Green chemistry synthesis: 2-amino-3-[(E)-(2-pyrid­yl)methyl­idene­amino]­but-2-enedinitrile monohydrate and 5-cyano-2-(2-pyrid­yl)-1-(2-pyridyl­meth­yl)-1H-imidazole-4-carboxamide

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.

S1. Comment

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 C7═N2 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 π–π 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 π–π 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

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).

S2. Experimental

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.

S3. Refinement

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 U_iso(H) = 1.5U_eq(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, U_iso(H) = 1.5U_eq(N), while for L2-II these U_iso 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 U_iso(H) = 1.2U_eq(C).

Computing details

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

	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.
	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.
	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.
	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.
	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.
	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

Crystal data

C10H7N5·H2O	F(000) = 1792
Mr = 215.22	Dx = 1.291 Mg m^−3
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 3163 reflections
a = 25.072 (6) Å	θ = 1.7–25.5°
b = 46.996 (8) Å	µ = 0.09 mm^−1
c = 3.7592 (7) Å	T = 173 K
V = 4429.4 (15) Å^3	Needle, brown
Z = 16	0.50 × 0.06 × 0.06 mm

Data collection

Stoe IPDS-2 diffractometer	1157 independent reflections
Radiation source: fine-focus sealed tube	843 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.131
ϕ + ω rotation scans	θmax = 25.1°, θmin = 1.7°
Absorption correction: multi-scan MULABS in PLATON (Spek, 2009)	h = −29→29
Tmin = 0.571, Tmax = 0.997	k = −56→54
5295 measured reflections	l = −4→4

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.063	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.158	w = 1/[σ^2(Fo^2) + (0.0875P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
1157 reflections	Δρmax = 0.35 e Å^−3
167 parameters	Δρmin = −0.24 e Å^−3
5 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc* = kFc[1+0.001Fc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0055 (9)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.11618 (15)	0.03926 (8)	0.0622 (12)	0.0477 (12)
N2	0.14876 (15)	0.11036 (8)	0.2869 (11)	0.0417 (12)
N3	0.20210 (16)	0.16259 (9)	0.3394 (13)	0.0520 (14)
N4	0.03201 (18)	0.12653 (9)	0.7236 (13)	0.0573 (14)
N5	0.10761 (18)	0.20157 (9)	0.7778 (16)	0.0613 (16)
C2	0.14790 (18)	0.06231 (9)	0.0865 (14)	0.0417 (16)
C3	0.20023 (19)	0.06265 (9)	−0.0335 (14)	0.0450 (16)
C4	0.22130 (19)	0.03834 (10)	−0.1845 (15)	0.0493 (17)
C5	0.18876 (19)	0.01427 (10)	−0.2065 (15)	0.0480 (16)
C6	0.1371 (2)	0.01566 (10)	−0.0850 (15)	0.0510 (17)
C7	0.12346 (19)	0.08706 (10)	0.2545 (14)	0.0453 (16)
C8	0.12507 (18)	0.13369 (9)	0.4535 (12)	0.0403 (14)
C9	0.15286 (18)	0.15863 (9)	0.4690 (13)	0.0420 (14)
C10	0.0728 (2)	0.13142 (9)	0.6025 (14)	0.0453 (16)
C11	0.12805 (18)	0.18276 (10)	0.6363 (13)	0.0447 (17)
O1A	0.0061 (4)	0.0326 (3)	0.056 (4)	0.076 (4)	0.500
O1B	0.0074 (5)	0.0323 (3)	0.283 (4)	0.076 (4)	0.500
H3	0.22130	0.07940	−0.01200	0.0540*
H3A	0.214 (2)	0.1483 (9)	0.213 (16)	0.0780*
H3B	0.217 (2)	0.1797 (7)	0.36 (2)	0.0780*
H4	0.25690	0.03800	−0.27100	0.0590*
H5	0.20220	−0.00290	−0.30470	0.0570*
H6	0.11520	−0.00080	−0.10600	0.0610*
H7	0.08800	0.08570	0.34150	0.0550*
H1A	0.035 (2)	0.0363 (17)	0.16 (3)	0.1140*
H1B	−0.007 (3)	0.0158 (8)	0.09 (3)	0.1140*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.047 (2)	0.041 (2)	0.055 (2)	0.0057 (17)	0.003 (2)	0.000 (2)
N2	0.048 (2)	0.039 (2)	0.038 (2)	0.0051 (17)	0.0019 (18)	−0.0025 (19)
N3	0.047 (2)	0.050 (2)	0.059 (3)	0.0035 (19)	0.006 (2)	−0.007 (2)
N4	0.053 (2)	0.057 (2)	0.062 (3)	0.005 (2)	0.017 (2)	−0.002 (2)
N5	0.065 (3)	0.049 (2)	0.070 (3)	0.012 (2)	−0.005 (3)	−0.014 (3)
C2	0.048 (3)	0.032 (2)	0.045 (3)	0.0021 (18)	0.000 (2)	0.001 (2)
C3	0.047 (3)	0.038 (2)	0.050 (3)	0.005 (2)	0.000 (2)	−0.001 (2)
C4	0.049 (3)	0.046 (3)	0.053 (3)	0.008 (2)	−0.003 (3)	−0.007 (2)
C5	0.057 (3)	0.039 (2)	0.048 (3)	0.008 (2)	−0.005 (2)	−0.006 (2)
C6	0.052 (3)	0.039 (3)	0.062 (3)	0.000 (2)	−0.005 (3)	−0.005 (2)
C7	0.046 (2)	0.046 (3)	0.044 (3)	0.007 (2)	0.004 (2)	0.001 (2)
C8	0.040 (2)	0.039 (2)	0.042 (3)	0.0050 (18)	0.001 (2)	−0.002 (2)
C9	0.043 (2)	0.042 (2)	0.041 (3)	0.0035 (19)	0.003 (2)	−0.004 (2)
C10	0.052 (3)	0.038 (2)	0.046 (3)	0.003 (2)	0.002 (3)	−0.002 (2)
C11	0.042 (3)	0.045 (3)	0.047 (3)	0.002 (2)	0.000 (2)	−0.001 (2)
O1A	0.046 (5)	0.084 (7)	0.098 (9)	0.004 (4)	0.002 (6)	0.018 (8)
O1B	0.060 (6)	0.098 (8)	0.071 (7)	0.008 (5)	0.000 (6)	−0.006 (7)

Geometric parameters (Å, º)

O1A—O1B	0.85 (2)	C2—C7	1.459 (7)
O1A—H1A	0.84 (8)	C2—C3	1.388 (7)
O1A—H1B	0.87 (5)	C3—C4	1.381 (7)
O1B—H1A	0.85 (7)	C4—C5	1.397 (7)
O1B—H1B	1.12 (8)	C5—C6	1.375 (7)
N1—C6	1.346 (6)	C8—C10	1.429 (7)
N1—C2	1.347 (6)	C8—C9	1.365 (6)
N2—C7	1.271 (6)	C9—C11	1.438 (6)
N2—C8	1.395 (6)	C3—H3	0.9500
N3—C9	1.340 (6)	C4—H4	0.9500
N4—C10	1.143 (7)	C5—H5	0.9500
N5—C11	1.152 (7)	C6—H6	0.9500
N3—H3A	0.88 (5)	C7—H7	0.9500
N3—H3B	0.89 (4)
O1B—O1A—H1A	60 (7)	N2—C8—C10	120.5 (4)
O1B—O1A—H1B	82 (7)	N2—C8—C9	118.5 (4)
H1A—O1A—H1B	117 (8)	C9—C8—C10	121.0 (4)
O1A—O1B—H1A	59 (7)	C8—C9—C11	118.4 (4)
O1A—O1B—H1B	50 (5)	N3—C9—C11	116.6 (4)
H1A—O1B—H1B	94 (8)	N3—C9—C8	125.0 (4)
C2—N1—C6	117.4 (4)	N4—C10—C8	172.6 (5)
C7—N2—C8	120.5 (4)	N5—C11—C9	178.0 (5)
C9—N3—H3A	114 (3)	C2—C3—H3	120.00
H3A—N3—H3B	127 (5)	C4—C3—H3	120.00
C9—N3—H3B	119 (4)	C3—C4—H4	121.00
C3—C2—C7	121.9 (4)	C5—C4—H4	121.00
N1—C2—C7	115.0 (4)	C6—C5—H5	120.00
N1—C2—C3	123.1 (4)	C4—C5—H5	120.00
C2—C3—C4	119.1 (4)	N1—C6—H6	119.00
C3—C4—C5	118.1 (4)	C5—C6—H6	119.00
C4—C5—C6	119.5 (4)	C2—C7—H7	119.00
N1—C6—C5	122.9 (4)	N2—C7—H7	119.00
N2—C7—C2	121.3 (4)
C6—N1—C2—C3	0.3 (8)	C3—C2—C7—N2	2.4 (8)
C6—N1—C2—C7	−178.8 (5)	C2—C3—C4—C5	−0.6 (8)
C2—N1—C6—C5	0.5 (8)	C3—C4—C5—C6	1.2 (8)
C8—N2—C7—C2	−179.0 (4)	C4—C5—C6—N1	−1.2 (8)
C7—N2—C8—C9	−177.3 (5)	N2—C8—C9—N3	−0.9 (7)
C7—N2—C8—C10	2.4 (7)	N2—C8—C9—C11	179.1 (4)
N1—C2—C3—C4	−0.2 (8)	C10—C8—C9—N3	179.4 (5)
C7—C2—C3—C4	178.9 (5)	C10—C8—C9—C11	−0.6 (7)
N1—C2—C7—N2	−178.5 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1A—H1A···N1	0.84 (8)	2.07 (5)	2.778 (11)	141 (10)
O1A—H1B···O1A^i	0.87 (5)	2.28 (4)	3.08 (2)	154 (8)
O1A—H1B···O1B^i	0.87 (5)	2.37 (5)	3.19 (2)	156 (6)
N3—H3A···N2	0.88 (5)	2.44 (5)	2.802 (6)	106 (4)
N3—H3A···N4^ii	0.88 (5)	2.25 (5)	3.047 (6)	151 (4)
N3—H3B···O1A^iii	0.89 (4)	2.04 (4)	2.913 (14)	169 (7)
N3—H3B···O1B^iii	0.89 (4)	2.15 (4)	3.027 (15)	167 (6)
C3—H3···N4^ii	0.95	2.57	3.518 (6)	173

Symmetry codes: (i) −x, −y, z; (ii) x+1/4, −y+1/4, z−3/4; (iii) x+1/4, −y+1/4, z+1/4.

(L2-I) 5-cyano-2-(2-pyridyl)-1-(2-pyridylmethyl)-1H-imidazole-4-carboxamide

Crystal data

C16H12N6O	F(000) = 632
Mr = 304.32	Dx = 1.403 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 22793 reflections
a = 10.5730 (11) Å	θ = 2.1–29.6°
b = 7.0457 (5) Å	µ = 0.10 mm^−1
c = 21.261 (2) Å	T = 173 K
β = 114.503 (8)°	Block, brown
V = 1441.2 (2) Å^3	0.50 × 0.45 × 0.40 mm
Z = 4

Data collection

Stoe IPDS-2 diffractometer	3413 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.030
Graphite monochromator	θmax = 29.3°, θmin = 2.1°
ϕ + ω rotation scans	h = −14→14
26827 measured reflections	k = −9→9
3903 independent reflections	l = −29→29

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.095	w = 1/[σ^2(Fo^2) + (0.0468P)^2 + 0.381P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
3903 reflections	Δρmax = 0.30 e Å^−3
215 parameters	Δρmin = −0.21 e Å^−3
2 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc* = kFc[1+0.001Fc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.016 (3)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.14915 (8)	0.42890 (13)	0.07780 (4)	0.0336 (2)
N1	0.75377 (9)	0.12915 (13)	0.06026 (4)	0.0280 (2)
N2	0.40304 (8)	0.30246 (12)	0.01428 (4)	0.0227 (2)
N3	0.56798 (8)	0.28035 (11)	0.12136 (4)	0.0217 (2)
N4	0.13402 (9)	0.44160 (13)	−0.03189 (4)	0.0281 (3)
N5	0.44191 (11)	0.42946 (18)	0.24182 (5)	0.0422 (3)
N6	0.78407 (10)	0.56578 (13)	0.15998 (4)	0.0300 (2)
C2	0.62619 (9)	0.19251 (13)	0.02013 (5)	0.0222 (2)
C3	0.57318 (11)	0.19677 (15)	−0.05194 (5)	0.0271 (3)
C4	0.65711 (12)	0.13597 (17)	−0.08345 (6)	0.0322 (3)
C5	0.78962 (12)	0.07243 (17)	−0.04239 (6)	0.0345 (3)
C6	0.83219 (11)	0.07035 (17)	0.02839 (6)	0.0338 (3)
C7	0.53505 (9)	0.25866 (13)	0.05251 (5)	0.0211 (2)
C8	0.34845 (9)	0.35395 (13)	0.05919 (5)	0.0225 (2)
C9	0.44815 (9)	0.34216 (13)	0.12607 (5)	0.0225 (2)
C10	0.20126 (10)	0.41226 (14)	0.03573 (5)	0.0246 (2)
C11	0.44334 (10)	0.38892 (15)	0.18996 (5)	0.0281 (3)
C12	0.70236 (9)	0.26147 (14)	0.18123 (5)	0.0241 (2)
C13	0.76731 (9)	0.45350 (14)	0.20661 (5)	0.0227 (3)
C14	0.80891 (12)	0.50516 (19)	0.27509 (5)	0.0345 (3)
C15	0.86972 (13)	0.6815 (2)	0.29657 (6)	0.0414 (3)
C16	0.88680 (12)	0.79944 (17)	0.24900 (6)	0.0376 (3)
C17	0.84217 (13)	0.73612 (17)	0.18170 (6)	0.0373 (3)
H3	0.48140	0.24050	−0.07880	0.0320*
H4	0.62430	0.13780	−0.13240	0.0390*
H4A	0.1811 (15)	0.437 (2)	−0.0576 (7)	0.0420*
H4B	0.0461 (14)	0.479 (2)	−0.0486 (7)	0.0420*
H5	0.85010	0.03110	−0.06250	0.0410*
H6	0.92280	0.02430	0.05610	0.0410*
H12A	0.76590	0.18410	0.16820	0.0290*
H12B	0.68880	0.19480	0.21900	0.0290*
H14	0.79600	0.42110	0.30690	0.0410*
H15	0.89910	0.72040	0.34330	0.0500*
H16	0.92820	0.92110	0.26210	0.0450*
H17	0.85330	0.81820	0.14890	0.0450*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0236 (3)	0.0519 (5)	0.0288 (4)	0.0107 (3)	0.0143 (3)	0.0104 (3)
N1	0.0211 (4)	0.0345 (4)	0.0286 (4)	0.0039 (3)	0.0105 (3)	−0.0014 (3)
N2	0.0181 (3)	0.0260 (4)	0.0240 (4)	0.0015 (3)	0.0086 (3)	0.0015 (3)
N3	0.0174 (3)	0.0255 (4)	0.0217 (4)	0.0011 (3)	0.0075 (3)	−0.0009 (3)
N4	0.0196 (4)	0.0388 (5)	0.0256 (4)	0.0066 (3)	0.0092 (3)	0.0043 (3)
N5	0.0341 (5)	0.0622 (7)	0.0317 (5)	0.0047 (5)	0.0151 (4)	−0.0080 (5)
N6	0.0328 (4)	0.0309 (4)	0.0225 (4)	−0.0016 (3)	0.0077 (3)	0.0017 (3)
C2	0.0204 (4)	0.0221 (4)	0.0252 (4)	−0.0003 (3)	0.0106 (3)	−0.0006 (3)
C3	0.0257 (4)	0.0299 (5)	0.0260 (5)	0.0018 (4)	0.0111 (4)	0.0013 (4)
C4	0.0368 (6)	0.0358 (5)	0.0286 (5)	0.0002 (4)	0.0183 (4)	−0.0017 (4)
C5	0.0326 (5)	0.0400 (6)	0.0391 (6)	0.0014 (4)	0.0232 (5)	−0.0051 (5)
C6	0.0233 (5)	0.0423 (6)	0.0372 (5)	0.0056 (4)	0.0140 (4)	−0.0032 (5)
C7	0.0184 (4)	0.0223 (4)	0.0219 (4)	0.0000 (3)	0.0077 (3)	0.0005 (3)
C8	0.0188 (4)	0.0250 (4)	0.0240 (4)	0.0020 (3)	0.0091 (3)	0.0021 (3)
C9	0.0186 (4)	0.0252 (4)	0.0244 (4)	0.0017 (3)	0.0096 (3)	−0.0001 (3)
C10	0.0190 (4)	0.0275 (4)	0.0272 (4)	0.0028 (3)	0.0095 (3)	0.0039 (4)
C11	0.0215 (4)	0.0349 (5)	0.0274 (5)	0.0027 (4)	0.0098 (4)	−0.0016 (4)
C12	0.0195 (4)	0.0289 (4)	0.0213 (4)	0.0029 (3)	0.0059 (3)	0.0023 (3)
C13	0.0157 (4)	0.0314 (5)	0.0194 (4)	0.0032 (3)	0.0057 (3)	−0.0002 (3)
C14	0.0346 (5)	0.0477 (6)	0.0227 (4)	−0.0044 (5)	0.0134 (4)	−0.0046 (4)
C15	0.0380 (6)	0.0527 (7)	0.0299 (5)	−0.0044 (5)	0.0104 (5)	−0.0161 (5)
C16	0.0273 (5)	0.0337 (5)	0.0443 (6)	−0.0024 (4)	0.0074 (4)	−0.0100 (5)
C17	0.0389 (6)	0.0326 (5)	0.0362 (6)	−0.0039 (4)	0.0114 (5)	0.0020 (4)

Geometric parameters (Å, º)

O1—C10	1.2354 (14)	C8—C9	1.3772 (14)
N1—C2	1.3387 (14)	C8—C10	1.4818 (15)
N1—C6	1.3358 (16)	C9—C11	1.4190 (14)
N2—C7	1.3278 (13)	C12—C13	1.5119 (14)
N2—C8	1.3541 (13)	C13—C14	1.3837 (14)
N3—C7	1.3655 (13)	C14—C15	1.3864 (19)
N3—C9	1.3821 (14)	C15—C16	1.3775 (18)
N3—C12	1.4685 (13)	C16—C17	1.3817 (17)
N4—C10	1.3294 (13)	C3—H3	0.9500
N5—C11	1.1452 (15)	C4—H4	0.9500
N6—C13	1.3364 (13)	C5—H5	0.9500
N6—C17	1.3400 (15)	C6—H6	0.9500
N4—H4B	0.887 (16)	C12—H12A	0.9900
N4—H4A	0.879 (16)	C12—H12B	0.9900
C2—C7	1.4731 (15)	C14—H14	0.9500
C2—C3	1.3966 (14)	C15—H15	0.9500
C3—C4	1.3831 (18)	C16—H16	0.9500
C4—C5	1.3824 (18)	C17—H17	0.9500
C5—C6	1.3804 (17)
C2—N1—C6	116.97 (9)	N3—C12—C13	111.18 (8)
C7—N2—C8	106.13 (8)	C12—C13—C14	120.67 (10)
C7—N3—C9	106.21 (8)	N6—C13—C12	116.44 (8)
C7—N3—C12	130.09 (9)	N6—C13—C14	122.88 (10)
C9—N3—C12	123.52 (8)	C13—C14—C15	118.95 (11)
C13—N6—C17	117.22 (9)	C14—C15—C16	118.87 (11)
H4A—N4—H4B	122.1 (13)	C15—C16—C17	118.24 (11)
C10—N4—H4B	118.8 (9)	N6—C17—C16	123.84 (11)
C10—N4—H4A	118.7 (10)	C2—C3—H3	121.00
C3—C2—C7	117.60 (9)	C4—C3—H3	121.00
N1—C2—C7	119.29 (9)	C3—C4—H4	121.00
N1—C2—C3	123.11 (10)	C5—C4—H4	121.00
C2—C3—C4	118.60 (10)	C4—C5—H5	121.00
C3—C4—C5	118.70 (11)	C6—C5—H5	121.00
C4—C5—C6	118.60 (12)	N1—C6—H6	118.00
N1—C6—C5	124.01 (11)	C5—C6—H6	118.00
N3—C7—C2	127.66 (9)	N3—C12—H12A	109.00
N2—C7—N3	111.48 (9)	N3—C12—H12B	109.00
N2—C7—C2	120.85 (9)	C13—C12—H12A	109.00
N2—C8—C9	110.14 (9)	C13—C12—H12B	109.00
N2—C8—C10	122.16 (9)	H12A—C12—H12B	108.00
C9—C8—C10	127.70 (9)	C13—C14—H14	121.00
C8—C9—C11	131.18 (10)	C15—C14—H14	121.00
N3—C9—C8	106.04 (8)	C14—C15—H15	121.00
N3—C9—C11	122.71 (9)	C16—C15—H15	121.00
O1—C10—C8	120.27 (9)	C15—C16—H16	121.00
O1—C10—N4	124.70 (11)	C17—C16—H16	121.00
N4—C10—C8	115.03 (9)	N6—C17—H17	118.00
N5—C11—C9	178.45 (12)	C16—C17—H17	118.00
C6—N1—C2—C3	0.84 (15)	N1—C2—C7—N2	−172.47 (9)
C6—N1—C2—C7	179.84 (9)	N1—C2—C7—N3	6.25 (15)
C2—N1—C6—C5	0.36 (17)	C3—C2—C7—N2	6.59 (14)
C8—N2—C7—N3	0.00 (11)	C3—C2—C7—N3	−174.69 (9)
C8—N2—C7—C2	178.91 (8)	C2—C3—C4—C5	0.39 (17)
C7—N2—C8—C9	0.12 (11)	C3—C4—C5—C6	0.70 (18)
C7—N2—C8—C10	−179.68 (9)	C4—C5—C6—N1	−1.13 (19)
C9—N3—C7—N2	−0.11 (11)	N2—C8—C9—N3	−0.18 (11)
C9—N3—C7—C2	−178.93 (9)	N2—C8—C9—C11	176.73 (10)
C12—N3—C7—N2	−175.16 (9)	C10—C8—C9—N3	179.60 (9)
C12—N3—C7—C2	6.02 (16)	C10—C8—C9—C11	−3.50 (18)
C7—N3—C9—C8	0.17 (10)	N2—C8—C10—O1	168.39 (10)
C7—N3—C9—C11	−177.06 (9)	N2—C8—C10—N4	−11.02 (14)
C12—N3—C9—C8	175.63 (8)	C9—C8—C10—O1	−11.36 (16)
C12—N3—C9—C11	−1.61 (14)	C9—C8—C10—N4	169.22 (10)
C7—N3—C12—C13	100.19 (11)	N3—C12—C13—N6	−54.97 (12)
C9—N3—C12—C13	−74.10 (11)	N3—C12—C13—C14	126.32 (11)
C17—N6—C13—C12	−179.66 (11)	N6—C13—C14—C15	0.53 (19)
C17—N6—C13—C14	−0.98 (17)	C12—C13—C14—C15	179.16 (11)
C13—N6—C17—C16	1.0 (2)	C13—C14—C15—C16	0.0 (2)
N1—C2—C3—C4	−1.21 (16)	C14—C15—C16—C17	0.0 (2)
C7—C2—C3—C4	179.77 (10)	C15—C16—C17—N6	−0.5 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···N2	0.879 (16)	2.401 (15)	2.7747 (14)	105.9 (10)
N4—H4A···N6^i	0.879 (16)	2.354 (15)	3.1821 (13)	157.1 (13)
N4—H4B···O1^ii	0.887 (16)	2.001 (16)	2.8853 (14)	174.9 (13)
C4—H4···N5^iii	0.95	2.61	3.4898 (16)	154
C15—H15···O1^iv	0.95	2.44	3.2641 (16)	145
C15—H15···CgB^i	0.95	2.89	3.6632 (15)	139

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, −y+1, −z; (iii) x, −y+1/2, z−1/2; (iv) −x+1, y+1/2, −z+1/2.

(L2-II) 5-cyano-2-(2-pyridyl)-1-(2-pyridylmethyl)-1H-imidazole-4-carboxamide

Crystal data

C16H12N6O	F(000) = 632
Mr = 304.32	Dx = 1.374 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 17872 reflections
a = 7.7315 (4) Å	θ = 2.1–29.6°
b = 15.8398 (9) Å	µ = 0.09 mm^−1
c = 12.0572 (8) Å	T = 173 K
β = 94.950 (5)°	Rod, brown
V = 1471.08 (15) Å^3	0.40 × 0.23 × 0.21 mm
Z = 4

Data collection

Stoe IPDS-2 diffractometer	3241 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.045
Graphite monochromator	θmax = 29.2°, θmin = 2.1°
ϕ + ω rotation scans	h = −9→10
21034 measured reflections	k = −21→21
3974 independent reflections	l = −16→16

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.097	w = 1/[σ^2(Fo^2) + (0.0509P)^2 + 0.2338P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
3974 reflections	Δρmax = 0.31 e Å^−3
217 parameters	Δρmin = −0.17 e Å^−3
2 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc* = kFc[1+0.001Fc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.010 (2)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	1.01156 (12)	0.09860 (5)	0.09066 (6)	0.0318 (3)
N1	0.75225 (13)	0.06697 (7)	0.61970 (8)	0.0326 (3)
N2	0.84501 (12)	0.01621 (6)	0.33797 (7)	0.0249 (2)
N3	0.89248 (11)	0.13893 (5)	0.42579 (7)	0.0217 (2)
N4	0.93337 (15)	−0.03545 (6)	0.13136 (8)	0.0344 (3)
N5	1.10636 (14)	0.28099 (6)	0.26524 (8)	0.0331 (3)
N6	0.65570 (13)	0.28481 (6)	0.41589 (8)	0.0308 (3)
C2	0.75565 (13)	0.02001 (7)	0.52803 (9)	0.0258 (3)
C3	0.69047 (15)	−0.06181 (8)	0.51919 (10)	0.0318 (3)
C4	0.61387 (16)	−0.09495 (9)	0.60960 (12)	0.0397 (4)
C5	0.60638 (17)	−0.04636 (9)	0.70374 (11)	0.0425 (4)
C6	0.67853 (18)	0.03328 (9)	0.70580 (11)	0.0395 (4)
C7	0.83060 (13)	0.05831 (7)	0.43182 (8)	0.0230 (3)
C8	0.91836 (13)	0.07055 (7)	0.26873 (8)	0.0230 (3)
C9	0.94908 (12)	0.14691 (6)	0.32093 (8)	0.0220 (3)
C10	0.95879 (14)	0.04588 (7)	0.15496 (8)	0.0252 (3)
C11	1.03424 (14)	0.22090 (7)	0.28779 (8)	0.0245 (3)
C12	0.89753 (14)	0.20790 (7)	0.50805 (8)	0.0256 (3)
C13	0.72230 (14)	0.24958 (7)	0.51130 (9)	0.0257 (3)
C14	0.63775 (16)	0.25007 (7)	0.60845 (10)	0.0316 (3)
C15	0.47485 (17)	0.28696 (8)	0.60593 (11)	0.0393 (4)
C16	0.40436 (17)	0.32329 (9)	0.50861 (13)	0.0424 (4)
C17	0.49924 (16)	0.32127 (8)	0.41640 (11)	0.0385 (4)
H3	0.69820	−0.09400	0.45330	0.0380*
H4	0.56720	−0.15050	0.60660	0.0480*
H4A	0.957 (2)	−0.0554 (10)	0.0645 (12)	0.045 (4)*
H4B	0.906 (2)	−0.0706 (9)	0.1830 (12)	0.042 (4)*
H5	0.55250	−0.06730	0.76610	0.0510*
H6	0.67580	0.06590	0.77170	0.0470*
H12A	0.98370	0.25060	0.48910	0.0310*
H12B	0.93520	0.18510	0.58270	0.0310*
H14	0.69030	0.22570	0.67500	0.0380*
H15	0.41270	0.28720	0.67050	0.0470*
H16	0.29320	0.34920	0.50480	0.0510*
H17	0.45080	0.34720	0.34970	0.0460*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0453 (5)	0.0273 (4)	0.0239 (4)	−0.0035 (3)	0.0102 (3)	−0.0025 (3)
N1	0.0364 (5)	0.0359 (5)	0.0268 (5)	0.0072 (4)	0.0110 (4)	0.0035 (4)
N2	0.0261 (4)	0.0248 (4)	0.0241 (4)	0.0014 (3)	0.0048 (3)	−0.0010 (3)
N3	0.0216 (4)	0.0251 (4)	0.0188 (4)	0.0012 (3)	0.0038 (3)	−0.0022 (3)
N4	0.0549 (6)	0.0253 (5)	0.0245 (5)	−0.0058 (4)	0.0119 (4)	−0.0052 (4)
N5	0.0386 (5)	0.0316 (5)	0.0291 (5)	−0.0053 (4)	0.0035 (4)	0.0001 (4)
N6	0.0306 (5)	0.0328 (5)	0.0294 (5)	0.0017 (4)	0.0044 (4)	−0.0009 (4)
C2	0.0222 (4)	0.0296 (5)	0.0259 (5)	0.0052 (4)	0.0045 (4)	0.0051 (4)
C3	0.0273 (5)	0.0334 (6)	0.0345 (6)	0.0008 (4)	0.0016 (4)	0.0065 (5)
C4	0.0313 (6)	0.0401 (7)	0.0479 (7)	−0.0008 (5)	0.0038 (5)	0.0176 (6)
C5	0.0351 (6)	0.0529 (8)	0.0414 (7)	0.0101 (6)	0.0150 (5)	0.0228 (6)
C6	0.0433 (7)	0.0471 (7)	0.0303 (6)	0.0133 (6)	0.0160 (5)	0.0095 (5)
C7	0.0217 (4)	0.0241 (5)	0.0234 (5)	0.0027 (4)	0.0031 (4)	0.0000 (4)
C8	0.0243 (5)	0.0243 (5)	0.0205 (4)	0.0016 (4)	0.0032 (4)	−0.0016 (4)
C9	0.0225 (4)	0.0253 (5)	0.0186 (4)	0.0018 (4)	0.0033 (3)	−0.0013 (3)
C10	0.0289 (5)	0.0264 (5)	0.0204 (4)	0.0000 (4)	0.0035 (4)	−0.0035 (4)
C11	0.0268 (5)	0.0271 (5)	0.0196 (4)	0.0015 (4)	0.0025 (4)	−0.0017 (4)
C12	0.0265 (5)	0.0296 (5)	0.0209 (4)	−0.0016 (4)	0.0033 (4)	−0.0071 (4)
C13	0.0282 (5)	0.0245 (5)	0.0250 (5)	−0.0017 (4)	0.0057 (4)	−0.0061 (4)
C14	0.0373 (6)	0.0305 (6)	0.0282 (5)	0.0002 (4)	0.0103 (5)	−0.0066 (4)
C15	0.0411 (7)	0.0353 (6)	0.0446 (7)	0.0021 (5)	0.0216 (6)	−0.0081 (5)
C16	0.0330 (6)	0.0379 (7)	0.0576 (8)	0.0082 (5)	0.0117 (6)	−0.0039 (6)
C17	0.0345 (6)	0.0373 (7)	0.0437 (7)	0.0056 (5)	0.0031 (5)	0.0036 (5)

Geometric parameters (Å, º)

O1—C10	1.2327 (13)	C8—C9	1.3747 (14)
N1—C2	1.3344 (15)	C8—C10	1.4853 (14)
N1—C6	1.3377 (17)	C9—C11	1.4185 (14)
N2—C7	1.3264 (13)	C12—C13	1.5106 (15)
N2—C8	1.3569 (14)	C13—C14	1.3898 (16)
N3—C7	1.3678 (14)	C14—C15	1.3864 (18)
N3—C9	1.3789 (13)	C15—C16	1.377 (2)
N3—C12	1.4738 (13)	C16—C17	1.384 (2)
N4—C10	1.3302 (15)	C3—H3	0.9500
N5—C11	1.1476 (15)	C4—H4	0.9500
N6—C13	1.3408 (15)	C5—H5	0.9500
N6—C17	1.3410 (16)	C6—H6	0.9500
N4—H4B	0.875 (14)	C12—H12A	0.9900
N4—H4A	0.899 (15)	C12—H12B	0.9900
C2—C7	1.4716 (15)	C14—H14	0.9500
C2—C3	1.3913 (17)	C15—H15	0.9500
C3—C4	1.3878 (18)	C16—H16	0.9500
C4—C5	1.377 (2)	C17—H17	0.9500
C5—C6	1.379 (2)
C2—N1—C6	117.43 (11)	N3—C12—C13	111.70 (9)
C7—N2—C8	106.04 (9)	C12—C13—C14	120.82 (10)
C7—N3—C9	105.93 (8)	N6—C13—C12	116.01 (9)
C7—N3—C12	130.19 (8)	N6—C13—C14	123.17 (10)
C9—N3—C12	123.85 (8)	C13—C14—C15	118.45 (11)
C13—N6—C17	117.07 (10)	C14—C15—C16	119.14 (12)
H4A—N4—H4B	119.7 (14)	C15—C16—C17	118.47 (12)
C10—N4—H4B	120.3 (9)	N6—C17—C16	123.67 (12)
C10—N4—H4A	119.6 (10)	C2—C3—H3	121.00
C3—C2—C7	119.23 (10)	C4—C3—H3	121.00
N1—C2—C7	117.41 (10)	C3—C4—H4	120.00
N1—C2—C3	123.35 (10)	C5—C4—H4	120.00
C2—C3—C4	117.94 (11)	C4—C5—H5	121.00
C3—C4—C5	119.16 (13)	C6—C5—H5	121.00
C4—C5—C6	118.73 (12)	N1—C6—H6	118.00
N1—C6—C5	123.36 (12)	C5—C6—H6	118.00
N3—C7—C2	126.17 (9)	N3—C12—H12A	109.00
N2—C7—N3	111.62 (9)	N3—C12—H12B	109.00
N2—C7—C2	122.21 (10)	C13—C12—H12A	109.00
N2—C8—C9	109.96 (9)	C13—C12—H12B	109.00
N2—C8—C10	122.26 (10)	H12A—C12—H12B	108.00
C9—C8—C10	127.77 (10)	C13—C14—H14	121.00
C8—C9—C11	131.61 (9)	C15—C14—H14	121.00
N3—C9—C8	106.45 (8)	C14—C15—H15	120.00
N3—C9—C11	121.72 (9)	C16—C15—H15	120.00
O1—C10—C8	120.67 (10)	C15—C16—H16	121.00
O1—C10—N4	124.91 (10)	C17—C16—H16	121.00
N4—C10—C8	114.42 (9)	N6—C17—H17	118.00
N5—C11—C9	177.24 (11)	C16—C17—H17	118.00
C6—N1—C2—C3	−1.49 (17)	N1—C2—C7—N2	177.90 (10)
C6—N1—C2—C7	177.67 (10)	N1—C2—C7—N3	−2.31 (16)
C2—N1—C6—C5	−0.32 (19)	C3—C2—C7—N2	−2.90 (16)
C8—N2—C7—N3	0.07 (12)	C3—C2—C7—N3	176.89 (10)
C8—N2—C7—C2	179.89 (9)	C2—C3—C4—C5	−0.40 (18)
C7—N2—C8—C9	−0.04 (10)	C3—C4—C5—C6	−1.25 (19)
C7—N2—C8—C10	178.88 (9)	C4—C5—C6—N1	1.7 (2)
C9—N3—C7—N2	−0.08 (11)	N2—C8—C9—N3	0.00 (11)
C9—N3—C7—C2	−179.88 (9)	N2—C8—C9—C11	174.51 (10)
C12—N3—C7—N2	177.99 (10)	C10—C8—C9—N3	−178.85 (10)
C12—N3—C7—C2	−1.81 (17)	C10—C8—C9—C11	−4.34 (18)
C7—N3—C9—C8	0.04 (12)	N2—C8—C10—O1	173.76 (10)
C7—N3—C9—C11	−175.14 (9)	N2—C8—C10—N4	−6.38 (15)
C12—N3—C9—C8	−178.18 (9)	C9—C8—C10—O1	−7.52 (17)
C12—N3—C9—C11	6.64 (15)	C9—C8—C10—N4	172.34 (11)
C7—N3—C12—C13	−77.76 (13)	N3—C12—C13—N6	−60.05 (12)
C9—N3—C12—C13	100.01 (11)	N3—C12—C13—C14	119.66 (11)
C17—N6—C13—C12	179.19 (10)	N6—C13—C14—C15	1.61 (17)
C17—N6—C13—C14	−0.51 (17)	C12—C13—C14—C15	−178.08 (11)
C13—N6—C17—C16	−0.79 (18)	C13—C14—C15—C16	−1.42 (18)
N1—C2—C3—C4	1.86 (17)	C14—C15—C16—C17	0.24 (19)
C7—C2—C3—C4	−177.29 (10)	C15—C16—C17—N6	0.9 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···O1^i	0.899 (15)	2.026 (15)	2.9231 (12)	175.1 (14)
N4—H4B···N2	0.875 (14)	2.399 (14)	2.7633 (13)	105.4 (11)
N4—H4B···N5^ii	0.875 (14)	2.436 (14)	3.1888 (14)	144.5 (12)
C12—H12B···N5^iii	0.99	2.53	3.3749 (14)	144
C3—H3···CgB^i	0.95	2.72	3.5854 (15)	151

Symmetry codes: (i) −x+2, −y, −z; (ii) −x+2, y−1/2, −z+1/2; (iii) x, −y+1/2, z+1/2.