N-Meth­yl-N-(2-nitro­phen­yl)nitramine and N-meth­yl-N-(3-nitro­phen­yl)­nitramine

The structures of the two title isomeric compounds (systematic names: N-meth­yl-N,2-dinitro­aniline and N-meth­yl-N,3-di­nitro­aniline, both C₇H₇N₃O₄) are slightly different because they exhibit different steric hindrances and hydrogen-bonding environments. The aromatic rings are planar. The –N(Me)NO₂ and –NO₂ groups are not coplanar with the rings. Comparison of the geometric parameters of the ortho, meta and para isomers together with those of N-meth­yl-N-phenyl­nitramine suggests that the position of the nitro group has a strong influence on the aromatic ring distortion. The crystal packing is stabilized by weak C—H...O hydrogen bonds to the nitramine group.

S1. Comment

Nitramines and related N-nitro compounds have attracted significant attention from researchers in view of their application in rocket fuel and as explosives (Williams 1982). The compounds of this series are particularly interesting, since the nitro group in N-methyl-N-nitroaniline and its derivatives can undergo a rearrangement at elevated temperatures, under acid conditions or on photolysis (Growenlock et al., 1997). Owing to the presence of an N—N bond, these compounds are also very active in photochemical reactions (Mialocq & Stephenson, 1986), and their structures have also been investigated in the past few years (Daszkiewicz et al., 2000; Prezhdo et al., 2001; Zhukhlistova et al., 2002). In the molecular structures of typical secondary aromatic nitramines, there are two planar π-electron fragments, viz. the aromatic ring and the nitramine (NNO₂) group, which are not coplanar. The π electrons of the nitramine group are not conjugated within the aromatic ring. The twisted conformation of N-methyl-N-phenylnitramines is probably a result of intermolecular interactions.

Our earlier investigations have been devoted to aromatic nitramines with selected substituents (Daszkiewicz et al., 1995, 2002). To obtain further information about the differences in structures of the compounds substituted by a nitramine group, since the structure of N-methyl-N-(4-nitrophenyl)nitramine has already been published (Anulewicz et al., 1993), we have prepared the ortho and meta derivatives.

The molecular structures of N-methyl-N-(2-nitrophenyl)nitramine, (I), and N-methyl-N-(3-nitrophenyl)nitramine, (II), are shown in Figs. 1 and 2. In both molecules, the aromatic rings are slightly deformed by electronic and steric interactions. In (I), the average C—C bond length is 1.389 (2) Å, whereas in (II) it is 1.395 (2) Å. The largest difference between the shortest and longest C—C bonds is in (I) 0.031 (3) Å, whereas in (II) the difference is 0.011 (3) Å. The bond-length difference is undoubtedly caused by the presence of the N(Me)NO₂ and NO₂ groups connected to atoms C1 and C2. Such a distortion of the aromatic ring has not been observed in the structure of unsubstituted N-methyl-N-phenylnitramine (Prezhdo et al., 2001), in which all C—C bonds are in the range 1.364 (4)–1.376 (4) Å.

Comparison of the geometric parameters of the ortho, meta and para isomers together with those of N-methyl-N-phenylnitramine suggests that the position of the nitro group has a strong influence on the aromatic ring distortion. The presence of the nitro group in the meta position in (II) significantly increases the C2—C3—C4 angle [to 123.4 (1)°]. It should be noted that the two neighbouring C—C—C angles are decreased [C1—C2—C3 = 117.5 (1)° and C3—C4—C5 = 117.8 (1)°] and the two subsequent ones are slightly increased [C6—C1—C2 = 120.8 (1)° and C4—C5—C6 = 120.6 (1)°]. Similar effects have also been found in 4-nitro-N-methyl-N-phenylnitramine; the C3—C4—C5 angle is similarly increased [to 122.9 (2)°], whereas the two neighbouring angles are decreased to 118.3 (2)° (Anulewicz et al., 1993).

At the position in which the nitramine group is connected in (II), the C6—C1—C2 angle is increased from 120 to 120.8 (1)°; in the para substituted compound, the increase is larger [1.7 (2)°]. In (I), however, this angle is decreased by 1.4 (1)°. It should be mentioned that the C—C—C angle to which the NO₂ group is connected and that to which the N(Me)NO₂ group is connected are quite similar [2.2 (1)° for ortho and para, but 2.6 (1)° for the meta compound]. Taking into account only the geometric structures of (I) and (II), it seems that the deformation of the aromatic ring is caused more by steric hindrance than by the π-electron interactions.

In both structures, the nitro groups are not coplanar with the aromatic rings. They are twisted by 11.9 (2)° for (I) and by 22.1 (2)° for (II) with respect to the ring plane. A much smaller twist [2.5 (2)°] is present in the para isomer (Anulewicz et al., 1993). In the overcrowded structure of (I), the position of the nitro group causes an increase of the C1—C2—N12 angle to 121.8 (1)° and a decrease of the C3—C2—N12 angle to 117.5 (1)°. In (II), both related angles are smaller than 120° [by 2.6 (1)° and 0.8 (1)°].

In both studied molecules, the N—NO₂ group is not coplanar with the aromatic ring, which suggests a lack of interaction between those two groups. In (I) and 4-nitro-N-methyl-N-phenylnitramine, the N-methylnitramine group is twisted along the C_ar—N bond by −80.4 (1) and −72.3 (2)°, respectively. This is a characteristic feature of N-methyl-N-phenylnitramine derivatives. It should be noted, however, that N-methyl-N-phenylnitramine has a smaller twist angle [−66.3 (2)°], whereas in (II), the group is twisted by even a smaller angle [−49.6 (1)°].

The bond lengths and angles of the nitramine group agree with the corresponding values found in 4-nitro-N-methyl-N-phenylnitramine. Atom N7 lies slightly out of the plane of the benzene ring [its deviation is 0.026 (1) Å in (I) and 0.109 (1) Å in (II)]. In (II), the sum of the valence angles around N7 [360.0 (1)°] indicates trigonal hybridization of the amine N atom. In (I), however, this sum is equal to 358.9 (1)° and N7 is 0.086 (1) Å from the C1/N8/C11 plane.

The N7—N8 bond lengths [1.349 (2) Å for (I) and 1.355 (1) Å for (II)] have intermediate values between those of typical single (1.45 Å) and double (1.25 Å) bonds, as expected (Allen et al., 1995; Daszkiewicz et al., 2002). Similar effects have also been observed in all derivatives of N-methyl-N-phenylnitramine (Cady, 1967; Prezhdo et al., 2001; Zhukhlistova et al., 2002).

In both structures the crystal packing is stabilized by weak intermolecular C—H···O hydrogen bonds, forming an extended three-dimensional network. The polarity of the nitramine group and the distribution of the partial charges influence the formation of hydrogen bonds. In both studied structures all hydrogen bonds include only the O atoms of the nitro group connected to N7. The NO₂ group bound to the phenyl ring does not participate in the hydrogen-bonding scheme in (I) or in (II).

S2. Experimental

For the preparation of (I), solid N-methyl-2-nitroaniline (3 g, 20 mmol) was added in portions to cold acetic anhydride (30 ml) containing nitric acid (1.7 ml, 41 mmol, HNO₃ d = 1.5). The solution was kept for 30 min at room temperature and evaporated in vacuum (323 K). The residue was crystallized from methanol and recrystallized from ethanol. N-Methyl-N-(2-nitrophenyl)nitramine was obtained (2.5 g, 63%) as colourless crystals melting at 340–341 K. MS (m/z) (intensity): 197 (M⁺, 4), 151 (97), 134 (100), 121 (11), 105 (38), 93 (60), 77 (69); IR (KBr, cm⁻¹): 1530, 1523 (ν_as N—O), 1345, 1295 (ν_s N—O); 1 H NMR (CDCl₃, p.p.m.): δ 8.24–7.43 (m, 4H, aromatic H atoms), 3.74 (s, 3H, N-methyl group). For the preparation of (II), N-methyl-N-(3-nitrophenyl)nitramine was prepared according to the above procedure. The nitramine was obtained with 72% yield as colourless crystals melting at 347–348 K. MS (m/z) (intensity): 197 (M⁺, 2), 151 (100), 122 (10), 105 (80), 93 (4), 77 (16); IR (KBr, cm⁻¹): 1528 (ν_as N—O), 1351, 1291 (ν_s N—O); 1 H NMR (CDCl₃, p.p.m.): δ 8.33–8.22 (m, 2H), 7.74–7.67 (m, 2H, aromatic H atoms), 3.78 (s, 3H, N-methyl group).

S3. Refinement

C—H bond distances are in the range 0.917 (17)–0.985 (19) Å, and U_iso(H) values are in the range 0.020 (4)–0.052 (6) Ų for compound (I). For compound (II), the ranges are 0.942 (16)–0.983 (17) Å and 0.013 (3)–0.031 (4) Ų, respectively.

Computing details

For both compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2002); cell refinement: CrysAlis RED (Oxford Diffraction, 2002); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1990); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. Molecular structure of (I), with atom labels. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Molecular structure of (II), with atom labels. Displacement ellipsoids are drawn at the 50% probability level.

(I) N-methyl-N,2-dinitroaniline

Crystal data

C7H7N3O4	F(000) = 408
Mr = 197.16	Dx = 1.585 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5344 reflections
a = 7.0470 (8) Å	θ = 3.2–26.0°
b = 14.4473 (12) Å	µ = 0.13 mm^−1
c = 8.1165 (8) Å	T = 100 K
β = 90.814 (8)°	Irregular, colourless
V = 826.26 (14) Å^3	0.2 × 0.2 × 0.15 mm
Z = 4

Data collection

Oxford Diffraction Xcalibur diffractometer	1294 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.030
Graphite monochromator	θmax = 26.0°, θmin = 3.2°
Detector resolution: 1024 x 1024 with blocks 2 x 2 pixels mm^-1	h = −8→8
ω scan	k = −17→11
5344 measured reflections	l = −10→10
1591 independent reflections

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)] = 0.032	All H-atom parameters refined
wR(F^2) = 0.089	w = 1/[σ^2(Fo^2) + (0.0566P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
1591 reflections	Δρmax = 0.24 e Å^−3
156 parameters	Δρmin = −0.23 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: 0.024 (4)

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
C1	0.22803 (17)	0.60607 (9)	0.36343 (16)	0.0149 (3)
C2	0.25099 (18)	0.50913 (9)	0.36322 (15)	0.0149 (3)
C3	0.26524 (18)	0.46040 (9)	0.50953 (16)	0.0174 (3)
C4	0.25786 (19)	0.50742 (10)	0.65795 (17)	0.0197 (3)
C5	0.23134 (19)	0.60261 (10)	0.65981 (17)	0.0207 (3)
C6	0.21559 (18)	0.65114 (9)	0.51269 (16)	0.0176 (3)
C11	0.0234 (2)	0.67519 (12)	0.1375 (2)	0.0284 (4)
N7	0.20631 (15)	0.66061 (7)	0.21752 (13)	0.0167 (3)
N8	0.36519 (16)	0.68446 (7)	0.13714 (13)	0.0179 (3)
N12	0.25991 (16)	0.45593 (7)	0.20892 (14)	0.0188 (3)
O9	0.51851 (13)	0.67029 (7)	0.20803 (12)	0.0258 (3)
O10	0.34606 (14)	0.72050 (6)	0.00036 (11)	0.0231 (3)
O13	0.24804 (17)	0.37197 (6)	0.21699 (13)	0.0346 (3)
O14	0.27871 (19)	0.49712 (7)	0.07924 (12)	0.0407 (3)
H3	0.285 (2)	0.3931 (10)	0.5033 (17)	0.020 (4)*
H4	0.272 (2)	0.4768 (10)	0.756 (2)	0.027 (4)*
H5	0.222 (2)	0.6350 (11)	0.761 (2)	0.025 (4)*
H6	0.194 (2)	0.7168 (11)	0.5149 (18)	0.024 (4)*
H11A	−0.075 (3)	0.6768 (11)	0.222 (2)	0.034 (5)*
H11B	0.003 (3)	0.6254 (14)	0.061 (2)	0.052 (6)*
H11C	0.027 (3)	0.7353 (13)	0.082 (2)	0.052 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0122 (6)	0.0149 (6)	0.0177 (7)	−0.0018 (5)	−0.0001 (5)	0.0014 (5)
C2	0.0145 (6)	0.0155 (6)	0.0147 (7)	−0.0013 (5)	0.0000 (5)	−0.0032 (5)
C3	0.0159 (7)	0.0154 (6)	0.0208 (7)	−0.0015 (5)	−0.0006 (5)	0.0009 (5)
C4	0.0175 (7)	0.0254 (7)	0.0161 (7)	−0.0032 (6)	0.0000 (5)	0.0045 (6)
C5	0.0181 (7)	0.0257 (7)	0.0184 (7)	−0.0027 (6)	0.0014 (6)	−0.0069 (6)
C6	0.0155 (6)	0.0150 (7)	0.0224 (7)	−0.0004 (5)	0.0000 (5)	−0.0031 (5)
C11	0.0199 (8)	0.0355 (9)	0.0295 (9)	−0.0012 (7)	−0.0071 (7)	0.0122 (7)
N7	0.0157 (6)	0.0155 (6)	0.0189 (6)	−0.0009 (4)	−0.0005 (5)	0.0033 (4)
N8	0.0210 (6)	0.0141 (5)	0.0185 (6)	−0.0006 (4)	−0.0005 (5)	0.0006 (4)
N12	0.0225 (6)	0.0155 (6)	0.0184 (6)	0.0002 (5)	0.0000 (5)	−0.0007 (5)
O9	0.0163 (5)	0.0310 (6)	0.0299 (6)	−0.0012 (4)	−0.0024 (4)	0.0103 (4)
O10	0.0305 (6)	0.0221 (5)	0.0166 (5)	−0.0035 (4)	−0.0009 (4)	0.0051 (4)
O13	0.0660 (8)	0.0123 (5)	0.0255 (6)	0.0006 (5)	−0.0008 (5)	−0.0030 (4)
O14	0.0849 (10)	0.0220 (5)	0.0152 (6)	−0.0032 (6)	0.0064 (5)	−0.0008 (5)

Geometric parameters (Å, º)

C1—C6	1.379 (2)	C6—H6	0.960 (15)
C1—C2	1.410 (2)	N7—N8	1.349 (2)
C1—N7	1.429 (2)	N7—C11	1.4500 (18)
C2—C3	1.383 (2)	C11—H11A	0.985 (19)
C2—N12	1.4714 (16)	C11—H11B	0.96 (2)
C3—C4	1.385 (2)	C11—H11C	0.980 (19)
C3—H3	0.984 (15)	N8—O10	1.2319 (13)
C4—C5	1.388 (2)	N8—O9	1.2340 (14)
C4—H4	0.917 (17)	N12—O13	1.2178 (14)
C5—C6	1.388 (2)	N12—O14	1.2180 (15)
C5—H5	0.947 (17)
C6—C1—C2	118.6 (1)	C5—C6—H6	119.6 (9)
C6—C1—N7	117.4 (1)	N8—N7—C1	117.51 (10)
C2—C1—N7	123.9 (1)	N8—N7—C11	119.01 (11)
C3—C2—C1	120.8 (1)	C1—N7—C11	122.36 (11)
C3—C2—N12	117.5 (1)	N7—C11—H11A	108.7 (10)
C1—C2—N12	121.8 (1)	N7—C11—H11B	107.8 (12)
C2—C3—C4	119.6 (1)	H11A—C11—H11B	111.7 (16)
C2—C3—H3	117.9 (8)	N7—C11—H11C	108.0 (11)
C4—C3—H3	122.5 (8)	H11A—C11—H11C	109.0 (15)
C3—C4—C5	120.2 (1)	H11B—C11—H11C	111.6 (14)
C3—C4—H4	121.0 (10)	O10—N8—O9	125.05 (11)
C5—C4—H4	118.8 (10)	O10—N8—N7	117.58 (11)
C6—C5—C4	120.0 (1)	O9—N8—N7	117.35 (11)
C6—C5—H5	119.3 (9)	O13—N12—O14	122.79 (12)
C4—C5—H5	120.7 (9)	O13—N12—C2	118.08 (11)
C1—C6—C5	120.8 (1)	O14—N12—C2	119.13 (10)
C1—C6—H6	119.6 (9)
C6—C1—C2—C3	−1.50 (18)	C2—C1—N7—N8	−82.2 (2)
N7—C1—C2—C3	−177.93 (11)	C6—C1—N7—C11	−90.85 (16)
C6—C1—C2—N12	178.23 (11)	C2—C1—N7—C11	85.63 (17)
N7—C1—C2—N12	1.80 (19)	C1—N7—N8—O10	170.44 (10)
C1—C2—C3—C4	−0.34 (19)	C11—N7—N8—O10	2.25 (17)
N12—C2—C3—C4	179.92 (11)	C1—N7—N8—O9	−11.10 (16)
C2—C3—C4—C5	1.7 (2)	C11—N7—N8—O9	−179.30 (12)
C3—C4—C5—C6	−1.2 (2)	C3—C2—N12—O13	11.8 (2)
C2—C1—C6—C5	2.02 (19)	C1—C2—N12—O13	−168.0 (1)
N7—C1—C6—C5	178.69 (11)	C3—C2—N12—O14	−168.2 (1)
C4—C5—C6—C1	−0.7 (2)	C1—C2—N12—O14	12.0 (2)
C6—C1—N7—N8	101.4 (1)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O10^i	0.95 (2)	2.46 (2)	3.336 (2)	155 (1)
C6—H6···O9^ii	0.96 (2)	2.59 (2)	3.341 (2)	135 (1)
C4—H4···O9^iii	0.92 (2)	2.60 (2)	3.195 (2)	123 (1)

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

(II) N-methyl-N,3-dinitroaniline

Crystal data

C7H7N3O4	F(000) = 408
Mr = 197.16	Dx = 1.560 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5281 reflections
a = 8.7322 (11) Å	θ = 3.3–26.0°
b = 13.6510 (16) Å	µ = 0.13 mm^−1
c = 7.5547 (12) Å	T = 100 K
β = 111.195 (13)°	Irregular, colourless
V = 839.6 (2) Å^3	0.4 × 0.4 × 0.3 mm
Z = 4

Data collection

Oxford Diffaction Xcalibur diffractometer	1417 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.013
Graphite monochromator	θmax = 26.0°, θmin = 3.3°
Detector resolution: 1024 x 1024 with blocks 2 x 2 pixels mm^-1	h = −10→10
ω scan	k = −16→16
5281 measured reflections	l = −9→6
1637 independent reflections

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.078	All H-atom parameters refined
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0418P)^2 + 0.2056P] where P = (Fo^2 + 2Fc^2)/3
1637 reflections	(Δ/σ)max < 0.001
155 parameters	Δρmax = 0.18 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
C1	0.76604 (14)	0.53991 (8)	0.20021 (16)	0.0140 (3)
C2	0.71685 (14)	0.53589 (9)	0.35665 (16)	0.0144 (3)
C3	0.74957 (14)	0.44999 (9)	0.46347 (16)	0.0157 (3)
C4	0.83294 (15)	0.37083 (9)	0.42600 (17)	0.0179 (3)
C5	0.88578 (15)	0.37831 (9)	0.27245 (18)	0.0182 (3)
C6	0.85025 (14)	0.46159 (9)	0.15780 (16)	0.0153 (3)
C11	0.55200 (16)	0.66311 (10)	0.00480 (19)	0.0217 (3)
N7	0.71971 (12)	0.62407 (7)	0.07874 (14)	0.0152 (2)
N8	0.83387 (12)	0.67065 (7)	0.02680 (14)	0.0175 (2)
N12	0.69043 (13)	0.44405 (8)	0.62346 (14)	0.0185 (2)
O9	0.97833 (11)	0.64514 (7)	0.09907 (13)	0.0241 (2)
O10	0.78501 (12)	0.73882 (7)	−0.08827 (13)	0.0260 (2)
O14	0.66200 (11)	0.52127 (7)	0.69134 (12)	0.0250 (2)
O13	0.66966 (11)	0.36210 (7)	0.68037 (13)	0.0265 (2)
H2	0.6596 (16)	0.5894 (10)	0.3894 (18)	0.013 (3)*
H4	0.8569 (18)	0.3123 (11)	0.505 (2)	0.025 (4)*
H5	0.9426 (17)	0.3252 (10)	0.2429 (18)	0.015 (3)*
H6	0.8838 (17)	0.4618 (10)	0.050 (2)	0.016 (3)*
H11A	0.508 (2)	0.6603 (11)	−0.135 (3)	0.031 (4)*
H11B	0.5512 (19)	0.7303 (12)	0.045 (2)	0.031 (4)*
H11C	0.488 (2)	0.6215 (11)	0.050 (2)	0.028 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0120 (5)	0.0132 (6)	0.0139 (6)	−0.0021 (4)	0.0013 (4)	−0.0011 (4)
C2	0.0125 (6)	0.0138 (6)	0.0157 (6)	−0.0017 (4)	0.0035 (5)	−0.0037 (4)
C3	0.0135 (6)	0.0194 (6)	0.0121 (6)	−0.0034 (4)	0.0022 (4)	−0.0013 (4)
C4	0.0174 (6)	0.0155 (6)	0.0169 (6)	0.0004 (5)	0.0016 (5)	0.0020 (5)
C5	0.0173 (6)	0.0155 (6)	0.0195 (6)	0.0029 (5)	0.0041 (5)	−0.0015 (5)
C6	0.0144 (6)	0.0172 (6)	0.0140 (6)	−0.0007 (4)	0.0045 (5)	−0.0025 (5)
C11	0.0185 (6)	0.0231 (7)	0.0216 (7)	0.0068 (5)	0.0050 (5)	0.0046 (6)
N7	0.0154 (5)	0.0142 (5)	0.0158 (5)	0.0008 (4)	0.0054 (4)	0.0010 (4)
N8	0.0202 (6)	0.0148 (5)	0.0171 (5)	−0.0030 (4)	0.0063 (4)	−0.0004 (4)
N12	0.0161 (5)	0.0233 (6)	0.0143 (5)	−0.0019 (4)	0.0033 (4)	0.0007 (4)
O9	0.0195 (5)	0.0234 (5)	0.0305 (5)	0.0002 (4)	0.0104 (4)	−0.0008 (4)
O10	0.0329 (5)	0.0186 (5)	0.0254 (5)	−0.0016 (4)	0.0092 (4)	0.0083 (4)
O14	0.0303 (5)	0.0279 (5)	0.0191 (5)	0.0004 (4)	0.0116 (4)	−0.0041 (4)
O13	0.0277 (5)	0.0269 (5)	0.0268 (5)	−0.0028 (4)	0.0122 (4)	0.0076 (4)

Geometric parameters (Å, º)

C1—C2	1.397 (2)	C6—H6	0.962 (14)
C1—C6	1.399 (2)	N7—N8	1.355 (1)
C1—N7	1.434 (2)	N7—C11	1.4660 (16)
C2—C3	1.393 (2)	C11—H11A	0.983 (17)
C2—H2	0.966 (14)	C11—H11B	0.967 (16)
C3—C4	1.388 (2)	C11—H11C	0.942 (16)
C3—N12	1.4784 (16)	N8—O9	1.2299 (14)
C4—C5	1.399 (2)	N8—O10	1.2391 (13)
C4—H4	0.973 (15)	N12—O13	1.2352 (14)
C5—C6	1.395 (2)	N12—O14	1.2360 (14)
C5—H5	0.950 (14)
C2—C1—C6	120.8 (1)	C1—C6—H6	122.6 (8)
C2—C1—N7	118.09 (10)	N8—N7—C1	119.64 (9)
C6—C1—N7	121.05 (10)	N8—N7—C11	117.22 (10)
C3—C2—C1	117.5 (1)	C1—N7—C11	123.15 (10)
C3—C2—H2	120.3 (8)	N7—C11—H11A	110.0 (9)
C1—C2—H2	122.2 (8)	N7—C11—H11B	110.1 (10)
C4—C3—C2	123.4 (1)	H11A—C11—H11B	109.4 (13)
C4—C3—N12	119.2 (1)	N7—C11—H11C	106.3 (10)
C2—C3—N12	117.4 (1)	H11A—C11—H11C	108.3 (13)
C3—C4—C5	117.8 (1)	H11B—C11—H11C	112.6 (13)
C3—C4—H4	121.9 (9)	O9—N8—O10	124.18 (10)
C5—C4—H4	120.2 (9)	O9—N8—N7	118.86 (10)
C6—C5—C4	120.6 (1)	O10—N8—N7	116.94 (10)
C6—C5—H5	119.6 (8)	O13—N12—O14	123.45 (10)
C4—C5—H5	119.8 (8)	O13—N12—C3	118.22 (10)
C5—C6—C1	119.9 (1)	O14—N12—C3	118.32 (10)
C5—C6—H6	117.5 (8)
C6—C1—C2—C3	−2.28 (16)	C6—C1—N7—N8	−51.32 (15)
N7—C1—C2—C3	174.29 (10)	C2—C1—N7—C11	−48.3 (2)
C1—C2—C3—C4	2.41 (17)	C6—C1—N7—C11	128.2 (1)
C1—C2—C3—N12	−177.16 (10)	C1—N7—N8—O9	−6.61 (16)
C2—C3—C4—C5	−0.23 (18)	C11—N7—N8—O9	173.80 (10)
N12—C3—C4—C5	179.33 (10)	C1—N7—N8—O10	175.31 (10)
C3—C4—C5—C6	−2.14 (17)	C11—N7—N8—O10	−4.28 (15)
C4—C5—C6—C1	2.24 (17)	C4—C3—N12—O13	−22.4 (2)
C2—C1—C6—C5	0.04 (17)	C2—C3—N12—O13	157.2 (1)
N7—C1—C6—C5	−176.43 (10)	C4—C3—N12—O14	158.7 (1)
C2—C1—N7—N8	132.12 (11)	C2—C3—N12—O14	−21.7 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O10^i	0.97 (1)	2.57 (1)	3.132 (2)	117 (1)
C6—H6···O9^ii	0.96 (1)	2.41 (1)	3.198 (2)	139 (1)

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