (12)0.0083 (10)0.0261 (10)0.0043 (10)
C40.0758 (16)0.0674 (14)0.0574 (14)0.0048 (12)0.0253 (12)0.0107 (11)
C50.0674 (14)0.0732 (15)0.0558 (13)0.0026 (12)0.0317 (11)0.0040 (11)
C60.0552 (12)0.0666 (13)0.0547 (13)0.0006 (10)0.0300 (10)0.0002 (11)
N70.0645 (11)0.0530 (10)0.0614 (10)0.0122 (8)0.0418 (9)0.0084 (8)
C80.0486 (11)0.0460 (11)0.0541 (12)0.0034 (9)0.0296 (10)0.0011 (9)
C90.052 (3)0.070 (4)0.040 (3)0.015 (3)0.021 (2)0.008 (2)
C100.046 (3)0.071 (4)0.043 (3)0.021 (3)0.018 (2)0.009 (2)
C110.0427 (11)0.0473 (11)0.0478 (11)0.0026 (8)0.0226 (9)0.0016 (9)
C120.053 (4)0.058 (4)0.044 (3)0.018 (3)0.028 (3)0.023 (3)
C130.053 (4)0.051 (4)0.056 (4)0.021 (3)0.032 (3)0.016 (3)
C9'0.110 (7)0.049 (4)0.096 (6)0.006 (4)0.079 (6)0.010 (4)
C10'0.097 (7)0.044 (4)0.099 (7)0.016 (4)0.072 (6)0.008 (4)
C12'0.083 (8)0.064 (6)0.109 (8)0.020 (4)0.073 (6)0.022 (5)
C13'0.094 (8)0.052 (5)0.089 (7)0.022 (4)0.062 (6)0.014 (4)
Geometric parameters (Å, º) top
C1A—O2A1.307 (2)C8—C131.359 (8)
C1A—C3Ai1.355 (2)C8—C13'1.387 (11)
C1A—C2A1.507 (2)C8—C91.397 (5)
C2A—O1A1.240 (2)C8—C9'1.398 (7)
C2A—C3A1.422 (2)C9—C101.378 (7)
C3A—C1Ai1.355 (2)C9—H90.9600
C3A—H3A0.9600C10—C111.400 (6)
O2A—H2O0.8502C10—H100.9600
N1—C61.344 (2)C11—C10'1.368 (7)
N1—C21.346 (2)C11—C121.375 (8)
N1—H10.9000C11—C12'1.392 (11)
C2—N71.370 (2)C11—C11ii1.487 (3)
C2—C31.397 (3)C12—C131.349 (11)
C3—C41.376 (3)C12—H120.9599
C3—H30.9600C13—H130.9600
C4—C51.377 (3)C9'—C10'1.381 (9)
C4—H40.9600C9'—H9'0.9600
C5—C61.353 (3)C10'—H10'0.9600
C5—H50.9599C12'—C13'1.389 (15)
C6—H60.9600C12'—H12'0.9600
N7—C81.409 (2)C13'—H13'0.9600
N7—H70.8996
O2A—C1A—C3Ai122.52 (17)C13'—C8—N7116.7 (5)
O2A—C1A—C2A117.28 (15)C9—C8—N7125.9 (3)
C3Ai—C1A—C2A120.21 (16)C9'—C8—N7126.1 (3)
O1A—C2A—C3A123.57 (17)C10—C9—C8119.8 (4)
O1A—C2A—C1A117.95 (16)C10—C9—H9117.2
C3A—C2A—C1A118.47 (15)C8—C9—H9122.1
C1Ai—C3A—C2A121.32 (17)C9—C10—C11123.0 (4)
C1Ai—C3A—H3A119.2C9—C10—H10117.1
C2A—C3A—H3A119.5C11—C10—H10119.3
C1A—O2A—H2O119.8C10'—C11—C12'116.7 (5)
C6—N1—C2120.13 (17)C12—C11—C10114.1 (4)
C6—N1—H1120.0C10'—C11—C11ii121.4 (3)
C2—N1—H1119.9C12—C11—C11ii123.0 (4)
N1—C2—N7113.75 (16)C12'—C11—C11ii121.8 (5)
N1—C2—C3120.02 (17)C10—C11—C11ii122.8 (3)
N7—C2—C3126.21 (17)C13—C12—C11123.5 (6)
C4—C3—C2118.17 (19)C13—C12—H12121.0
C4—C3—H3120.9C11—C12—H12115.5
C2—C3—H3120.9C12—C13—C8122.4 (7)
C3—C4—C5121.3 (2)C12—C13—H13120.9
C3—C4—H4117.9C8—C13—H13116.7
C5—C4—H4120.7C10'—C9'—C8120.4 (6)
C6—C5—C4117.59 (19)C10'—C9'—H9'121.2
C6—C5—H5124.5C8—C9'—H9'118.4
C4—C5—H5117.9C11—C10'—C9'123.1 (6)
N1—C6—C5122.75 (19)C11—C10'—H10'121.2
N1—C6—H6112.4C9'—C10'—H10'115.7
C5—C6—H6124.8C13'—C12'—C11121.3 (9)
C2—N7—C8130.73 (16)C13'—C12'—H12'120.2
C2—N7—H7115.0C11—C12'—H12'117.6
C8—N7—H7110.4C8—C13'—C12'121.5 (9)
C13—C8—C9116.8 (4)C8—C13'—H13'116.8
C13'—C8—C9'117.0 (5)C12'—C13'—H13'121.7
C13—C8—N7117.0 (4)
C3—C2—N7—C821.3 (3)C2—N7—C8—C13145.8 (4)
N1—C2—N7—C8160.57 (18)C2—N7—C8—C9'2.4 (8)
C2—N7—C8—C940.7 (5)C2—N7—C8—C13'177.3 (7)
Symmetry codes: (i) x+1, y, z+1; (ii) x, y+2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2A—H2O···N10.851.912.687 (2)150
N1—H1···O2A0.901.882.687 (2)148
N7—H7···O1A0.901.992.891 (2)176

Experimental details

(I)(II)
Crystal data
Chemical formulaC16H14N4·C6H4O4C22H18N4·C6H4O4
Mr402.40478.50
Crystal system, space groupMonoclinic, C2/cMonoclinic, P21/c
Temperature (K)296294
a, b, c (Å)25.166 (3), 5.0290 (5), 15.1590 (16)14.8368 (18), 5.0801 (6), 16.0207 (16)
β (°) 97.648 (9) 114.106 (11)
V3)1901.5 (4)1102.2 (2)
Z42
Radiation typeMo KαMo Kα
µ (mm1)0.100.10
Crystal size (mm)0.20 × 0.10 × 0.020.20 × 0.15 × 0.02
Data collection
DiffractometerKuma KM-4 CCD κ geometry
diffractometer
Kuma KM-4 CCD κ geometry
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
4700, 1665, 909 5270, 1919, 1195
Rint0.0430.024
(sin θ/λ)max1)0.5950.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.088, 0.94 0.037, 0.100, 0.93
No. of reflections16651919
No. of parameters160204
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.13, 0.130.12, 0.12

Computer programs: CrysAlis (Oxford Diffraction, 2000), CrysAlis, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), Stereochemical Workstation Operation Manual (Siemens, 1989), SHELXL97.

Selected geometric parameters (Å, º) for (I) top
O1A—C2A1.247 (2)C1A—C2A1.521 (3)
O2A—C1A1.292 (2)C2A—C3A1.410 (3)
C1A—C3Ai1.359 (3)
C6—N1—C2120.9 (2)
C3—C2—N7—C86.0 (4)C2—N7—C8—C9'50.0 (4)
C2—N7—C8—C1043.2 (4)
Symmetry code: (i) x+1/2, y1/2, z.
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O2A—H2O···N10.851.862.650 (3)154
N1—H1···O2A0.901.832.650 (3)151
N7—H7···O1A0.901.862.756 (3)172
Selected geometric parameters (Å, º) for (II) top
C1A—O2A1.307 (2)C2A—O1A1.240 (2)
C1A—C3Ai1.355 (2)C2A—C3A1.422 (2)
C1A—C2A1.507 (2)
C6—N1—C2120.13 (17)
C3—C2—N7—C821.3 (3)C2—N7—C8—C9'2.4 (8)
C2—N7—C8—C940.7 (5)
Symmetry code: (i) x+1, y, z+1.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O2A—H2O···N10.851.912.687 (2)150
N1—H1···O2A0.901.882.687 (2)148
N7—H7···O1A0.901.992.891 (2)176
 

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