Cyano–cyano and chloro–cyano interactions in two imidazole derivatives

In two closely related 1-aryl-2-methyl-4-nitro-5-cyano­imid­azoles, namely 2-methyl-4-nitro-1-phenyl-1H-imidazole-5-carbo­nitrile, C₁₁H₈N₄O₂, and 1-(4-chloro­phenyl)-2-methyl-4-nitro-1H-imidazole-5-carbo­nitrile, C₁₁H₇ClN₄O₂, different weak intermolecular interactions determine the crystal packing. In the 1-phenyl derivative, dipole–dipole interactions between antiparallel cyano groups connect mol­ecules into centrosymmetric dimers, while in the 1-(4-chloro­phenyl) derivative, the dimers are connected by C[triple bond]N...Cl—C halogen bonds. These interactions, together with weak C—H...O(N) hydrogen bonds, connect mol­ecules related by subsequent centres of inversion into infinite tapes.

S1. Comment

Weak intermolecular interactions play decisive role in the determination of three-dimensional structure of molecular crystals. By far the most important – and best known – are hydrogen bonds, but in the absence of strong hydrogen-bond donors or acceptors (or sometimes in spite of their presence) other weak interactions stabilize certain structures. The list of these interactions is long and still growing.

Among these, the attractive interaction between a carbon-bound halogen and atoms having electron lone pairs has been known for a long time (Hassel & Rømming, 1962; Hassel, 1970). This interaction has been termed `halogen bonding' (Dumas et al., 1983; Legon, 1998) in order to stress the analogy with hydrogen bonding [for recent reviews see, for example, Legon (1999), Metrangolo & Resnati (2001) and Metrangolo et al. (2003)]. The reorganization of electron-density distribution connected with this interaction is directed from a Lewis base electron-donor site to the halogen atom, which acts as a Lewis acid. The acidity scale I>Br>Cl (for fluorine there is no detectable tendency to form this type of interaction) was established on the basis of Cambridge Structural Database (CSD; Allen, 2002) studies (Lommerse et al., 1996) and quantum-chemical calculations (Valerio et al., 2000). A special case of this interaction involves the cyano group as an electron donor. The existence of short C≡ N···X—C contacts was postulated over 40 years ago (Hassel & Rømming, 1962) and confirmed by the structures of some simple cyano–halogen compounds (Witt et al., 1972). The role of the cyano–halogen interactions in the crystal structures of 4-halobenzonitriles was described by Desiraju & Harlow (1989), and C≡N···Cl—C halogen bonds were used as the supramolecular synthon [as defined by Desiraju (1995)] to create linear zigzag arrays of flat molecules (molecular tapes; Reddy et al., 1993a). These contacts were also identified in the series of tetrachlorodicyanobenzenes (Britton, 2002, and references therein).

In addition, the cyano group can accept hydrogen bonds (Ziao et al., 2001) and it can be involved in dipole–dipole interactions, analogous to the carbonyl···carbonyl interactions that were found to be able to compete successfully with hydrogen bonds (Allen et al., 1998).

In the course of studies of weak interactions in nitroimidazoles (Kubicki et al., 2001, 2002), the crystal structures of two closely related 5-cyano derivatives have been determined, namely 1-phenyl-2-methyl-4-nitro-5-cyanoimidazole, (I), and 1-(4'-chlorophenyl)-2-methyl-4-nitro-5-cyanoimidazole, (II). Because of the lack of strong hydrogen-bond donors, these compounds offer the opportunity of comparing the weak interactions described above.

Figs. 1 and 2 show the anisotropic displacement-ellipsoid representations of the molecules of (I) and (II), respectively. The bond lengths and angles are almost identical; the only – and obvious – differences are connected to the presence of the Cl substituent in (II). This substituent causes modest changes in the intra-annular bond angles of the benzene ring, in general agreement with those described by Domenicano & Murray-Rust (1979) for monosubstituted benzene derivatives; in the chloro-derivative (II), the angle at the site of substitution (C13—C14—C15) is larger and the two adjacent angles (C12—C13—C14 and C14—C15—C16) are smaller than the equivalent angles in (I).

The conformations of (I) and (II) are slightly different. The dihedral angles involving the three effectively planar fragments, viz. the imidazole ring (A), the benzene ring (B) and the nitro group (C), are larger in (II); the angle between planes A and B is 87.64 (6)° in (II) and 76.29 (4)° in (I), and the angle between planes A and C is 7.65 (2) in (II) and 0.59 (13) in (I).

In the crystal structure of (I), relatively short contacts exist between antiparallel C≡N groups from molecules connected (related?) by a center of inversion. The distance between the mid-points of these bonds is 3.271 (2) Å and the C5—C51···N51 angle is 82.9 (1)°. These dipole···dipole interactions lead to the formation of centrosymmetric dimers in (I). The only other intermolecular interaction that plays role in the crystal packing is the weak C12—H12···O41 hydrogen bond, which also closes the dimers related by another center of inversion (Fig. 1).

In (II), the presence of the Cl atom changes the hierarchy of intermolecular interactions. In this case, the main driving force of crystal packing is the C—Cl···N≡C interactions, which also close the centrosymmetric dimers (Fig. 2). The Cl···N distance is short but typical for this kind of interaction [3.250 (2) Å], and the linearity of the C—Cl···N contact [168.30 (8)°] testifies to the proposed mechanism of the charge donation (the donation of the lone pair into the σ antibonding orbital of C—X). The C—H···N hydrogen bonds between neighboring molecules (connected by another center of inversion) also take part in the crystal packing (Fig. 2).

There are some similarities in the crystal-packing modes of (I) and (II). In both cases, the structure consists of tapes of molecules connected by alternating pairs of weak interactions [~dipole···dipole ~ C—H···O ~in (I) and ~C≡N···Cl—C ~C—H···N ~in (II)], and these tapes utilize the consecutive centers of inversion. No other symmetry elements are used in creating the principal packing motifs, even though the space group (P2₁/n) contains such elements.

S2. Experimental

The method of synthesis of (I) and (II) was described by Salwińska & Suwiński (1990) and Suwiński et al. (1994). Crystals suitable for data collection were grown from a methanol solution.

S3. Refinement

The positional parameters of H atoms in aryl groups were refined isotropically, giving C—H distances in the range 0.89 (2)–0.97 (3) Å; methyl H atoms were treated as riding, with C—H distances of 0.96 Å.

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2002) for (I). For both compounds, cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).

Figures

	Fig. 1. A view of the molecule of (I). Displacement ellipsoids are drawn at the 30% probability level and H atoms are depicted as spheres of arbitrary radii.
	Fig. 2. A view of the molecule of (II). Displacement ellipsoids are drawn at the 30% probability level and H atoms are depicted as spheres of arbitrary radii.
	Fig. 3. The chain of molecules of (I), connected by dipole···dipole and C—H···O interactions, as seen approximately along the [010] direction. [Symmetry codes: (i) 2 - x,-y,1 - z; (ii) 1 - x,-y,1 - z; (iii) -1 + x,y,z.]
	Fig. 4. The chain of molecules of (II), connected by C≡N···Cl—C and C—H···N interactions, as seen approximately along the [100] direction. [Symmetry codes: (i) 1 - x,1 - y,2 - z; (ii) 1 - x,2 - y,1 - z; (iii) x,1 + y,-1 + z.]

(I) 2-methyl-4-nitro-1-phenyl-1H-imidazole-5-carbonitrile

Crystal data

C11H8N4O2	F(000) = 472
Mr = 228.21	Dx = 1.402 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2418 reflections
a = 9.8976 (9) Å	θ = 3–21°
b = 9.6168 (9) Å	µ = 0.10 mm^−1
c = 11.670 (1) Å	T = 293 K
β = 103.313 (7)°	Prism, colourless
V = 1080.94 (17) Å^3	0.3 × 0.25 × 0.15 mm
Z = 4

Data collection

KUMA KM-4 CCD four-circle diffractometer	1380 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.027
Graphite monochromator	θmax = 29.3°, θmin = 4.7°
ω scan	h = −13→11
6917 measured reflections	k = −11→13
2708 independent reflections	l = −14→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 0.91	w = 1/[σ^2(Fo^2) + (0.04P)^2] where P = (Fo^2 + 2Fc^2)/3
2708 reflections	(Δ/σ)max = 0.003
176 parameters	Δρmax = 0.11 e Å^−3
0 restraints	Δρmin = −0.18 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
N1	0.68836 (11)	0.07163 (12)	0.35541 (10)	0.0422 (3)
C11	0.72914 (14)	0.05299 (14)	0.24477 (12)	0.0401 (3)
C12	0.64864 (17)	−0.02692 (16)	0.15774 (13)	0.0498 (4)
H12	0.5670 (16)	−0.0706 (15)	0.1701 (12)	0.054 (4)*
C13	0.68759 (18)	−0.0407 (2)	0.05250 (15)	0.0607 (5)
H13	0.6374 (17)	−0.0988 (17)	−0.0065 (15)	0.069 (5)*
C14	0.80361 (18)	0.02539 (19)	0.03470 (16)	0.0618 (5)
H14	0.8225 (16)	0.0164 (18)	−0.0381 (17)	0.080 (6)*
C15	0.88281 (19)	0.10485 (19)	0.12165 (15)	0.0588 (5)
H15	0.9612 (18)	0.1520 (16)	0.1141 (14)	0.068 (5)*
C16	0.84701 (16)	0.11851 (17)	0.22847 (15)	0.0494 (4)
H16	0.9023 (16)	0.1678 (14)	0.2905 (14)	0.054 (4)*
C2	0.58798 (14)	0.15987 (15)	0.37605 (13)	0.0464 (4)
C21	0.50057 (17)	0.24700 (17)	0.28327 (15)	0.0623 (5)
H21A	0.4376	0.3009	0.3167	0.146 (5)*
H21B	0.4488	0.1884	0.2221	0.146 (5)*
H21C	0.5587	0.3083	0.2508	0.146 (5)*
N3	0.58068 (12)	0.15680 (13)	0.48740 (11)	0.0504 (3)
C4	0.67827 (15)	0.06517 (16)	0.53828 (12)	0.0467 (4)
N4	0.70230 (15)	0.03338 (16)	0.66203 (12)	0.0599 (4)
O41	0.63201 (15)	0.09102 (14)	0.72030 (11)	0.0862 (4)
O42	0.79373 (14)	−0.05070 (16)	0.70153 (10)	0.0839 (4)
C5	0.74742 (14)	0.00858 (15)	0.46121 (12)	0.0429 (4)
C51	0.85333 (16)	−0.09359 (17)	0.47370 (12)	0.0485 (4)
N51	0.93848 (15)	−0.17517 (16)	0.48416 (12)	0.0680 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0431 (7)	0.0448 (7)	0.0402 (7)	−0.0005 (6)	0.0128 (5)	−0.0010 (6)
C11	0.0421 (8)	0.0412 (8)	0.0380 (8)	0.0021 (6)	0.0115 (6)	0.0018 (6)
C12	0.0445 (9)	0.0534 (10)	0.0511 (10)	−0.0031 (8)	0.0100 (7)	−0.0046 (7)
C13	0.0588 (11)	0.0735 (13)	0.0461 (10)	0.0050 (9)	0.0042 (8)	−0.0127 (9)
C14	0.0638 (12)	0.0829 (13)	0.0420 (10)	0.0137 (10)	0.0188 (9)	0.0035 (9)
C15	0.0542 (10)	0.0687 (12)	0.0597 (11)	−0.0004 (9)	0.0257 (9)	0.0107 (9)
C16	0.0470 (9)	0.0531 (10)	0.0483 (9)	−0.0032 (8)	0.0114 (8)	−0.0018 (8)
C2	0.0470 (9)	0.0434 (9)	0.0519 (10)	−0.0005 (7)	0.0179 (7)	−0.0020 (7)
C21	0.0643 (11)	0.0568 (10)	0.0669 (11)	0.0157 (9)	0.0173 (9)	0.0089 (8)
N3	0.0499 (7)	0.0541 (8)	0.0508 (8)	−0.0019 (6)	0.0192 (6)	−0.0040 (6)
C4	0.0477 (9)	0.0550 (10)	0.0392 (8)	−0.0109 (7)	0.0140 (7)	−0.0018 (7)
N4	0.0580 (10)	0.0777 (11)	0.0462 (8)	−0.0130 (8)	0.0168 (7)	−0.0014 (8)
O41	0.0985 (10)	0.1148 (11)	0.0573 (8)	−0.0010 (8)	0.0428 (7)	−0.0084 (8)
O42	0.0812 (9)	0.1163 (12)	0.0531 (8)	0.0112 (9)	0.0132 (7)	0.0181 (7)
C5	0.0412 (8)	0.0468 (9)	0.0409 (8)	−0.0050 (7)	0.0096 (6)	0.0002 (7)
C51	0.0479 (9)	0.0529 (10)	0.0426 (9)	−0.0036 (8)	0.0063 (7)	0.0002 (7)
N51	0.0661 (9)	0.0689 (10)	0.0644 (10)	0.0127 (8)	0.0056 (7)	−0.0014 (8)

Geometric parameters (Å, º)

N1—C2	1.3695 (17)	C16—H16	0.930 (15)
N1—C5	1.3790 (17)	C2—N3	1.3183 (17)
N1—C11	1.4499 (17)	C2—C21	1.480 (2)
C11—C12	1.3726 (19)	C21—H21A	0.9600
C11—C16	1.377 (2)	C21—H21B	0.9600
C12—C13	1.376 (2)	C21—H21C	0.9600
C12—H12	0.951 (15)	N3—C4	1.3408 (18)
C13—C14	1.370 (2)	C4—C5	1.3628 (19)
C13—H13	0.935 (17)	C4—N4	1.4413 (19)
C14—C15	1.365 (2)	N4—O41	1.2131 (16)
C14—H14	0.914 (19)	N4—O42	1.2220 (17)
C15—C16	1.379 (2)	C5—C51	1.419 (2)
C15—H15	0.920 (17)	C51—N51	1.1372 (18)
C2—N1—C5	106.86 (11)	N3—C2—N1	111.48 (13)
C2—N1—C11	126.53 (12)	N3—C2—C21	125.32 (13)
C5—N1—C11	126.55 (11)	N1—C2—C21	123.20 (13)
C12—C11—C16	121.32 (14)	C2—C21—H21A	109.5
C12—C11—N1	119.66 (12)	C2—C21—H21B	109.5
C16—C11—N1	119.00 (13)	H21A—C21—H21B	109.5
C11—C12—C13	118.71 (16)	C2—C21—H21C	109.5
C11—C12—H12	120.2 (9)	H21A—C21—H21C	109.5
C13—C12—H12	121.1 (9)	H21B—C21—H21C	109.5
C14—C13—C12	120.5 (2)	C2—N3—C4	104.70 (12)
C14—C13—H13	119.1 (10)	N3—C4—C5	112.97 (13)
C12—C13—H13	120.3 (10)	N3—C4—N4	121.26 (13)
C15—C14—C13	120.4 (2)	C5—C4—N4	125.77 (15)
C15—C14—H14	122.6 (11)	O41—N4—O42	124.15 (15)
C13—C14—H14	117.0 (11)	O41—N4—C4	118.76 (16)
C14—C15—C16	120.2 (2)	O42—N4—C4	117.09 (14)
C14—C15—H15	123.9 (11)	C4—C5—N1	103.98 (12)
C16—C15—H15	115.9 (11)	C4—C5—C51	132.83 (14)
C11—C16—C15	118.92 (16)	N1—C5—C51	123.17 (12)
C11—C16—H16	119.4 (9)	N51—C51—C5	179.70 (19)
C15—C16—H16	121.7 (9)
C2—N1—C11—C12	−78.56 (17)	N1—C2—N3—C4	0.09 (16)
C5—N1—C11—C12	104.58 (16)	C21—C2—N3—C4	−179.67 (14)
C2—N1—C11—C16	100.17 (17)	C2—N3—C4—C5	−0.46 (16)
C5—N1—C11—C16	−76.69 (18)	C2—N3—C4—N4	179.88 (12)
C16—C11—C12—C13	−0.1 (2)	N3—C4—N4—O41	0.2 (2)
N1—C11—C12—C13	178.59 (13)	C5—C4—N4—O41	−179.43 (14)
C11—C12—C13—C14	−0.7 (2)	N3—C4—N4—O42	−179.59 (14)
C12—C13—C14—C15	0.6 (3)	C5—C4—N4—O42	0.8 (2)
C13—C14—C15—C16	0.4 (3)	N3—C4—C5—N1	0.63 (16)
C12—C11—C16—C15	1.1 (2)	N4—C4—C5—N1	−179.73 (12)
N1—C11—C16—C15	−177.63 (13)	N3—C4—C5—C51	−177.70 (14)
C14—C15—C16—C11	−1.2 (2)	N4—C4—C5—C51	1.9 (3)
C5—N1—C2—N3	0.29 (15)	C2—N1—C5—C4	−0.53 (14)
C11—N1—C2—N3	−177.07 (12)	C11—N1—C5—C4	176.83 (12)
C5—N1—C2—C21	−179.95 (13)	C2—N1—C5—C51	178.01 (13)
C11—N1—C2—C21	2.7 (2)	C11—N1—C5—C51	−4.6 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···O41^i	0.95 (2)	2.59 (2)	3.456 (2)	151 (1)

Symmetry code: (i) −x+1, −y, −z+1.

(II) 1-(4-chlorophenyl)-2-methyl-4-nitro-1H-imidazole-5-carbonitrile

Crystal data

C11H7ClN4O2	F(000) = 536
Mr = 262.66	Dx = 1.464 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2798 reflections
a = 12.6819 (16) Å	θ = 3–18°
b = 6.8018 (11) Å	µ = 0.32 mm^−1
c = 15.1799 (16) Å	T = 293 K
β = 114.497 (11)°	Plate, colourless
V = 1191.5 (3) Å^3	0.6 × 0.5 × 0.1 mm
Z = 4

Data collection

KUMA KM-4 CCD four-circle diffractometer	2968 independent reflections
Radiation source: fine-focus sealed tube	1647 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
ω scan	θmax = 29.3°, θmin = 4.9°
Absorption correction: multi-scan (SORTAV; Blessing, 1989)	h = −17→15
Tmin = 0.889, Tmax = 0.971	k = −9→6
7375 measured reflections	l = −20→20

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)] = 0.042	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.102	w = 1/[σ^2(Fo^2) + (0.045P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.97	(Δ/σ)max = 0.001
2968 reflections	Δρmax = 0.17 e Å^−3
182 parameters	Δρmin = −0.21 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.011 (2)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
N1	0.46832 (11)	0.6630 (2)	0.67776 (9)	0.0434 (3)
C11	0.50749 (14)	0.6680 (2)	0.78171 (11)	0.0412 (4)
C12	0.60610 (17)	0.5694 (3)	0.83926 (13)	0.0568 (5)
H12	0.6452 (19)	0.502 (3)	0.8121 (15)	0.069 (6)*
C13	0.64644 (18)	0.5812 (3)	0.93858 (13)	0.0585 (5)
H13	0.717 (2)	0.515 (3)	0.9801 (18)	0.086 (7)*
C14	0.58618 (15)	0.6907 (2)	0.97752 (11)	0.0455 (4)
Cl14	0.63698 (5)	0.71140 (8)	1.10216 (3)	0.0664 (2)
C15	0.48501 (17)	0.7841 (3)	0.91997 (13)	0.0553 (5)
H15	0.4392 (18)	0.857 (3)	0.9473 (15)	0.074 (6)*
C16	0.44623 (17)	0.7743 (3)	0.82106 (13)	0.0518 (4)
H16	0.3826 (19)	0.841 (3)	0.7848 (16)	0.070 (6)*
C2	0.49558 (15)	0.7966 (3)	0.62366 (12)	0.0498 (4)
C21	0.5734 (2)	0.9650 (3)	0.66616 (15)	0.0724 (6)
H21A	0.6519	0.9192	0.6975	0.121 (6)*
H21B	0.5521	1.0291	0.7128	0.121 (6)*
H21C	0.5668	1.0563	0.6159	0.121 (6)*
N3	0.44591 (13)	0.7517 (2)	0.53080 (10)	0.0554 (4)
C4	0.38577 (14)	0.5863 (3)	0.52677 (12)	0.0488 (4)
N4	0.32041 (14)	0.4909 (3)	0.43596 (11)	0.0599 (4)
O41	0.32955 (13)	0.5505 (2)	0.36420 (9)	0.0753 (4)
O42	0.25971 (16)	0.3541 (3)	0.43678 (11)	0.0949 (6)
C5	0.39676 (14)	0.5250 (2)	0.61538 (11)	0.0449 (4)
C51	0.35382 (16)	0.3609 (3)	0.64710 (13)	0.0539 (5)
N51	0.32224 (18)	0.2276 (3)	0.67366 (13)	0.0802 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0430 (8)	0.0511 (8)	0.0326 (7)	−0.0039 (6)	0.0120 (6)	0.0026 (6)
C11	0.0416 (9)	0.0457 (9)	0.0326 (8)	−0.0030 (7)	0.0116 (7)	0.0034 (7)
C12	0.0513 (11)	0.0714 (13)	0.0456 (10)	0.0165 (10)	0.0180 (9)	0.0046 (9)
C13	0.0538 (11)	0.0682 (12)	0.0422 (10)	0.0157 (10)	0.0087 (8)	0.0078 (9)
C14	0.0528 (10)	0.0429 (9)	0.0345 (8)	−0.0070 (8)	0.0119 (7)	0.0023 (7)
Cl14	0.0829 (4)	0.0685 (3)	0.0350 (2)	−0.0038 (3)	0.0118 (2)	0.0012 (2)
C15	0.0573 (11)	0.0619 (11)	0.0428 (10)	0.0092 (9)	0.0169 (9)	−0.0037 (9)
C16	0.0482 (10)	0.0581 (11)	0.0400 (9)	0.0118 (9)	0.0091 (8)	0.0012 (8)
C2	0.0496 (10)	0.0570 (10)	0.0373 (9)	−0.0077 (8)	0.0125 (7)	0.0072 (7)
C21	0.0798 (14)	0.0720 (13)	0.0528 (11)	−0.0289 (11)	0.0150 (10)	0.0049 (10)
N3	0.0544 (9)	0.0680 (10)	0.0349 (8)	−0.0095 (8)	0.0097 (6)	0.0071 (7)
C4	0.0431 (9)	0.0605 (11)	0.0361 (9)	−0.0036 (8)	0.0097 (7)	−0.0007 (8)
N4	0.0548 (9)	0.0760 (11)	0.0392 (9)	−0.0057 (9)	0.0098 (7)	−0.0029 (8)
O41	0.0754 (10)	0.1053 (12)	0.0353 (7)	−0.0050 (8)	0.0132 (6)	−0.0005 (7)
O42	0.1028 (12)	0.1071 (13)	0.0618 (10)	−0.0528 (11)	0.0211 (9)	−0.0194 (8)
C5	0.0406 (9)	0.0529 (10)	0.0384 (9)	−0.0058 (8)	0.0135 (7)	−0.0012 (7)
C51	0.0537 (11)	0.0610 (12)	0.0423 (9)	−0.0105 (9)	0.0153 (8)	−0.0021 (9)
N51	0.0887 (14)	0.0836 (13)	0.0651 (11)	−0.0305 (11)	0.0285 (10)	0.0002 (10)

Geometric parameters (Å, º)

N1—C2	1.362 (2)	C16—H16	0.89 (2)
N1—C5	1.374 (2)	C2—N3	1.319 (2)
N1—C11	1.445 (2)	C2—C21	1.475 (3)
C11—C16	1.367 (3)	C21—H21A	0.9600
C11—C12	1.368 (2)	C21—H21B	0.9600
C12—C13	1.379 (3)	C21—H21C	0.9600
C12—H12	0.89 (2)	N3—C4	1.346 (2)
C13—C14	1.365 (3)	C4—C5	1.359 (2)
C13—H13	0.97 (3)	C4—N4	1.435 (2)
C14—C15	1.372 (3)	N4—O42	1.211 (2)
C14—Cl14	1.7333 (17)	N4—O41	1.212 (2)
C15—C16	1.374 (3)	C5—C51	1.411 (3)
C15—H15	0.98 (2)	C51—N51	1.131 (2)
C2—N1—C5	107.49 (13)	N3—C2—N1	111.21 (15)
C2—N1—C11	125.77 (13)	N3—C2—C21	125.70 (16)
C5—N1—C11	126.74 (13)	N1—C2—C21	123.07 (15)
C16—C11—C12	121.00 (16)	C2—C21—H21A	109.5
C16—C11—N1	119.30 (15)	C2—C21—H21B	109.5
C12—C11—N1	119.68 (16)	H21A—C21—H21B	109.5
C11—C12—C13	119.75 (19)	C2—C21—H21C	109.5
C11—C12—H12	119.5 (14)	H21A—C21—H21C	109.5
C13—C12—H12	120.7 (14)	H21B—C21—H21C	109.5
C14—C13—C12	119.00 (18)	C2—N3—C4	104.62 (14)
C14—C13—H13	120.4 (14)	N3—C4—C5	112.82 (15)
C12—C13—H13	120.6 (14)	N3—C4—N4	120.79 (15)
C13—C14—C15	121.36 (16)	C5—C4—N4	126.38 (17)
C13—C14—Cl14	119.72 (14)	O42—N4—O41	124.35 (16)
C15—C14—Cl14	118.91 (14)	O42—N4—C4	116.99 (16)
C14—C15—C16	119.32 (19)	O41—N4—C4	118.66 (17)
C14—C15—H15	121.9 (12)	C4—C5—N1	103.86 (14)
C16—C15—H15	118.8 (12)	C4—C5—C51	133.21 (16)
C11—C16—C15	119.50 (18)	N1—C5—C51	122.90 (14)
C11—C16—H16	122.3 (13)	N51—C51—C5	178.2 (2)
C15—C16—H16	118.1 (13)
C2—N1—C11—C16	86.5 (2)	C11—N1—C2—C21	1.8 (3)
C5—N1—C11—C16	−93.0 (2)	N1—C2—N3—C4	0.2 (2)
C2—N1—C11—C12	−92.4 (2)	C21—C2—N3—C4	178.7 (2)
C5—N1—C11—C12	88.1 (2)	C2—N3—C4—C5	−0.3 (2)
C16—C11—C12—C13	−1.8 (3)	C2—N3—C4—N4	−179.28 (17)
N1—C11—C12—C13	177.10 (17)	N3—C4—N4—O42	−173.07 (19)
C11—C12—C13—C14	0.5 (3)	C5—C4—N4—O42	8.0 (3)
C12—C13—C14—C15	1.9 (3)	N3—C4—N4—O41	7.3 (3)
C12—C13—C14—Cl14	−178.72 (15)	C5—C4—N4—O41	−171.58 (18)
C13—C14—C15—C16	−2.9 (3)	N3—C4—C5—N1	0.2 (2)
Cl14—C14—C15—C16	177.70 (15)	N4—C4—C5—N1	179.15 (16)
C12—C11—C16—C15	0.7 (3)	N3—C4—C5—C51	−177.94 (19)
N1—C11—C16—C15	−178.13 (17)	N4—C4—C5—C51	1.0 (3)
C14—C15—C16—C11	1.6 (3)	C2—N1—C5—C4	−0.05 (18)
C5—N1—C2—N3	−0.1 (2)	C11—N1—C5—C4	179.57 (15)
C11—N1—C2—N3	−179.73 (15)	C2—N1—C5—C51	178.32 (17)
C5—N1—C2—C21	−178.61 (19)	C11—N1—C5—C51	−2.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C21—H21A···O41^i	0.96	2.61	3.392 (3)	139
C21—H21C···N3^ii	0.96	2.53	3.479 (3)	171

Symmetry codes: (i) x+1/2, −y+3/2, z+1/2; (ii) −x+1, −y+2, −z+1.