2-Amino-4-chloro-5-formyl-6-[meth­yl­(2-methyl­phen­yl)amino]pyrimidine and 2-amino-4-chloro-5-formyl-6-[(2-methoxy­phen­yl)methyl­amino]­pyrimidine are isostructural and form hydrogen-bonded sheets of R₂²(8) and R₆⁶(32) rings

2-Amino-4-chloro-5-formyl-6-[meth­yl(2-methyl­phen­yl)­amino]pyrimidine, C₁₃H₁₃ClN₄O, (I), and 2-amino-4-chloro-5-formyl-6-[(2-methoxy­phen­yl)methyl­amino]pyrimidine, C₁₃H₁₃ClN₄O₂, (II), are isostructural and essentially isomorphous. Although the pyrimidine rings in each compound are planar, the ring-substituent atoms show significant displacements from this plane, and the bond distances provide evidence for polarization of the electronic structures. In each compound, a combination of N-H...N and N-H...O hydrogen bonds links the mol­ecules into sheets built from centrosymmetric R₂²(8) and R₆⁶(32) rings. The significance of this study lies in its observation of the isostructural nature of (I) and (II), and in the comparison of their crystal and mol­ecular structures with those of analogous compounds.

S1. Comment

We have recently reported the molecular and supramolecular structures of a number of N⁶-substituted 2-amino-4-chloro-5-formyl pyrimidines (Cobo et al., 2008). Two features of the molecular structures that vary independently amongst the 12 examples studied are the orientation of the formyl group and the shape of the pyrimidine ring, while in all cases the bond distances provide strong evidence for the development of polarized electronic structures. In the majority of the compounds studied earlier (Cobo et al., 2008), the formyl orientation has the formyl C—H bond approximately parallel to the C—Cl bond, while in the remainder, the formyl C═O bond is approximately parallel to the C—Cl bond; these two conformations are denoted (A) and (B), respectively. For both conformers, examples were observed in which the pyrimidine rings were planar within experimental uncertainty, while in others these rings were significantly puckered into boat, screw-boat or twist-boat conformations. The puckering of the pyridine rings in these examples did not appear to inhibit to any degree the development of the polarized electronic structures, exactly as found in other heavily-substituted pyrimidines previously reported (Low et al., 2007; Melguizo et al., 2003; Quesada et al., 2003, 2004; Trilleras et al., 2007), In all, of the 12 compounds previously studied, nine had formyl conformations of type (A) and three of type (B); independently, five of them contained planar pyrimidine rings and seven contained puckered rings.

As a continuation of this study, we have now investigated two further examples, (I) and (II), which both turn out to have type (B) conformations and to contain planar pyrimidine rings. Compounds (I) and (II) were prepared by selective monosubstitution (Taylor & Gillespie, 1992; Quiroga et al., 2008) of the 6-chloro substituent in 2-amino-4,6-dichloro-5-formylpyrimidine (Seela & Sterker, 1986), and their constitutions differ only in the identity of the substituent in the aryl ring, i.e. 2-methyl in (I) and 2-methoxy in (II) (Figs. 1 and 2). Compounds (I) and (II) crystallize in the same space group with fairly similar unit-cell dimensions; the coordinates of corresponding atoms are also similar, while the patterns of the hydrogen bonds are identical (Table 2). Accordingly, the compounds are isostructural and effectively isomorphous.

The corresponding bond distances and torsion angles for compounds (I) and (II) are very similar (Table 1). The distances show many of the characteristics observed previously in other compounds of this type (Cobo et al., 2008). Thus, the ring distances N1—C2 and C6—N1 and the exocyclic distances C2—N2 are all very similar, while the ring distances N3—C4 are, by some margin, the shortest of all the N—C distances; the formyl C51—O51 bonds are long for their type [mean value (Allen et al., 1987) 1.192 Å], while the C5—C51 bonds are short (mean value 1.488 Å). Taken together these distances provide evidence for an important contribution to the overall electronic structure in (I) and (II) from the polarized forms (Ia) and (IIa). This is so despite the fact that the formyl O atom is not coplanar with the pyrimidine ring, as indicated by the non-zero values of the C4—C5—C51—O51 torsion angle (Table 1).

Although the pyrimidine ring in each of (I) and (II) is essentially planar, with the maximum deviation of a ring atom from the mean plane occurring in each compound for atom C5, displaced from the plane by 0.042 (3) Å in (I) and 0.048 (3) Å in (II), the substituent atoms attached to the pyrimidine ring all show significant deviations from the ring plane. In particular, the three adjacent substituent atoms Cl4, C51 and N61 are displaced to alternate sides of the ring plane, with the central substituent atom C51 showing much the largest displacement in each compound (Table 1). The methoxy atom C68 in (II) is almost coplanar with the adjacent phenyl ring, having a deviation from the ring plane of only 0.013 (4) Å; accordingly, the two exocyclic C—C—O angles associated with the methoxy substituent differ by ca 10°, as normally observed in such cases.

Compounds (I) and (II) exhibit identical patterns of hydrogen bonding (Table 2), with similar dimensions for the hydrogen bonds in the two compounds. The N—H···N hydrogen bond generates a centrosymmetric R₂²(8) (Bernstein et al., 1995) motif, centred at (0, 0, 1/2). The action of the N—H···O hydrogen bond is to link this dimeric unit at (0, 0, 1/2) to the four adjacent dimers centred at (-1/2, -1/2, 0), (-1/2, 1/2, 0), (1/2, -1/2, 1) and (1/2, 1/2, 1), thereby generating a sheet parallel to (101) and built from alternating R₂²(8) and R₆⁶(32) rings (Fig. 3), in which both ring types are centrosymmetric. There are no direction-specific interactions between adjacent sheets; in particular, both C—H···π(arene) hydrogen bonds and aromatic π–π stacking interactions are absent, nor does the methoxy O atom in (II) play any part in the hydrogen bonding.

Within the hydrogen-bonded sheets formed in each of (I) and (II) there is a fairly short N—H···Cl contact (Table 2). However, it has been amply shown (Aakeröy et al., 1999; Brammer et al., 2001; Thallapally & Nangia, 2001) that Cl atoms covalently bonded to C atoms are very poor hydrogen-bond acceptors, and that such contacts are probably no more than ordinary van der Waals contacts. It is thus safer to regard the N—H···Cl contacts in (I) and (II) as adventitious contacts consequent upon the geometry of the N—H···O hydrogen bonds and not of themselves structurally significant. In any event such an interaction would not have any bearing on the overall forms of the hydrogen-bonded structures.

Of the analogues studied previously (Cobo et al., 2008), those closest in constitution to (I) and (II) are (III) (see scheme), which differs from (I) and (II) only in carrying no substituent on the phenyl ring, and (IV), which is an isomer of (I). Compounds (III) and (IV) both adopt type (B) conformations, but while (III) contains a planar pyrimidine ring, in (IV) this ring adopts a boat conformation. Although dimers characterized by R₂²(8) motifs and built from paired N—H···N hydrogen bonds can be identified in the structures of each of (III) and (IV), just as in (I) and (II), the further linking of these dimeric units in (III) and (IV) does not resemble that in (I) and (II). In (III), a combination of N—H···N and C—H···π(arene) hydrogen bonds leads to the formation of a chain of edge-fused rings, but the formyl O atom plays no role in the hydrogen bonding. In (IV), by contrast, a combination of N—H···N and N—H···O hydrogen bonds generates a chain of alternating centrosymmetric R₂²(8) and R⁴₄(16) rings.

The only other example in this series of a sheet of alternating R₂²(8) and R₆⁶(32) rings built from N—H···N and N—H···O hydrogen bonds, as in (I) and (II), was found in the structure of (V). This differs from (I) and (II), both in adopting a type (A) conformation and in the constitution of the NR₂ group bonded to C6. This substituent contains an N—H bond that forms an intramolecular N—H···O hydrogen bond to the formyl O atom but otherwise plays no role in the supramolecular aggregation.

Related literature

For related literature, see: Aakeröy et al. (1999); Bernstein et al. (1995); Brammer et al. (2001); Cobo et al. (2008); Low et al. (2007); Melguizo et al. (2003); Quesada et al. (2003, 2004); Quiroga et al. (2008); Seela & Sterker (1986); Taylor & Gillespie (1992); Thallapally & Nangia (2001); Trilleras et al. (2007).

S2. Experimental

A solution containing 1 mmol of each of 2-amino-4,6-dichloro-5-formylpyrimidine, the appropriate secondary amine [methyl(2-methylphenyl)amine for (I) and methyl(2-methoxyphenyl)amine for (II)] and triethylamine as a base, in ethanol (5 ml), was heated under reflux for 3 h. The mixtures were cooled to ambient temperature and the resulting solid products were collected by filtration, washed with cold ethanol and dried in air before being recrystallized from ethanol to give yellow crystals of (I) and (II) suitable for single-crystal X-ray diffraction. Compound (I) (yield 80%, m.p. 456–458 K): MS (70 eV) m/z (%) 278/276 (M+2/M+, 13/42), 261/260 (55/17), 259 (100), 212 (13), 198 (23), 129/128 (31/8), 92/91 (6/20); HR–MS calculated for C₁₃H₁₃ClN₄O: 276.0778, found 276.0780. Compound (II) (yield 81%, m.p. 454–456 K): MS (70 eV) m/z (%) 294/292 (M+2/M+, 7/21), 263/261 (35/100), 234/233 (4/11), 131/129 (8/21); HR–MS calculated for C₁₃H₁₃ClN₄O₂ 292.0727, found 292.0727.

S3. Refinement

All H atoms were located in difference maps and then treated as riding atoms with C—H distances of 0.95 Å (aromatic) or 0.98 Å (methyl) and N—H distances of 0.88 Å, and with U_iso(H) = kU_eq(carrier), where k = 1.5 for the methyl groups and k = 1.2 for all other H atoms.

Computing details

For both compounds, data collection: COLLECT (Hooft, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: Sir2004 (Burla et al., 2005); program(s) used to refine structure: OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The molecular structure of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 3. Part of the crystal structure of (I), showing the formation of a hydrogen-bonded sheet of R2^2(8) and R6^6(32) rings parallel to (101). For the sake of clarity, H atoms bonded to C atoms have been omitted.

(I) 2-Amino-4-chloro-5-formyl-6-[methyl(2-methylphenyl)amino]pyrimidine

Crystal data

C13H13ClN4O	F(000) = 576
Mr = 276.72	Dx = 1.431 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2946 reflections
a = 11.1502 (8) Å	θ = 3.0–27.5°
b = 8.7271 (8) Å	µ = 0.30 mm^−1
c = 13.7129 (13) Å	T = 120 K
β = 105.676 (7)°	Block, yellow
V = 1284.75 (19) Å^3	0.47 × 0.37 × 0.26 mm
Z = 4

Data collection

Bruker–Nonius KappaCCD diffractometer	2946 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	1999 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.059
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.0°
ϕ & ω scans	h = −14→14
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −11→11
Tmin = 0.874, Tmax = 0.927	l = −17→17
23784 measured 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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.155	H-atom parameters constrained
S = 1.14	w = 1/[σ^2(Fo^2) + (0.0691P)^2 + 1.3411P] where P = (Fo^2 + 2Fc^2)/3
2946 reflections	(Δ/σ)max = 0.001
174 parameters	Δρmax = 0.38 e Å^−3
0 restraints	Δρmin = −0.46 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cl4	0.27600 (6)	0.19726 (7)	0.66110 (5)	0.0266 (2)
O51	0.33885 (18)	0.5202 (2)	0.66011 (14)	0.0312 (5)
N1	0.0135 (2)	0.3502 (2)	0.37571 (16)	0.0229 (5)
N2	−0.0730 (2)	0.1130 (3)	0.37337 (17)	0.0296 (6)
H21	−0.1203	0.1273	0.3114	0.036*
H22	−0.0780	0.0250	0.4034	0.036*
N3	0.09352 (19)	0.1658 (2)	0.50572 (16)	0.0219 (5)
N61	0.10068 (19)	0.5865 (2)	0.37734 (16)	0.0220 (5)
C2	0.0124 (2)	0.2136 (3)	0.4185 (2)	0.0233 (6)
C4	0.1747 (2)	0.2680 (3)	0.55218 (19)	0.0208 (5)
C5	0.1818 (2)	0.4178 (3)	0.52155 (19)	0.0201 (5)
C6	0.0981 (2)	0.4508 (3)	0.42417 (19)	0.0205 (5)
C51	0.2510 (2)	0.5387 (3)	0.58651 (19)	0.0228 (6)
H51	0.2248	0.6412	0.5696	0.027*
C61	0.2129 (2)	0.6742 (3)	0.39104 (19)	0.0236 (6)
C62	0.3198 (3)	0.6077 (3)	0.3760 (2)	0.0260 (6)
C63	0.4239 (3)	0.7010 (3)	0.3885 (2)	0.0303 (6)
H63	0.4989	0.6588	0.3798	0.036*
C64	0.4202 (3)	0.8535 (4)	0.4133 (2)	0.0336 (7)
H64	0.4926	0.9151	0.4216	0.040*
C65	0.3128 (3)	0.9177 (3)	0.4261 (2)	0.0314 (7)
H65	0.3106	1.0231	0.4427	0.038*
C66	0.2091 (3)	0.8281 (3)	0.4148 (2)	0.0279 (6)
H66	0.1344	0.8716	0.4233	0.033*
C67	0.0030 (2)	0.6215 (3)	0.2848 (2)	0.0273 (6)
H671	0.0264	0.5799	0.2262	0.041*
H672	−0.0072	0.7328	0.2776	0.041*
H673	−0.0756	0.5752	0.2888	0.041*
C68	0.3276 (3)	0.4439 (3)	0.3470 (2)	0.0317 (7)
H681	0.2470	0.4112	0.3029	0.048*
H682	0.3489	0.3802	0.4081	0.048*
H683	0.3919	0.4327	0.3109	0.048*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl4	0.0291 (4)	0.0224 (3)	0.0232 (3)	−0.0017 (3)	−0.0019 (2)	0.0032 (3)
O51	0.0336 (11)	0.0268 (11)	0.0271 (10)	−0.0027 (8)	−0.0025 (8)	−0.0017 (8)
N1	0.0236 (11)	0.0198 (11)	0.0239 (11)	−0.0013 (9)	0.0037 (9)	0.0000 (9)
N2	0.0361 (13)	0.0223 (12)	0.0231 (12)	−0.0083 (10)	−0.0044 (10)	0.0034 (9)
N3	0.0239 (11)	0.0190 (11)	0.0200 (11)	−0.0019 (9)	0.0013 (9)	0.0007 (8)
N61	0.0214 (10)	0.0207 (11)	0.0226 (11)	−0.0014 (9)	0.0037 (9)	0.0044 (9)
C2	0.0234 (13)	0.0218 (14)	0.0241 (13)	−0.0014 (11)	0.0053 (10)	−0.0002 (11)
C4	0.0195 (12)	0.0243 (14)	0.0181 (12)	0.0004 (10)	0.0040 (10)	−0.0003 (10)
C5	0.0185 (12)	0.0191 (12)	0.0222 (13)	−0.0005 (10)	0.0046 (10)	−0.0010 (10)
C6	0.0200 (12)	0.0204 (13)	0.0211 (12)	0.0003 (10)	0.0055 (10)	0.0001 (10)
C51	0.0257 (13)	0.0215 (13)	0.0213 (13)	−0.0012 (11)	0.0062 (11)	−0.0003 (10)
C61	0.0256 (13)	0.0229 (14)	0.0217 (13)	−0.0024 (11)	0.0056 (10)	0.0037 (10)
C62	0.0299 (14)	0.0262 (14)	0.0231 (13)	−0.0002 (11)	0.0092 (11)	0.0015 (11)
C63	0.0238 (13)	0.0380 (17)	0.0296 (15)	−0.0026 (12)	0.0080 (11)	0.0017 (13)
C64	0.0299 (14)	0.0364 (16)	0.0347 (16)	−0.0120 (13)	0.0088 (12)	−0.0031 (13)
C65	0.0406 (16)	0.0196 (14)	0.0354 (16)	−0.0050 (12)	0.0127 (13)	−0.0010 (12)
C66	0.0306 (14)	0.0255 (15)	0.0281 (14)	−0.0007 (11)	0.0088 (11)	0.0024 (11)
C67	0.0286 (14)	0.0249 (14)	0.0263 (14)	0.0024 (11)	0.0039 (11)	0.0079 (11)
C68	0.0324 (15)	0.0287 (15)	0.0352 (16)	0.0003 (12)	0.0113 (13)	−0.0043 (12)

Geometric parameters (Å, º)

Cl4—C4	1.725 (3)	C61—C62	1.391 (4)
O51—C51	1.212 (3)	C62—C63	1.391 (4)
N1—C6	1.328 (3)	C62—C68	1.492 (4)
N1—C2	1.331 (3)	C63—C64	1.377 (4)
N2—C2	1.320 (3)	C63—H63	0.9500
N2—H21	0.8800	C64—C65	1.376 (4)
N2—H22	0.8800	C64—H64	0.9500
N3—C4	1.307 (3)	C65—C66	1.370 (4)
N3—C2	1.355 (3)	C65—H65	0.9500
N61—C6	1.351 (3)	C66—H66	0.9500
N61—C61	1.435 (3)	C67—H671	0.9800
N61—C67	1.464 (3)	C67—H672	0.9800
C4—C5	1.382 (4)	C67—H673	0.9800
C5—C6	1.437 (3)	C68—H681	0.9800
C5—C51	1.460 (4)	C68—H682	0.9800
C51—H51	0.9500	C68—H683	0.9800
C61—C66	1.385 (4)
C6—N1—C2	117.5 (2)	C63—C62—C68	119.2 (3)
C2—N2—H21	121.8	C61—C62—C68	123.6 (3)
C2—N2—H22	119.3	C64—C63—C62	121.2 (3)
H21—N2—H22	118.6	C64—C63—H63	119.4
C4—N3—C2	115.4 (2)	C62—C63—H63	119.4
C6—N61—C61	122.4 (2)	C65—C64—C63	120.6 (3)
C6—N61—C67	119.2 (2)	C65—C64—H64	119.7
C61—N61—C67	114.9 (2)	C63—C64—H64	119.7
N2—C2—N1	118.7 (2)	C66—C65—C64	119.4 (3)
N2—C2—N3	115.7 (2)	C66—C65—H65	120.3
N1—C2—N3	125.6 (2)	C64—C65—H65	120.3
N3—C4—C5	125.9 (2)	C65—C66—C61	120.1 (3)
N3—C4—Cl4	112.53 (19)	C65—C66—H66	120.0
C5—C4—Cl4	121.58 (19)	C61—C66—H66	120.0
C4—C5—C6	113.3 (2)	N61—C67—H671	109.5
C4—C5—C51	124.2 (2)	N61—C67—H672	109.5
C6—C5—C51	121.7 (2)	H671—C67—H672	109.5
N1—C6—N61	116.4 (2)	N61—C67—H673	109.5
N1—C6—C5	121.9 (2)	H671—C67—H673	109.5
N61—C6—C5	121.7 (2)	H672—C67—H673	109.5
O51—C51—C5	125.9 (2)	C62—C68—H681	109.5
O51—C51—H51	117.0	C62—C68—H682	109.5
C5—C51—H51	117.0	H681—C68—H682	109.5
C66—C61—C62	121.5 (2)	C62—C68—H683	109.5
C66—C61—N61	117.9 (2)	H681—C68—H683	109.5
C62—C61—N61	120.6 (2)	H682—C68—H683	109.5
C63—C62—C61	117.2 (3)
C6—N1—C2—N2	178.1 (2)	C51—C5—C6—N61	16.0 (4)
C6—N1—C2—N3	−2.7 (4)	C4—C5—C51—O51	24.5 (4)
C4—N3—C2—N2	−177.4 (2)	C6—C5—C51—O51	−165.8 (3)
C4—N3—C2—N1	3.4 (4)	C6—N61—C61—C66	−130.2 (3)
C2—N3—C4—C5	1.8 (4)	C67—N61—C61—C66	71.3 (3)
C2—N3—C4—Cl4	−178.96 (18)	C6—N61—C61—C62	52.9 (3)
N3—C4—C5—C6	−6.7 (4)	C67—N61—C61—C62	−105.7 (3)
Cl4—C4—C5—C6	174.11 (18)	C66—C61—C62—C63	1.7 (4)
N3—C4—C5—C51	163.7 (2)	N61—C61—C62—C63	178.6 (2)
Cl4—C4—C5—C51	−15.4 (4)	C66—C61—C62—C68	−178.0 (3)
C2—N1—C6—N61	177.4 (2)	N61—C61—C62—C68	−1.1 (4)
C2—N1—C6—C5	−3.1 (4)	C61—C62—C63—C64	−1.0 (4)
C61—N61—C6—N1	−150.2 (2)	C68—C62—C63—C64	178.7 (3)
C67—N61—C6—N1	7.4 (3)	C62—C63—C64—C65	−0.1 (5)
C61—N61—C6—C5	30.3 (4)	C63—C64—C65—C66	0.5 (4)
C67—N61—C6—C5	−172.0 (2)	C64—C65—C66—C61	0.2 (4)
C4—C5—C6—N1	7.3 (4)	C62—C61—C66—C65	−1.4 (4)
C51—C5—C6—N1	−163.5 (2)	N61—C61—C66—C65	−178.3 (2)
C4—C5—C6—N61	−173.3 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O51^i	0.88	2.38	3.052 (3)	134
N2—H21···Cl4^i	0.88	2.58	3.377 (2)	152
N2—H22···N3^ii	0.88	2.11	2.988 (3)	171

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

(II) 2-amino-4-chloro-5-formyl-6-[(2-methoxyphenyl)methylamino]pyrimidine,

Crystal data

C13H13ClN4O2	F(000) = 608
Mr = 292.72	Dx = 1.465 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3028 reflections
a = 11.301 (4) Å	θ = 5.1–27.5°
b = 8.642 (3) Å	µ = 0.30 mm^−1
c = 14.568 (5) Å	T = 120 K
β = 111.13 (3)°	Block, yellow
V = 1327.1 (8) Å^3	0.27 × 0.15 × 0.10 mm
Z = 4

Data collection

Bruker–Nonius KappaCCD diffractometer	3028 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	2010 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.103
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 5.1°
ϕ & ω scans	h = −14→14
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −11→11
Tmin = 0.939, Tmax = 0.971	l = −17→18
18363 measured 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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.143	H-atom parameters constrained
S = 1.11	w = 1/[σ^2(Fo^2) + (0.0331P)^2 + 2.2466P] where P = (Fo^2 + 2Fc^2)/3
3028 reflections	(Δ/σ)max = 0.001
183 parameters	Δρmax = 0.52 e Å^−3
0 restraints	Δρmin = −0.43 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cl4	0.29508 (7)	0.19761 (9)	0.66058 (5)	0.0241 (2)
O51	0.3466 (2)	0.5266 (3)	0.66721 (16)	0.0321 (6)
O62	0.2775 (2)	0.4567 (3)	0.35443 (16)	0.0278 (5)
N1	0.0035 (2)	0.3539 (3)	0.38243 (18)	0.0209 (6)
N2	−0.0827 (3)	0.1147 (3)	0.37770 (19)	0.0278 (6)
H21	−0.1363	0.1346	0.3180	0.033*
H22	−0.0845	0.0245	0.4053	0.033*
N3	0.0973 (2)	0.1654 (3)	0.50714 (17)	0.0201 (6)
N61	0.0854 (2)	0.5970 (3)	0.38828 (17)	0.0200 (6)
C2	0.0078 (3)	0.2147 (4)	0.4235 (2)	0.0220 (7)
C4	0.1823 (3)	0.2694 (4)	0.5542 (2)	0.0190 (6)
C5	0.1841 (3)	0.4226 (3)	0.5264 (2)	0.0195 (6)
C6	0.0915 (3)	0.4556 (3)	0.4320 (2)	0.0192 (6)
C51	0.2564 (3)	0.5449 (4)	0.5920 (2)	0.0207 (6)
H51	0.2300	0.6484	0.5738	0.025*
C61	0.1985 (3)	0.6808 (4)	0.3990 (2)	0.0216 (6)
C62	0.2965 (3)	0.6083 (4)	0.3790 (2)	0.0233 (7)
C63	0.4026 (3)	0.6926 (4)	0.3836 (2)	0.0291 (7)
H63	0.4708	0.6435	0.3715	0.035*
C64	0.4090 (3)	0.8477 (4)	0.4057 (2)	0.0329 (8)
H64	0.4814	0.9056	0.4080	0.039*
C65	0.3121 (3)	0.9202 (4)	0.4247 (2)	0.0332 (8)
H65	0.3179	1.0274	0.4402	0.040*
C66	0.2063 (3)	0.8368 (4)	0.4212 (2)	0.0262 (7)
H66	0.1390	0.8867	0.4341	0.031*
C67	−0.0184 (3)	0.6270 (4)	0.2956 (2)	0.0240 (7)
H671	0.0002	0.5782	0.2416	0.036*
H672	−0.0280	0.7389	0.2844	0.036*
H673	−0.0973	0.5840	0.2985	0.036*
C68	0.3775 (3)	0.3746 (4)	0.3389 (3)	0.0337 (8)
H681	0.3985	0.4248	0.2864	0.051*
H682	0.3507	0.2678	0.3198	0.051*
H683	0.4523	0.3744	0.3998	0.051*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl4	0.0249 (4)	0.0228 (4)	0.0192 (4)	0.0006 (3)	0.0013 (3)	0.0023 (3)
O51	0.0321 (13)	0.0264 (13)	0.0283 (12)	−0.0041 (10)	−0.0004 (10)	−0.0012 (10)
O62	0.0305 (12)	0.0250 (12)	0.0334 (13)	−0.0005 (10)	0.0181 (10)	−0.0061 (10)
N1	0.0257 (14)	0.0181 (13)	0.0170 (12)	−0.0019 (11)	0.0054 (11)	0.0007 (10)
N2	0.0332 (15)	0.0217 (14)	0.0194 (13)	−0.0063 (12)	−0.0015 (11)	0.0052 (11)
N3	0.0239 (13)	0.0184 (13)	0.0170 (12)	−0.0024 (11)	0.0060 (10)	−0.0001 (10)
N61	0.0208 (13)	0.0194 (13)	0.0193 (13)	−0.0009 (11)	0.0066 (10)	0.0025 (10)
C2	0.0265 (16)	0.0210 (16)	0.0182 (14)	−0.0018 (13)	0.0075 (12)	0.0008 (12)
C4	0.0195 (14)	0.0218 (16)	0.0147 (13)	0.0019 (12)	0.0049 (11)	0.0007 (11)
C5	0.0212 (15)	0.0202 (16)	0.0174 (14)	−0.0021 (12)	0.0074 (12)	−0.0008 (12)
C6	0.0209 (15)	0.0196 (15)	0.0199 (15)	0.0011 (12)	0.0108 (12)	0.0010 (12)
C51	0.0227 (15)	0.0212 (16)	0.0208 (15)	−0.0029 (13)	0.0109 (13)	0.0010 (12)
C61	0.0240 (15)	0.0230 (16)	0.0195 (15)	−0.0030 (13)	0.0099 (12)	0.0012 (12)
C62	0.0264 (16)	0.0247 (17)	0.0185 (14)	−0.0022 (14)	0.0078 (13)	0.0004 (13)
C63	0.0239 (16)	0.0367 (19)	0.0277 (17)	−0.0025 (15)	0.0107 (13)	0.0000 (15)
C64	0.0322 (19)	0.035 (2)	0.0314 (18)	−0.0133 (16)	0.0118 (15)	−0.0004 (15)
C65	0.040 (2)	0.0245 (18)	0.0307 (18)	−0.0068 (16)	0.0078 (16)	0.0010 (14)
C66	0.0310 (17)	0.0235 (18)	0.0261 (16)	−0.0024 (14)	0.0126 (14)	0.0011 (13)
C67	0.0263 (16)	0.0225 (16)	0.0228 (16)	−0.0011 (13)	0.0081 (13)	0.0045 (13)
C68	0.0337 (19)	0.035 (2)	0.0366 (19)	0.0052 (16)	0.0173 (16)	−0.0061 (16)

Geometric parameters (Å, º)

Cl4—C4	1.728 (3)	C51—H51	0.9500
O51—C51	1.208 (4)	C61—C66	1.382 (5)
O62—C62	1.355 (4)	C61—C62	1.392 (4)
O62—C68	1.420 (4)	C62—C63	1.383 (4)
N1—C6	1.328 (4)	C63—C64	1.375 (5)
N1—C2	1.336 (4)	C63—H63	0.9500
N2—C2	1.322 (4)	C64—C65	1.373 (5)
N2—H21	0.8800	C64—H64	0.9500
N2—H22	0.8800	C65—C66	1.381 (5)
N3—C4	1.314 (4)	C65—H65	0.9500
N3—C2	1.342 (4)	C66—H66	0.9500
N61—C6	1.369 (4)	C67—H671	0.9800
N61—C61	1.428 (4)	C67—H672	0.9800
N61—C67	1.458 (4)	C67—H673	0.9800
C4—C5	1.387 (4)	C68—H681	0.9800
C5—C6	1.425 (4)	C68—H682	0.9800
C5—C51	1.461 (4)	C68—H683	0.9800
C62—O62—C68	117.8 (3)	O62—C62—C63	125.1 (3)
C6—N1—C2	116.9 (3)	O62—C62—C61	115.3 (3)
C2—N2—H21	120.2	C63—C62—C61	119.6 (3)
C2—N2—H22	119.3	C64—C63—C62	119.8 (3)
H21—N2—H22	120.3	C64—C63—H63	120.1
C4—N3—C2	115.3 (3)	C62—C63—H63	120.1
C6—N61—C61	120.6 (3)	C65—C64—C63	120.9 (3)
C6—N61—C67	118.6 (3)	C65—C64—H64	119.5
C61—N61—C67	113.6 (2)	C63—C64—H64	119.5
N2—C2—N1	117.8 (3)	C64—C65—C66	119.8 (3)
N2—C2—N3	116.3 (3)	C64—C65—H65	120.1
N1—C2—N3	125.9 (3)	C66—C65—H65	120.1
N3—C4—C5	125.8 (3)	C65—C66—C61	119.9 (3)
N3—C4—Cl4	112.8 (2)	C65—C66—H66	120.0
C5—C4—Cl4	121.4 (2)	C61—C66—H66	120.0
C4—C5—C6	112.9 (3)	N61—C67—H671	109.5
C4—C5—C51	124.2 (3)	N61—C67—H672	109.5
C6—C5—C51	122.0 (3)	H671—C67—H672	109.5
N1—C6—N61	115.8 (3)	N61—C67—H673	109.5
N1—C6—C5	122.6 (3)	H671—C67—H673	109.5
N61—C6—C5	121.6 (3)	H672—C67—H673	109.5
O51—C51—C5	126.1 (3)	O62—C68—H681	109.5
O51—C51—H51	116.9	O62—C68—H682	109.5
C5—C51—H51	116.9	H681—C68—H682	109.5
C66—C61—C62	120.0 (3)	O62—C68—H683	109.5
C66—C61—N61	120.0 (3)	H681—C68—H683	109.5
C62—C61—N61	119.8 (3)	H682—C68—H683	109.5
C6—N1—C2—N2	176.6 (3)	C4—C5—C51—O51	20.8 (5)
C6—N1—C2—N3	−4.3 (5)	C6—C5—C51—O51	−170.3 (3)
C4—N3—C2—N2	−176.4 (3)	C6—N61—C61—C66	−134.2 (3)
C4—N3—C2—N1	4.6 (4)	C67—N61—C61—C66	75.8 (3)
C2—N3—C4—C5	2.0 (4)	C6—N61—C61—C62	51.2 (4)
C2—N3—C4—Cl4	−179.5 (2)	C67—N61—C61—C62	−98.8 (3)
N3—C4—C5—C6	−7.6 (4)	C68—O62—C62—C63	4.7 (4)
Cl4—C4—C5—C6	174.1 (2)	C68—O62—C62—C61	−176.3 (3)
N3—C4—C5—C51	162.2 (3)	C66—C61—C62—O62	−177.6 (3)
Cl4—C4—C5—C51	−16.1 (4)	N61—C61—C62—O62	−3.0 (4)
C2—N1—C6—N61	179.8 (3)	C66—C61—C62—C63	1.4 (4)
C2—N1—C6—C5	−2.3 (4)	N61—C61—C62—C63	176.0 (3)
C61—N61—C6—N1	−145.5 (3)	O62—C62—C63—C64	177.5 (3)
C67—N61—C6—N1	3.1 (4)	C61—C62—C63—C64	−1.4 (5)
C61—N61—C6—C5	36.6 (4)	C62—C63—C64—C65	0.9 (5)
C67—N61—C6—C5	−174.8 (3)	C63—C64—C65—C66	−0.3 (5)
C4—C5—C6—N1	7.6 (4)	C64—C65—C66—C61	0.2 (5)
C51—C5—C6—N1	−162.4 (3)	C62—C61—C66—C65	−0.8 (5)
C4—C5—C6—N61	−174.6 (3)	N61—C61—C66—C65	−175.4 (3)
C51—C5—C6—N61	15.4 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O51^i	0.88	2.55	3.125 (4)	124
N2—H21···Cl4^i	0.88	2.58	3.375 (3)	150
N2—H22···N3^ii	0.88	2.12	2.983 (4)	168

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