3,5-Di­methyl-6-(4-nitro­anilino)-2,3,4,5-tetra­hydro-1,3,5-triazine-2,4-dione, (II), 3,5-di­methyl-6-(N-methyl-4-nitroanilino)-2,3,4,5-tetra­hydro-1,3,5-triazine-2,4-dione, (III), and 1,3,5-tri­methyl-6-(4-nitro­phenyl­imino)-1,3,5-triazinane-2,4-dione, (IV)

Methyl rearrangement in the solid state of 2,4-di­methoxy-6-(4-nitro­anilino)-1,3,5-triazine reveals three different products: (II), C₁₁H₁₁N₅O₄·H₂O, (III), C₁₂H₁₃N₅O₄, and (IV), C₁₂H₁₃N₅O₄. (II) crystallizes with a mol­ecule of water and (IV) crystallizes in two polymorphic forms. The conformation of the mol­ecules is expressed by the torsion about the bond joining the triazine and the aniline moieties. The two moieties are almost coplanar in (II) due to an intramolecular hydrogen bond between a triazine-N atom and a phenyl-H atom. The methyl groups of the triazine exert severe steric repulsion in the other two compounds, affecting not only the conformation but also the exocyclic bond angles.

S1. Comment

Methoxy-s-triazines and their thio-analogues tend to undergo methyl rearrangement either in the liquid state or in the solid-tate (Paolini et al., 1968; Tosato, 1982, 1984; Kaftory & Handelsman-Benory, 1994; Handelsman-Benory et al., 1995, 2000; Greenberg et al., 2000). In the course of a study on the alkyl rearrangement of four derivatives of 2-anilino-4,6-dialkoxy-1,3,5-triazines, it was found that while three of the compounds undergo rearrangement in the liquid state, the fourth, (I), undergoes methyl rearrangement in the solid state (see scheme. The crystal structures and the thermal behaviours of these compounds are described elsewhere (Taycher et al., 2000). Based on the crystal structure of 2,4-dimethoxy-6-(4-nitroanilino)-1,3,5-triazine, it was concluded that the rearrangement is not topochemically controlled. As a result of the rearrangement, a mixture of products are produced, of which three were analyzed by ¹H NMR and by single-crystal structure determination. One of the products, (II), crystallizes with a molecule of water, which is hydrogen bonded to the amino hydrogen atom. A second product (IV) crystallizes in two polymorphic forms. The crystal structures of all four compounds, (II)-(IV), are shown in Figures 1–4. \sch

Comparison of bond lengths and angles of the s-triazine moiety is given in Table 5. Some differences of bond angles should be noted. The endocyclic bond angles at the carbon atoms (C1, C2, C3) in the two polymorphs [(IV) and (V)] are significantly smaller than the endocyclic bond angles at the nitrogen atoms (N1, N2, N3); 114.8 (2)–116.9 (2)° compared with 123.1 (2)–124.7 (2)°. In compounds (II) and (III), however, only the N1—C3—N3 bond angle is significantly smaller [115.6 (3), 115.5 (2)°]. Similar differences between the endocyclic bond angles are found in all s-triazine moieties whenever the carbonyl carbon atom is bonded to two N—CH₃ groups (Greenberg et al., 2000; Thaladi et al., 1998; Handelsman-Benory et al., 1995).

Selected intermolecular hydrogen-bond geometries are given in Tables 1–4. Weak C—H···O and C—H···N hydrogen bonds have only little effect on the conformation of the molecules but they determine the packing of molecules in the unit cell of each of the compounds. The intramolecular hydrogen bond in (II), N2···H5 [2.32 (4) Å], forces the triazine and the aniline moieties to be almost coplanar [the C2—N4—C4—C5 torsion angle is 21.5 (8)°]. The molecules pack in layers where the water molecules, through hydrogen bonds, form the glue between neighbour molecules in the layer.

Severe steric effect determines the conformation in regards with the torsion angles N2—C2—N4—C4, and C2—N4—C4—C5 and in regards with the external ring bond angles at C2. The only difference between compounds (II) and (III) is the substituent on N4, a hydrogen atom and a methyl group, respectively. The presence of the smaller H atom is not followed by a rotation of the aniline moiety about C2—N4, thus the produced torsion angle is only −1.8 (8)°, the torsion angle about N4—C4 bond is 21.5 (8)°. This conformation is also stabilized by the hydrogen bond discussed above. Replacing the hydrogen atom by a CH₃ group causes an increase of the rotation of the aniline moiety, thus the torsion angle about C2—N4 bond increases to −131.2 (2)°, and the torsion about N4—C4 bond increases to 36.0 (3)°. As a result, the two moieties are perpendicular to each other and the close proximity of the two methyl groups C11 and C12 is avoided.

One of the two degrees of freedom available in (II) and (III) to overcome steric repulsion is lost in (IV) due to the replacement of the single to double bond of C2═N4. Partial relief of the steric repulsion is achieved by rotation of the phenyl ring about N4—C4 bond [71.1 (2) and −64.7 (2)° in polymorphs (IV) and (V), respectively], and also by a small rotation about the double bond [8.5 (2) and −18.3 (2)° in (IV) and (V), respectively] which indicates that there is some π-delocalization along the chain joining the triazine to the phenyl. Moreover, the N2—C2—N4 bond angle opens up to 128.5 (2)°, N3—C2—N4 bond angle closes to 116.6 (2)° in both polymorphs. Similar differences between the exocyclic bond angles is found to a lesser extent (124.8, 118.2°) in N-methylthio-N'-(2,6-dimethylphenyl)-2,6-dimethyl-1,4- quinonedi-imine (Klerks et al., 1981) and to a higher extent (134.1, 113.9°) when the N—CH₃ is replaced by N—C-(CH₃)₂ (Al-Talib et al., 1985).

S2. Experimental

The title compounds were obtained by heating 2-(4'-nitroanilino)-4,6-dimethyoxy-1,3,5-triazine to 493 K. Crystals of (II) and (IV) were obtained from MeOH solution, crystals of (III) from CHCl₃ solution and crystals of (V) from MeOH/EtOH solution.

S3. Refinement

No attempt has been made to find the absolute structure of (II). Hydrogen atoms were treated by a mixture of independent (H atoms of the water molecule) and by constrained refinement. Crystals of (III) were unstable and poorly diffracted, therefore the data was not collected to completeness, and the R_int was greater than expected.

Computing details

Data collection: Philips PW 1110/20 (Philips, 1973) for (II); COLLECT (Nonius, 1998) for (III), (IV), (V). Cell refinement: Philips PW 1110/20 for (II); DENZO (Otwinowski & Minor, 1997) for (III), (IV), (V). Data reduction: PROCN (Philips, 1973) for (II); DENZO for (III), (IV), (V). For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: ORTEPII (Johnson, 1976) and TEXSAN (Molecular Structure Corporation, 1995) for (II); TEXSAN for (III), (IV), (V). For all compounds, software used to prepare material for publication: SHELXL97.

Figures

Figure 1. ORTEP-3 (Johnson, 1976; Farrugia, 1998) drawing of (II) showing atomic numbering. Ellipsoids of atomic displacement for non-hydrogen atoms are drawn at the 50% probability level. H atoms are drawn as small circles of arbitrary radius. Figure 2. ORTEP-3 (Johnson, 1976; Farrugia, 1998) drawing of (III) showing atomic numbering. Ellipsoids are drawn as in Figure 1. Figure 3. ORTEP-3 (Johnson, 1976; Farrugia, 1998) drawing of (IV) showing atomic numbering. Ellipsoids are drawn as in Figure 1. Figure 4. ORTEP-3 (Johnson, 1976; Farrugia, 1998) drawing of (V) showing atomic numbering. Ellipsoids are drawn as in Figure 1. Table 1. Comparison of bond lengths and bond angles of the s-triazine moiety. Table 5. Selected intermolecular hydrogen bond geometries.

(II)

Crystal data

C11H11N5O4·H2O	F(000) = 616
Mr = 295.26	Dx = 1.470 Mg m^−3
Orthorhombic, P_21_21_21	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: P 2ac 2ab	Cell parameters from 25 reflections
a = 18.170 (4) Å	θ = 3.2–19.7°
b = 10.530 (3) Å	µ = 0.12 mm^−1
c = 6.972 (2) Å	T = 293 K
V = 1334.0 (6) Å^3	Prism, pale yellow
Z = 4	0.80 × 0.50 × 0.40 mm

Data collection

Philips PW 1100 diffractometer	Rint = 0.000
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 2.2°
Graphite monochromator	h = 0→21
ω/2θ scans	k = 0→12
1339 measured reflections	l = 0→8
1339 independent reflections	3 standard reflections every 120 min reflections
1152 reflections with I > 2σ(I)	intensity decay: 2.1%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.049	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.130	w = 1/[σ^2(Fo^2) + (0.0499P)^2 + 0.9787P] where P = (Fo^2 + 2Fc^2)/3
S = 1.19	(Δ/σ)max = 0.030
1339 reflections	Δρmax = 0.20 e Å^−3
205 parameters	Δρmin = −0.20 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.024 (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
O1	0.78975 (17)	0.3631 (3)	0.1258 (7)	0.0577 (11)
O2	0.54559 (15)	0.2910 (3)	0.1905 (6)	0.0533 (10)
O3	1.02148 (19)	−0.3010 (4)	0.1898 (8)	0.0930 (16)
O4	0.9512 (2)	−0.4611 (4)	0.1494 (8)	0.0876 (15)
O5	0.60984 (19)	−0.2423 (4)	0.3599 (7)	0.0629 (12)
N1	0.66752 (18)	0.3310 (3)	0.1619 (6)	0.0372 (9)
N2	0.75229 (17)	0.1604 (3)	0.1721 (6)	0.0348 (9)
N3	0.62488 (16)	0.1245 (3)	0.2113 (6)	0.0335 (9)
N4	0.70773 (18)	−0.0424 (3)	0.2157 (6)	0.0353 (9)
N5	0.9609 (2)	−0.3478 (4)	0.1737 (7)	0.0580 (12)
C1	0.7403 (2)	0.2863 (4)	0.1523 (7)	0.0384 (11)
C2	0.6969 (2)	0.0845 (4)	0.2002 (6)	0.0296 (9)
C3	0.6085 (2)	0.2528 (4)	0.1892 (7)	0.0348 (10)
C4	0.7747 (2)	−0.1104 (4)	0.2001 (6)	0.0318 (10)
C5	0.8446 (2)	−0.0583 (4)	0.2259 (7)	0.0372 (10)
H5	0.8502	0.0281	0.2501	0.045*
C6	0.9055 (2)	−0.1370 (4)	0.2148 (7)	0.0411 (11)
H6	0.9524	−0.1035	0.2308	0.049*
C7	0.8966 (2)	−0.2643 (4)	0.1804 (7)	0.0385 (10)
C8	0.8276 (2)	−0.3176 (4)	0.1545 (8)	0.0433 (12)
H8	0.8224	−0.4043	0.1324	0.052*
C9	0.7672 (2)	−0.2396 (4)	0.1621 (7)	0.0373 (10)
H9	0.7206	−0.2735	0.1415	0.045*
C10	0.6534 (3)	0.4680 (4)	0.1406 (10)	0.0593 (15)
H10A	0.6794	0.4995	0.0306	0.089*
H10B	0.6699	0.5118	0.2533	0.089*
H10C	0.6015	0.4819	0.1238	0.089*
C11	0.5629 (2)	0.0363 (4)	0.2329 (9)	0.0518 (14)
H11A	0.5176	0.0834	0.2362	0.078*
H11B	0.5683	−0.0106	0.3501	0.078*
H11C	0.5621	−0.0215	0.1264	0.078*
H1N4	0.674 (2)	−0.089 (4)	0.241 (7)	0.037 (13)*
H1O5	0.621 (3)	−0.277 (6)	0.463 (9)	0.07 (2)*
H2O5	0.559 (5)	−0.243 (8)	0.358 (12)	0.16 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0364 (17)	0.0297 (15)	0.107 (3)	−0.0058 (14)	0.008 (2)	−0.004 (2)
O2	0.0268 (15)	0.0418 (17)	0.091 (3)	0.0082 (13)	−0.0015 (17)	−0.003 (2)
O3	0.040 (2)	0.089 (3)	0.150 (5)	0.021 (2)	−0.013 (3)	−0.025 (4)
O4	0.061 (2)	0.049 (2)	0.153 (4)	0.0231 (19)	0.012 (3)	−0.005 (3)
O5	0.0311 (18)	0.057 (2)	0.100 (3)	0.0003 (16)	0.000 (2)	0.019 (3)
N1	0.0311 (18)	0.0258 (17)	0.055 (2)	0.0055 (14)	0.0010 (18)	−0.0007 (18)
N2	0.0284 (17)	0.0260 (16)	0.050 (2)	−0.0006 (14)	0.0022 (18)	−0.0006 (18)
N3	0.0219 (15)	0.0284 (17)	0.050 (2)	−0.0025 (13)	−0.0016 (16)	−0.0004 (19)
N4	0.0227 (16)	0.0262 (17)	0.057 (2)	0.0005 (14)	0.0027 (18)	0.002 (2)
N5	0.036 (2)	0.065 (3)	0.072 (3)	0.020 (2)	0.003 (2)	−0.002 (3)
C1	0.033 (2)	0.030 (2)	0.052 (3)	−0.0016 (19)	0.002 (2)	−0.006 (2)
C2	0.0254 (17)	0.0270 (19)	0.037 (2)	−0.0002 (16)	0.0032 (19)	−0.0017 (19)
C3	0.032 (2)	0.029 (2)	0.044 (2)	0.0021 (18)	0.003 (2)	−0.004 (2)
C4	0.0281 (19)	0.031 (2)	0.036 (2)	0.0040 (17)	0.0032 (19)	0.004 (2)
C5	0.032 (2)	0.029 (2)	0.051 (3)	−0.0024 (18)	−0.004 (2)	−0.002 (2)
C6	0.027 (2)	0.049 (3)	0.047 (3)	−0.0002 (19)	−0.001 (2)	−0.003 (3)
C7	0.030 (2)	0.042 (2)	0.043 (2)	0.0116 (19)	0.003 (2)	0.003 (2)
C8	0.042 (2)	0.033 (2)	0.055 (3)	0.0043 (19)	0.006 (2)	−0.002 (2)
C9	0.029 (2)	0.032 (2)	0.051 (3)	−0.0019 (17)	0.001 (2)	0.001 (2)
C10	0.047 (3)	0.025 (2)	0.105 (5)	0.003 (2)	0.005 (3)	−0.005 (3)
C11	0.028 (2)	0.037 (2)	0.091 (4)	−0.0060 (18)	0.000 (2)	0.008 (3)

Geometric parameters (Å, º)

O1—C1	1.223 (5)	N5—C7	1.462 (5)
O2—C3	1.212 (5)	C4—C9	1.393 (6)
O3—N5	1.210 (6)	C4—C5	1.395 (6)
O4—N5	1.218 (6)	C5—C6	1.385 (6)
O5—H1O5	0.83 (6)	C5—H5	0.9300
O5—H2O5	0.93 (8)	C6—C7	1.372 (7)
N1—C3	1.365 (5)	C6—H6	0.9300
N1—C1	1.404 (5)	C7—C8	1.386 (6)
N1—C10	1.473 (5)	C8—C9	1.372 (6)
N2—C2	1.300 (5)	C8—H8	0.9300
N2—C1	1.351 (5)	C9—H9	0.9300
N3—C2	1.377 (5)	C10—H10A	0.9600
N3—C3	1.391 (5)	C10—H10B	0.9600
N3—C11	1.468 (5)	C10—H10C	0.9600
N4—C2	1.355 (5)	C11—H11A	0.9600
N4—C4	1.416 (5)	C11—H11B	0.9600
N4—H1N4	0.80 (4)	C11—H11C	0.9600
H1O5—O5—H2O5	104 (6)	C6—C5—H5	120.5
C3—N1—C1	122.9 (3)	C4—C5—H5	120.5
C3—N1—C10	117.9 (3)	C7—C6—C5	120.1 (4)
C1—N1—C10	119.2 (4)	C7—C6—H6	120.0
C2—N2—C1	119.5 (3)	C5—C6—H6	120.0
C2—N3—C3	119.6 (3)	C6—C7—C8	121.7 (4)
C2—N3—C11	122.8 (3)	C6—C7—N5	120.0 (4)
C3—N3—C11	117.5 (3)	C8—C7—N5	118.4 (4)
C2—N4—C4	128.2 (4)	C9—C8—C7	118.4 (4)
C2—N4—H1N4	121 (3)	C9—C8—H8	120.8
C4—N4—H1N4	111 (3)	C7—C8—H8	120.8
O3—N5—O4	122.9 (4)	C8—C9—C4	121.0 (4)
O3—N5—C7	118.6 (4)	C8—C9—H9	119.5
O4—N5—C7	118.5 (4)	C4—C9—H9	119.5
O1—C1—N2	123.0 (4)	N1—C10—H10A	109.5
O1—C1—N1	118.5 (4)	N1—C10—H10B	109.5
N2—C1—N1	118.4 (4)	H10A—C10—H10B	109.5
N2—C2—N4	120.4 (4)	N1—C10—H10C	109.5
N2—C2—N3	123.8 (3)	H10A—C10—H10C	109.5
N4—C2—N3	115.8 (4)	H10B—C10—H10C	109.5
O2—C3—N1	122.8 (4)	N3—C11—H11A	109.5
O2—C3—N3	121.6 (4)	N3—C11—H11B	109.5
N1—C3—N3	115.6 (3)	H11A—C11—H11B	109.5
C9—C4—C5	119.8 (4)	N3—C11—H11C	109.5
C9—C4—N4	115.2 (3)	H11A—C11—H11C	109.5
C5—C4—N4	125.0 (3)	H11B—C11—H11C	109.5
C6—C5—C4	119.0 (4)
C2—N2—C1—O1	179.9 (5)	C11—N3—C3—O2	1.1 (8)
C2—N2—C1—N1	−0.3 (7)	C2—N3—C3—N1	−1.5 (7)
C3—N1—C1—O1	179.4 (5)	C11—N3—C3—N1	−177.5 (4)
C10—N1—C1—O1	−0.2 (8)	C2—N4—C4—C9	−160.6 (5)
C3—N1—C1—N2	−0.4 (7)	C2—N4—C4—C5	21.5 (8)
C10—N1—C1—N2	−180.0 (5)	C9—C4—C5—C6	−0.6 (7)
C1—N2—C2—N4	178.4 (5)	N4—C4—C5—C6	177.2 (4)
C1—N2—C2—N3	0.1 (7)	C4—C5—C6—C7	−0.5 (7)
C4—N4—C2—N2	−1.8 (8)	C5—C6—C7—C8	0.5 (8)
C4—N4—C2—N3	176.6 (4)	C5—C6—C7—N5	−178.4 (5)
C3—N3—C2—N2	0.9 (7)	O3—N5—C7—C6	−3.5 (8)
C11—N3—C2—N2	176.6 (5)	O4—N5—C7—C6	177.5 (6)
C3—N3—C2—N4	−177.5 (4)	O3—N5—C7—C8	177.5 (6)
C11—N3—C2—N4	−1.7 (7)	O4—N5—C7—C8	−1.4 (8)
C1—N1—C3—O2	−177.2 (5)	C6—C7—C8—C9	0.6 (8)
C10—N1—C3—O2	2.3 (7)	N5—C7—C8—C9	179.5 (5)
C1—N1—C3—N3	1.3 (7)	C7—C8—C9—C4	−1.7 (8)
C10—N1—C3—N3	−179.1 (5)	C5—C4—C9—C8	1.8 (8)
C2—N3—C3—O2	177.1 (4)	N4—C4—C9—C8	−176.2 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H1N4···O5	0.81 (5)	2.16 (5)	2.933 (5)	162 (5)
O5—H2O5···O2^i	0.92 (11)	1.96 (11)	2.867 (5)	166 (10)
O5—H1O5···O1^ii	0.83 (6)	2.18 (6)	2.895 (6)	145 (5)
O9—H9···O5	0.93 (5)	2.55 (5)	3.175 (6)	125 (4)
C5—H5···N2	0.93 (5)	2.32 (4)	2.874 (5)	117 (4)
C6—H6···O4^iii	0.93 (5)	2.45 (5)	3.333 (6)	158 (4)
C8—H8···O1^iv	0.93 (5)	2.52 (5)	3.438 (6)	169 (4)

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

(III)

Crystal data

C12H13N5O4	F(000) = 608
Mr = 291.27	Dx = 1.495 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: -P 2ybc	Cell parameters from 15151 reflections
a = 11.3330 (12) Å	θ = 2.2–27.5°
b = 16.0250 (14) Å	µ = 0.12 mm^−1
c = 7.1620 (7) Å	T = 293 K
β = 95.587 (5)°	Prism, pale yellow
V = 1294.5 (2) Å^3	0.40 × 0.18 × 0.10 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	1216 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.115
Graphite monochromator	θmax = 27.6°, θmin = 2.2°
phi scan	h = 0→14
16754 measured reflections	k = 0→20
2776 independent reflections	l = −9→9

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.048	All H-atom parameters refined
wR(F^2) = 0.141	w = 1/[σ^2(Fo^2) + (0.0927P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.73	(Δ/σ)max < 0.001
2776 reflections	Δρmax = 0.19 e Å^−3
243 parameters	Δρmin = −0.20 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.040 (6)

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
O1	0.08281 (17)	0.37408 (11)	0.7172 (3)	0.0739 (6)
O2	−0.11797 (15)	0.13533 (12)	0.5758 (3)	0.0681 (6)
O3	0.36497 (18)	−0.12662 (12)	0.1907 (3)	0.0749 (6)
O4	0.4256 (2)	−0.20089 (12)	0.4296 (3)	0.0851 (7)
N1	−0.02049 (17)	0.25642 (12)	0.6440 (3)	0.0452 (5)
N2	0.17820 (17)	0.25231 (12)	0.7828 (3)	0.0450 (5)
N3	0.07128 (16)	0.12819 (11)	0.7127 (3)	0.0448 (5)
N4	0.27060 (17)	0.12495 (12)	0.8331 (3)	0.0469 (5)
N5	0.38699 (19)	−0.13619 (14)	0.3597 (4)	0.0554 (6)
C1	0.0819 (2)	0.29840 (15)	0.7175 (3)	0.0473 (6)
C2	0.1728 (2)	0.17107 (14)	0.7743 (3)	0.0408 (6)
C3	−0.0293 (2)	0.17154 (15)	0.6385 (3)	0.0467 (6)
C4	0.3068 (2)	0.05973 (14)	0.7139 (3)	0.0427 (6)
C5	0.2938 (2)	0.07099 (15)	0.5228 (4)	0.0469 (6)
C6	0.3218 (2)	0.00644 (15)	0.4054 (4)	0.0484 (7)
C7	0.3643 (2)	−0.06716 (14)	0.4848 (3)	0.0432 (6)
C8	0.3815 (2)	−0.07856 (16)	0.6750 (4)	0.0514 (7)
C9	0.3523 (2)	−0.01390 (16)	0.7914 (4)	0.0525 (7)
C10	−0.1269 (3)	0.3047 (2)	0.5811 (5)	0.0645 (9)
C11	0.0564 (3)	0.03802 (17)	0.7479 (5)	0.0590 (8)
C12	0.3655 (3)	0.1676 (2)	0.9503 (5)	0.0636 (9)
H5	0.266 (2)	0.1269 (16)	0.471 (3)	0.057 (7)*
H6	0.310 (2)	0.0144 (14)	0.283 (4)	0.053 (8)*
H8	0.411 (2)	−0.1327 (16)	0.727 (3)	0.062 (7)*
H9	0.358 (2)	−0.0271 (17)	0.931 (4)	0.081 (9)*
H101	−0.100 (3)	0.356 (2)	0.510 (5)	0.106 (11)*
H102	−0.185 (5)	0.273 (3)	0.546 (7)	0.18 (2)*
H103	−0.150 (4)	0.341 (3)	0.668 (6)	0.143 (18)*
H111	−0.026 (3)	0.0301 (18)	0.771 (4)	0.089 (10)*
H112	0.099 (3)	0.026 (2)	0.870 (5)	0.106 (13)*
H113	0.085 (3)	0.0064 (18)	0.642 (5)	0.089 (10)*
H121	0.398 (3)	0.2053 (19)	0.881 (5)	0.088 (12)*
H122	0.425 (3)	0.126 (2)	0.997 (4)	0.102 (11)*
H123	0.341 (3)	0.194 (2)	1.064 (6)	0.131 (14)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0752 (14)	0.0388 (11)	0.1032 (17)	0.0023 (9)	−0.0141 (11)	−0.0062 (10)
O2	0.0438 (11)	0.0661 (12)	0.0920 (16)	−0.0100 (10)	−0.0057 (10)	−0.0098 (10)
O3	0.0897 (16)	0.0787 (14)	0.0561 (13)	0.0127 (11)	0.0054 (11)	−0.0114 (11)
O4	0.1127 (18)	0.0559 (13)	0.0856 (16)	0.0348 (12)	0.0042 (13)	−0.0015 (11)
N1	0.0404 (12)	0.0439 (12)	0.0505 (13)	0.0058 (9)	0.0003 (9)	−0.0035 (10)
N2	0.0439 (12)	0.0413 (11)	0.0491 (12)	−0.0035 (9)	0.0015 (9)	−0.0067 (9)
N3	0.0397 (12)	0.0392 (11)	0.0555 (13)	−0.0039 (9)	0.0042 (9)	−0.0027 (9)
N4	0.0407 (12)	0.0507 (12)	0.0476 (12)	0.0055 (10)	−0.0041 (9)	−0.0076 (10)
N5	0.0525 (14)	0.0497 (13)	0.0642 (16)	0.0067 (11)	0.0061 (11)	−0.0057 (12)
C1	0.0508 (16)	0.0438 (15)	0.0473 (15)	−0.0007 (12)	0.0047 (12)	−0.0021 (12)
C2	0.0385 (14)	0.0453 (14)	0.0385 (14)	−0.0021 (11)	0.0029 (11)	−0.0043 (11)
C3	0.0404 (15)	0.0526 (15)	0.0473 (15)	−0.0034 (12)	0.0060 (12)	−0.0048 (12)
C4	0.0397 (14)	0.0423 (14)	0.0457 (15)	0.0023 (11)	0.0019 (11)	−0.0021 (11)
C5	0.0472 (15)	0.0420 (14)	0.0510 (16)	0.0034 (12)	0.0029 (12)	0.0027 (12)
C6	0.0503 (16)	0.0519 (16)	0.0427 (17)	0.0027 (12)	0.0039 (12)	0.0015 (13)
C7	0.0383 (14)	0.0410 (13)	0.0500 (15)	0.0021 (10)	0.0030 (11)	−0.0031 (11)
C8	0.0456 (16)	0.0482 (15)	0.0596 (18)	0.0082 (12)	0.0001 (13)	0.0060 (13)
C9	0.0560 (17)	0.0526 (16)	0.0474 (16)	0.0086 (12)	−0.0026 (13)	−0.0003 (13)
C10	0.058 (2)	0.0604 (19)	0.073 (2)	0.0151 (16)	−0.0050 (17)	0.0042 (17)
C11	0.057 (2)	0.0439 (16)	0.077 (2)	−0.0081 (13)	0.0113 (17)	0.0001 (15)
C12	0.0498 (19)	0.077 (2)	0.061 (2)	0.0046 (17)	−0.0120 (16)	−0.0182 (18)

Geometric parameters (Å, º)

O1—C1	1.213 (3)	C5—C6	1.389 (3)
O2—C3	1.209 (3)	C5—H5	1.01 (2)
O3—N5	1.222 (3)	C6—C7	1.376 (3)
O4—N5	1.214 (3)	C6—H6	0.88 (2)
N1—C3	1.364 (3)	C7—C8	1.369 (3)
N1—C1	1.399 (3)	C8—C9	1.389 (3)
N1—C10	1.467 (3)	C8—H8	0.99 (3)
N2—C2	1.304 (3)	C9—H9	1.01 (3)
N2—C1	1.362 (3)	C10—H101	1.04 (4)
N3—C2	1.375 (3)	C10—H102	0.85 (5)
N3—C3	1.395 (3)	C10—H103	0.90 (5)
N3—C11	1.479 (3)	C11—H111	0.97 (3)
N4—C2	1.364 (3)	C11—H112	0.98 (4)
N4—C4	1.435 (3)	C11—H113	0.99 (3)
N4—C12	1.467 (3)	C12—H121	0.89 (3)
N5—C7	1.462 (3)	C12—H122	0.98 (3)
C4—C5	1.374 (3)	C12—H123	0.98 (4)
C4—C9	1.382 (3)
C3—N1—C1	123.1 (2)	C7—C6—H6	123.3 (16)
C3—N1—C10	117.5 (2)	C5—C6—H6	118.1 (16)
C1—N1—C10	119.3 (2)	C8—C7—C6	122.4 (2)
C2—N2—C1	119.5 (2)	C8—C7—N5	119.5 (2)
C2—N3—C3	120.0 (2)	C6—C7—N5	118.1 (2)
C2—N3—C11	122.6 (2)	C7—C8—C9	118.5 (2)
C3—N3—C11	116.7 (2)	C7—C8—H8	120.1 (14)
C2—N4—C4	118.80 (19)	C9—C8—H8	121.3 (14)
C2—N4—C12	116.9 (2)	C4—C9—C8	119.8 (3)
C4—N4—C12	116.3 (2)	C4—C9—H9	123.9 (15)
O4—N5—O3	123.1 (2)	C8—C9—H9	115.9 (15)
O4—N5—C7	118.1 (2)	N1—C10—H101	107.2 (19)
O3—N5—C7	118.8 (2)	N1—C10—H102	111 (3)
O1—C1—N2	122.4 (2)	H101—C10—H102	127 (4)
O1—C1—N1	119.1 (2)	N1—C10—H103	114 (3)
N2—C1—N1	118.4 (2)	H101—C10—H103	87 (3)
N2—C2—N4	119.5 (2)	H102—C10—H103	109 (4)
N2—C2—N3	123.2 (2)	N3—C11—H111	106.5 (18)
N4—C2—N3	117.2 (2)	N3—C11—H112	106.6 (19)
O2—C3—N1	123.0 (2)	H111—C11—H112	103 (3)
O2—C3—N3	121.4 (2)	N3—C11—H113	108.5 (17)
N1—C3—N3	115.5 (2)	H111—C11—H113	117 (2)
C5—C4—C9	120.8 (2)	H112—C11—H113	115 (3)
C5—C4—N4	119.2 (2)	N4—C12—H121	109 (2)
C9—C4—N4	120.0 (2)	N4—C12—H122	108.9 (19)
C4—C5—C6	119.8 (2)	H121—C12—H122	110 (3)
C4—C5—H5	118.9 (14)	N4—C12—H123	115 (2)
C6—C5—H5	121.3 (14)	H121—C12—H123	110 (3)
C7—C6—C5	118.6 (3)	H122—C12—H123	104 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O2^i	1.01 (2)	2.62 (2)	3.204 (3)	117 (2)
C5—H5···N3^i	1.01 (2)	2.51 (2)	3.500 (3)	168 (2)
C9—H9···O3^ii	1.02 (3)	2.45 (3)	3.374 (3)	151 (2)
C10—H101···O2^iii	0.97 (3)	2.58 (3)	3.087 (3)	112 (2)
C12—H123···N3^iv	0.98 (4)	2.68 (4)	3.579 (4)	153 (3)

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

(IV) 2-(4'-nitrophenylimino)-1,3,5-trimethyl-1,3,5-triazine-4,6,-dione

Crystal data

C12H13N5O4	Z = 2
Mr = 291.27	F(000) = 304
Triclinic, P1	Dx = 1.445 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71093 Å
a = 8.253 (6) Å	Cell parameters from 25 reflections
b = 8.493 (3) Å	θ = 2.5–16.6°
c = 10.084 (2) Å	µ = 0.11 mm^−1
α = 78.79°	T = 293 K
β = 88.52°	Plate, pale yellow
γ = 74.95°	0.9 × 0.45 × 0.1 mm
V = 669.3 (6) Å^3

Data collection

Philips PW 1100 diffractometer	Rint = 0.068
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 2.1°
Graphite monochromator	h = −9→9
ω/2θ scans	k = −9→10
2494 measured reflections	l = 0→11
2349 independent reflections	3 standard reflections every 120 min min
1806 reflections with I > 2σ(I)	intensity decay: 2.4%

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)] = 0.048	Hydrogen site location: difference Fourier map
wR(F^2) = 0.144	All H-atom parameters refined
S = 0.91	w = 1/[σ^2(Fo^2) + (0.0885P)^2 + 0.2017P] where P = (Fo^2 + 2Fc^2)/3
2349 reflections	(Δ/σ)max = 0.011
242 parameters	Δρmax = 0.24 e Å^−3
0 restraints	Δρmin = −0.25 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
O1	0.2041 (2)	0.03085 (18)	0.10070 (18)	0.0649 (5)
O2	0.28833 (19)	0.54925 (18)	0.04935 (16)	0.0576 (4)
O3	−0.6043 (3)	0.0763 (3)	0.6994 (2)	0.0991 (7)
O4	−0.7843 (2)	0.1975 (3)	0.5373 (2)	0.0852 (6)
N1	0.2571 (2)	0.2852 (2)	0.08282 (17)	0.0463 (4)
N2	0.0088 (2)	0.23124 (19)	0.18234 (17)	0.0452 (4)
N3	0.0641 (2)	0.49373 (19)	0.16930 (16)	0.0443 (4)
N4	−0.1612 (2)	0.4446 (2)	0.29049 (18)	0.0529 (5)
N5	−0.6431 (3)	0.1652 (3)	0.5889 (2)	0.0643 (6)
C1	0.1604 (3)	0.1725 (2)	0.1215 (2)	0.0462 (5)
C2	−0.0375 (2)	0.3867 (2)	0.22033 (19)	0.0422 (5)
C3	0.2081 (2)	0.4500 (2)	0.09606 (19)	0.0424 (5)
C4	−0.2752 (3)	0.3656 (3)	0.3637 (2)	0.0468 (5)
C5	−0.2292 (3)	0.2499 (3)	0.4837 (2)	0.0543 (6)
C6	−0.3488 (3)	0.1846 (3)	0.5591 (2)	0.0568 (6)
C7	−0.5143 (3)	0.2354 (3)	0.5129 (2)	0.0487 (5)
C8	−0.5634 (3)	0.3523 (3)	0.3965 (2)	0.0550 (6)
C9	−0.4453 (3)	0.4195 (3)	0.3222 (2)	0.0568 (6)
C10	−0.1086 (4)	0.1228 (3)	0.1970 (3)	0.0607 (6)
C11	0.0211 (4)	0.6619 (3)	0.2030 (3)	0.0582 (6)
C12	0.4186 (3)	0.2265 (3)	0.0171 (3)	0.0618 (6)
H5	−0.116 (3)	0.216 (3)	0.512 (2)	0.059 (6)*
H6	−0.322 (3)	0.109 (3)	0.635 (3)	0.066 (7)*
H8	−0.678 (3)	0.385 (3)	0.368 (3)	0.070 (7)*
H9	−0.478 (3)	0.505 (4)	0.242 (3)	0.076 (8)*
H101	−0.088 (4)	0.063 (4)	0.123 (3)	0.102 (10)*
H102	−0.223 (4)	0.194 (4)	0.184 (3)	0.082 (9)*
H103	−0.093 (3)	0.053 (4)	0.282 (3)	0.075 (8)*
H111	−0.095 (4)	0.723 (4)	0.172 (3)	0.094 (10)*
H112	0.094 (4)	0.721 (4)	0.163 (3)	0.098 (10)*
H113	0.026 (4)	0.641 (4)	0.303 (4)	0.099 (10)*
H121	0.487 (4)	0.122 (5)	0.071 (4)	0.105 (11)*
H122	0.481 (4)	0.308 (4)	0.003 (3)	0.098 (10)*
H123	0.401 (4)	0.209 (4)	−0.069 (4)	0.102 (11)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0702 (10)	0.0404 (8)	0.0865 (12)	−0.0141 (7)	0.0127 (9)	−0.0200 (8)
O2	0.0582 (9)	0.0497 (8)	0.0684 (10)	−0.0242 (7)	0.0111 (7)	−0.0074 (7)
O3	0.1157 (17)	0.1218 (18)	0.0681 (13)	−0.0642 (15)	0.0160 (12)	0.0051 (12)
O4	0.0597 (11)	0.1067 (16)	0.1006 (15)	−0.0372 (11)	0.0201 (10)	−0.0286 (12)
N1	0.0468 (9)	0.0426 (9)	0.0506 (10)	−0.0135 (7)	0.0060 (7)	−0.0100 (7)
N2	0.0515 (10)	0.0400 (9)	0.0501 (10)	−0.0203 (7)	0.0073 (7)	−0.0120 (7)
N3	0.0484 (9)	0.0384 (9)	0.0506 (10)	−0.0165 (7)	0.0043 (7)	−0.0128 (7)
N4	0.0543 (10)	0.0546 (10)	0.0574 (11)	−0.0213 (8)	0.0132 (8)	−0.0205 (8)
N5	0.0720 (14)	0.0709 (13)	0.0616 (13)	−0.0326 (11)	0.0211 (11)	−0.0241 (11)
C1	0.0504 (11)	0.0403 (11)	0.0488 (11)	−0.0134 (9)	0.0012 (9)	−0.0083 (8)
C2	0.0467 (10)	0.0410 (10)	0.0418 (10)	−0.0153 (8)	−0.0003 (8)	−0.0099 (8)
C3	0.0441 (10)	0.0403 (10)	0.0426 (10)	−0.0127 (8)	−0.0039 (8)	−0.0046 (8)
C4	0.0496 (11)	0.0486 (11)	0.0485 (11)	−0.0174 (9)	0.0090 (9)	−0.0192 (9)
C5	0.0450 (12)	0.0606 (13)	0.0568 (13)	−0.0120 (10)	−0.0030 (10)	−0.0119 (10)
C6	0.0651 (14)	0.0579 (13)	0.0455 (12)	−0.0162 (11)	0.0008 (10)	−0.0052 (10)
C7	0.0516 (12)	0.0544 (12)	0.0467 (11)	−0.0204 (10)	0.0111 (9)	−0.0178 (9)
C8	0.0448 (12)	0.0655 (14)	0.0560 (13)	−0.0154 (10)	0.0003 (10)	−0.0136 (11)
C9	0.0552 (13)	0.0636 (14)	0.0501 (13)	−0.0174 (11)	−0.0016 (10)	−0.0044 (11)
C10	0.0702 (17)	0.0532 (14)	0.0729 (17)	−0.0344 (13)	0.0192 (13)	−0.0231 (13)
C11	0.0668 (16)	0.0454 (12)	0.0710 (17)	−0.0219 (11)	0.0083 (13)	−0.0228 (11)
C12	0.0519 (13)	0.0576 (15)	0.0753 (18)	−0.0114 (11)	0.0165 (12)	−0.0174 (13)

Geometric parameters (Å, º)

O1—C1	1.221 (2)	N3—C2	1.409 (3)
O2—C3	1.221 (2)	N3—C11	1.483 (3)
O3—N5	1.216 (3)	N4—C2	1.274 (3)
O4—N5	1.231 (3)	N4—C4	1.406 (3)
N1—C3	1.384 (3)	N5—C7	1.478 (3)
N1—C1	1.393 (3)	C4—C5	1.394 (3)
N1—C12	1.484 (3)	C4—C9	1.406 (3)
N2—C1	1.395 (3)	C5—C6	1.393 (3)
N2—C2	1.401 (2)	C6—C7	1.385 (3)
N2—C10	1.487 (3)	C7—C8	1.375 (3)
N3—C3	1.388 (3)	C8—C9	1.386 (3)
C3—N1—C1	124.02 (17)	N4—C2—N2	128.54 (18)
C3—N1—C12	118.21 (17)	N4—C2—N3	116.58 (17)
C1—N1—C12	117.69 (18)	N2—C2—N3	114.84 (16)
C1—N2—C2	123.14 (16)	O2—C3—N1	122.25 (18)
C1—N2—C10	115.77 (17)	O2—C3—N3	122.23 (18)
C2—N2—C10	120.97 (17)	N1—C3—N3	115.50 (16)
C3—N3—C2	124.68 (16)	C5—C4—N4	122.34 (19)
C3—N3—C11	117.18 (17)	C5—C4—C9	118.84 (19)
C2—N3—C11	118.02 (17)	N4—C4—C9	118.4 (2)
C2—N4—C4	130.02 (18)	C6—C5—C4	120.6 (2)
O3—N5—O4	122.8 (2)	C7—C6—C5	119.1 (2)
O3—N5—C7	118.5 (2)	C8—C7—C6	121.3 (2)
O4—N5—C7	118.7 (2)	C8—C7—N5	118.3 (2)
O1—C1—N2	121.64 (18)	C6—C7—N5	120.3 (2)
O1—C1—N1	121.83 (19)	C7—C8—C9	119.7 (2)
N2—C1—N1	116.51 (17)	C8—C9—C4	120.3 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O4^i	0.94 (2)	2.72 (3)	3.624 (4)	163 (2)
C12—H121···O3^ii	0.98 (3)	2.62 (4)	3.529 (3)	153 (3)
C12—H122···O2^iii	0.95 (4)	2.50 (4)	3.426 (4)	163 (3)

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

(V) 2-(4'-nitrophenylimino)-1,3,5-trimethyl-1,3,5-triazine-4,6,-dione

Crystal data

C12H13N5O4	F(000) = 608
Mr = 291.27	Dx = 1.473 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: -P 2ybc	Cell parameters from 4397 reflections
a = 11.1270 (6) Å	θ = 1.0–25.4°
b = 9.1950 (9) Å	µ = 0.11 mm^−1
c = 13.0940 (11) Å	T = 293 K
β = 101.264 (5)°	Cube, pale yellow
V = 1313.88 (18) Å^3	0.25 × 0.25 × 0.20 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	1739 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.035
Graphite monochromator	θmax = 25.4°, θmin = 1.9°
phi scan	h = 0→13
7133 measured reflections	k = 0→11
2404 independent reflections	l = −15→15

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.050	All H-atom parameters refined
wR(F^2) = 0.142	w = 1/[σ^2(Fo^2) + (0.0636P)^2 + 0.3001P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
2404 reflections	Δρmax = 0.19 e Å^−3
243 parameters	Δρmin = −0.16 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.016 (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
O1	0.17723 (18)	0.3667 (2)	0.54611 (15)	0.0837 (6)
O2	0.50592 (14)	0.65544 (19)	0.65163 (13)	0.0662 (5)
O3	0.02820 (19)	0.6423 (3)	−0.14645 (15)	0.0953 (7)
O4	0.1423 (2)	0.4526 (3)	−0.13815 (17)	0.1060 (8)
N1	0.34684 (16)	0.50221 (19)	0.59971 (13)	0.0499 (5)
N2	0.23395 (16)	0.5199 (2)	0.42872 (13)	0.0520 (5)
N3	0.39908 (14)	0.67631 (19)	0.48649 (13)	0.0460 (5)
N4	0.30495 (15)	0.6909 (2)	0.31697 (14)	0.0530 (5)
N5	0.1031 (2)	0.5582 (3)	−0.09866 (17)	0.0699 (7)
C1	0.2480 (2)	0.4572 (3)	0.52613 (18)	0.0550 (6)
C2	0.30940 (17)	0.6280 (2)	0.40360 (17)	0.0446 (5)
C3	0.42251 (18)	0.6142 (2)	0.58353 (17)	0.0479 (5)
C4	0.24684 (18)	0.6488 (2)	0.21708 (16)	0.0475 (5)
C5	0.2826 (2)	0.5246 (3)	0.1702 (2)	0.0612 (7)
C6	0.2346 (2)	0.4938 (3)	0.0680 (2)	0.0627 (7)
C7	0.15078 (19)	0.5877 (3)	0.01162 (17)	0.0522 (6)
C8	0.1117 (2)	0.7097 (3)	0.05584 (18)	0.0546 (6)
C9	0.1611 (2)	0.7414 (3)	0.15849 (18)	0.0529 (6)
C10	0.1216 (3)	0.4781 (5)	0.3542 (3)	0.0846 (11)
C11	0.4765 (3)	0.7988 (3)	0.4680 (2)	0.0615 (7)
C12	0.3638 (3)	0.4393 (4)	0.7049 (2)	0.0715 (8)
H5	0.340 (3)	0.462 (3)	0.209 (2)	0.082 (8)*
H6	0.256 (3)	0.412 (3)	0.033 (2)	0.092 (10)*
H8	0.049 (2)	0.768 (3)	0.018 (2)	0.071 (7)*
H9	0.136 (2)	0.833 (3)	0.1891 (19)	0.065 (7)*
H101	0.062 (4)	0.443 (5)	0.391 (4)	0.173 (19)*
H102	0.148 (3)	0.409 (4)	0.314 (3)	0.109 (14)*
H103	0.093 (3)	0.558 (4)	0.313 (3)	0.116 (13)*
H111	0.510 (3)	0.782 (4)	0.408 (3)	0.112 (12)*
H112	0.539 (3)	0.817 (4)	0.536 (3)	0.120 (11)*
H113	0.426 (3)	0.888 (4)	0.447 (3)	0.114 (12)*
H121	0.298 (4)	0.380 (5)	0.707 (3)	0.145 (16)*
H122	0.356 (4)	0.520 (5)	0.758 (3)	0.150 (16)*
H123	0.438 (3)	0.399 (4)	0.723 (3)	0.117 (13)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0977 (14)	0.0841 (14)	0.0648 (12)	−0.0418 (11)	0.0048 (10)	0.0142 (10)
O2	0.0609 (10)	0.0734 (11)	0.0533 (10)	−0.0043 (8)	−0.0162 (8)	−0.0060 (9)
O3	0.0811 (13)	0.148 (2)	0.0479 (11)	−0.0086 (14)	−0.0085 (10)	0.0071 (13)
O4	0.137 (2)	0.1195 (19)	0.0654 (14)	−0.0160 (15)	0.0293 (13)	−0.0373 (13)
N1	0.0581 (10)	0.0493 (10)	0.0387 (10)	0.0000 (8)	0.0008 (8)	0.0028 (8)
N2	0.0525 (10)	0.0593 (12)	0.0403 (11)	−0.0169 (9)	−0.0005 (8)	0.0007 (9)
N3	0.0442 (9)	0.0487 (10)	0.0408 (10)	−0.0064 (8)	−0.0023 (7)	−0.0024 (8)
N4	0.0531 (10)	0.0596 (11)	0.0424 (11)	−0.0093 (9)	−0.0001 (8)	0.0041 (9)
N5	0.0642 (13)	0.1011 (18)	0.0455 (13)	−0.0279 (13)	0.0135 (11)	−0.0084 (13)
C1	0.0626 (14)	0.0551 (14)	0.0447 (14)	−0.0097 (11)	0.0040 (10)	0.0008 (11)
C2	0.0414 (10)	0.0467 (12)	0.0430 (13)	−0.0032 (9)	0.0018 (9)	−0.0012 (10)
C3	0.0470 (11)	0.0474 (12)	0.0444 (13)	0.0060 (9)	−0.0032 (9)	−0.0048 (10)
C4	0.0439 (10)	0.0551 (13)	0.0411 (12)	−0.0091 (9)	0.0022 (9)	0.0033 (10)
C5	0.0575 (14)	0.0559 (15)	0.0631 (17)	0.0026 (11)	−0.0058 (12)	−0.0005 (12)
C6	0.0621 (15)	0.0622 (15)	0.0627 (17)	−0.0025 (12)	0.0094 (12)	−0.0116 (13)
C7	0.0479 (12)	0.0715 (15)	0.0367 (12)	−0.0140 (11)	0.0070 (9)	−0.0023 (11)
C8	0.0461 (12)	0.0744 (16)	0.0419 (13)	0.0015 (11)	0.0052 (10)	0.0070 (12)
C9	0.0518 (12)	0.0599 (14)	0.0464 (13)	0.0043 (11)	0.0081 (10)	0.0009 (11)
C10	0.077 (2)	0.114 (3)	0.0532 (18)	−0.050 (2)	−0.0122 (15)	0.009 (2)
C11	0.0600 (14)	0.0588 (16)	0.0627 (17)	−0.0197 (12)	0.0043 (13)	−0.0025 (13)
C12	0.085 (2)	0.080 (2)	0.0450 (15)	0.0042 (17)	0.0023 (14)	0.0147 (15)

Geometric parameters (Å, º)

O1—C1	1.209 (3)	C5—C6	1.371 (4)
O2—C3	1.215 (2)	C5—H5	0.93 (3)
O3—N5	1.217 (3)	C6—C7	1.375 (4)
O4—N5	1.220 (3)	C6—H6	0.94 (3)
N1—C3	1.373 (3)	C7—C8	1.372 (3)
N1—C1	1.377 (3)	C8—C9	1.380 (3)
N1—C12	1.471 (3)	C8—H8	0.94 (3)
N2—C1	1.381 (3)	C9—H9	1.00 (2)
N2—C2	1.381 (3)	C10—H101	0.95 (5)
N2—C10	1.478 (3)	C10—H102	0.91 (4)
N3—C3	1.371 (3)	C10—H103	0.93 (4)
N3—C2	1.396 (3)	C11—H111	0.95 (4)
N3—C11	1.466 (3)	C11—H112	1.03 (4)
N4—C2	1.265 (3)	C11—H113	1.00 (4)
N4—C4	1.396 (3)	C12—H121	0.91 (4)
N5—C7	1.463 (3)	C12—H122	1.03 (5)
C4—C5	1.391 (3)	C12—H123	0.89 (4)
C4—C9	1.392 (3)
C3—N1—C1	123.22 (18)	C5—C6—H6	123.6 (19)
C3—N1—C12	118.0 (2)	C7—C6—H6	117.1 (19)
C1—N1—C12	118.4 (2)	C8—C7—C6	121.6 (2)
C1—N2—C2	123.78 (18)	C8—C7—N5	119.0 (2)
C1—N2—C10	115.4 (2)	C6—C7—N5	119.3 (2)
C2—N2—C10	120.3 (2)	C7—C8—C9	119.0 (2)
C3—N3—C2	124.47 (18)	C7—C8—H8	120.2 (16)
C3—N3—C11	117.49 (18)	C9—C8—H8	120.7 (16)
C2—N3—C11	118.01 (19)	C8—C9—C4	120.5 (2)
C2—N4—C4	130.05 (19)	C8—C9—H9	118.6 (14)
O3—N5—O4	123.6 (2)	C4—C9—H9	120.9 (14)
O3—N5—C7	118.0 (3)	N2—C10—H101	110 (3)
O4—N5—C7	118.4 (3)	N2—C10—H102	104 (2)
O1—C1—N1	121.4 (2)	H101—C10—H102	113 (4)
O1—C1—N2	121.8 (2)	N2—C10—H103	109 (2)
N1—C1—N2	116.87 (19)	H101—C10—H103	112 (4)
N4—C2—N2	128.53 (19)	H102—C10—H103	109 (3)
N4—C2—N3	116.64 (18)	N3—C11—H111	111 (2)
N2—C2—N3	114.79 (18)	N3—C11—H112	107.3 (19)
O2—C3—N3	122.0 (2)	H111—C11—H112	116 (3)
O2—C3—N1	121.6 (2)	N3—C11—H113	111 (2)
N3—C3—N1	116.37 (17)	H111—C11—H113	102 (3)
C5—C4—C9	118.9 (2)	H112—C11—H113	110 (3)
C5—C4—N4	121.4 (2)	N1—C12—H121	108 (3)
C9—C4—N4	119.3 (2)	N1—C12—H122	110 (2)
C6—C5—C4	120.7 (2)	H121—C12—H122	103 (3)
C6—C5—H5	119.9 (18)	N1—C12—H123	111 (2)
C4—C5—H5	119.5 (18)	H121—C12—H123	117 (3)
C5—C6—C7	119.2 (3)	H122—C12—H123	108 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O2^i	0.93 (3)	2.49 (3)	3.402 (3)	165 (2)
C6—H6···O1^ii	0.94 (3)	2.72 (3)	3.377 (3)	128 (2)
C8—H8···O1^iii	0.94 (2)	2.65 (2)	3.539 (3)	157 (2)
C9—H9···O3^iv	1.00 (3)	2.67 (3)	3.366 (3)	127 (2)
C10—H102···O3^v	0.91 (4)	2.68 (3)	3.104 (4)	109 (3)

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