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The title compounds, C10H9N5O·H2O (L1·H2O) and C16H12N6O (L2), were synthesized by solvent-free aldol condensation at room temperature. L1, prepared by grinding picolin­aldehyde with 2,3-diamino-3-isocyano­acrylonitrile in a 1:1 molar ratio, crystallized as a monohydrate. L2 was prepared by grinding picolinaldehyde with 2,3-diamino-3-isocyano­acrylonitrile in a 2:1 molar ratio. By varying the conditions of crystallization it was possible to obtain two polymorphs, viz. L2-I and L2-II; both crystallized in the monoclinic space group P21/c. They differ in the orientation of one pyridine ring with respect to the plane of the imidazole ring. In L2-I, this ring is oriented towards and above the imidazole ring, while in L2-II it is rotated away from and below the imidazole ring. In all three mol­ecules, there is a short intra­molecular N—H...N contact inherent to the planarity of the systems. In L1·H2O, this involves an amino H atom and the C=N N atom, while in L2 it involves an amino H atom and an imidazole N atom. In the crystal structure of L1·H2O, there are N—H...O and O—H...O inter­molecular hydrogen bonds which link the mol­ecules to form two-dimensional networks which stack along [001]. These networks are further linked via inter­molecular N—H...N(cyano) hydrogen bonds to form an extended three-dimensional network. In the crystal structure of L2-I, symmetry-related mol­ecules are linked via N—H...N hydrogen bonds, leading to the formation of dimers centred about inversion centres. These dimers are further linked via N—H...O hydrogen bonds involving the amide group, also centred about inversion centres, to form a one-dimensional arrangement propagating in [100]. In the crystal structure of L2-II, the presence of inter­molecular N—H...O hydrogen bonds involving the amide group results in the formation of dimers centred about inversion centres. These are linked via N—H...N hydrogen bonds involving the second amide H atom and the cyano N atom, to form two-dimensional networks in the bc plane. In L2-I and L2-II, C—H...π and π–π inter­actions are also present.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110029021/bm3095sup1.cif
Contains datablocks L1.H2O, L2-I, L2-II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110029021/bm3095L1.H2Osup2.hkl
Contains datablock L1.H2O

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110029021/bm3095L2-Isup3.hkl
Contains datablock L2-I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110029021/bm3095L2-IIsup4.hkl
Contains datablock L2-II

CCDC references: 796069; 796070; 796071

Comment top

Green chemistry is a well established field of research, enhanced by its numerous applications in high-technology industries and because of the need for environmentally friendly syntheses. An excellent review of the subject has been provided by Clark & Macquarrie (2002). The perfect `green reaction' has been described as one which proceeds at room temperature, requires no organic solvent, is highly selective and exhibits high atom efficiency, yet produces no waste products (Raston & Scott, 2000). It is a multidisciplinary field, requiring integrated study in the chemical, biological and physical sciences, as well as many aspects of engineering. The main objective is to remove organic solvents from chemical synthesis, which is important in the drive towards benign chemical technologies. Organic solvents are high on the list of toxic or otherwise damaging compounds because of the large volumes used in industry and the difficulties of containing volatile compounds (Cave et al., 2001; Anastas, 2001). In recent decades, numerous reactions using mechanical activation have been reported to give 100% yield (Kaupp, 2005). In all of these reactions, due to activation and molecular migration the product phase can be formed much faster than in solvent-assisted reactions. The process has a number of advantages, such as rapid and qualitatively solvent-free synthesis, with no need for a subsequent work-up procedure (Kaupp, 2003; Suess et al., 2005). On the other hand, there are a number of disadvantages, such as the use of harmful sodium hydroxide or other sodium salts and acetic acid as intermediates in the reaction work-up procedures, which can represent major drawbacks for these approaches (Rothenberg et al., 2001). Imidazoles, amines, enamines and amides are all very useful as pharmaceutical and biologically active substances, analytical reagents, dyes and fine chemicals (Rowan et al., 2006; Gao et al., 2005; Kajdan et al., 2000). Conventional methods for the synthesis of imidazoles are time-consuming and require the use of organic solvents.

Here, we have used a very simple method for the synthesis of L1 and the new and unusual imidazole derivative, L2. The synthesis and crystal structure of the 4-pyridyl analogue of L1 have been reported previously (Wu et al., 2006). The synthesis of L1 and the 3- and 4-pyridyl analogues have been reported as being precursors for the synthesis of pyridyl-4,5-dicyanoimidazoles (Takagi et al., 1975). The crystal structure of an iron(II) complex of L1 has also been reported (Mazzarella et al., 1986). The solvent-free aldol condensation reactions used here involve a solid amine and a liquid aldehyde. They have proved to be highly chemo-selective, and have led to the formation of compounds L1 and L2 in 90–99% yields with no waste products, hence fulfilling the requirements for a pure green reaction (Raston & Scott, 2000). It can be envisaged that this simple synthetic method could be used to produce a number of novel substituted imidazoles of potential biological interest.

The molecular structure of L1.H2O is illustrated in Fig. 1. It was prepared by the reaction of picolinaldehyde and 2,3-diamino-3-isocyanoacrylonitrile in a 1:1 molar ratio. It crystallized with one solvent water molecule, which is disordered over two positions (O1A/O1B). The geometric parameters in L1.H2O are normal (Allen et al., 1987) and close to those in, for example, the 4-pyridyl analogue (Wu et al., 2006). L1 is a Schiff base with an E-configuration about the C7N2 bond. The molecule is almost planar, with the 2,3-diamino-3-isocyanoacrylonitrile moiety [atoms N2–N5/C8–C11; planar to within 0.028 (5) Å] being inclined at 5.68 (18)° to the 2-pyridylmethylene moiety [atoms N1/C2–C7; planar to within 0.013 (5) Å]. There is a short N—H···N contact involving an amine H atom (N3—H3A) and atom N2 (Table 1), as a consequence of the inherent planarity of the system.

In the crystal structure of L1.H2O, intermolecular N—H···O and O—H···O hydrogen bonds involving the amine H atoms and the solvent water molecule result in the formation of two-dimensional networks in the ab plane (Fig. 2a, Table 1). These sheets are linked via N—H···N hydrogen bonds involving the second NH2 H atom, H3B, and cyano atom N4 to form a three-dimensional network (Fig. 2b, Table 1). As a consequence, short C—H···N contacts are also observed (Table 1).

The reaction of a 2:1 molar ratio of picolinaldehyde and 2,3-diamino-3-isocyanoacrylonitrile led to the formation of compound L2, which contains two pyridine rings (A and B) and one imidazole ring. The molecular structure of polymorph L2-I is depicted in Fig. 3. The bond lengths in the molecule are normal (Allen et al., 1987). In the molecule there is a short N—H···N contact involving an amine H atom (N4—H4B) and atom N2 (Table 2), again as a consequence of the inherent planarity of the system. Pyridine ring A (N1/C2–C6) is almost coplanar with the imidazole ring (N2/C7/N3/C8/C9), with a dihedral angle of only 6.66 (5)°. Pyridine ring B (N6/C13–C17) is almost orthogonal to the rest of the molecule: the dihedral angles with ring A and the imidazole ring are 88.32 (6) and 83.57 (6)°, respectively.

In the crystal structure of L2-I, symmetry-related molecules are linked via N—H···N hydrogen bonds involving the N4-amide H atom H4A and pyridine atom N6, forming dimers [graph-set notation R22(18); Bernstein et al., 1995] centred about inversion centres (Fig. 4a, Table 2). These dimers are further linked by intermolecular N—H···O hydrogen bonds involving the amide group [graph-set notation R22(8)], also centred about inversion centres (Fig. 4a, Table 2). In this manner, a one-dimensional chain-like arrangement is formed, propagating in [100]. The molecules stack back-to-back, with ππ stacking interactions involving pyridine ring A and the imidazole ring of a molecule related by an inversion centre, with the shortest centroid-to-centroid distance being 3.5431 (7) Å (Fig. 4b). There are also C—H···π interactions involving pyridine ring B (C15—H15···CgBi; see Table 2) [Please check changes]. Short C—H···O and C—H···N contacts are also observed (Table 2).

The molecular structure of polymorph L2-II is depicted in Fig. 5. The bond lengths in the molecule are normal (Allen et al., 1987) and similar to those in L2-I. Here again, there is a short N—H···N contact in the molecule, involving an amine H atom (N4—H4B) and atom N2 (Table 3). Pyridine ring A is inclined to the mean plane of the imidazole ring by 3.50 (6)°, compared with 6.66 (5)° in L2-I. The dihedral angles involving ring B with respect to the imidazole ring mean plane and pyridine ring A are 79.53 (6) and 82.79 (6)°, respectively, similar to the situation in L2-I. The two polymorphs differ essentially in the orientation of pyridine ring B with respect to the rest of the molecule. On comparing the two forms (Figs. 3 and 5) it can be seen that pyridine ring B in L2-II has been rotated about the N3—C12 bond by almost 180° relative to the position of the same ring in L2-I.

In the crystal structure of L2-II, the presence of intermolecular N—H···O hydrogen bonds involving the amide group results in the formation of dimers [graph-set notation R22(8)] about an inversion centre (Fig. 6a, Table 3), similar to the situation observed in L2-I. Symmetry-related molecules are further linked via N—H···N hydrogen bonds, involving the second amide H atom (H4B) and cyano atom N5 (Table 3), thereby leading to the formation of an undulating two-dimensional network in the bc plane (Fig. 6a). Here too the molecules stack back-to-back, with ππ stacking interactions involving pyridyl ring A and the imidazole ring of a molecule related by an inversion centre, with the shortest centroid-to-centroid distance being 3.5057 (7) Å (Fig. 6b). There are also C—H···π interactions involving the two pyridine rings A and B (C3—H3···CgBi; see Table 3) [Please check changes]. Short C—H···N contacts are also present.

The presence of the amide group in L2-I and L2-II leads to the formation of hydrogen-bonded dimers. In L1.H2O and L2-II there are intermolecular N—H···N hydrogen bonds involving the cyano and NH2 groups. Interestingly, this same interaction is absent in L2-I, where the second NH2 H atom forms an intermolecular N—H···N hydrogen bond with pyridine atom N6. Classical hydrogen bonding leads to the formation of a three-dimensional network in the case of L1.H2O, a one-dimensional arrangement in the case of L2-I, and a two-dimensional network in the case of L2-II.

Related literature top

For related literature, see: Allen et al. (1987); Anastas (2001); Bernstein et al. (1995); Cave et al. (2001); Clark & Macquarrie (2002); Gao et al. (2005); Kajdan et al. (2000); Kaupp (2003, 2005); Mazzarella et al. (1986); Raston & Scott (2000); Rothenberg et al. (2001); Rowan et al. (2006); Suess et al. (2005); Takagi et al. (1975); Wu et al. (2006).

Experimental top

The syntheses of L1 and L2 are outlined in the scheme. The synthesis of L1 was carried out by mixing by hand in a mortar a 1:1 molar ratio of picolinaldehyde and 2,3-diamino-3-isocyanoacrylonitrile. A viscous reddish-brown mixture was obtained which, on drying in air, gave a brown microcrystalline powder (yield 98.78%). Crystals suitable for X-ray analysis were obtained during a failed attempt at complexation of L1 with Ni(NO3)2.6H2O in a methanol–water solution [Solvent ratio?]. L1 and the nickel salt [Quantities or molar ratio?] were mixed together and stirred vigorously for 15 min at room temperature. A reddish-brown solution was obtained which was then filtered and the filtrate kept undisturbed for slow evaporation at room temperature. After 1 h, a large quantity of thread-like brownish crystals were obtained. The crystalline product, L1.H2O, was filtered off, washed with a small amount of ice-cold water and air dried. Elemental analysis (%), calculated for C10H9N5O: C 55.73, H 4.18, N 32.51%; found: C 55.93, H 4.08, N 31.99%. IR (KBr disc, ν, cm-1): 34123, 2224, 2203, 1618, 1638, 1594, 1565, 14712, 1366, 1295, 964, 757 and 614.

The synthesis of L2 was carried out in the same manner as described above, but using a 2:1 molar ratio of picolinaldehyde and 2,3-diamino-3-isocyanoacrylonitrile. A pale-brown viscous product was obtained. This was immediately poured into an excess of distilled water in a 50 ml beaker and gently heated with continuous mechanical stirring. A small amount of methanol was added to obtain a clear solution. This solution was filtered to remove any impurities and the filtrate left to cool slowly to room temperature. After a few hours, rod-like colourless crystals began to appear. The process of crystallization was assumed to be complete within 7 h (yield 90.23%). A crystal suitable for X-ray crystallographic analysis was shown to be polymorph L2-I. A second polymorph, L2-II, was obtained by direct recrystallization from methanol of the original brown viscous product. Elemental analysis (%), calculated for C16H12N6O: C 63.15, H 3.94, N 27.63%; found: C 63.15, H 3.94, N 27.63%. IR (KBr disk, ν, cm-1): 3337, 3150, 3073, 2995, 2969, 227, 1684, 1612, 1587, 1437, 1303, 1230, 1130, 999, 767 and 616.

Refinement top

In the final cycles of refinement of crystal structure L1.H2O, in the absence of significant anomalous scattering effects, the Friedel pairs were merged and Δf'' set to zero. In L1.H2O, the water molecule of crystallization was positionally disordered and each disorder component was refined as half-occupied. [Please confirm change to wording] The H atoms of this disordered water molecule were refined with distance restraints of O—H = 0.84 (2) Å and Uiso(H) = 1.5Ueq(O). For L1.H2O, L2-I and L2-II, the NH2 H atoms were refined with distance restraints of N—H = 0.88 (2) Å. For L1.H2O and L2-I, Uiso(H) = 1.5Ueq(N), while for L2-II these Uiso values were refined freely. [Please check change] The C-bound H atoms in all three crystal structures were included in calculated positions and treated as riding on their parent atoms, with C—H(aromatic) = 0.95 Å and C—H(methylene) = 0.99 Å, both with Uiso(H) = 1.2Ueq(C).

Computing details top

For all compounds, data collection: X-AREA (Version 1.23; Stoe & Cie, 2009); cell refinement: X-AREA (Version 1.23; Stoe & Cie, 2009); data reduction: X-RED32 (Version 1.05; Stoe & Cie, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. A view of the molecular structure of L1.H2O, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. The O—H···N hydrogen bond is shown by a dashed line.
[Figure 2] Fig. 2. (a) A partial view of the crystal packing of L1.H2O, showing the N—H···O and O—H···N hydrogen bonds resulting in the formation of the two-dimensional network (see Table 1 for details). Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity. (b) A view, along the c axis, of the crystal packing of L1.H2O, showing the N—H···O, N—H···N, O—H···N and O—H···O hydrogen bonds as light lines (cyan in the electronic version of the journal). H atoms not involved in hydrogen bonding have been omitted for clarity. See Table 1 for details.
[Figure 3] Fig. 3. A view of the molecular structure of polymorph L2-I, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 4] Fig. 4. (a) A partial view of the crystal packing of L2-I, showing the formation of the N—H···N and N—H···O hydrogen-bonded dimers (dashed lines; see Table 2 for details). H atoms not involved in hydrogen bonding have been omitted for clarity. (b) A view, along the b axis, of the crystal packing of polymorph L2-I, showing the N—H···O and N—H···N hydrogen bonds as light lines (cyan in the electronic version of the journal). H atoms not involved in hydrogen bonding have been omitted for clarity. See Table 2 for details.
[Figure 5] Fig. 5. A view of the molecular structure of polymorph L2-II, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 6] Fig. 6. (a) A partial view of the crystal packing of L2-II, showing the N—H···N hydrogen bonds (dashed lines) and the N—H···O hydrogen-bonded dimers (see Table 3 for details). H atoms not involved in hydrogen bonding have been omitted for clarity. (b) A view, along the a axis, of the crystal packing of polymorph L2-II, showing the N—H···O and N—H···N hydrogen bonds as light lines (cyan in the electronic version of the journal). H atoms not involved in hydrogen bonding have been omitted for clarity. See Table 3 for details.
(L1.H2O) 2-amino-3-[(E)-(2-pyridyl)methylideneamino]but-2-enedinitrile monohydrate top
Crystal data top
C10H7N5·H2OF(000) = 1792
Mr = 215.22Dx = 1.291 Mg m3
Orthorhombic, Fdd2Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2dCell parameters from 3163 reflections
a = 25.072 (6) Åθ = 1.7–25.5°
b = 46.996 (8) ŵ = 0.09 mm1
c = 3.7592 (7) ÅT = 173 K
V = 4429.4 (15) Å3Needle, brown
Z = 160.50 × 0.06 × 0.06 mm
Data collection top
Stoe IPDS-2
diffractometer
1157 independent reflections
Radiation source: fine-focus sealed tube843 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.131
ϕ + ω rotation scansθmax = 25.1°, θmin = 1.7°
Absorption correction: multi-scan
MULABS in PLATON (Spek, 2009)
h = 2929
Tmin = 0.571, Tmax = 0.997k = 5654
5295 measured reflectionsl = 44
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)] = 0.063H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.158 w = 1/[σ2(Fo2) + (0.0875P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
1157 reflectionsΔρmax = 0.35 e Å3
167 parametersΔρmin = 0.24 e Å3
5 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc* = kFc[1+0.001Fc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0055 (9)
Crystal data top
C10H7N5·H2OV = 4429.4 (15) Å3
Mr = 215.22Z = 16
Orthorhombic, Fdd2Mo Kα radiation
a = 25.072 (6) ŵ = 0.09 mm1
b = 46.996 (8) ÅT = 173 K
c = 3.7592 (7) Å0.50 × 0.06 × 0.06 mm
Data collection top
Stoe IPDS-2
diffractometer
1157 independent reflections
Absorption correction: multi-scan
MULABS in PLATON (Spek, 2009)
843 reflections with I > 2σ(I)
Tmin = 0.571, Tmax = 0.997Rint = 0.131
5295 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0635 restraints
wR(F2) = 0.158H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.35 e Å3
1157 reflectionsΔρmin = 0.24 e Å3
167 parameters
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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 > 2sigma(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)
N10.11618 (15)0.03926 (8)0.0622 (12)0.0477 (12)
N20.14876 (15)0.11036 (8)0.2869 (11)0.0417 (12)
N30.20210 (16)0.16259 (9)0.3394 (13)0.0520 (14)
N40.03201 (18)0.12653 (9)0.7236 (13)0.0573 (14)
N50.10761 (18)0.20157 (9)0.7778 (16)0.0613 (16)
C20.14790 (18)0.06231 (9)0.0865 (14)0.0417 (16)
C30.20023 (19)0.06265 (9)0.0335 (14)0.0450 (16)
C40.22130 (19)0.03834 (10)0.1845 (15)0.0493 (17)
C50.18876 (19)0.01427 (10)0.2065 (15)0.0480 (16)
C60.1371 (2)0.01566 (10)0.0850 (15)0.0510 (17)
C70.12346 (19)0.08706 (10)0.2545 (14)0.0453 (16)
C80.12507 (18)0.13369 (9)0.4535 (12)0.0403 (14)
C90.15286 (18)0.15863 (9)0.4690 (13)0.0420 (14)
C100.0728 (2)0.13142 (9)0.6025 (14)0.0453 (16)
C110.12805 (18)0.18276 (10)0.6363 (13)0.0447 (17)
O1A0.0061 (4)0.0326 (3)0.056 (4)0.076 (4)0.500
O1B0.0074 (5)0.0323 (3)0.283 (4)0.076 (4)0.500
H30.221300.079400.012000.0540*
H3A0.214 (2)0.1483 (9)0.213 (16)0.0780*
H3B0.217 (2)0.1797 (7)0.36 (2)0.0780*
H40.256900.038000.271000.0590*
H50.202200.002900.304700.0570*
H60.115200.000800.106000.0610*
H70.088000.085700.341500.0550*
H1A0.035 (2)0.0363 (17)0.16 (3)0.1140*
H1B0.007 (3)0.0158 (8)0.09 (3)0.1140*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.047 (2)0.041 (2)0.055 (2)0.0057 (17)0.003 (2)0.000 (2)
N20.048 (2)0.039 (2)0.038 (2)0.0051 (17)0.0019 (18)0.0025 (19)
N30.047 (2)0.050 (2)0.059 (3)0.0035 (19)0.006 (2)0.007 (2)
N40.053 (2)0.057 (2)0.062 (3)0.005 (2)0.017 (2)0.002 (2)
N50.065 (3)0.049 (2)0.070 (3)0.012 (2)0.005 (3)0.014 (3)
C20.048 (3)0.032 (2)0.045 (3)0.0021 (18)0.000 (2)0.001 (2)
C30.047 (3)0.038 (2)0.050 (3)0.005 (2)0.000 (2)0.001 (2)
C40.049 (3)0.046 (3)0.053 (3)0.008 (2)0.003 (3)0.007 (2)
C50.057 (3)0.039 (2)0.048 (3)0.008 (2)0.005 (2)0.006 (2)
C60.052 (3)0.039 (3)0.062 (3)0.000 (2)0.005 (3)0.005 (2)
C70.046 (2)0.046 (3)0.044 (3)0.007 (2)0.004 (2)0.001 (2)
C80.040 (2)0.039 (2)0.042 (3)0.0050 (18)0.001 (2)0.002 (2)
C90.043 (2)0.042 (2)0.041 (3)0.0035 (19)0.003 (2)0.004 (2)
C100.052 (3)0.038 (2)0.046 (3)0.003 (2)0.002 (3)0.002 (2)
C110.042 (3)0.045 (3)0.047 (3)0.002 (2)0.000 (2)0.001 (2)
O1A0.046 (5)0.084 (7)0.098 (9)0.004 (4)0.002 (6)0.018 (8)
O1B0.060 (6)0.098 (8)0.071 (7)0.008 (5)0.000 (6)0.006 (7)
Geometric parameters (Å, º) top
O1A—O1B0.85 (2)C2—C71.459 (7)
O1A—H1A0.84 (8)C2—C31.388 (7)
O1A—H1B0.87 (5)C3—C41.381 (7)
O1B—H1A0.85 (7)C4—C51.397 (7)
O1B—H1B1.12 (8)C5—C61.375 (7)
N1—C61.346 (6)C8—C101.429 (7)
N1—C21.347 (6)C8—C91.365 (6)
N2—C71.271 (6)C9—C111.438 (6)
N2—C81.395 (6)C3—H30.9500
N3—C91.340 (6)C4—H40.9500
N4—C101.143 (7)C5—H50.9500
N5—C111.152 (7)C6—H60.9500
N3—H3A0.88 (5)C7—H70.9500
N3—H3B0.89 (4)
O1B—O1A—H1A60 (7)N2—C8—C10120.5 (4)
O1B—O1A—H1B82 (7)N2—C8—C9118.5 (4)
H1A—O1A—H1B117 (8)C9—C8—C10121.0 (4)
O1A—O1B—H1A59 (7)C8—C9—C11118.4 (4)
O1A—O1B—H1B50 (5)N3—C9—C11116.6 (4)
H1A—O1B—H1B94 (8)N3—C9—C8125.0 (4)
C2—N1—C6117.4 (4)N4—C10—C8172.6 (5)
C7—N2—C8120.5 (4)N5—C11—C9178.0 (5)
C9—N3—H3A114 (3)C2—C3—H3120.00
H3A—N3—H3B127 (5)C4—C3—H3120.00
C9—N3—H3B119 (4)C3—C4—H4121.00
C3—C2—C7121.9 (4)C5—C4—H4121.00
N1—C2—C7115.0 (4)C6—C5—H5120.00
N1—C2—C3123.1 (4)C4—C5—H5120.00
C2—C3—C4119.1 (4)N1—C6—H6119.00
C3—C4—C5118.1 (4)C5—C6—H6119.00
C4—C5—C6119.5 (4)C2—C7—H7119.00
N1—C6—C5122.9 (4)N2—C7—H7119.00
N2—C7—C2121.3 (4)
C6—N1—C2—C30.3 (8)C3—C2—C7—N22.4 (8)
C6—N1—C2—C7178.8 (5)C2—C3—C4—C50.6 (8)
C2—N1—C6—C50.5 (8)C3—C4—C5—C61.2 (8)
C8—N2—C7—C2179.0 (4)C4—C5—C6—N11.2 (8)
C7—N2—C8—C9177.3 (5)N2—C8—C9—N30.9 (7)
C7—N2—C8—C102.4 (7)N2—C8—C9—C11179.1 (4)
N1—C2—C3—C40.2 (8)C10—C8—C9—N3179.4 (5)
C7—C2—C3—C4178.9 (5)C10—C8—C9—C110.6 (7)
N1—C2—C7—N2178.5 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1A—H1A···N10.84 (8)2.07 (5)2.778 (11)141 (10)
O1A—H1B···O1Ai0.87 (5)2.28 (4)3.08 (2)154 (8)
O1A—H1B···O1Bi0.87 (5)2.37 (5)3.19 (2)156 (6)
N3—H3A···N20.88 (5)2.44 (5)2.802 (6)106 (4)
N3—H3A···N4ii0.88 (5)2.25 (5)3.047 (6)151 (4)
N3—H3B···O1Aiii0.89 (4)2.04 (4)2.913 (14)169 (7)
N3—H3B···O1Biii0.89 (4)2.15 (4)3.027 (15)167 (6)
C3—H3···N4ii0.952.573.518 (6)173
Symmetry codes: (i) x, y, z; (ii) x+1/4, y+1/4, z3/4; (iii) x+1/4, y+1/4, z+1/4.
(L2-I) 5-cyano-2-(2-pyridyl)-1-(2-pyridylmethyl)-1H-imidazole-4-carboxamide top
Crystal data top
C16H12N6OF(000) = 632
Mr = 304.32Dx = 1.403 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 22793 reflections
a = 10.5730 (11) Åθ = 2.1–29.6°
b = 7.0457 (5) ŵ = 0.10 mm1
c = 21.261 (2) ÅT = 173 K
β = 114.503 (8)°Block, brown
V = 1441.2 (2) Å30.50 × 0.45 × 0.40 mm
Z = 4
Data collection top
Stoe IPDS-2
diffractometer
3413 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.030
Graphite monochromatorθmax = 29.3°, θmin = 2.1°
ϕ + ω rotation scansh = 1414
26827 measured reflectionsk = 99
3903 independent reflectionsl = 2929
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)] = 0.037H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.095 w = 1/[σ2(Fo2) + (0.0468P)2 + 0.381P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
3903 reflectionsΔρmax = 0.30 e Å3
215 parametersΔρmin = 0.21 e Å3
2 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc* = kFc[1+0.001Fc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.016 (3)
Crystal data top
C16H12N6OV = 1441.2 (2) Å3
Mr = 304.32Z = 4
Monoclinic, P21/cMo Kα radiation
a = 10.5730 (11) ŵ = 0.10 mm1
b = 7.0457 (5) ÅT = 173 K
c = 21.261 (2) Å0.50 × 0.45 × 0.40 mm
β = 114.503 (8)°
Data collection top
Stoe IPDS-2
diffractometer
3413 reflections with I > 2σ(I)
26827 measured reflectionsRint = 0.030
3903 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0372 restraints
wR(F2) = 0.095H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.30 e Å3
3903 reflectionsΔρmin = 0.21 e Å3
215 parameters
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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 > 2sigma(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
O10.14915 (8)0.42890 (13)0.07780 (4)0.0336 (2)
N10.75377 (9)0.12915 (13)0.06026 (4)0.0280 (2)
N20.40304 (8)0.30246 (12)0.01428 (4)0.0227 (2)
N30.56798 (8)0.28035 (11)0.12136 (4)0.0217 (2)
N40.13402 (9)0.44160 (13)0.03189 (4)0.0281 (3)
N50.44191 (11)0.42946 (18)0.24182 (5)0.0422 (3)
N60.78407 (10)0.56578 (13)0.15998 (4)0.0300 (2)
C20.62619 (9)0.19251 (13)0.02013 (5)0.0222 (2)
C30.57318 (11)0.19677 (15)0.05194 (5)0.0271 (3)
C40.65711 (12)0.13597 (17)0.08345 (6)0.0322 (3)
C50.78962 (12)0.07243 (17)0.04239 (6)0.0345 (3)
C60.83219 (11)0.07035 (17)0.02839 (6)0.0338 (3)
C70.53505 (9)0.25866 (13)0.05251 (5)0.0211 (2)
C80.34845 (9)0.35395 (13)0.05919 (5)0.0225 (2)
C90.44815 (9)0.34216 (13)0.12607 (5)0.0225 (2)
C100.20126 (10)0.41226 (14)0.03573 (5)0.0246 (2)
C110.44334 (10)0.38892 (15)0.18996 (5)0.0281 (3)
C120.70236 (9)0.26147 (14)0.18123 (5)0.0241 (2)
C130.76731 (9)0.45350 (14)0.20661 (5)0.0227 (3)
C140.80891 (12)0.50516 (19)0.27509 (5)0.0345 (3)
C150.86972 (13)0.6815 (2)0.29657 (6)0.0414 (3)
C160.88680 (12)0.79944 (17)0.24900 (6)0.0376 (3)
C170.84217 (13)0.73612 (17)0.18170 (6)0.0373 (3)
H30.481400.240500.078800.0320*
H40.624300.137800.132400.0390*
H4A0.1811 (15)0.437 (2)0.0576 (7)0.0420*
H4B0.0461 (14)0.479 (2)0.0486 (7)0.0420*
H50.850100.031100.062500.0410*
H60.922800.024300.056100.0410*
H12A0.765900.184100.168200.0290*
H12B0.688800.194800.219000.0290*
H140.796000.421100.306900.0410*
H150.899100.720400.343300.0500*
H160.928200.921100.262100.0450*
H170.853300.818200.148900.0450*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0236 (3)0.0519 (5)0.0288 (4)0.0107 (3)0.0143 (3)0.0104 (3)
N10.0211 (4)0.0345 (4)0.0286 (4)0.0039 (3)0.0105 (3)0.0014 (3)
N20.0181 (3)0.0260 (4)0.0240 (4)0.0015 (3)0.0086 (3)0.0015 (3)
N30.0174 (3)0.0255 (4)0.0217 (4)0.0011 (3)0.0075 (3)0.0009 (3)
N40.0196 (4)0.0388 (5)0.0256 (4)0.0066 (3)0.0092 (3)0.0043 (3)
N50.0341 (5)0.0622 (7)0.0317 (5)0.0047 (5)0.0151 (4)0.0080 (5)
N60.0328 (4)0.0309 (4)0.0225 (4)0.0016 (3)0.0077 (3)0.0017 (3)
C20.0204 (4)0.0221 (4)0.0252 (4)0.0003 (3)0.0106 (3)0.0006 (3)
C30.0257 (4)0.0299 (5)0.0260 (5)0.0018 (4)0.0111 (4)0.0013 (4)
C40.0368 (6)0.0358 (5)0.0286 (5)0.0002 (4)0.0183 (4)0.0017 (4)
C50.0326 (5)0.0400 (6)0.0391 (6)0.0014 (4)0.0232 (5)0.0051 (5)
C60.0233 (5)0.0423 (6)0.0372 (5)0.0056 (4)0.0140 (4)0.0032 (5)
C70.0184 (4)0.0223 (4)0.0219 (4)0.0000 (3)0.0077 (3)0.0005 (3)
C80.0188 (4)0.0250 (4)0.0240 (4)0.0020 (3)0.0091 (3)0.0021 (3)
C90.0186 (4)0.0252 (4)0.0244 (4)0.0017 (3)0.0096 (3)0.0001 (3)
C100.0190 (4)0.0275 (4)0.0272 (4)0.0028 (3)0.0095 (3)0.0039 (4)
C110.0215 (4)0.0349 (5)0.0274 (5)0.0027 (4)0.0098 (4)0.0016 (4)
C120.0195 (4)0.0289 (4)0.0213 (4)0.0029 (3)0.0059 (3)0.0023 (3)
C130.0157 (4)0.0314 (5)0.0194 (4)0.0032 (3)0.0057 (3)0.0002 (3)
C140.0346 (5)0.0477 (6)0.0227 (4)0.0044 (5)0.0134 (4)0.0046 (4)
C150.0380 (6)0.0527 (7)0.0299 (5)0.0044 (5)0.0104 (5)0.0161 (5)
C160.0273 (5)0.0337 (5)0.0443 (6)0.0024 (4)0.0074 (4)0.0100 (5)
C170.0389 (6)0.0326 (5)0.0362 (6)0.0039 (4)0.0114 (5)0.0020 (4)
Geometric parameters (Å, º) top
O1—C101.2354 (14)C8—C91.3772 (14)
N1—C21.3387 (14)C8—C101.4818 (15)
N1—C61.3358 (16)C9—C111.4190 (14)
N2—C71.3278 (13)C12—C131.5119 (14)
N2—C81.3541 (13)C13—C141.3837 (14)
N3—C71.3655 (13)C14—C151.3864 (19)
N3—C91.3821 (14)C15—C161.3775 (18)
N3—C121.4685 (13)C16—C171.3817 (17)
N4—C101.3294 (13)C3—H30.9500
N5—C111.1452 (15)C4—H40.9500
N6—C131.3364 (13)C5—H50.9500
N6—C171.3400 (15)C6—H60.9500
N4—H4B0.887 (16)C12—H12A0.9900
N4—H4A0.879 (16)C12—H12B0.9900
C2—C71.4731 (15)C14—H140.9500
C2—C31.3966 (14)C15—H150.9500
C3—C41.3831 (18)C16—H160.9500
C4—C51.3824 (18)C17—H170.9500
C5—C61.3804 (17)
C2—N1—C6116.97 (9)N3—C12—C13111.18 (8)
C7—N2—C8106.13 (8)C12—C13—C14120.67 (10)
C7—N3—C9106.21 (8)N6—C13—C12116.44 (8)
C7—N3—C12130.09 (9)N6—C13—C14122.88 (10)
C9—N3—C12123.52 (8)C13—C14—C15118.95 (11)
C13—N6—C17117.22 (9)C14—C15—C16118.87 (11)
H4A—N4—H4B122.1 (13)C15—C16—C17118.24 (11)
C10—N4—H4B118.8 (9)N6—C17—C16123.84 (11)
C10—N4—H4A118.7 (10)C2—C3—H3121.00
C3—C2—C7117.60 (9)C4—C3—H3121.00
N1—C2—C7119.29 (9)C3—C4—H4121.00
N1—C2—C3123.11 (10)C5—C4—H4121.00
C2—C3—C4118.60 (10)C4—C5—H5121.00
C3—C4—C5118.70 (11)C6—C5—H5121.00
C4—C5—C6118.60 (12)N1—C6—H6118.00
N1—C6—C5124.01 (11)C5—C6—H6118.00
N3—C7—C2127.66 (9)N3—C12—H12A109.00
N2—C7—N3111.48 (9)N3—C12—H12B109.00
N2—C7—C2120.85 (9)C13—C12—H12A109.00
N2—C8—C9110.14 (9)C13—C12—H12B109.00
N2—C8—C10122.16 (9)H12A—C12—H12B108.00
C9—C8—C10127.70 (9)C13—C14—H14121.00
C8—C9—C11131.18 (10)C15—C14—H14121.00
N3—C9—C8106.04 (8)C14—C15—H15121.00
N3—C9—C11122.71 (9)C16—C15—H15121.00
O1—C10—C8120.27 (9)C15—C16—H16121.00
O1—C10—N4124.70 (11)C17—C16—H16121.00
N4—C10—C8115.03 (9)N6—C17—H17118.00
N5—C11—C9178.45 (12)C16—C17—H17118.00
C6—N1—C2—C30.84 (15)N1—C2—C7—N2172.47 (9)
C6—N1—C2—C7179.84 (9)N1—C2—C7—N36.25 (15)
C2—N1—C6—C50.36 (17)C3—C2—C7—N26.59 (14)
C8—N2—C7—N30.00 (11)C3—C2—C7—N3174.69 (9)
C8—N2—C7—C2178.91 (8)C2—C3—C4—C50.39 (17)
C7—N2—C8—C90.12 (11)C3—C4—C5—C60.70 (18)
C7—N2—C8—C10179.68 (9)C4—C5—C6—N11.13 (19)
C9—N3—C7—N20.11 (11)N2—C8—C9—N30.18 (11)
C9—N3—C7—C2178.93 (9)N2—C8—C9—C11176.73 (10)
C12—N3—C7—N2175.16 (9)C10—C8—C9—N3179.60 (9)
C12—N3—C7—C26.02 (16)C10—C8—C9—C113.50 (18)
C7—N3—C9—C80.17 (10)N2—C8—C10—O1168.39 (10)
C7—N3—C9—C11177.06 (9)N2—C8—C10—N411.02 (14)
C12—N3—C9—C8175.63 (8)C9—C8—C10—O111.36 (16)
C12—N3—C9—C111.61 (14)C9—C8—C10—N4169.22 (10)
C7—N3—C12—C13100.19 (11)N3—C12—C13—N654.97 (12)
C9—N3—C12—C1374.10 (11)N3—C12—C13—C14126.32 (11)
C17—N6—C13—C12179.66 (11)N6—C13—C14—C150.53 (19)
C17—N6—C13—C140.98 (17)C12—C13—C14—C15179.16 (11)
C13—N6—C17—C161.0 (2)C13—C14—C15—C160.0 (2)
N1—C2—C3—C41.21 (16)C14—C15—C16—C170.0 (2)
C7—C2—C3—C4179.77 (10)C15—C16—C17—N60.5 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4—H4A···N20.879 (16)2.401 (15)2.7747 (14)105.9 (10)
N4—H4A···N6i0.879 (16)2.354 (15)3.1821 (13)157.1 (13)
N4—H4B···O1ii0.887 (16)2.001 (16)2.8853 (14)174.9 (13)
C4—H4···N5iii0.952.613.4898 (16)154
C15—H15···O1iv0.952.443.2641 (16)145
C15—H15···CgBi0.952.893.6632 (15)139
Symmetry codes: (i) x+1, y+1, z; (ii) x, y+1, z; (iii) x, y+1/2, z1/2; (iv) x+1, y+1/2, z+1/2.
(L2-II) 5-cyano-2-(2-pyridyl)-1-(2-pyridylmethyl)-1H-imidazole-4-carboxamide top
Crystal data top
C16H12N6OF(000) = 632
Mr = 304.32Dx = 1.374 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 17872 reflections
a = 7.7315 (4) Åθ = 2.1–29.6°
b = 15.8398 (9) ŵ = 0.09 mm1
c = 12.0572 (8) ÅT = 173 K
β = 94.950 (5)°Rod, brown
V = 1471.08 (15) Å30.40 × 0.23 × 0.21 mm
Z = 4
Data collection top
Stoe IPDS-2
diffractometer
3241 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.045
Graphite monochromatorθmax = 29.2°, θmin = 2.1°
ϕ + ω rotation scansh = 910
21034 measured reflectionsk = 2121
3974 independent reflectionsl = 1616
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)] = 0.039H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.097 w = 1/[σ2(Fo2) + (0.0509P)2 + 0.2338P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
3974 reflectionsΔρmax = 0.31 e Å3
217 parametersΔρmin = 0.17 e Å3
2 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc* = kFc[1+0.001Fc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.010 (2)
Crystal data top
C16H12N6OV = 1471.08 (15) Å3
Mr = 304.32Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.7315 (4) ŵ = 0.09 mm1
b = 15.8398 (9) ÅT = 173 K
c = 12.0572 (8) Å0.40 × 0.23 × 0.21 mm
β = 94.950 (5)°
Data collection top
Stoe IPDS-2
diffractometer
3241 reflections with I > 2σ(I)
21034 measured reflectionsRint = 0.045
3974 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0392 restraints
wR(F2) = 0.097H atoms treated by a mixture of independent and constrained refinement
S = 1.02Δρmax = 0.31 e Å3
3974 reflectionsΔρmin = 0.17 e Å3
217 parameters
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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 > 2sigma(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
O11.01156 (12)0.09860 (5)0.09066 (6)0.0318 (3)
N10.75225 (13)0.06697 (7)0.61970 (8)0.0326 (3)
N20.84501 (12)0.01621 (6)0.33797 (7)0.0249 (2)
N30.89248 (11)0.13893 (5)0.42579 (7)0.0217 (2)
N40.93337 (15)0.03545 (6)0.13136 (8)0.0344 (3)
N51.10636 (14)0.28099 (6)0.26524 (8)0.0331 (3)
N60.65570 (13)0.28481 (6)0.41589 (8)0.0308 (3)
C20.75565 (13)0.02001 (7)0.52803 (9)0.0258 (3)
C30.69047 (15)0.06181 (8)0.51919 (10)0.0318 (3)
C40.61387 (16)0.09495 (9)0.60960 (12)0.0397 (4)
C50.60638 (17)0.04636 (9)0.70374 (11)0.0425 (4)
C60.67853 (18)0.03328 (9)0.70580 (11)0.0395 (4)
C70.83060 (13)0.05831 (7)0.43182 (8)0.0230 (3)
C80.91836 (13)0.07055 (7)0.26873 (8)0.0230 (3)
C90.94908 (12)0.14691 (6)0.32093 (8)0.0220 (3)
C100.95879 (14)0.04588 (7)0.15496 (8)0.0252 (3)
C111.03424 (14)0.22090 (7)0.28779 (8)0.0245 (3)
C120.89753 (14)0.20790 (7)0.50805 (8)0.0256 (3)
C130.72230 (14)0.24958 (7)0.51130 (9)0.0257 (3)
C140.63775 (16)0.25007 (7)0.60845 (10)0.0316 (3)
C150.47485 (17)0.28696 (8)0.60593 (11)0.0393 (4)
C160.40436 (17)0.32329 (9)0.50861 (13)0.0424 (4)
C170.49924 (16)0.32127 (8)0.41640 (11)0.0385 (4)
H30.698200.094000.453300.0380*
H40.567200.150500.606600.0480*
H4A0.957 (2)0.0554 (10)0.0645 (12)0.045 (4)*
H4B0.906 (2)0.0706 (9)0.1830 (12)0.042 (4)*
H50.552500.067300.766100.0510*
H60.675800.065900.771700.0470*
H12A0.983700.250600.489100.0310*
H12B0.935200.185100.582700.0310*
H140.690300.225700.675000.0380*
H150.412700.287200.670500.0470*
H160.293200.349200.504800.0510*
H170.450800.347200.349700.0460*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0453 (5)0.0273 (4)0.0239 (4)0.0035 (3)0.0102 (3)0.0025 (3)
N10.0364 (5)0.0359 (5)0.0268 (5)0.0072 (4)0.0110 (4)0.0035 (4)
N20.0261 (4)0.0248 (4)0.0241 (4)0.0014 (3)0.0048 (3)0.0010 (3)
N30.0216 (4)0.0251 (4)0.0188 (4)0.0012 (3)0.0038 (3)0.0022 (3)
N40.0549 (6)0.0253 (5)0.0245 (5)0.0058 (4)0.0119 (4)0.0052 (4)
N50.0386 (5)0.0316 (5)0.0291 (5)0.0053 (4)0.0035 (4)0.0001 (4)
N60.0306 (5)0.0328 (5)0.0294 (5)0.0017 (4)0.0044 (4)0.0009 (4)
C20.0222 (4)0.0296 (5)0.0259 (5)0.0052 (4)0.0045 (4)0.0051 (4)
C30.0273 (5)0.0334 (6)0.0345 (6)0.0008 (4)0.0016 (4)0.0065 (5)
C40.0313 (6)0.0401 (7)0.0479 (7)0.0008 (5)0.0038 (5)0.0176 (6)
C50.0351 (6)0.0529 (8)0.0414 (7)0.0101 (6)0.0150 (5)0.0228 (6)
C60.0433 (7)0.0471 (7)0.0303 (6)0.0133 (6)0.0160 (5)0.0095 (5)
C70.0217 (4)0.0241 (5)0.0234 (5)0.0027 (4)0.0031 (4)0.0000 (4)
C80.0243 (5)0.0243 (5)0.0205 (4)0.0016 (4)0.0032 (4)0.0016 (4)
C90.0225 (4)0.0253 (5)0.0186 (4)0.0018 (4)0.0033 (3)0.0013 (3)
C100.0289 (5)0.0264 (5)0.0204 (4)0.0000 (4)0.0035 (4)0.0035 (4)
C110.0268 (5)0.0271 (5)0.0196 (4)0.0015 (4)0.0025 (4)0.0017 (4)
C120.0265 (5)0.0296 (5)0.0209 (4)0.0016 (4)0.0033 (4)0.0071 (4)
C130.0282 (5)0.0245 (5)0.0250 (5)0.0017 (4)0.0057 (4)0.0061 (4)
C140.0373 (6)0.0305 (6)0.0282 (5)0.0002 (4)0.0103 (5)0.0066 (4)
C150.0411 (7)0.0353 (6)0.0446 (7)0.0021 (5)0.0216 (6)0.0081 (5)
C160.0330 (6)0.0379 (7)0.0576 (8)0.0082 (5)0.0117 (6)0.0039 (6)
C170.0345 (6)0.0373 (7)0.0437 (7)0.0056 (5)0.0031 (5)0.0036 (5)
Geometric parameters (Å, º) top
O1—C101.2327 (13)C8—C91.3747 (14)
N1—C21.3344 (15)C8—C101.4853 (14)
N1—C61.3377 (17)C9—C111.4185 (14)
N2—C71.3264 (13)C12—C131.5106 (15)
N2—C81.3569 (14)C13—C141.3898 (16)
N3—C71.3678 (14)C14—C151.3864 (18)
N3—C91.3789 (13)C15—C161.377 (2)
N3—C121.4738 (13)C16—C171.384 (2)
N4—C101.3302 (15)C3—H30.9500
N5—C111.1476 (15)C4—H40.9500
N6—C131.3408 (15)C5—H50.9500
N6—C171.3410 (16)C6—H60.9500
N4—H4B0.875 (14)C12—H12A0.9900
N4—H4A0.899 (15)C12—H12B0.9900
C2—C71.4716 (15)C14—H140.9500
C2—C31.3913 (17)C15—H150.9500
C3—C41.3878 (18)C16—H160.9500
C4—C51.377 (2)C17—H170.9500
C5—C61.379 (2)
C2—N1—C6117.43 (11)N3—C12—C13111.70 (9)
C7—N2—C8106.04 (9)C12—C13—C14120.82 (10)
C7—N3—C9105.93 (8)N6—C13—C12116.01 (9)
C7—N3—C12130.19 (8)N6—C13—C14123.17 (10)
C9—N3—C12123.85 (8)C13—C14—C15118.45 (11)
C13—N6—C17117.07 (10)C14—C15—C16119.14 (12)
H4A—N4—H4B119.7 (14)C15—C16—C17118.47 (12)
C10—N4—H4B120.3 (9)N6—C17—C16123.67 (12)
C10—N4—H4A119.6 (10)C2—C3—H3121.00
C3—C2—C7119.23 (10)C4—C3—H3121.00
N1—C2—C7117.41 (10)C3—C4—H4120.00
N1—C2—C3123.35 (10)C5—C4—H4120.00
C2—C3—C4117.94 (11)C4—C5—H5121.00
C3—C4—C5119.16 (13)C6—C5—H5121.00
C4—C5—C6118.73 (12)N1—C6—H6118.00
N1—C6—C5123.36 (12)C5—C6—H6118.00
N3—C7—C2126.17 (9)N3—C12—H12A109.00
N2—C7—N3111.62 (9)N3—C12—H12B109.00
N2—C7—C2122.21 (10)C13—C12—H12A109.00
N2—C8—C9109.96 (9)C13—C12—H12B109.00
N2—C8—C10122.26 (10)H12A—C12—H12B108.00
C9—C8—C10127.77 (10)C13—C14—H14121.00
C8—C9—C11131.61 (9)C15—C14—H14121.00
N3—C9—C8106.45 (8)C14—C15—H15120.00
N3—C9—C11121.72 (9)C16—C15—H15120.00
O1—C10—C8120.67 (10)C15—C16—H16121.00
O1—C10—N4124.91 (10)C17—C16—H16121.00
N4—C10—C8114.42 (9)N6—C17—H17118.00
N5—C11—C9177.24 (11)C16—C17—H17118.00
C6—N1—C2—C31.49 (17)N1—C2—C7—N2177.90 (10)
C6—N1—C2—C7177.67 (10)N1—C2—C7—N32.31 (16)
C2—N1—C6—C50.32 (19)C3—C2—C7—N22.90 (16)
C8—N2—C7—N30.07 (12)C3—C2—C7—N3176.89 (10)
C8—N2—C7—C2179.89 (9)C2—C3—C4—C50.40 (18)
C7—N2—C8—C90.04 (10)C3—C4—C5—C61.25 (19)
C7—N2—C8—C10178.88 (9)C4—C5—C6—N11.7 (2)
C9—N3—C7—N20.08 (11)N2—C8—C9—N30.00 (11)
C9—N3—C7—C2179.88 (9)N2—C8—C9—C11174.51 (10)
C12—N3—C7—N2177.99 (10)C10—C8—C9—N3178.85 (10)
C12—N3—C7—C21.81 (17)C10—C8—C9—C114.34 (18)
C7—N3—C9—C80.04 (12)N2—C8—C10—O1173.76 (10)
C7—N3—C9—C11175.14 (9)N2—C8—C10—N46.38 (15)
C12—N3—C9—C8178.18 (9)C9—C8—C10—O17.52 (17)
C12—N3—C9—C116.64 (15)C9—C8—C10—N4172.34 (11)
C7—N3—C12—C1377.76 (13)N3—C12—C13—N660.05 (12)
C9—N3—C12—C13100.01 (11)N3—C12—C13—C14119.66 (11)
C17—N6—C13—C12179.19 (10)N6—C13—C14—C151.61 (17)
C17—N6—C13—C140.51 (17)C12—C13—C14—C15178.08 (11)
C13—N6—C17—C160.79 (18)C13—C14—C15—C161.42 (18)
N1—C2—C3—C41.86 (17)C14—C15—C16—C170.24 (19)
C7—C2—C3—C4177.29 (10)C15—C16—C17—N60.9 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4—H4A···O1i0.899 (15)2.026 (15)2.9231 (12)175.1 (14)
N4—H4B···N20.875 (14)2.399 (14)2.7633 (13)105.4 (11)
N4—H4B···N5ii0.875 (14)2.436 (14)3.1888 (14)144.5 (12)
C12—H12B···N5iii0.992.533.3749 (14)144
C3—H3···CgBi0.952.723.5854 (15)151
Symmetry codes: (i) x+2, y, z; (ii) x+2, y1/2, z+1/2; (iii) x, y+1/2, z+1/2.

Experimental details

(L1.H2O)(L2-I)(L2-II)
Crystal data
Chemical formulaC10H7N5·H2OC16H12N6OC16H12N6O
Mr215.22304.32304.32
Crystal system, space groupOrthorhombic, Fdd2Monoclinic, P21/cMonoclinic, P21/c
Temperature (K)173173173
a, b, c (Å)25.072 (6), 46.996 (8), 3.7592 (7)10.5730 (11), 7.0457 (5), 21.261 (2)7.7315 (4), 15.8398 (9), 12.0572 (8)
α, β, γ (°)90, 90, 9090, 114.503 (8), 9090, 94.950 (5), 90
V3)4429.4 (15)1441.2 (2)1471.08 (15)
Z1644
Radiation typeMo KαMo KαMo Kα
µ (mm1)0.090.100.09
Crystal size (mm)0.50 × 0.06 × 0.060.50 × 0.45 × 0.400.40 × 0.23 × 0.21
Data collection
DiffractometerStoe IPDS2
diffractometer
Stoe IPDS2
diffractometer
Stoe IPDS2
diffractometer
Absorption correctionMulti-scan
MULABS in PLATON (Spek, 2009)
Tmin, Tmax0.571, 0.997
No. of measured, independent and
observed [I > 2σ(I)] reflections
5295, 1157, 843 26827, 3903, 3413 21034, 3974, 3241
Rint0.1310.0300.045
(sin θ/λ)max1)0.5970.6890.687
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.063, 0.158, 1.03 0.037, 0.095, 1.04 0.039, 0.097, 1.02
No. of reflections115739033974
No. of parameters167215217
No. of restraints522
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.35, 0.240.30, 0.210.31, 0.17

Computer programs: X-AREA (Version 1.23; Stoe & Cie, 2009), X-RED32 (Version 1.05; Stoe & Cie, 2009), SHELXS97 (Sheldrick, 2008), PLATON (Spek, 2009) and Mercury (Macrae et al., 2006), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) for (L1.H2O) top
D—H···AD—HH···AD···AD—H···A
O1A—H1A···N10.84 (8)2.07 (5)2.778 (11)141 (10)
O1A—H1B···O1Ai0.87 (5)2.28 (4)3.08 (2)154 (8)
O1A—H1B···O1Bi0.87 (5)2.37 (5)3.19 (2)156 (6)
N3—H3A···N20.88 (5)2.44 (5)2.802 (6)106 (4)
N3—H3A···N4ii0.88 (5)2.25 (5)3.047 (6)151 (4)
N3—H3B···O1Aiii0.89 (4)2.04 (4)2.913 (14)169 (7)
N3—H3B···O1Biii0.89 (4)2.15 (4)3.027 (15)167 (6)
C3—H3···N4ii0.952.573.518 (6)173
Symmetry codes: (i) x, y, z; (ii) x+1/4, y+1/4, z3/4; (iii) x+1/4, y+1/4, z+1/4.
Hydrogen-bond geometry (Å, º) for (L2-I) top
D—H···AD—HH···AD···AD—H···A
N4—H4A···N20.879 (16)2.401 (15)2.7747 (14)105.9 (10)
N4—H4A···N6i0.879 (16)2.354 (15)3.1821 (13)157.1 (13)
N4—H4B···O1ii0.887 (16)2.001 (16)2.8853 (14)174.9 (13)
C4—H4···N5iii0.952.613.4898 (16)154
C15—H15···O1iv0.952.443.2641 (16)145
C15—H15···CgBi0.952.893.6632 (15)139
Symmetry codes: (i) x+1, y+1, z; (ii) x, y+1, z; (iii) x, y+1/2, z1/2; (iv) x+1, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) for (L2-II) top
D—H···AD—HH···AD···AD—H···A
N4—H4A···O1i0.899 (15)2.026 (15)2.9231 (12)175.1 (14)
N4—H4B···N20.875 (14)2.399 (14)2.7633 (13)105.4 (11)
N4—H4B···N5ii0.875 (14)2.436 (14)3.1888 (14)144.5 (12)
C12—H12B···N5iii0.992.533.3749 (14)144
C3—H3···CgBi0.952.723.5854 (15)151
Symmetry codes: (i) x+2, y, z; (ii) x+2, y1/2, z+1/2; (iii) x, y+1/2, z+1/2.
 

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