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In the title compound, C14H10N6, which crystallizes with Z′ = 2 in the C2/c space group, the mol­ecules are linked by N—H...N hydrogen bonds into chains, which are arranged in a wave-like form stabilized by aromatic π–π stacking inter­actions. This work demonstrates the usefulness of aromatic triazine derivatives in crystal engineering.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108003831/gd3192sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108003831/gd3192Isup2.hkl
Contains datablock I

CCDC reference: 668333

Comment top

A productive strategy in crystal engineering utilizes molecules which can form multiple interactions with their neighbours (Wuest, 2005). Hydrogen bonds are widely used as the principal interactions in this strategy since they are directional and relatively strong (Moulton & Zaworotko, 2001; Seiter, 2002). Many different self-complementary hydrogen-bonding groups can be used to control association in crystal engineering and to produce different arrangements, such as chains, sheets, ribbons, tapes, rosettes etc., having predictable structural features (Desiraju, 1990, 2002). Several studies have demonstrated the usefulness of melamine and its organic and inorganic complexes or salts in crystal engineering (Whitesides et al. 1995; Janczak & Perpétuo, 2001, 2002, 2003, 2004, 2008; Perpétuo & Janczak, 2003, 2005, 2007), since their components contain complementary arrays of hydrogen-bonding sites. While ππ interactions are intermolecular forces whose nature is still a matter of discussion (Hunter & Sanders, 1990; Janiak, 2000; Cozzi et al. 2003; Kobayashi & Saigo, 2005), in general, two aromatic rings are arranged in a face-to-face orientation with a distance of 3.2–3.8 Å between the planes of the rings.

In an effort to engineer expanded versions of the structures formed during the transformation of the cyano group in dicyanobenzene isomers in the presence of cyanoguanidine (Janczak & Kubiak, 2005a,b), we have replaced the phenyl rings with naphthyl systems, using 2,3-dicyanonaphthalene, and we have investigated the role of ππ stacking interactions in the organization and stabilization of the resulting structures. We present here the crystal structure of one of these, the title compound, (I).

Compound (I) crystallizes with Z' = 2 and the two independent molecules, M1 and M2, are linked by N—H···N hydrogen bonds (Table 2) into a dimeric unit (Fig. 1). These units are linked by further N—H···N hydrogen bonds to form a zigzag chain (Fig. 3a). Although the bond lengths and angles in the two independent molecules are very similar, their conformations differ in the rotation angle of the triazine ring relative to the naphthalene ring around the inter-ring bond. The dihedral angles between the planes of triazine and naphthalene rings are 27.0 (2) and 10.7 (2)° in molecules M1 and M2, respectively. The rotation is caused by an interaction of the highly polar CN group with the triazine ring.

The gas-phase geometry obtained by ab initio molecular orbital calculations at the B3LYP/6–31+G* level (GAUSSIAN98; Frisch et al., 1998) confirms the non-planar conformation (Fig. 2). The calculated dihedral angle between the planes of the triazine and naphthalene rings, 14.7°, represents a global minimum on the potential energy surface (PES). During rotation of the triazine ring relative to naphthalene around the inter-ring bond from 0 to 360°, four equivalent minima and two pairs of maxima are found. The minima are observed at rotation angles of ±14.7° and (180±14.7)° (165.3 and 194.7°), while the maxima are observed at 0° (and 180°) with a barrier energy of ~5.85 kJ mol-1, and at 90° (and 270°) with a barrier energy of ~14.35 kJ mol-1.

The difference between the barrier energy of the conformation at 0 and 90° (ΔE = 8.5 kJ mol-1) can be attributed to the π-delocalization energy of the π electrons along the inter-ring bond. At a rotation angle of 90° (rings perpendicular), delocalization of the π electrons between the rings is impossible due to the symmetry of the orbitals. The lengthening of the inter-ring bond, from 1.488 Å for the most stable conformation to 1.511 Å for a rotation angle of 90°, supports this fact. The estimated energy of molecule M1 in the conformation as present in the crystal structure is greater by ~6.75 kJ mol-1, while for the second molecule it is greater only by ~1.85 kJ mol-1. The differences between the energies of the molecules in the crystal structure and in the gas phase (obtained by molecular orbital calculations) are compensated for by ππ interactions between the aromatic rings in the crystal structure.

Considering both conformations of the independent molecules M1 and M2 in the crystal structure of (I) (Fig. 1, Table 1) and in the gas-phase conformation (Fig. 2) in more detail, besides the main difference mentioned above in the rotation angle of the rings, several other differences can also be found. For example, the C—CN angle in molecule M1 [173.9 (2)°] is closer to 180° than that in molecule M2 [167.7 (2)°]. These values correlate well with the rotation angles of the triazine ring in relation to the naphthalene ring. The greater rotation angle around the inter-ring C—C bond lengthens the distance between the polar CN group and the triazine ring and results in a decrease in the repulsion between the substituents at positions 2 and 3 in the naphthalene ring.

In the dimer unit formed by the independent molecules M1 and M2 (Fig. 1), the two triazine rings are not coplanar; the dihedral angle between their planes is 22.6 (1)°. Dimers related by a c-glide plane interact via two pairs of N—H···N hydrogen bonds, forming infinite chains along the c axis (Fig. 3a). There is no hydrogen bonding between the chains, and the chains interact only via van der Waals forces and ππ stacking interactions. Although the triazine rings each contain one potential hydrogen-bonding site (atoms N1 and N21), these sites are inactive due to steric hindrance from the cyano groups.

The various chains along [001] form a wave-like architecture (Fig. 3b) with a distance of ca 3.45 Å between adjacent aromatic ring systems, consistent with the occurrence of ππ stacking interactions, since this distance is comparable with the sum of the van der Waals radii of two C atoms in an aromatic ring system (Pauling, 1967). The sheets of the wave-like structure lie parallel to the (010) plane (Fig. 3b).

Our observations underscore the potential utility of (I) in crystal engineering. The amine groups can donate hydrogen bonds to the N atoms of neighbouring triazine rings, which act as acceptors, thus forming a characteristic dimeric motif. The dimeric motif containing hydrogen-bonding active sites can interact with neighbouring molecules via two pairs of N—H···N hydrogen bonds, favouring the formation of one-dimensional-polymers. In the absence of hydrogen bonds between these one-dimensional-polymers, ππ interactions between offset aromatic rings stabilize the overall structure.

Related literature top

For related literature, see: Cozzi et al. (2003); Desiraju (1990, 2002); Frisch (1998); Hunter & Sanders (1990); Janczak & Kubiak (2005a, 2005b); Janczak & Perpétuo (2001, 2002, 2003, 2004, 2008); Janiak (2000); Kobayashi & Saigo (2005); Moulton & Zaworotko (2001); Pauling (1967); Perpétuo & Janczak (2003, 2005, 2007); Seiter (2002); Whitesides et al. (1995); Wuest (2005).

Experimental top

2,3-Dicyanonaphthalene (99% purity) and cyanoguanidine (99% purity) were purchased from Sigma–Aldrich. They were mixed together in a 1:1 molar ratio and the mixture was pressed into pellets. The pellets were inserted into an evacuated glass ampoule and annealed in the temperature gradient ?–? K [Please give values for temperature gradient]. Crystals of 2-(4,6-diamino-1,3,5-triazin-2-yl)-3-naphthonitrile, (I), were formed in the low-temperature zone during migration from the high-temperature zone at which the compound is formed (Janczak & Kubiak, 2005a,b). Elemental analysis, found: C 64.21, N 32.00, H 3.79%; calculated for C14H10N6: C 64.11, N 32.05, H 3.84%.

Refinement top

The H atoms were treated as riding atoms in geometrically idealized positions with distances C—H = 0.93 Å and N—H = 0.86 Å, with Uiso=1.2Ueq(parent).

Structure description top

A productive strategy in crystal engineering utilizes molecules which can form multiple interactions with their neighbours (Wuest, 2005). Hydrogen bonds are widely used as the principal interactions in this strategy since they are directional and relatively strong (Moulton & Zaworotko, 2001; Seiter, 2002). Many different self-complementary hydrogen-bonding groups can be used to control association in crystal engineering and to produce different arrangements, such as chains, sheets, ribbons, tapes, rosettes etc., having predictable structural features (Desiraju, 1990, 2002). Several studies have demonstrated the usefulness of melamine and its organic and inorganic complexes or salts in crystal engineering (Whitesides et al. 1995; Janczak & Perpétuo, 2001, 2002, 2003, 2004, 2008; Perpétuo & Janczak, 2003, 2005, 2007), since their components contain complementary arrays of hydrogen-bonding sites. While ππ interactions are intermolecular forces whose nature is still a matter of discussion (Hunter & Sanders, 1990; Janiak, 2000; Cozzi et al. 2003; Kobayashi & Saigo, 2005), in general, two aromatic rings are arranged in a face-to-face orientation with a distance of 3.2–3.8 Å between the planes of the rings.

In an effort to engineer expanded versions of the structures formed during the transformation of the cyano group in dicyanobenzene isomers in the presence of cyanoguanidine (Janczak & Kubiak, 2005a,b), we have replaced the phenyl rings with naphthyl systems, using 2,3-dicyanonaphthalene, and we have investigated the role of ππ stacking interactions in the organization and stabilization of the resulting structures. We present here the crystal structure of one of these, the title compound, (I).

Compound (I) crystallizes with Z' = 2 and the two independent molecules, M1 and M2, are linked by N—H···N hydrogen bonds (Table 2) into a dimeric unit (Fig. 1). These units are linked by further N—H···N hydrogen bonds to form a zigzag chain (Fig. 3a). Although the bond lengths and angles in the two independent molecules are very similar, their conformations differ in the rotation angle of the triazine ring relative to the naphthalene ring around the inter-ring bond. The dihedral angles between the planes of triazine and naphthalene rings are 27.0 (2) and 10.7 (2)° in molecules M1 and M2, respectively. The rotation is caused by an interaction of the highly polar CN group with the triazine ring.

The gas-phase geometry obtained by ab initio molecular orbital calculations at the B3LYP/6–31+G* level (GAUSSIAN98; Frisch et al., 1998) confirms the non-planar conformation (Fig. 2). The calculated dihedral angle between the planes of the triazine and naphthalene rings, 14.7°, represents a global minimum on the potential energy surface (PES). During rotation of the triazine ring relative to naphthalene around the inter-ring bond from 0 to 360°, four equivalent minima and two pairs of maxima are found. The minima are observed at rotation angles of ±14.7° and (180±14.7)° (165.3 and 194.7°), while the maxima are observed at 0° (and 180°) with a barrier energy of ~5.85 kJ mol-1, and at 90° (and 270°) with a barrier energy of ~14.35 kJ mol-1.

The difference between the barrier energy of the conformation at 0 and 90° (ΔE = 8.5 kJ mol-1) can be attributed to the π-delocalization energy of the π electrons along the inter-ring bond. At a rotation angle of 90° (rings perpendicular), delocalization of the π electrons between the rings is impossible due to the symmetry of the orbitals. The lengthening of the inter-ring bond, from 1.488 Å for the most stable conformation to 1.511 Å for a rotation angle of 90°, supports this fact. The estimated energy of molecule M1 in the conformation as present in the crystal structure is greater by ~6.75 kJ mol-1, while for the second molecule it is greater only by ~1.85 kJ mol-1. The differences between the energies of the molecules in the crystal structure and in the gas phase (obtained by molecular orbital calculations) are compensated for by ππ interactions between the aromatic rings in the crystal structure.

Considering both conformations of the independent molecules M1 and M2 in the crystal structure of (I) (Fig. 1, Table 1) and in the gas-phase conformation (Fig. 2) in more detail, besides the main difference mentioned above in the rotation angle of the rings, several other differences can also be found. For example, the C—CN angle in molecule M1 [173.9 (2)°] is closer to 180° than that in molecule M2 [167.7 (2)°]. These values correlate well with the rotation angles of the triazine ring in relation to the naphthalene ring. The greater rotation angle around the inter-ring C—C bond lengthens the distance between the polar CN group and the triazine ring and results in a decrease in the repulsion between the substituents at positions 2 and 3 in the naphthalene ring.

In the dimer unit formed by the independent molecules M1 and M2 (Fig. 1), the two triazine rings are not coplanar; the dihedral angle between their planes is 22.6 (1)°. Dimers related by a c-glide plane interact via two pairs of N—H···N hydrogen bonds, forming infinite chains along the c axis (Fig. 3a). There is no hydrogen bonding between the chains, and the chains interact only via van der Waals forces and ππ stacking interactions. Although the triazine rings each contain one potential hydrogen-bonding site (atoms N1 and N21), these sites are inactive due to steric hindrance from the cyano groups.

The various chains along [001] form a wave-like architecture (Fig. 3b) with a distance of ca 3.45 Å between adjacent aromatic ring systems, consistent with the occurrence of ππ stacking interactions, since this distance is comparable with the sum of the van der Waals radii of two C atoms in an aromatic ring system (Pauling, 1967). The sheets of the wave-like structure lie parallel to the (010) plane (Fig. 3b).

Our observations underscore the potential utility of (I) in crystal engineering. The amine groups can donate hydrogen bonds to the N atoms of neighbouring triazine rings, which act as acceptors, thus forming a characteristic dimeric motif. The dimeric motif containing hydrogen-bonding active sites can interact with neighbouring molecules via two pairs of N—H···N hydrogen bonds, favouring the formation of one-dimensional-polymers. In the absence of hydrogen bonds between these one-dimensional-polymers, ππ interactions between offset aromatic rings stabilize the overall structure.

For related literature, see: Cozzi et al. (2003); Desiraju (1990, 2002); Frisch (1998); Hunter & Sanders (1990); Janczak & Kubiak (2005a, 2005b); Janczak & Perpétuo (2001, 2002, 2003, 2004, 2008); Janiak (2000); Kobayashi & Saigo (2005); Moulton & Zaworotko (2001); Pauling (1967); Perpétuo & Janczak (2003, 2005, 2007); Seiter (2002); Whitesides et al. (1995); Wuest (2005).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis CCD (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The independent components of compound (I), showing the atom-labelling scheme and the hydrogen bonds within the selected asymmetric unit. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. Hydrogen bonds are shown as dashed lines.
[Figure 2] Fig. 2. Results of the optimized molecular orbital calculations (B3LYP/6–31+G* level) for (I) (Å, °).
[Figure 3] Fig. 3. (a) A view of the N—H···N hydrogen-bonded chains of (I), which exhibit R22(8) topology. (b) The wave-like structure in the crystal structure of (I). For the sake of clarity, H atoms bonded to C atoms have been omitted.
3-(4,6-diamino-1,3,5-triazin-2-yl)-2-naphthonitrile top
Crystal data top
C14H10N6F(000) = 2176
Mr = 262.28Dx = 1.417 Mg m3
Dm = 1.41 Mg m3
Dm measured by flotation
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1203 reflections
a = 35.798 (7) Åθ = 2.9–28.0°
b = 7.319 (1) ŵ = 0.09 mm1
c = 21.459 (4) ÅT = 295 K
β = 118.96 (3)°Paralellepiped, colourless
V = 4919 (2) Å30.32 × 0.26 × 0.18 mm
Z = 16
Data collection top
Kuma KM-4 with CCD area-detector
diffractometer
5875 independent reflections
Radiation source: fine-focus sealed tube3357 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
Detector resolution: 1024x1024 with blocks 2x2 pixels mm-1θmax = 28.0°, θmin = 2.9°
ω–scanh = 4647
Absorption correction: analytical
face-indexed (SHELXTL; Sheldrick, 2008)
k = 98
Tmin = 0.974, Tmax = 0.981l = 2728
27666 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.045H-atom parameters constrained
wR(F2) = 0.071 w = 1/[σ2(Fo2) + (0.0055P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.002
5875 reflectionsΔρmax = 0.23 e Å3
362 parametersΔρmin = 0.24 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.000643 (13)
Crystal data top
C14H10N6V = 4919 (2) Å3
Mr = 262.28Z = 16
Monoclinic, C2/cMo Kα radiation
a = 35.798 (7) ŵ = 0.09 mm1
b = 7.319 (1) ÅT = 295 K
c = 21.459 (4) Å0.32 × 0.26 × 0.18 mm
β = 118.96 (3)°
Data collection top
Kuma KM-4 with CCD area-detector
diffractometer
5875 independent reflections
Absorption correction: analytical
face-indexed (SHELXTL; Sheldrick, 2008)
3357 reflections with I > 2σ(I)
Tmin = 0.974, Tmax = 0.981Rint = 0.034
27666 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.071H-atom parameters constrained
S = 1.04Δρmax = 0.23 e Å3
5875 reflectionsΔρmin = 0.24 e Å3
362 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*/Ueq
N10.24088 (5)0.0920 (2)0.36585 (8)0.0428 (4)
N20.16587 (5)0.0631 (3)0.32362 (8)0.0436 (4)
N30.19370 (4)0.0352 (2)0.24293 (7)0.0409 (4)
N40.21289 (5)0.1033 (3)0.44220 (8)0.0545 (5)
H4A0.19160.09940.45050.065*
H4B0.23840.11830.47680.065*
N50.12212 (5)0.0133 (3)0.20440 (8)0.0590 (6)
H5A0.10050.01390.21180.071*
H5B0.11830.00320.16200.071*
N60.33079 (7)0.1134 (4)0.46499 (10)0.0747 (7)
C10.34280 (6)0.0222 (3)0.32101 (12)0.0554 (6)
H10.36960.06190.35570.066*
C20.31020 (6)0.0096 (3)0.33764 (10)0.0433 (5)
C30.26894 (5)0.0503 (3)0.28489 (9)0.0384 (4)
C40.26267 (6)0.0921 (3)0.21832 (10)0.0449 (5)
H40.23570.13000.18370.054*
C50.29570 (7)0.0799 (3)0.20034 (11)0.0514 (6)
C60.28874 (9)0.1225 (4)0.13115 (13)0.0526 (7)
H60.26170.15710.09580.065*
C70.32178 (13)0.1126 (5)0.11631 (19)0.0641 (11)
H70.31720.14100.07090.089*
C80.36263 (12)0.0600 (5)0.1694 (2)0.0779 (12)
H80.38500.05520.15890.101*
C90.36997 (9)0.0161 (5)0.23543 (18)0.0669 (10)
H90.39730.01930.26970.083*
C100.33665 (7)0.0233 (3)0.25343 (13)0.0567 (6)
C110.31975 (6)0.0652 (3)0.40836 (11)0.0512 (6)
C120.23228 (5)0.0616 (3)0.29931 (9)0.0378 (4)
C130.20624 (6)0.0861 (3)0.37555 (9)0.0412 (5)
C140.16155 (5)0.0379 (3)0.25874 (9)0.0416 (5)
N210.06563 (5)0.0934 (3)0.42305 (7)0.0420 (4)
N220.13485 (4)0.0428 (2)0.47121 (7)0.0408 (4)
N230.10629 (4)0.0448 (2)0.54784 (7)0.0393 (4)
N240.09287 (5)0.0056 (3)0.35111 (8)0.0593 (6)
H24A0.11270.04140.34440.071*
H24B0.06960.04400.31540.071*
N250.17220 (5)0.0912 (3)0.59144 (8)0.0514 (5)
H25A0.19220.13970.58570.062*
H25B0.17480.08390.63340.062*
N260.03217 (6)0.1319 (4)0.30228 (9)0.0725 (7)
C210.03870 (6)0.2784 (3)0.44141 (10)0.0434 (5)
H210.06480.29850.40080.052*
C220.00531 (5)0.2085 (3)0.43414 (9)0.0387 (4)
C230.03541 (5)0.1792 (3)0.49551 (9)0.0364 (4)
C240.03951 (6)0.2220 (3)0.56061 (9)0.0429 (5)
H240.06600.20560.60090.052*
C250.00547 (6)0.2899 (3)0.56967 (9)0.0421 (5)
C260.00936 (7)0.3294 (4)0.63708 (11)0.0601 (7)
H260.03530.31030.67820.072*
C270.02471 (8)0.3955 (4)0.64224 (13)0.0709 (8)
H270.02170.42090.68690.085*
C280.06406 (7)0.4255 (4)0.58130 (13)0.0627 (7)
H280.08690.47130.58570.075*
C290.06891 (7)0.3884 (3)0.51653 (12)0.0521 (6)
H290.09530.40800.47640.062*
C2100.03451 (6)0.3201 (3)0.50836 (10)0.0407 (5)
C2110.01620 (6)0.1632 (3)0.36179 (10)0.0492 (5)
C2120.07168 (5)0.1017 (3)0.48856 (9)0.0360 (4)
C2130.09817 (5)0.0186 (3)0.41668 (9)0.0404 (5)
C2140.13691 (5)0.0271 (3)0.53504 (9)0.0387 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0310 (7)0.0648 (12)0.0361 (8)0.0009 (8)0.0189 (6)0.0031 (8)
N20.0302 (7)0.0707 (13)0.0340 (8)0.0007 (8)0.0187 (6)0.0022 (8)
N30.0290 (7)0.0645 (12)0.0311 (7)0.0007 (8)0.0161 (6)0.0025 (7)
N40.0368 (8)0.0960 (16)0.0352 (8)0.0048 (9)0.0209 (7)0.0075 (9)
N50.0272 (8)0.1163 (18)0.0338 (8)0.0001 (10)0.0151 (6)0.0016 (9)
N60.0628 (12)0.1080 (19)0.0539 (12)0.0209 (13)0.0288 (10)0.0155 (12)
C10.0355 (10)0.0742 (17)0.0616 (13)0.0006 (11)0.0275 (9)0.0109 (12)
C20.0320 (9)0.0559 (14)0.0445 (10)0.0039 (9)0.0205 (8)0.0086 (9)
C30.0309 (9)0.0495 (13)0.0390 (9)0.0043 (9)0.0202 (7)0.0056 (8)
C40.0414 (10)0.0558 (14)0.0436 (10)0.0061 (10)0.0254 (8)0.0037 (9)
C50.0622 (13)0.0536 (14)0.0575 (12)0.0138 (11)0.0442 (11)0.0093 (10)
C60.0677 (19)0.0524 (18)0.0571 (15)0.0132 (15)0.0424 (15)0.0089 (13)
C70.068 (3)0.062 (2)0.066 (2)0.014 (2)0.040 (2)0.0106 (19)
C80.079 (3)0.078 (3)0.072 (3)0.0040 (19)0.047 (3)0.0160 (19)
C90.0660 (18)0.065 (3)0.0700 (18)0.0024 (18)0.0420 (19)0.0143 (19)
C100.0547 (12)0.0653 (16)0.0705 (14)0.0053 (12)0.0415 (11)0.0039 (12)
C110.0344 (9)0.0695 (16)0.0488 (12)0.0055 (10)0.0195 (9)0.0018 (11)
C120.0309 (8)0.0513 (13)0.0345 (9)0.0007 (9)0.0186 (7)0.0016 (8)
C130.0332 (9)0.0581 (14)0.0355 (9)0.0019 (9)0.0192 (7)0.0002 (8)
C140.0296 (8)0.0625 (14)0.0345 (9)0.0022 (9)0.0171 (7)0.0051 (9)
N210.0317 (7)0.0628 (12)0.0331 (8)0.0051 (8)0.0170 (6)0.0024 (7)
N220.0300 (7)0.0641 (12)0.0311 (7)0.0018 (8)0.0170 (6)0.0022 (7)
N230.0285 (7)0.0607 (11)0.0305 (7)0.0010 (7)0.0157 (6)0.0014 (7)
N240.0485 (8)0.0930 (17)0.0415 (8)0.0193 (10)0.0210 (7)0.0094 (9)
N250.0352 (8)0.0856 (14)0.0325 (8)0.0126 (9)0.0158 (7)0.0048 (8)
N260.0426 (9)0.127 (2)0.0391 (10)0.0062 (11)0.0129 (8)0.0198 (11)
C210.0313 (9)0.0568 (14)0.0406 (10)0.0027 (9)0.0162 (8)0.0022 (9)
C220.0336 (9)0.0507 (13)0.0339 (9)0.0024 (9)0.0149 (8)0.0054 (8)
C230.0292 (8)0.0458 (12)0.0358 (9)0.0033 (8)0.0171 (7)0.0020 (8)
C240.0316 (9)0.0611 (14)0.0355 (9)0.0037 (9)0.0158 (8)0.0040 (9)
C250.0399 (10)0.0526 (13)0.0407 (10)0.0069 (9)0.0251 (8)0.0070 (9)
C260.0557 (12)0.084 (2)0.0476 (11)0.0083 (13)0.0277 (10)0.0130 (12)
C270.0697 (15)0.095 (2)0.0682 (14)0.0047 (15)0.0469 (13)0.0195 (14)
C280.0570 (13)0.0817 (19)0.0691 (14)0.0034 (13)0.0461 (12)0.0088 (13)
C290.0427 (11)0.0630 (15)0.0589 (12)0.0033 (11)0.0312 (10)0.0033 (11)
C2100.0365 (9)0.0460 (12)0.0457 (10)0.0028 (9)0.0248 (8)0.0028 (9)
C2110.0397 (9)0.0643 (17)0.0409 (11)0.0019 (10)0.0150 (8)0.0088 (10)
C2120.0320 (8)0.0442 (12)0.0331 (8)0.0051 (8)0.0159 (7)0.0028 (8)
C2130.0356 (9)0.0524 (14)0.0381 (9)0.0109 (9)0.0204 (7)0.0020 (9)
C2140.0314 (8)0.0517 (13)0.0343 (9)0.0037 (9)0.0160 (7)0.0001 (8)
Geometric parameters (Å, º) top
N1—C121.325 (2)N21—C2121.316 (2)
N1—C131.352 (2)N21—C2131.351 (2)
N2—C141.337 (2)N22—C2141.340 (2)
N2—C131.340 (2)N22—C2131.343 (2)
N3—C121.337 (2)N23—C2121.341 (2)
N3—C141.347 (2)N23—C2141.357 (2)
N4—C131.337 (2)N24—C2131.329 (2)
N4—H4A0.8600N24—H24A0.8600
N4—H4B0.8600N24—H24B0.8600
N5—C141.337 (2)N25—C2141.340 (2)
N5—H5A0.8600N25—H25A0.8600
N5—H5B0.8600N25—H25B0.8600
N6—C111.136 (3)N26—C2111.141 (2)
C1—C21.378 (2)C21—C221.375 (2)
C1—C101.397 (3)C21—C2101.404 (2)
C1—H10.9300C21—H210.9300
C2—C31.425 (3)C22—C231.429 (2)
C2—C111.443 (3)C22—C2111.444 (2)
C3—C41.369 (3)C23—C241.368 (2)
C3—C121.488 (2)C23—C2121.488 (2)
C4—C51.412 (3)C24—C251.412 (3)
C4—H40.9300C24—H240.9300
C5—C101.413 (3)C25—C261.414 (2)
C5—C61.415 (3)C25—C2101.414 (3)
C6—C71.366 (4)C26—C271.364 (3)
C6—H60.9300C26—H260.9300
C7—C81.402 (5)C27—C281.398 (3)
C7—H70.9300C27—H270.9300
C8—C91.349 (4)C28—C291.342 (3)
C8—H80.9300C28—H280.9300
C9—C101.420 (3)C29—C2101.415 (3)
C9—H90.9300C29—H290.9300
C12—N1—C13114.13 (15)C212—N21—C213115.00 (15)
C14—N2—C13114.67 (15)C214—N22—C213114.09 (15)
C12—N3—C14113.74 (15)C212—N23—C214113.13 (14)
C13—N4—H4A120.0C213—N24—H24A120.0
C13—N4—H4B120.0C213—N24—H24B120.0
H4A—N4—H4B120.0H24A—N24—H24B120.0
C14—N5—H5A120.0C214—N25—H25A120.0
C14—N5—H5B120.0C214—N25—H25B120.0
H5A—N5—H5B120.0H25A—N25—H25B120.0
C2—C1—C10121.7 (2)C22—C21—C210121.92 (17)
C2—C1—H1119.2C22—C21—H21119.0
C10—C1—H1119.2C210—C21—H21119.0
C1—C2—C3119.68 (18)C21—C22—C23120.29 (16)
C1—C2—C11117.03 (19)C21—C22—C211114.23 (16)
C3—C2—C11123.26 (16)C23—C22—C211125.43 (16)
C4—C3—C2118.72 (16)C24—C23—C22117.62 (16)
C4—C3—C12119.29 (17)C24—C23—C212121.48 (16)
C2—C3—C12121.95 (16)C22—C23—C212120.90 (15)
C3—C4—C5122.35 (19)C23—C24—C25123.21 (17)
C3—C4—H4118.8C23—C24—H24118.4
C5—C4—H4118.8C25—C24—H24118.4
C4—C5—C10118.41 (19)C24—C25—C26123.25 (18)
C4—C5—C6121.8 (2)C24—C25—C210118.50 (16)
C10—C5—C6119.8 (2)C26—C25—C210118.25 (18)
C7—C6—C5120.0 (3)C27—C26—C25120.4 (2)
C7—C6—H6120.0C27—C26—H26119.8
C5—C6—H6120.0C25—C26—H26119.8
C6—C7—C8120.2 (3)C26—C27—C28120.9 (2)
C6—C7—H7119.9C26—C27—H27119.5
C8—C7—H7119.9C28—C27—H27119.5
C9—C8—C7120.9 (2)C29—C28—C27120.2 (2)
C9—C8—H8119.5C29—C28—H28119.9
C7—C8—H8119.5C27—C28—H28119.9
C8—C9—C10121.0 (3)C28—C29—C210121.0 (2)
C8—C9—H9119.5C28—C29—H29119.5
C10—C9—H9119.5C210—C29—H29119.5
C1—C10—C5119.13 (18)C21—C210—C25118.43 (16)
C1—C10—C9122.8 (2)C21—C210—C29122.37 (18)
C5—C10—C9118.0 (2)C25—C210—C29119.19 (17)
N6—C11—C2173.9 (2)N26—C211—C22167.7 (2)
N1—C12—N3126.72 (16)N21—C212—N23126.70 (16)
N1—C12—C3117.74 (16)N21—C212—C23115.11 (15)
N3—C12—C3115.52 (15)N23—C212—C23118.18 (15)
N4—C13—N2117.57 (16)N24—C213—N22118.44 (16)
N4—C13—N1117.39 (16)N24—C213—N21116.61 (16)
N2—C13—N1125.04 (16)N22—C213—N21124.95 (15)
N2—C14—N5117.86 (16)N22—C214—N25116.99 (16)
N2—C14—N3125.60 (16)N22—C214—N23126.13 (16)
N5—C14—N3116.54 (16)N25—C214—N23116.87 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4—H4A···N220.862.323.171 (2)172
N5—H5B···N23i0.862.303.132 (2)163
N24—H24A···N20.862.162.984 (2)161
N24—H24B···N26ii0.862.303.078 (3)150
N25—H25B···N3iii0.862.283.096 (2)158
Symmetry codes: (i) x, y, z1/2; (ii) x, y, z+1/2; (iii) x, y, z+1/2.

Experimental details

Crystal data
Chemical formulaC14H10N6
Mr262.28
Crystal system, space groupMonoclinic, C2/c
Temperature (K)295
a, b, c (Å)35.798 (7), 7.319 (1), 21.459 (4)
β (°) 118.96 (3)
V3)4919 (2)
Z16
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.32 × 0.26 × 0.18
Data collection
DiffractometerKuma KM-4 with CCD area-detector
Absorption correctionAnalytical
face-indexed (SHELXTL; Sheldrick, 2008)
Tmin, Tmax0.974, 0.981
No. of measured, independent and
observed [I > 2σ(I)] reflections
27666, 5875, 3357
Rint0.034
(sin θ/λ)max1)0.661
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.071, 1.04
No. of reflections5875
No. of parameters362
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.23, 0.24

Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2006).

Selected geometric parameters (Å, º) top
N6—C111.136 (3)N26—C2111.141 (2)
C2—C31.425 (3)C22—C2111.444 (2)
C2—C111.443 (3)C23—C2121.488 (2)
C3—C121.488 (2)
C12—N1—C13114.13 (15)C212—N21—C213115.00 (15)
C14—N2—C13114.67 (15)C214—N22—C213114.09 (15)
C12—N3—C14113.74 (15)C212—N23—C214113.13 (14)
N6—C11—C2173.9 (2)N26—C211—C22167.7 (2)
N1—C12—N3126.72 (16)N21—C212—N23126.70 (16)
N2—C13—N1125.04 (16)N22—C213—N21124.95 (15)
N2—C14—N3125.60 (16)N22—C214—N23126.13 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4—H4A···N220.862.323.171 (2)172
N5—H5B···N23i0.862.303.132 (2)163
N24—H24A···N20.862.162.984 (2)161
N24—H24B···N26ii0.862.303.078 (3)150
N25—H25B···N3iii0.862.283.096 (2)158
Symmetry codes: (i) x, y, z1/2; (ii) x, y, z+1/2; (iii) x, y, z+1/2.
 

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