Crystal packing of two 5-substituted 2-methyl-4-nitro-1H-imidazoles

Infinite chains connected by N—H...N hydrogen bonding form the primary packing motif in two closely related 4-­nitro­imidazole derivatives, viz. 5-bromo-2-methyl-4-nitro-1H-imidazole, C₄H₄BrN₃O₂, (I), and 2-methyl-4-nitro-1H-imidazole-5-carbonitrile, C₅H₄N₄O₂, (II). These chains are almost identical, even though in (II) there are two symmetry-independent mol­ecules in the asymmetric unit. The differences appear in the inter­actions between the chains; in (I), there are strong C—Br...O halogen bonds, which connect the chains into a two-dimensional grid, while in (II), the cyano group does not participate in specific inter­actions and the chains are only loosely connected into a three-dimensional structure.

S1. Comment

Nitroimidazoles have been intensively investigated as radiosensitizers of hypoxic tumor cells and as veterinary drugs (Smithen & Hardy, 1982). Moreover, the 5(4)-bromo and 5(4)-cyano derivatives of nitroimidazoles have been proved to be excelent starting materials for purine derivatives synthesis (e.g. Suwiński et al., 1996, and references therein). For some time, we have studied weak intermolecular interactions in 4-nitroimidazole derivatives (e.g. Kubicki et al., 2001, 2002). We decribe here the intermolecular interactions in two closely related 4(5)-nitroimidazole derivatives, viz. 5(4)-bromo-4(5)-nitro-2-methyl-1H-imidazole, (I), and 5(4)-cyano-4(5)-nitro-2-methylimidazole, (II). In the previously reported pair of 5-cyanoimidazoles with blocked N1 atom (Kubicki, 2004a), which differed by the presence of a Cl atom, we observed chloro–cyano halogen bonds or cyano–cyano interactions.

The conformation of the molecules can be defined by the dihedral angle between the planar imidazole ring [the maximum deviation from the plane is 0.001 (3) Å in (I) and 0.002 (1) Å in (II)] and the nitro group. The values of these angles are small [2.3 (6)° in (I), and 5.2 (3) and 2.3 (2)° in the two independent molecules of (II)]; therefore, the whole molecules are approximately planar.

In both crystal structures, N—H···N hydrogen bonds form the primary motif of crystal packing (Table 1). Such chains are often observed in the crystal structures of the N-unsubstituted nitroimidazole derivatives (e.g. De Bondt et al., 1993). The chains created by these hydrogen bonds are almost identical in both cases (Figs. 3 and 4), even though in the asymmetric part of the unit cell of (II) there are two symmetry-independent molecules. It has been shown (Kubicki, 2005) that the percentage of structures with Z' > 1 (i.e. more than one symmetry-independent molecule) for simple imidazole derivatives is above the average value for organic molecules. In the structue of (II), the symmetry- independent molecules are almost identical, and the intermolecular interactions in which they take part are also almost identical. The only difference is that one of these molecule is connected with its centrosymmetric partner by a very weak, in fact disputable, C—N···C—N interaction [N···C distances of 3.516 (3) Å].

The differences in crystal packing are clearly seen at the next level of analysis, in the interactions between the chains. In (I), relatively short C—Br···O(nitro) halogen bonds connect the neighbouring chains. It might be noted that the Br···O contact of 2.986 (4) Å is one of the shortest contacts of this type. The contact to the other O atom of the nitro group is relatively long [3.363 (4) Å]. Such an unsymmetrical situation is quite typical; examples of (almost) symmetrical halogen bonds of this type are rare (cf. Kubicki, 2004b, and references therein). In (I), additional weak π–π interactions between molecules related by a b-glide plane perpendicular to x can also contribute to the determination of the structure. The molecules are almost parallel, the dihedral angle between the mean planes is 1.3 (3)°, and the distance between these planes is 3.487 Å (taking into account the offset; the distance between the mid-points is 3.730 Å).

On the other hand, in (II), it is hard to indicate any specific, directional interactions that could act between the chains (the cyano–cyano distances are far too long to play any role in the determination of crystal packing). Therefore, it is probable that just van der Waals forces are the driving factor for the packing of the hydrogen-bonded chains.

Related literature

For related literature, see: De Bondt, Ragia, Blaton, Peeters & De Ranter (1993); Kubicki (2004a, 2004b, 2005); Kubicki et al. (2001, 2002); Salgado-Zamora, Campos, Jimenez, Sanchez-Pavon & Cervantez (1999); Smithen & Hardy (1982); Suwiński & Świerczek (1998); Suwiński et al. (1996).

S2. Experimental

Compound (I) was synthesized by N-bromosuccinimide bromination of 4(5)-nitro-2-methylimidazole according to a previously described procedure (Salgado-Zamora et al. 1999). Compound (II) was obtained by cine nucleophilic substitution of nitro group from 1,4-dinitro-2-methylimidazole (Suwiński & Świerczek, 1998).

S3. Refinement

In (I), H atoms were placed in ideal positions and refined as riding, with U_iso(H) set at 1.2 (NH) and 1.3 (CH) times U_eq of their carrier atoms. In (II), methyl H atoms were again treated as riding, as in (I). The remaining H atom was refined freely.

Computing details

For both compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis CCD; data reduction: CrysAlis CCD [or RED????]; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Stereochemical Workstation (Siemens, 1989); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. An anisotropic displacement ellipsoid representation (at the 50% probability level) of the molecule of (I), together with the atomic numbering scheme.
	Fig. 2. An anisotropic displacement ellipsoid representation (at the 50% probability level) of both symmetry-independent molecules of (II), together with the atomic numbering scheme. The N—H···N hydrogen bond is shown as a dashed line.
	Fig. 3. A fragment of the hydrogen- and halogen-bonded structure of (I). [Symmetry codes: (i) x + 1/2, y, -z + 1/2; (ii) x - 1/2, y, -z + 1/2; (iii) x + 1/2, -y + 3/2, -z + 1; (iv) x, -y + 3/2, z + 1/2; (v) x - 1/2, -y + 3/2, -z + 1.]
	Fig. 4. The hydrogen-bonded chain of molecules in (II). [Symmetry code: (vi) x + 1, y - 1, z.]

(I) 2-Methyl-4-nitro-5-bromo-1H-imidazole

Crystal data

C4H4BrN3O2	F(000) = 800
Mr = 206.01	Dx = 2.133 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 5849 reflections
a = 10.5281 (10) Å	θ = 3–25°
b = 7.4585 (11) Å	µ = 6.34 mm^−1
c = 16.341 (2) Å	T = 100 K
V = 1283.2 (3) Å^3	Block, colourless
Z = 8	0.2 × 0.15 × 0.15 mm

Data collection

KUMA KM-4 CCD four-circle diffractometer	1187 independent reflections
Radiation source: fine-focus sealed tube	965 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.073
ω scan	θmax = 25.5°, θmin = 4.6°
Absorption correction: multi-scan (CrysAlis RED; Version 1.171.31.5; Oxford Diffraction, 2006)	h = −12→12
Tmin = 0.281, Tmax = 0.386	k = −8→9
9177 measured reflections	l = −19→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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.139	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0896P)^2 + 3.8475P] where P = (Fo^2 + 2Fc^2)/3
1187 reflections	(Δ/σ)max < 0.001
92 parameters	Δρmax = 1.47 e Å^−3
0 restraints	Δρmin = −0.89 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	0.6414 (4)	0.9470 (6)	0.2655 (2)	0.0186 (9)
H1	0.5651	0.9602	0.2478	0.022*
C2	0.7510 (5)	0.9843 (7)	0.2230 (3)	0.0200 (10)
C21	0.7500 (5)	1.0539 (7)	0.1368 (3)	0.0214 (11)
H21A	0.8289	1.1135	0.1256	0.028*
H21B	0.6811	1.1370	0.1303	0.028*
H21C	0.7393	0.9557	0.0995	0.028*
N3	0.8528 (4)	0.9494 (6)	0.2671 (2)	0.0182 (9)
C4	0.8068 (5)	0.8874 (8)	0.3406 (3)	0.0198 (10)
N4	0.8932 (5)	0.8309 (5)	0.4051 (3)	0.0198 (10)
O41	1.0049 (4)	0.8405 (6)	0.3908 (3)	0.0299 (10)
O42	0.8436 (4)	0.7756 (6)	0.4684 (2)	0.0311 (9)
C5	0.6761 (5)	0.8849 (8)	0.3412 (3)	0.0212 (11)
Br5	0.55768 (5)	0.81942 (8)	0.41977 (3)	0.0228 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0096 (18)	0.026 (2)	0.021 (2)	−0.0005 (17)	0.0011 (15)	0.0027 (18)
C2	0.015 (2)	0.022 (3)	0.022 (3)	−0.001 (2)	0.0045 (19)	0.000 (2)
C21	0.016 (2)	0.028 (3)	0.020 (3)	0.001 (2)	0.0034 (18)	0.005 (2)
N3	0.0094 (17)	0.027 (2)	0.019 (2)	0.0005 (17)	−0.0010 (15)	0.0028 (18)
C4	0.014 (2)	0.027 (3)	0.019 (2)	0.002 (2)	−0.005 (2)	0.000 (2)
N4	0.026 (3)	0.017 (2)	0.016 (2)	−0.0010 (18)	0.0084 (19)	−0.0019 (16)
O41	0.013 (2)	0.045 (3)	0.031 (2)	0.0031 (16)	−0.0065 (16)	0.0063 (18)
O42	0.0231 (19)	0.048 (3)	0.0228 (19)	0.0009 (18)	0.0018 (16)	0.0048 (18)
C5	0.019 (2)	0.028 (3)	0.016 (2)	0.002 (2)	0.0035 (19)	−0.001 (2)
Br5	0.0136 (4)	0.0340 (4)	0.0209 (4)	−0.00205 (19)	0.00243 (17)	0.00123 (19)

Geometric parameters (Å, º)

N1—C5	1.370 (6)	C21—H21C	0.9600
N1—C2	1.375 (7)	N3—C4	1.376 (6)
N1—H1	0.8600	C4—C5	1.376 (7)
C2—N3	1.317 (7)	C4—N4	1.454 (7)
C2—C21	1.501 (8)	N4—O41	1.201 (7)
C21—H21A	0.9600	N4—O42	1.230 (6)
C21—H21B	0.9600	C5—Br5	1.855 (5)
C5—N1—C2	107.5 (4)	H21B—C21—H21C	109.5
C5—N1—H1	126.3	C2—N3—C4	104.9 (4)
C2—N1—H1	126.2	N3—C4—C5	111.3 (4)
N3—C2—N1	111.5 (4)	N3—C4—N4	120.6 (4)
N3—C2—C21	125.9 (5)	C5—C4—N4	128.1 (5)
N1—C2—C21	122.6 (5)	O41—N4—O42	126.7 (5)
C2—C21—H21A	109.5	O41—N4—C4	117.1 (4)
C2—C21—H21B	109.5	O42—N4—C4	116.2 (5)
H21A—C21—H21B	109.5	N1—C5—C4	104.8 (4)
C2—C21—H21C	109.5	N1—C5—Br5	122.3 (4)
H21A—C21—H21C	109.5	C4—C5—Br5	132.9 (4)
C5—N1—C2—N3	0.1 (6)	N3—C4—N4—O42	−179.2 (5)
C5—N1—C2—C21	179.4 (5)	C5—C4—N4—O42	−0.8 (8)
N1—C2—N3—C4	−0.1 (6)	C2—N1—C5—C4	−0.1 (6)
C21—C2—N3—C4	−179.3 (5)	C2—N1—C5—Br5	179.5 (4)
C2—N3—C4—C5	0.0 (6)	N3—C4—C5—N1	0.1 (6)
C2—N3—C4—N4	178.6 (5)	N4—C4—C5—N1	−178.4 (5)
N3—C4—N4—O41	−0.3 (7)	N3—C4—C5—Br5	−179.5 (4)
C5—C4—N4—O41	178.2 (5)	N4—C4—C5—Br5	2.0 (9)

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

Crystal data

C5H4N4O2	Z = 4
Mr = 152.12	F(000) = 312
Triclinic, P1	Dx = 1.477 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7166 (15) Å	Cell parameters from 1961 reflections
b = 8.1716 (11) Å	θ = 3–25°
c = 11.715 (2) Å	µ = 0.12 mm^−1
α = 74.278 (14)°	T = 295 K
β = 77.630 (17)°	Block, colourless
γ = 77.150 (14)°	0.3 × 0.2 × 0.15 mm
V = 683.9 (2) Å^3

Data collection

KUMA KM- 4 CCD four-circle diffractometer	1325 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.025
Graphite monochromator	θmax = 25.0°, θmin = 2.8°
ω scan	h = −8→9
4954 measured reflections	k = −9→9
2360 independent reflections	l = −13→13

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.105	H atoms treated by a mixture of independent and constrained refinement
S = 0.97	w = 1/[σ^2(Fo^2) + (0.050P)^2] where P = (Fo^2 + 2Fc^2)/3
2360 reflections	(Δ/σ)max < 0.001
209 parameters	Δρmax = 0.23 e Å^−3
0 restraints	Δρmin = −0.22 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
N1A	0.8507 (3)	0.1883 (3)	0.22523 (19)	0.0467 (6)
H1A	0.914 (4)	0.086 (3)	0.257 (2)	0.066 (9)*
C2A	0.7128 (3)	0.2733 (3)	0.2904 (2)	0.0438 (6)
C21A	0.6577 (4)	0.2122 (3)	0.4221 (2)	0.0639 (8)
H21A	0.6004	0.3092	0.4560	0.083*
H21B	0.7622	0.1541	0.4582	0.083*
H21C	0.5751	0.1337	0.4371	0.083*
N3A	0.6344 (3)	0.4164 (2)	0.22188 (17)	0.0430 (5)
C4A	0.7283 (3)	0.4186 (3)	0.1106 (2)	0.0394 (6)
N4A	0.6838 (3)	0.5552 (3)	0.0095 (2)	0.0484 (5)
O41A	0.5503 (3)	0.6657 (2)	0.02416 (17)	0.0633 (6)
O42A	0.7840 (3)	0.5540 (2)	−0.08683 (17)	0.0660 (6)
C5A	0.8630 (3)	0.2795 (3)	0.1082 (2)	0.0407 (6)
C51A	0.9956 (4)	0.2282 (3)	0.0134 (3)	0.0494 (7)
N51A	1.1037 (3)	0.1872 (3)	−0.0616 (2)	0.0735 (8)
N1B	0.3036 (3)	0.6445 (3)	0.2744 (2)	0.0488 (6)
H1B	0.409 (4)	0.595 (3)	0.262 (2)	0.062 (9)*
C2B	0.2551 (3)	0.8185 (3)	0.2516 (2)	0.0454 (6)
C21B	0.3835 (4)	0.9400 (3)	0.1984 (3)	0.0649 (8)
H21D	0.3663	0.9966	0.1174	0.084*
H21E	0.5046	0.8775	0.1984	0.084*
H21F	0.3629	1.0247	0.2451	0.084*
N3B	0.0778 (3)	0.8635 (2)	0.28113 (17)	0.0438 (5)
C4B	0.0171 (3)	0.7125 (3)	0.3227 (2)	0.0406 (6)
N4B	−0.1719 (3)	0.7083 (3)	0.36126 (18)	0.0522 (6)
O41B	−0.2764 (2)	0.8462 (3)	0.35371 (17)	0.0688 (6)
O42B	−0.2175 (3)	0.5666 (2)	0.40155 (18)	0.0739 (6)
C5B	0.1519 (3)	0.5732 (3)	0.3201 (2)	0.0431 (6)
C51B	0.1527 (4)	0.3925 (3)	0.3542 (2)	0.0523 (7)
N51B	0.1538 (4)	0.2480 (3)	0.3824 (2)	0.0787 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1A	0.0434 (14)	0.0403 (12)	0.0471 (14)	0.0000 (11)	−0.0031 (11)	−0.0039 (11)
C2A	0.0412 (15)	0.0389 (13)	0.0451 (15)	−0.0026 (11)	0.0000 (12)	−0.0085 (12)
C21A	0.077 (2)	0.0524 (16)	0.0468 (18)	−0.0038 (15)	0.0013 (15)	−0.0009 (13)
N3A	0.0404 (12)	0.0397 (11)	0.0422 (13)	−0.0010 (9)	−0.0017 (10)	−0.0076 (9)
C4A	0.0376 (14)	0.0370 (12)	0.0387 (15)	−0.0044 (11)	−0.0056 (12)	−0.0029 (11)
N4A	0.0516 (14)	0.0459 (12)	0.0472 (15)	−0.0131 (11)	−0.0082 (12)	−0.0065 (11)
O41A	0.0560 (12)	0.0456 (10)	0.0766 (14)	0.0032 (9)	−0.0155 (10)	−0.0014 (9)
O42A	0.0820 (15)	0.0694 (13)	0.0404 (12)	−0.0163 (11)	−0.0026 (11)	−0.0056 (9)
C5A	0.0375 (14)	0.0421 (13)	0.0404 (15)	−0.0066 (11)	−0.0013 (12)	−0.0107 (11)
C51A	0.0474 (16)	0.0493 (15)	0.0511 (17)	−0.0076 (13)	−0.0056 (14)	−0.0138 (13)
N51A	0.0617 (17)	0.0902 (19)	0.0675 (17)	−0.0078 (14)	0.0069 (14)	−0.0345 (15)
N1B	0.0405 (14)	0.0442 (13)	0.0526 (15)	0.0077 (11)	−0.0060 (11)	−0.0097 (10)
C2B	0.0458 (16)	0.0416 (14)	0.0437 (15)	0.0014 (12)	−0.0058 (12)	−0.0101 (11)
C21B	0.0484 (17)	0.0552 (16)	0.086 (2)	−0.0101 (13)	−0.0031 (15)	−0.0137 (15)
N3B	0.0404 (13)	0.0407 (11)	0.0454 (13)	−0.0003 (10)	−0.0060 (10)	−0.0080 (9)
C4B	0.0377 (15)	0.0443 (14)	0.0365 (14)	−0.0031 (12)	−0.0037 (11)	−0.0090 (11)
N4B	0.0537 (15)	0.0552 (14)	0.0466 (14)	−0.0081 (12)	−0.0055 (11)	−0.0135 (11)
O41B	0.0467 (11)	0.0677 (13)	0.0783 (15)	0.0038 (10)	−0.0024 (10)	−0.0117 (11)
O42B	0.0718 (14)	0.0652 (13)	0.0864 (15)	−0.0291 (11)	0.0054 (12)	−0.0210 (11)
C5B	0.0484 (16)	0.0399 (14)	0.0360 (14)	−0.0019 (12)	−0.0021 (12)	−0.0091 (11)
C51B	0.0680 (19)	0.0443 (15)	0.0387 (16)	−0.0021 (14)	−0.0029 (14)	−0.0108 (12)
N51B	0.116 (2)	0.0491 (14)	0.0657 (17)	−0.0103 (14)	−0.0086 (15)	−0.0130 (12)

Geometric parameters (Å, º)

N1A—C2A	1.345 (3)	N1B—C2B	1.354 (3)
N1A—C5A	1.366 (3)	N1B—C5B	1.365 (3)
N1A—H1A	0.90 (3)	N1B—H1B	0.82 (3)
C2A—N3A	1.328 (3)	C2B—N3B	1.330 (3)
C2A—C21A	1.485 (3)	C2B—C21B	1.481 (3)
C21A—H21A	0.9600	C21B—H21D	0.9600
C21A—H21B	0.9600	C21B—H21E	0.9600
C21A—H21C	0.9600	C21B—H21F	0.9600
N3A—C4A	1.346 (3)	N3B—C4B	1.347 (3)
C4A—C5A	1.361 (3)	C4B—C5B	1.363 (3)
C4A—N4A	1.434 (3)	C4B—N4B	1.437 (3)
N4A—O42A	1.224 (2)	N4B—O41B	1.225 (3)
N4A—O41A	1.225 (2)	N4B—O42B	1.225 (2)
C5A—C51A	1.425 (4)	C5B—C51B	1.420 (3)
C51A—N51A	1.141 (3)	C51B—N51B	1.135 (3)
C2A—N1A—C5A	108.0 (2)	C2B—N1B—C5B	108.4 (2)
C2A—N1A—H1A	122.6 (16)	C2B—N1B—H1B	123.5 (18)
C5A—N1A—H1A	129.2 (17)	C5B—N1B—H1B	128.1 (18)
N3A—C2A—N1A	111.2 (2)	N3B—C2B—N1B	110.7 (2)
N3A—C2A—C21A	125.3 (2)	N3B—C2B—C21B	125.3 (2)
N1A—C2A—C21A	123.5 (2)	N1B—C2B—C21B	123.9 (2)
C2A—C21A—H21A	109.5	C2B—C21B—H21D	109.5
C2A—C21A—H21B	109.5	C2B—C21B—H21E	109.5
H21A—C21A—H21B	109.5	H21D—C21B—H21E	109.5
C2A—C21A—H21C	109.5	C2B—C21B—H21F	109.5
H21A—C21A—H21C	109.5	H21D—C21B—H21F	109.5
H21B—C21A—H21C	109.5	H21E—C21B—H21F	109.5
C2A—N3A—C4A	104.37 (19)	C2B—N3B—C4B	104.48 (18)
N3A—C4A—C5A	112.4 (2)	N3B—C4B—C5B	112.7 (2)
N3A—C4A—N4A	121.5 (2)	N3B—C4B—N4B	121.0 (2)
C5A—C4A—N4A	126.2 (2)	C5B—C4B—N4B	126.3 (2)
O42A—N4A—O41A	124.1 (2)	O41B—N4B—O42B	124.4 (2)
O42A—N4A—C4A	117.2 (2)	O41B—N4B—C4B	118.0 (2)
O41A—N4A—C4A	118.7 (2)	O42B—N4B—C4B	117.6 (2)
C4A—C5A—N1A	104.0 (2)	C4B—C5B—N1B	103.7 (2)
C4A—C5A—C51A	132.4 (2)	C4B—C5B—C51B	132.6 (2)
N1A—C5A—C51A	123.6 (2)	N1B—C5B—C51B	123.7 (2)
N51A—C51A—C5A	179.0 (3)	N51B—C51B—C5B	179.3 (3)
C5A—N1A—C2A—N3A	−0.3 (3)	C2A—N1A—C5A—C51A	179.4 (2)
C5A—N1A—C2A—C21A	179.6 (2)	C5B—N1B—C2B—N3B	0.3 (3)
N1A—C2A—N3A—C4A	0.0 (3)	C5B—N1B—C2B—C21B	−178.4 (2)
C21A—C2A—N3A—C4A	−180.0 (2)	N1B—C2B—N3B—C4B	−0.2 (3)
C2A—N3A—C4A—C5A	0.3 (3)	C21B—C2B—N3B—C4B	178.6 (2)
C2A—N3A—C4A—N4A	179.9 (2)	C2B—N3B—C4B—C5B	0.0 (3)
N3A—C4A—N4A—O42A	174.8 (2)	C2B—N3B—C4B—N4B	−178.5 (2)
C5A—C4A—N4A—O42A	−5.7 (4)	N3B—C4B—N4B—O41B	0.9 (3)
N3A—C4A—N4A—O41A	−4.8 (3)	C5B—C4B—N4B—O41B	−177.3 (2)
C5A—C4A—N4A—O41A	174.7 (2)	N3B—C4B—N4B—O42B	−177.8 (2)
N3A—C4A—C5A—N1A	−0.5 (3)	C5B—C4B—N4B—O42B	4.0 (4)
N4A—C4A—C5A—N1A	180.0 (2)	N3B—C4B—C5B—N1B	0.2 (3)
N3A—C4A—C5A—C51A	−179.3 (2)	N4B—C4B—C5B—N1B	178.6 (2)
N4A—C4A—C5A—C51A	1.2 (4)	C2B—N1B—C5B—C4B	−0.3 (3)
C2A—N1A—C5A—C4A	0.5 (3)	C2B—N1B—C5B—C51B	179.9 (2)