Two polymorphs, with Z' = 1 and 2, of 2-amino-4-chloro-6-morpholino­pyrimidine in P2₁/c, and 2-amino-4-chloro-6-piperidino­pyrimidine, which is isomorphous and almost isostructural with the Z' = 2 polymorph

Crystallization of 2-amino-4-chloro-6-morpholino­pyrimidine, C₈H₁₁ClN₄O, (I), yields two polymorphs, both with space group P2₁/c, having Z' = 1 (from diethyl ether solution) and Z' = 2 (from di­chloro­methane solution), denoted (Ia) and (Ib), respectively. In polymorph (Ia), the mol­ecules are linked by an N-H...O and an N-H...N hydrogen bond into sheets built from alternating R(8) and R(40) rings. In polymorph (Ib), one mol­ecule acts as a triple acceptor of hydrogen bonds and the other acts as a single acceptor; one N-H...O and three N-H...N hydrogen bonds link the mol­ecules in a complex chain containing two types of R(8) and one type of R(18) ring. 2-Amino-4-chloro-6-piperidino­pyrimidine, C₉H₁₃ClN₄, (II), which is isomorphous with polymorph (Ib), also has Z' = 2 in P2₁/c, and the mol­ecules are linked by three N-­H...N hydrogen bonds into a centrosymmetric four-mol­ecule aggregate containing three R(8) rings.

S1. Comment

Aminochloropyrimidines are key intermediates for the synthesis of O⁶-benzyloxy-5-nitrosopyrimidines, which can themselves be converted into a wide range of alkoxy- and amino-substituted O⁶-benzyloxy-5-nitrosopyrimidines (Quesada, Marchal, Melguizo et al., 2002; Quesada, Marchal, Nogueras et al., 2002), important as potential, or proven, in vitro inhibitors of the human DNA-repair protein O6-alkylguanine-DNA-transferase (Chae et al., 1995; Quesada, Marchal, Melguizo et al., 2002). We report here the molecular and supramolecular structures of two examples of this class of pyrimidine, namely 2-amino-4-chloro-6-morpholinopyrimidine, (I), which crystallizes in two polymorphic forms, and 2-amino-4-chloro-6-piperidinopyrimidine, (II), which is isomorphous and almost isostructural with one of the polymorphs of (I).

The simpler polymorph (Ia) (Fig. 1) of compound (I) has Z' = 1 in P2₁/c, and the molecules are linked into sheets by two hydrogen bonds, one each of the N—H···O and N—H···N types (Table 1). Amino atom N2 in the molecule at (x, y, z) acts as hydrogen-bond donor, via H1, to the morpholine atom O64 in the molecule at (2 − x, −0.5 + y, 0.5 − z), while atom N2 at (2 − x, −0.5 + y, 0.5 − z) likewise acts as donor to O64 at (x, −1 + y, z), so producing a C(9) chain running parallel to the [010] direction and generated by the 2₁ screw axis along (1, y, 1/4) (Fig. 2). Adjacent [010] chains are linked into (102) sheets by means of N—H···N hydrogen bonding. Amine atom N2 in the molecule at (x, y, z), which lies in the [010] chain along (1, y, 1/4), acts as hydrogen-bond donor, via H2, to atom N3 in the molecule at (1 − x, 1 − y, 1 − z), which lies in the antiparallel chain along (0, −y, 3/4), so forming an R²₂(8) ring centred at (1/2, 1/2, 1/2). In a similar way, the molecule at (2 − x, −0.5 + y, 0.5 − z), a component of the (1, y, 1/4) chain, is linked via the R²₂(8) motif to the molecule at (1 + x, 0.5 − y, −0.5 + z), which lies in the chain along (2, −y, −0.25). In this manner, [010] chains are linked into a (102) sheet, built from alternating R²₂(8) and R⁶₆(40) rings (Fig. 2). If the individual molecules are regarded as the nodes of the net defining the (102) sheet, then this net is of the (6,3)-type (Batten & Robson, 1998), while if the R²₂(8) dimers are taken to be the nodes the net is of (4,4)-type. There are no direction-specific interactions between adjacent sheets.

In the Z' = 2 polymorph of compound (I), viz. (Ib), the two independent molecules (Fig. 3) exhibit different hydrogen-bonding behaviour and the hydrogen bonds (Table 2) generate a rather elaborate one-dimensional structure. In both molecules, the amino group acts as a double donor, but molecule 1 (containing atom N11; Fig. 3) acts as a triple acceptor of hydrogen bonds, via atoms N11, N13 and O164, whereas in molecule 2, there is just a single acceptor, N23. These facts alone preclude an additional symmetry. Within the selected asymmetric unit (Fig. 3), the molecules are linked by paired N—H···N hydrogen bonds, forming an R²₂(8) dimer in which the orientation of the morpholine substituents precludes even approximate additional symmetry. In analysing the structure of this polymorph, it is convenient to employ the substructure approach (Gregson et al., 2000), where the key substructural unit is the R²₂(8) dimer; the formation of this dimer leaves two N—H bonds, N12—H12 and N22—H21, available for the formation of further hydrogen bonds. Amino atom N12 in the type-1 molecule at (x, y, z) acts as hydrogen-bond donor, via H12, to atom N13 in the type-1 molecule at (2 − x, 1 − y, 1 − z), so generating a centrosymmetric R²₂(8) motif, centred at (1, 1/2, 1/2), while atom N22 in the type-2 molecule at (x, y, z) acts as donor, via H21, to atom O164 in the type-1 molecule at (1 − x, −y, 1 − z), so generating a centrosymmetric R⁴₄(18) motif centred at (1/2, 0, 1/2). Propagation by inversion of these hydrogen bonds thus leads to formation of a chain of rings running parallel to the [110] direction (Fig. 4), such that the type-2 morpholine groups containing atom O264 are pendent from the chain with no plausible hydrogen-bond donors within hydrogen-bonding distance.

Compound (II) has so far been isolated in only one crystalline form and this is isomorphous with the Z' = 2 polymorph of compound (I); the cell dimensions of these two P2₁/c, Z' = 2 phases are very similar and it is possible to refine either structure starting from the coordinates of the other, paying due regard to the difference in atom types between the morpholino substituent in (I) and the piperidine substituent in (II). Since, however, there can be no N—H···O hydrogen bonds in (II) (Table 3), the supramolecular aggregation in (II) must be different from that in either polymorph of (I), where such hydrogen bonds are present in both polymorphs, and hence the two Z' = 2 phases are not, strictly speaking, properly isostructural, although they are nearly so. The asymmetric unit selected for compound (II) resembles that for the Z' = 2 polymorph of (I) in forming an R²₂(8) dimer which itself exhibits no symmetry (Fig. 5). Pairs of these dimers are linked into a centrosymmetric four-molecule aggregate centred at (1, 1/2, 1/2); atom N12 at (x, y, z) acts as hydrogen-bond donor, via H12, to atom N13 at (2 − x, 1 − y, 1 − z), but the N22—H21 bond does not participate in the hydrogen bonding, so that this aggregate is strictly finite (Fig. 6).

It is notable that even in (II), where there is an exact match between the number of hard hydrogen-bond donors and the number of hard hydrogen-bond acceptors, not all of these donors and acceptors are involved in the supramolecular aggregation. Thus, atom N21 does not accept any hydrogen bond, nor is N22—H21 involved. In both (Ia) and (Ib), there is an excess of acceptors over donors, and in (Ia), atom N1 is unused as an acceptor, while in (Ib) both N21 and O264 are unused. The structures of (Ia), (Ib) and (II) do not contain any soft hydrogen bonds of the C—H···A (A = N or O) or D—H···π types (D = C or N), nor do they contain any π–π-stacking interactions; they thus have hydrogen-bonded supramolecular structures which are two-dimensional, one-dimensional and (finite) zero-dimensional, respectively.

In each of (Ib) and (II), there are rather short contacts between pairs of Cl atoms, across the inversion centre at (1, 1/2, 1/2) (Figs. 4 and 6); in (Ib), the Cl14···Cl24ⁱ distance is 3.375 (2) Å [symmetry code: (i) 2 − x, 1 − y, 1 − z], associated with a C—Cl···Cl angle of 145.14 (5)°, while in (II), the corresponding values are 3.425 (2) Å and 150.08 (5)°. For Cl bonded to neutral arene groups, Bondi (1964) recommended a van der Waals radius of 1.77 Å; the Cl···Cl contact distances in (Ib) and (II) are thus significantly shorter than twice the van der Waals radius. Database analysis of such halogen–halogen contacts has shown than when the X···X contact distance (X = halogen) is significantly less than the van der Waals sum, the associated C—X···X angles are clustered around 180 and 90° (Ramasabbu et al., 1986); the C—Cl···Cl angles observed are not particularly close to either cluster, and almost certainly their values are constrained by the formation of the centrosymmetric hydrogen-bonded R²₂(8) rings.

Within the molecules, the morpholine and piperidine substituents adopt the usual chair conformation, but with the N atoms in these rings almost planar; the sum of the angles at this N atom ranges from 352.3 (2)° in (Ia) to 359.9 (2)° in molecule 1 of (Ib). Consistent with this planarity, the associated C—N distances for the bond linking the two rings within each molecule range from 1.352 (2) to 1.372 (2) Å, with a mean of 1.361 (2) Å, typical of Ar—N(C)₂ distances involving di-N-substituted anilines with a planar N atom (mean value 1.371 Å; Allen et al., 1987). By way of comparison, the C—NH₂ distances here range from 1.338 (2) to 1.358 (2) Å, with a mean value of 1.348 (2) Å, again typical of Ar—NH₂ distances in simple anilines with an unsubstituted planar N atom (mean value 1.355 Å; Allen et al., 1987). The other intramolecular distances and angles show no unusual features; in particular, there is no evidence for any bond fixation within the pyrimidine rings.

The very different cell dimensions for the two polymorphs (Ia) and (Ib) effectively rule out any possibility of a simple displacive phase transition between these two polymorphs. While we have not investigated the relative stability of these two polymorphs, we note that (Ia) has a significantly higher density than (Ib) and thus is probably the thermodynamically more stable form (Burger & Ramberger, 1979). Although polymorph (Ib) was the first to be isolated, both forms can readily be reproduced by crystallization from the appropriate solvent; hence there is no question here of any disappearing polymorph (Dunitz & Bernstein, 1995).

S2. Experimental

Samples of (I) and (II) were synthesized from 2-amino-4,6-dichloropyrimidine (purchased from Aldrich). Morpholine [for (I)] or piperidine [for (II)] (3.1 mmol), and triethylamine (6.5 mmol) were added to a stirred solution of 2-amino-4,6-dichloropyrimidine (3.0 mmol) in 3-methylbutan-2-ol (20 ml). The mixtures were heated under reflux, with stirring, for 2 h. After cooling, the solvent was removed, excess distilled water was added, and the resulting solid was filtered off and washed with water. After drying, the solid products were recrystallized first from ethyl acetate and then from dichloromethane; m.p. 485 K [for (I)] and 431 K [for (II)]. NMR for (I), δ ¹H (CHCl₃): 3.55 (4H, t, J = 5.2 Hz, N—CH₂), 3.74 (4H, t, J = 5.2 Hz, O—CH₂), 4.90 (2H, br, NH₂, exchanges with D₂O), 5.94 [1H, s, C(5)—H]; δ ¹³C (CDCl₃): 45.3, 66.6, 82.4, 160.2, 162.3, 163.3; NMR for (II), δ ¹H (CHCl₃): 1.58–1.68 (6H, m, 3 × CH₂), 3.54 (4H, t, J = 45.0 Hz, N—CH₂), 4.76 (2H, br, NH₂, exchanges with D₂O), 5.96 [1H, s, C(5)—H]; δ ¹³C (CDCl₃): 24.6, 25.5, 45.3, 82.4, 160.2, 162.2, 163.3. Crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation of solutions in diethyl ether [for (Ia)] or dichloromethane [for (Ib) and (II)].

S3. Refinement

Polymorphs (Ia) and (Ib) and compound (II) all crystallize in space group P2₁/c, the space group being uniquely assigned from the systematic absences in each case. All H atoms were treated as riding atoms, with C—H distances of 0.95 (heteroaromatic) or 0.99 Å (CH₂), and N—H distances of 0.88 Å.

Computing details

For all compounds, data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997). Data reduction: DENZO–SMN for (Ia); DENZO–SMN (Otwinowski & Minor, 1997) for (Ib), (II). For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2002); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. The molecule of compound (I) in the Z' = 1 polymorph, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Part of the crystal structure of the Z' = 1 polymorph of (I), showing the formation of a (102) sheet built from alternating R^22(8) and R^66(40) rings. For the sake of clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*), hash (#) or dollar sign ($) are at the symmetry positions (1 − x, 1 − y, 1 − z), (2 − x, −0.5 + y, 0.5 − z) and (2 − x, 0.5 + y, 0.5 − z), respectively.
	Fig. 3. The two independent molecules of compound (I) in the Z' = 2 polymorph, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 4. Stereoview of part of the crystal structure of the Z' = 2 polymorph of (I), showing the formation of a chain of edge-fused R^22(8) and R^44(18) rings along [110]. For the sake of clarity, H atoms bonded to C atoms have been omitted.
	Fig. 5. The two independent molecules of compound (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 6. Part of the crystal structure of (II), showing the formation of a four-molecule aggregate containing three R^22(8) rings. For the sake of clarity, H atoms bonded to C atoms and the unit-cell box have been omitted. Atoms marked with an asterisk (*) are at the symmetry position (2 − x, 1 − y, 1 − z).

(Ia) 2-Amino-4-chloro-6-morpholinopyrimidine, Z' = 1 polymorph

Crystal data

C8H11ClN4O	F(000) = 448
Mr = 214.66	Dx = 1.537 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2102 reflections
a = 9.4143 (4) Å	θ = 3.1–27.5°
b = 13.0869 (4) Å	µ = 0.38 mm^−1
c = 7.5774 (2) Å	T = 120 K
β = 96.4260 (13)°	Block, colourless
V = 927.70 (5) Å^3	0.42 × 0.22 × 0.16 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	2102 independent reflections
Radiation source: fine-focus sealed X-ray tube	1705 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
ϕ scans, and ω scans with κ offsets	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (DENZO–SMN; Otwinowski & Minor, 1997)	h = −12→12
Tmin = 0.856, Tmax = 0.941	k = −16→12
6031 measured reflections	l = −8→9

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.092	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0371P)^2 + 0.4718P] where P = (Fo^2 + 2Fc^2)/3
2102 reflections	(Δ/σ)max < 0.001
127 parameters	Δρmax = 0.35 e Å^−3
0 restraints	Δρmin = −0.38 e Å^−3

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

	x	y	z	Uiso*/Ueq
N1	0.71414 (14)	0.68239 (10)	0.31515 (17)	0.0145 (3)
C2	0.61611 (17)	0.61494 (13)	0.3565 (2)	0.0153 (3)
N2	0.64679 (15)	0.51494 (11)	0.33258 (19)	0.0210 (3)
N3	0.48967 (14)	0.63653 (10)	0.41696 (17)	0.0162 (3)
C4	0.46540 (16)	0.73618 (13)	0.4275 (2)	0.0151 (3)
Cl4	0.29987 (4)	0.76873 (3)	0.49579 (5)	0.02164 (14)
C5	0.55396 (16)	0.81388 (12)	0.3899 (2)	0.0146 (3)
C6	0.68472 (17)	0.78156 (12)	0.3325 (2)	0.0133 (3)
N61	0.78585 (14)	0.84916 (10)	0.28931 (18)	0.0148 (3)
C62	0.78964 (18)	0.95378 (13)	0.3586 (2)	0.0184 (4)
C63	0.88104 (18)	1.02158 (13)	0.2538 (2)	0.0208 (4)
O64	1.01967 (12)	0.97951 (9)	0.24329 (15)	0.0205 (3)
C65	1.00464 (18)	0.88308 (13)	0.1556 (2)	0.0191 (4)
C66	0.92618 (17)	0.80832 (13)	0.2607 (2)	0.0190 (4)
H1	0.7274	0.4976	0.2920	0.025*
H2	0.5861	0.4674	0.3577	0.025*
H51	0.5298	0.8839	0.4012	0.017*
H3	0.8293	0.9535	0.4852	0.022*
H4	0.6913	0.9815	0.3504	0.022*
H5	0.8323	1.0311	0.1323	0.025*
H6	0.8911	1.0896	0.3111	0.025*
H7	1.1004	0.8555	0.1401	0.023*
H8	0.9515	0.8922	0.0363	0.023*
H9	0.9142	0.7427	0.1957	0.023*
H10	0.9827	0.7952	0.3767	0.023*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0145 (6)	0.0133 (7)	0.0159 (7)	−0.0003 (5)	0.0025 (5)	0.0019 (5)
C2	0.0160 (8)	0.0151 (8)	0.0146 (8)	−0.0018 (6)	0.0001 (6)	0.0012 (6)
N2	0.0217 (8)	0.0125 (7)	0.0298 (8)	−0.0013 (6)	0.0081 (6)	0.0009 (6)
N3	0.0142 (7)	0.0163 (7)	0.0182 (7)	−0.0019 (5)	0.0017 (5)	0.0035 (5)
C4	0.0121 (7)	0.0207 (9)	0.0126 (8)	0.0006 (6)	0.0019 (6)	0.0019 (6)
Cl4	0.0133 (2)	0.0262 (3)	0.0268 (2)	0.00021 (16)	0.00769 (15)	0.00222 (17)
C5	0.0147 (8)	0.0139 (8)	0.0151 (8)	0.0008 (6)	0.0017 (6)	0.0011 (6)
C6	0.0139 (8)	0.0147 (8)	0.0110 (7)	−0.0002 (6)	0.0002 (6)	0.0024 (6)
N61	0.0130 (7)	0.0124 (7)	0.0198 (7)	−0.0011 (5)	0.0054 (5)	0.0001 (5)
C62	0.0192 (8)	0.0146 (8)	0.0225 (9)	−0.0022 (7)	0.0075 (6)	−0.0032 (7)
C63	0.0189 (8)	0.0155 (9)	0.0288 (9)	−0.0026 (7)	0.0064 (7)	−0.0009 (7)
O64	0.0169 (6)	0.0189 (6)	0.0263 (6)	−0.0054 (5)	0.0053 (5)	−0.0027 (5)
C65	0.0176 (8)	0.0185 (9)	0.0225 (9)	−0.0027 (7)	0.0077 (6)	−0.0010 (7)
C66	0.0144 (8)	0.0163 (8)	0.0272 (9)	0.0014 (7)	0.0071 (6)	0.0021 (7)

Geometric parameters (Å, º)

N1—C6	1.337 (2)	N61—C62	1.465 (2)
N1—C2	1.339 (2)	C62—C63	1.520 (2)
C2—N3	1.352 (2)	C62—H3	0.99
C2—N2	1.357 (2)	C62—H4	0.99
N2—H1	0.88	C63—O64	1.427 (2)
N2—H2	0.88	C63—H5	0.99
N3—C4	1.328 (2)	C63—H6	0.99
C4—C5	1.365 (2)	O64—C65	1.426 (2)
C4—Cl4	1.7489 (16)	C65—C66	1.506 (2)
C5—C6	1.415 (2)	C65—H7	0.99
C5—H51	0.95	C65—H8	0.99
C6—N61	1.366 (2)	C66—H9	0.99
N61—C66	1.464 (2)	C66—H10	0.99
C6—N1—C2	117.46 (14)	N61—C62—H4	109.5
N1—C2—N3	126.68 (15)	C63—C62—H4	109.5
N1—C2—N2	116.23 (15)	H3—C62—H4	108.1
N3—C2—N2	117.09 (15)	O64—C63—C62	112.25 (14)
C2—N2—H1	120.0	O64—C63—H5	109.2
C2—N2—H2	120.0	C62—C63—H5	109.2
H1—N2—H2	120.0	O64—C63—H6	109.2
C4—N3—C2	112.91 (14)	C62—C63—H6	109.2
N3—C4—C5	127.29 (15)	H5—C63—H6	107.9
N3—C4—Cl4	114.95 (12)	C65—O64—C63	108.90 (12)
C5—C4—Cl4	117.75 (13)	O64—C65—C66	110.93 (13)
C4—C5—C6	114.46 (15)	O64—C65—H7	109.5
C4—C5—H51	122.8	C66—C65—H7	109.5
C6—C5—H51	122.8	O64—C65—H8	109.5
N1—C6—N61	116.59 (14)	C66—C65—H8	109.5
N1—C6—C5	121.15 (14)	H7—C65—H8	108.0
N61—C6—C5	122.25 (15)	N61—C66—C65	110.21 (14)
C6—N61—C66	117.64 (13)	N61—C66—H9	109.6
C6—N61—C62	120.60 (13)	C65—C66—H9	109.6
C66—N61—C62	114.08 (13)	N61—C66—H10	109.6
N61—C62—C63	110.55 (13)	C65—C66—H10	109.6
N61—C62—H3	109.5	H9—C66—H10	108.1
C63—C62—H3	109.5
C6—N1—C2—N3	−1.0 (2)	N1—C6—N61—C66	−11.2 (2)
C6—N1—C2—N2	178.08 (14)	C5—C6—N61—C66	169.94 (14)
N1—C2—N3—C4	2.3 (2)	N1—C6—N61—C62	−158.81 (14)
N2—C2—N3—C4	−176.68 (14)	C5—C6—N61—C62	22.3 (2)
C2—N3—C4—C5	−2.1 (2)	C6—N61—C62—C63	−164.05 (14)
C2—N3—C4—Cl4	177.36 (11)	C66—N61—C62—C63	47.21 (19)
N3—C4—C5—C6	0.5 (2)	N61—C62—C63—O64	−52.48 (19)
Cl4—C4—C5—C6	−178.94 (11)	C62—C63—O64—C65	60.71 (17)
C2—N1—C6—N61	−179.85 (14)	C63—O64—C65—C66	−63.06 (17)
C2—N1—C6—C5	−0.9 (2)	C6—N61—C66—C65	160.42 (14)
C4—C5—C6—N1	1.1 (2)	C62—N61—C66—C65	−49.86 (18)
C4—C5—C6—N61	−179.99 (14)	O64—C65—C66—N61	57.46 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···O64^i	0.88	2.44	3.288 (2)	163
N2—H2···N3^ii	0.88	2.36	3.119 (2)	145

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

(Ib) 2-Amino-4-chloro-6-morpholinopyrimidine, Z' = 2 polymorph

Crystal data

C8H11ClN4O	F(000) = 896
Mr = 214.66	Dx = 1.497 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4346 reflections
a = 13.9215 (3) Å	θ = 3.0–27.5°
b = 8.1803 (2) Å	µ = 0.37 mm^−1
c = 19.6390 (4) Å	T = 150 K
β = 121.6130 (12)°	Plate, colourless
V = 1904.65 (8) Å^3	0.30 × 0.25 × 0.02 mm
Z = 8

Data collection

Nonius KappaCCD diffractometer	4346 independent reflections
Radiation source: fine-focus sealed X-ray tube	3612 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
ϕ scans, and ω scans with κ offsets	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (DENZO–SMN; Otwinowski & Minor, 1997)	h = −18→16
Tmin = 0.961, Tmax = 0.995	k = −10→10
17326 measured reflections	l = −25→25

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.097	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0488P)^2 + 0.656P] where P = (Fo^2 + 2Fc^2)/3
4346 reflections	(Δ/σ)max = 0.001
253 parameters	Δρmax = 0.32 e Å^−3
0 restraints	Δρmin = −0.40 e Å^−3

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

	x	y	z	Uiso*/Ueq
N11	0.79843 (10)	0.20269 (15)	0.47727 (7)	0.0157 (3)
C12	0.87493 (13)	0.31923 (18)	0.49071 (9)	0.0159 (3)
N12	0.83577 (11)	0.46261 (16)	0.45255 (8)	0.0196 (3)
N13	0.98819 (10)	0.30662 (16)	0.53999 (7)	0.0171 (3)
C14	1.02161 (12)	0.16575 (18)	0.57935 (9)	0.0161 (3)
Cl14	1.16729 (3)	0.14980 (5)	0.64376 (2)	0.02322 (12)
C15	0.95440 (12)	0.03841 (18)	0.57365 (9)	0.0163 (3)
C16	0.83789 (12)	0.06163 (18)	0.51820 (8)	0.0151 (3)
N161	0.76117 (10)	−0.05594 (16)	0.50384 (7)	0.0189 (3)
C162	0.78149 (14)	−0.19507 (19)	0.55632 (10)	0.0216 (3)
C163	0.68697 (13)	−0.2016 (2)	0.57320 (9)	0.0223 (3)
O164	0.57956 (9)	−0.21304 (13)	0.50117 (7)	0.0214 (2)
C165	0.55954 (13)	−0.07493 (19)	0.45042 (9)	0.0197 (3)
C166	0.65010 (12)	−0.0603 (2)	0.43037 (9)	0.0184 (3)
N21	0.41915 (10)	0.52848 (15)	0.36586 (7)	0.0160 (3)
C22	0.52244 (12)	0.47297 (18)	0.38765 (8)	0.0155 (3)
N22	0.57501 (11)	0.37564 (16)	0.45215 (8)	0.0192 (3)
N23	0.57955 (10)	0.50596 (15)	0.35056 (7)	0.0153 (3)
C24	0.52311 (12)	0.60138 (18)	0.28705 (8)	0.0148 (3)
Cl24	0.59211 (3)	0.64279 (5)	0.23570 (2)	0.01897 (11)
C25	0.41932 (13)	0.66938 (18)	0.25868 (9)	0.0165 (3)
C26	0.36881 (12)	0.62934 (18)	0.30311 (9)	0.0153 (3)
N261	0.26690 (11)	0.69436 (16)	0.28426 (8)	0.0177 (3)
C262	0.19982 (13)	0.78362 (19)	0.20911 (9)	0.0187 (3)
C263	0.10854 (14)	0.8840 (2)	0.20937 (10)	0.0251 (4)
O264	0.04106 (10)	0.78723 (16)	0.22870 (7)	0.0278 (3)
C265	0.11157 (14)	0.7239 (2)	0.30760 (10)	0.0269 (4)
C266	0.20157 (13)	0.6115 (2)	0.31349 (9)	0.0205 (3)
H11	0.7628	0.4775	0.4203	0.024*
H12	0.8832	0.5416	0.4598	0.024*
H151	0.9836	−0.0584	0.6046	0.020*
H13	0.8550	−0.1824	0.6069	0.026*
H14	0.7832	−0.2976	0.5302	0.026*
H15	0.6981	−0.2974	0.6074	0.027*
H16	0.6894	−0.1021	0.6027	0.027*
H17	0.5580	0.0260	0.4777	0.024*
H18	0.4851	−0.0868	0.4005	0.024*
H19	0.6457	−0.1546	0.3972	0.022*
H110	0.6383	0.0409	0.3992	0.022*
H21	0.5419	0.3503	0.4785	0.023*
H22	0.6426	0.3372	0.4681	0.023*
H251	0.3839	0.7380	0.2129	0.020*
H23	0.1647	0.7051	0.1641	0.022*
H24	0.2497	0.8568	0.2011	0.022*
H25	0.1439	0.9736	0.2488	0.030*
H26	0.0598	0.9338	0.1560	0.030*
H27	0.0646	0.6634	0.3233	0.032*
H28	0.1479	0.8159	0.3454	0.032*
H29	0.2526	0.5779	0.3698	0.025*
H210	0.1660	0.5119	0.2813	0.025*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N11	0.0126 (6)	0.0174 (6)	0.0162 (6)	−0.0020 (5)	0.0069 (5)	0.0000 (5)
C12	0.0148 (7)	0.0184 (7)	0.0149 (7)	−0.0014 (6)	0.0080 (6)	−0.0011 (6)
N12	0.0120 (6)	0.0177 (6)	0.0232 (7)	−0.0021 (5)	0.0051 (5)	0.0030 (5)
N13	0.0125 (6)	0.0180 (6)	0.0187 (6)	−0.0022 (5)	0.0068 (5)	0.0001 (5)
C14	0.0108 (7)	0.0198 (7)	0.0158 (7)	0.0003 (5)	0.0057 (6)	−0.0013 (6)
Cl14	0.01039 (19)	0.0251 (2)	0.0273 (2)	−0.00093 (14)	0.00509 (17)	0.00521 (15)
C15	0.0139 (7)	0.0163 (7)	0.0182 (7)	0.0005 (6)	0.0080 (6)	0.0010 (6)
C16	0.0149 (7)	0.0172 (7)	0.0145 (7)	−0.0024 (6)	0.0086 (6)	−0.0030 (6)
N161	0.0126 (6)	0.0210 (7)	0.0178 (6)	−0.0040 (5)	0.0043 (5)	0.0031 (5)
C162	0.0172 (8)	0.0184 (7)	0.0256 (8)	−0.0018 (6)	0.0087 (7)	0.0040 (6)
C163	0.0185 (8)	0.0232 (8)	0.0212 (8)	−0.0029 (6)	0.0077 (7)	0.0049 (6)
O164	0.0161 (6)	0.0202 (6)	0.0254 (6)	−0.0028 (4)	0.0092 (5)	0.0048 (5)
C165	0.0170 (7)	0.0188 (8)	0.0209 (7)	−0.0009 (6)	0.0084 (6)	0.0038 (6)
C166	0.0139 (7)	0.0216 (8)	0.0157 (7)	−0.0045 (6)	0.0049 (6)	−0.0003 (6)
N21	0.0136 (6)	0.0170 (6)	0.0162 (6)	0.0002 (5)	0.0070 (5)	0.0001 (5)
C22	0.0143 (7)	0.0143 (7)	0.0140 (7)	−0.0028 (5)	0.0047 (6)	−0.0021 (5)
N22	0.0156 (6)	0.0222 (7)	0.0196 (7)	0.0032 (5)	0.0090 (6)	0.0069 (5)
N23	0.0131 (6)	0.0151 (6)	0.0152 (6)	−0.0011 (5)	0.0057 (5)	−0.0001 (5)
C24	0.0137 (7)	0.0163 (7)	0.0149 (7)	−0.0042 (6)	0.0079 (6)	−0.0034 (6)
Cl24	0.01498 (19)	0.0246 (2)	0.01833 (19)	−0.00025 (14)	0.00942 (16)	0.00275 (14)
C25	0.0149 (7)	0.0174 (7)	0.0147 (7)	0.0013 (6)	0.0060 (6)	0.0014 (6)
C26	0.0118 (7)	0.0148 (7)	0.0153 (7)	−0.0021 (5)	0.0044 (6)	−0.0036 (6)
N261	0.0135 (6)	0.0197 (6)	0.0189 (6)	0.0022 (5)	0.0079 (5)	0.0024 (5)
C262	0.0155 (7)	0.0191 (8)	0.0192 (7)	0.0032 (6)	0.0076 (6)	0.0022 (6)
C263	0.0201 (8)	0.0256 (8)	0.0278 (9)	0.0057 (7)	0.0112 (7)	0.0026 (7)
O264	0.0161 (6)	0.0385 (7)	0.0269 (6)	0.0065 (5)	0.0099 (5)	0.0041 (5)
C265	0.0218 (9)	0.0367 (10)	0.0246 (8)	0.0060 (7)	0.0138 (7)	0.0008 (7)
C266	0.0162 (8)	0.0263 (8)	0.0194 (8)	0.0006 (6)	0.0095 (7)	0.0015 (6)

Geometric parameters (Å, º)

N11—C16	1.348 (2)	N21—C26	1.3361 (19)
N11—C12	1.3483 (19)	N21—C22	1.3460 (19)
C12—N12	1.3440 (19)	C22—N22	1.3425 (19)
C12—N13	1.354 (2)	C22—N23	1.3575 (19)
N12—H11	0.88	N22—H21	0.88
N12—H12	0.88	N22—H22	0.88
N13—C14	1.328 (2)	N23—C24	1.3247 (19)
C14—C15	1.365 (2)	C24—C25	1.365 (2)
C14—Cl14	1.7438 (15)	C24—Cl24	1.7521 (14)
C15—C16	1.415 (2)	C25—C26	1.417 (2)
C15—H151	0.95	C25—H251	0.95
C16—N161	1.3526 (19)	C26—N261	1.3719 (19)
N161—C162	1.460 (2)	N261—C262	1.462 (2)
N161—C166	1.4612 (19)	N261—C266	1.471 (2)
C162—C163	1.517 (2)	C262—C263	1.515 (2)
C162—H13	0.99	C262—H23	0.99
C162—H14	0.99	C262—H24	0.99
C163—O164	1.4242 (19)	C263—O264	1.424 (2)
C163—H15	0.99	C263—H25	0.99
C163—H16	0.99	C263—H26	0.99
O164—C165	1.4339 (18)	O264—C265	1.428 (2)
C165—C166	1.510 (2)	C265—C266	1.509 (2)
C165—H17	0.99	C265—H27	0.99
C165—H18	0.99	C265—H28	0.99
C166—H19	0.99	C266—H29	0.99
C166—H110	0.99	C266—H210	0.99
C16—N11—C12	117.09 (13)	C26—N21—C22	117.26 (13)
N12—C12—N11	117.39 (13)	N22—C22—N21	117.59 (13)
N12—C12—N13	116.43 (13)	N22—C22—N23	116.18 (13)
N11—C12—N13	126.18 (14)	N21—C22—N23	126.22 (13)
C12—N12—H11	120.0	C22—N22—H21	120.0
C12—N12—H12	120.0	C22—N22—H22	120.0
H11—N12—H12	120.0	H21—N22—H22	120.0
C14—N13—C12	113.80 (13)	C24—N23—C22	113.40 (12)
N13—C14—C15	126.74 (14)	N23—C24—C25	127.08 (13)
N13—C14—Cl14	113.99 (11)	N23—C24—Cl24	114.98 (11)
C15—C14—Cl14	119.27 (12)	C25—C24—Cl24	117.94 (11)
C14—C15—C16	114.88 (13)	C24—C25—C26	114.54 (14)
C14—C15—H151	122.6	C24—C25—H251	122.7
C16—C15—H151	122.6	C26—C25—H251	122.7
N11—C16—N161	117.00 (13)	N21—C26—N261	117.16 (13)
N11—C16—C15	121.23 (13)	N21—C26—C25	121.41 (13)
N161—C16—C15	121.77 (14)	N261—C26—C25	121.41 (14)
C16—N161—C162	124.57 (12)	C26—N261—C262	119.26 (12)
C16—N161—C166	122.30 (13)	C26—N261—C266	118.65 (13)
C162—N161—C166	113.04 (12)	C262—N261—C266	115.19 (12)
N161—C162—C163	108.21 (13)	N261—C262—C263	111.11 (13)
N161—C162—H13	110.1	N261—C262—H23	109.4
C163—C162—H13	110.1	C263—C262—H23	109.4
N161—C162—H14	110.1	N261—C262—H24	109.4
C163—C162—H14	110.1	C263—C262—H24	109.4
H13—C162—H14	108.4	H23—C262—H24	108.0
O164—C163—C162	111.39 (12)	O264—C263—C262	111.80 (14)
O164—C163—H15	109.4	O264—C263—H25	109.3
C162—C163—H15	109.4	C262—C263—H25	109.3
O164—C163—H16	109.4	O264—C263—H26	109.3
C162—C163—H16	109.4	C262—C263—H26	109.3
H15—C163—H16	108.0	H25—C263—H26	107.9
C163—O164—C165	111.04 (11)	C263—O264—C265	108.46 (13)
O164—C165—C166	111.05 (12)	O264—C265—C266	112.04 (13)
O164—C165—H17	109.4	O264—C265—H27	109.2
C166—C165—H17	109.4	C266—C265—H27	109.2
O164—C165—H18	109.4	O264—C265—H28	109.2
C166—C165—H18	109.4	C266—C265—H28	109.2
H17—C165—H18	108.0	H27—C265—H28	107.9
N161—C166—C165	109.91 (12)	N261—C266—C265	110.33 (14)
N161—C166—H19	109.7	N261—C266—H29	109.6
C165—C166—H19	109.7	C265—C266—H29	109.6
N161—C166—H110	109.7	N261—C266—H210	109.6
C165—C166—H110	109.7	C265—C266—H210	109.6
H19—C166—H110	108.2	H29—C266—H210	108.1
C16—N11—C12—N12	−177.36 (13)	C26—N21—C22—N22	177.98 (13)
C16—N11—C12—N13	1.8 (2)	C26—N21—C22—N23	−2.0 (2)
N12—C12—N13—C14	176.55 (13)	N22—C22—N23—C24	179.49 (13)
N11—C12—N13—C14	−2.6 (2)	N21—C22—N23—C24	−0.6 (2)
C12—N13—C14—C15	0.8 (2)	C22—N23—C24—C25	1.9 (2)
C12—N13—C14—Cl14	−179.31 (10)	C22—N23—C24—Cl24	−178.38 (10)
N13—C14—C15—C16	1.5 (2)	N23—C24—C25—C26	−0.7 (2)
Cl14—C14—C15—C16	−178.35 (10)	Cl24—C24—C25—C26	179.62 (10)
C12—N11—C16—N161	−179.14 (12)	C22—N21—C26—N261	−175.78 (13)
C12—N11—C16—C15	0.9 (2)	C22—N21—C26—C25	3.3 (2)
C14—C15—C16—N11	−2.4 (2)	C24—C25—C26—N21	−2.1 (2)
C14—C15—C16—N161	177.63 (13)	C24—C25—C26—N261	176.93 (14)
N11—C16—N161—C162	−162.15 (14)	N21—C26—N261—C262	−170.17 (13)
C15—C16—N161—C162	17.8 (2)	C25—C26—N261—C262	10.8 (2)
N11—C16—N161—C166	21.6 (2)	N21—C26—N261—C266	−20.6 (2)
C15—C16—N161—C166	−158.45 (14)	C25—C26—N261—C266	160.32 (14)
C16—N161—C162—C163	128.11 (15)	C26—N261—C262—C263	−164.34 (13)
C166—N161—C162—C163	−55.31 (17)	C266—N261—C262—C263	45.09 (18)
N161—C162—C163—O164	57.28 (17)	N261—C262—C263—O264	−53.19 (18)
C162—C163—O164—C165	−59.90 (16)	C262—C263—O264—C265	62.16 (17)
C163—O164—C165—C166	58.06 (16)	C263—O264—C265—C266	−63.17 (18)
C16—N161—C166—C165	−128.64 (15)	C26—N261—C266—C265	163.75 (13)
C162—N161—C166—C165	54.70 (17)	C262—N261—C266—C265	−45.50 (18)
O164—C165—C166—N161	−54.54 (17)	O264—C265—C266—N261	54.32 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N12—H11···N23	0.88	2.19	3.061 (2)	174
N22—H22···N11	0.88	2.35	3.211 (2)	165
N12—H12···N13^i	0.88	2.18	3.036 (2)	165
N22—H21···O164^ii	0.88	2.23	3.051 (2)	155

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

(II) 2-Amino-4-chloro-6-piperidinopyrimidine

Crystal data

C9H13ClN4	F(000) = 896
Mr = 212.68	Dx = 1.414 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4533 reflections
a = 13.8139 (2) Å	θ = 3.0–27.5°
b = 8.4804 (1) Å	µ = 0.35 mm^−1
c = 19.8379 (3) Å	T = 120 K
β = 120.6770 (9)°	Block, colourless
V = 1998.74 (5) Å^3	0.45 × 0.35 × 0.25 mm
Z = 8

Data collection

Nonius KappaCCD diffractometer	4533 independent reflections
Radiation source: fine-focus sealed X-ray tube	3726 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
ϕ scans, and ω scans with κ offsets	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (DENZO–SMN; Otwinowski & Minor, 1997)	h = −17→16
Tmin = 0.826, Tmax = 0.911	k = −10→11
15693 measured reflections	l = −25→25

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.087	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0419P)^2 + 0.5327P] where P = (Fo^2 + 2Fc^2)/3
4533 reflections	(Δ/σ)max = 0.001
250 parameters	Δρmax = 0.25 e Å^−3
0 restraints	Δρmin = −0.28 e Å^−3

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

	x	y	z	Uiso*/Ueq
N11	0.81471 (10)	0.18328 (13)	0.47002 (6)	0.0157 (2)
C12	0.88591 (12)	0.30463 (16)	0.48551 (8)	0.0152 (3)
N12	0.84403 (10)	0.43638 (14)	0.44331 (7)	0.0191 (3)
N13	0.99700 (10)	0.30808 (13)	0.54099 (7)	0.0167 (2)
C14	1.03363 (12)	0.17721 (16)	0.58336 (8)	0.0163 (3)
Cl14	1.17375 (3)	0.18345 (4)	0.65928 (2)	0.02326 (10)
C15	0.97273 (11)	0.04391 (16)	0.57347 (8)	0.0169 (3)
C16	0.85855 (12)	0.04946 (16)	0.51163 (8)	0.0153 (3)
N161	0.79034 (10)	−0.07770 (14)	0.49192 (7)	0.0181 (3)
C162	0.82073 (10)	−0.21876 (12)	0.54089 (6)	0.0234 (3)
C163	0.76888 (10)	−0.20812 (12)	0.59229 (6)	0.0256 (3)
C164	0.64137 (14)	−0.19517 (18)	0.54122 (9)	0.0254 (3)
C165	0.60693 (13)	−0.06015 (18)	0.48212 (9)	0.0233 (3)
C166	0.66895 (12)	−0.06769 (17)	0.43709 (8)	0.0200 (3)
N21	0.44603 (10)	0.53187 (14)	0.37572 (7)	0.0176 (3)
C22	0.54302 (12)	0.47010 (16)	0.38853 (8)	0.0177 (3)
N22	0.60167 (11)	0.38106 (15)	0.45416 (7)	0.0237 (3)
N23	0.59066 (9)	0.48844 (14)	0.34421 (7)	0.0175 (3)
C24	0.53063 (12)	0.57948 (16)	0.28197 (8)	0.0166 (3)
Cl24	0.58707 (3)	0.60594 (4)	0.22147 (2)	0.02286 (10)
C25	0.43078 (12)	0.65039 (16)	0.26070 (8)	0.0174 (3)
C26	0.38803 (11)	0.62230 (15)	0.31114 (8)	0.0153 (3)
N261	0.28892 (10)	0.68526 (13)	0.29758 (7)	0.0164 (2)
C262	0.21643 (12)	0.76963 (17)	0.22408 (8)	0.0180 (3)
C263	0.13674 (13)	0.88200 (18)	0.23172 (9)	0.0237 (3)
C264	0.07035 (13)	0.8005 (2)	0.26391 (9)	0.0270 (4)
C265	0.15162 (13)	0.72011 (19)	0.34120 (9)	0.0239 (3)
C266	0.22795 (12)	0.60598 (17)	0.33079 (8)	0.0182 (3)
H11	0.7723	0.4414	0.4070	0.023*
H12	0.8882	0.5180	0.4519	0.023*
H151	1.0044	−0.0465	0.6057	0.020*
H13	0.9036	−0.2268	0.5740	0.028*
H14	0.7926	−0.3140	0.5074	0.028*
H15	0.7990	−0.1146	0.6268	0.031*
H16	0.7889	−0.3031	0.6258	0.031*
H17	0.6088	−0.1771	0.5750	0.030*
H18	0.6106	−0.2956	0.5127	0.030*
H19	0.5248	−0.0654	0.4447	0.028*
H110	0.6234	0.0418	0.5102	0.028*
H111	0.6435	−0.1611	0.4023	0.024*
H112	0.6517	0.0276	0.4041	0.024*
H21	0.5753	0.3665	0.4858	0.028*
H22	0.6660	0.3380	0.4650	0.028*
H251	0.3923	0.7143	0.2152	0.021*
H23	0.1720	0.6924	0.1820	0.022*
H24	0.2639	0.8300	0.2090	0.022*
H25	0.0836	0.9272	0.1796	0.028*
H26	0.1807	0.9699	0.2670	0.028*
H27	0.0245	0.8791	0.2723	0.032*
H28	0.0189	0.7213	0.2258	0.032*
H29	0.1980	0.8008	0.3807	0.029*
H210	0.1085	0.6621	0.3607	0.029*
H211	0.2828	0.5597	0.3822	0.022*
H212	0.1821	0.5191	0.2956	0.022*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N11	0.0130 (6)	0.0191 (6)	0.0141 (6)	−0.0005 (5)	0.0063 (5)	−0.0001 (4)
C12	0.0139 (7)	0.0203 (7)	0.0124 (6)	−0.0001 (5)	0.0075 (6)	−0.0014 (5)
N12	0.0129 (6)	0.0197 (6)	0.0183 (6)	−0.0016 (5)	0.0032 (5)	0.0022 (5)
N13	0.0128 (6)	0.0205 (6)	0.0150 (6)	−0.0010 (5)	0.0058 (5)	0.0002 (5)
C14	0.0115 (7)	0.0232 (7)	0.0136 (6)	0.0008 (6)	0.0060 (6)	−0.0015 (5)
Cl14	0.01206 (18)	0.0289 (2)	0.02026 (19)	−0.00127 (14)	0.00206 (15)	0.00288 (14)
C15	0.0138 (7)	0.0187 (7)	0.0166 (7)	0.0023 (6)	0.0065 (6)	0.0025 (5)
C16	0.0149 (7)	0.0184 (7)	0.0152 (7)	0.0001 (5)	0.0096 (6)	−0.0013 (5)
N161	0.0131 (6)	0.0200 (6)	0.0179 (6)	−0.0019 (5)	0.0055 (5)	0.0005 (5)
C162	0.0208 (8)	0.0152 (7)	0.0288 (8)	−0.0006 (6)	0.0087 (7)	0.0007 (6)
C163	0.0314 (9)	0.0193 (7)	0.0224 (8)	−0.0032 (6)	0.0110 (7)	0.0048 (6)
C164	0.0284 (9)	0.0234 (8)	0.0294 (8)	−0.0042 (6)	0.0185 (7)	0.0009 (6)
C165	0.0182 (8)	0.0228 (8)	0.0275 (8)	−0.0009 (6)	0.0105 (7)	0.0007 (6)
C166	0.0138 (7)	0.0243 (7)	0.0174 (7)	−0.0041 (6)	0.0049 (6)	0.0010 (6)
N21	0.0136 (6)	0.0186 (6)	0.0167 (6)	0.0003 (5)	0.0049 (5)	0.0025 (5)
C22	0.0141 (7)	0.0151 (7)	0.0172 (7)	−0.0020 (5)	0.0032 (6)	0.0004 (5)
N22	0.0173 (7)	0.0288 (7)	0.0221 (7)	0.0064 (5)	0.0079 (6)	0.0100 (5)
N23	0.0124 (6)	0.0183 (6)	0.0164 (6)	0.0000 (5)	0.0034 (5)	−0.0009 (5)
C24	0.0139 (7)	0.0187 (7)	0.0146 (7)	−0.0029 (6)	0.0054 (6)	−0.0032 (5)
Cl24	0.01552 (19)	0.0342 (2)	0.01862 (18)	0.00228 (15)	0.00853 (15)	0.00171 (14)
C25	0.0152 (7)	0.0187 (7)	0.0142 (7)	0.0009 (6)	0.0045 (6)	0.0021 (5)
C26	0.0126 (7)	0.0143 (7)	0.0144 (7)	−0.0016 (5)	0.0036 (6)	−0.0013 (5)
N261	0.0130 (6)	0.0185 (6)	0.0164 (6)	0.0022 (5)	0.0064 (5)	0.0037 (4)
C262	0.0152 (7)	0.0201 (7)	0.0161 (7)	0.0024 (6)	0.0061 (6)	0.0032 (5)
C263	0.0229 (8)	0.0242 (8)	0.0230 (8)	0.0086 (6)	0.0110 (7)	0.0056 (6)
C264	0.0194 (8)	0.0382 (9)	0.0250 (8)	0.0107 (7)	0.0125 (7)	0.0041 (7)
C265	0.0239 (8)	0.0316 (8)	0.0194 (7)	0.0034 (7)	0.0134 (7)	0.0005 (6)
C266	0.0174 (7)	0.0204 (7)	0.0167 (7)	−0.0009 (6)	0.0086 (6)	0.0013 (5)

Geometric parameters (Å, º)

N11—C12	1.3463 (18)	N21—C22	1.3366 (18)
N11—C16	1.3512 (17)	N21—C26	1.3505 (17)
C12—N12	1.3377 (18)	C22—N23	1.3494 (18)
C12—N13	1.3578 (18)	C22—N22	1.3583 (18)
N12—H11	0.88	N22—H21	0.88
N12—H12	0.88	N22—H22	0.88
N13—C14	1.3267 (18)	N23—C24	1.3279 (18)
C14—C15	1.3622 (19)	C24—C25	1.359 (2)
C14—Cl14	1.7444 (14)	C24—Cl24	1.7474 (13)
C15—C16	1.4215 (19)	C25—C26	1.4177 (19)
C15—H151	0.95	C25—H251	0.95
C16—N161	1.3519 (18)	C26—N261	1.3624 (17)
N161—C162	1.4611 (15)	N261—C262	1.4666 (17)
N161—C166	1.4632 (18)	N261—C266	1.4702 (17)
C162—C163	1.5186 (19)	C262—C263	1.521 (2)
C162—H13	0.99	C262—H23	0.99
C162—H14	0.99	C262—H24	0.99
C163—C164	1.5233 (19)	C263—C264	1.524 (2)
C163—H15	0.99	C263—H25	0.99
C163—H16	0.99	C263—H26	0.99
C164—C165	1.531 (2)	C264—C265	1.523 (2)
C164—H17	0.99	C264—H27	0.99
C164—H18	0.99	C264—H28	0.99
C165—C166	1.5221 (19)	C265—C266	1.521 (2)
C165—H19	0.99	C265—H29	0.99
C165—H110	0.99	C265—H210	0.99
C166—H111	0.99	C266—H211	0.99
C166—H112	0.99	C266—H212	0.99
C12—N11—C16	117.07 (12)	C22—N21—C26	117.06 (11)
N12—C12—N11	117.60 (12)	N21—C22—N23	127.28 (12)
N12—C12—N13	115.99 (12)	N21—C22—N22	116.74 (12)
N11—C12—N13	126.40 (12)	N23—C22—N22	115.97 (12)
C12—N12—H11	120.0	C22—N22—H21	120.0
C12—N12—H12	120.0	C22—N22—H22	120.0
H11—N12—H12	120.0	H21—N22—H22	120.0
C14—N13—C12	113.80 (12)	C24—N23—C22	113.08 (11)
N13—C14—C15	126.51 (13)	N23—C24—C25	126.81 (13)
N13—C14—Cl14	114.72 (10)	N23—C24—Cl24	115.30 (10)
C15—C14—Cl14	118.76 (11)	C25—C24—Cl24	117.87 (11)
C14—C15—C16	115.38 (12)	C24—C25—C26	115.38 (13)
C14—C15—H151	122.3	C24—C25—H251	122.3
C16—C15—H151	122.3	C26—C25—H251	122.3
N11—C16—N161	117.66 (12)	N21—C26—N261	117.38 (12)
N11—C16—C15	120.60 (12)	N21—C26—C25	120.38 (12)
N161—C16—C15	121.73 (12)	N261—C26—C25	122.23 (12)
C16—N161—C162	122.64 (11)	C26—N261—C262	119.68 (11)
C16—N161—C166	122.28 (12)	C26—N261—C266	118.69 (11)
C162—N161—C166	111.92 (10)	C262—N261—C266	114.32 (11)
N161—C162—C163	108.90 (6)	N261—C262—C263	111.62 (11)
N161—C162—H13	109.9	N261—C262—H23	109.3
C163—C162—H13	109.9	C263—C262—H23	109.3
N161—C162—H14	109.9	N261—C262—H24	109.3
C163—C162—H14	109.9	C263—C262—H24	109.3
H13—C162—H14	108.3	H23—C262—H24	108.0
C162—C163—C164	109.82 (7)	C262—C263—C264	112.24 (12)
C162—C163—H15	109.7	C262—C263—H25	109.2
C164—C163—H15	109.7	C264—C263—H25	109.2
C162—C163—H16	109.7	C262—C263—H26	109.2
C164—C163—H16	109.7	C264—C263—H26	109.2
H15—C163—H16	108.2	H25—C263—H26	107.9
C163—C164—C165	111.44 (11)	C265—C264—C263	109.43 (13)
C163—C164—H17	109.3	C265—C264—H27	109.8
C165—C164—H17	109.3	C263—C264—H27	109.8
C163—C164—H18	109.3	C265—C264—H28	109.8
C165—C164—H18	109.3	C263—C264—H28	109.8
H17—C164—H18	108.0	H27—C264—H28	108.2
C166—C165—C164	111.71 (12)	C266—C265—C264	110.75 (12)
C166—C165—H19	109.3	C266—C265—H29	109.5
C164—C165—H19	109.3	C264—C265—H29	109.5
C166—C165—H110	109.3	C266—C265—H210	109.5
C164—C165—H110	109.3	C264—C265—H210	109.5
H19—C165—H110	107.9	H29—C265—H210	108.1
N161—C166—C165	109.93 (11)	N261—C266—C265	111.42 (11)
N161—C166—H111	109.7	N261—C266—H211	109.3
C165—C166—H111	109.7	C265—C266—H211	109.3
N161—C166—H112	109.7	N261—C266—H212	109.3
C165—C166—H112	109.7	C265—C266—H212	109.3
H111—C166—H112	108.2	H211—C266—H212	108.0
C16—N11—C12—N12	178.36 (11)	C26—N21—C22—N23	0.4 (2)
C16—N11—C12—N13	−2.62 (19)	C26—N21—C22—N22	179.12 (12)
N12—C12—N13—C14	177.46 (11)	N21—C22—N23—C24	0.2 (2)
N11—C12—N13—C14	−1.57 (18)	N22—C22—N23—C24	−178.53 (12)
C12—N13—C14—C15	3.22 (19)	C22—N23—C24—C25	−0.4 (2)
C12—N13—C14—Cl14	−175.95 (9)	C22—N23—C24—Cl24	−179.26 (10)
N13—C14—C15—C16	−0.6 (2)	N23—C24—C25—C26	0.0 (2)
Cl14—C14—C15—C16	178.51 (9)	Cl24—C24—C25—C26	178.83 (10)
C12—N11—C16—N161	−174.25 (11)	C22—N21—C26—N261	179.80 (12)
C12—N11—C16—C15	5.34 (18)	C22—N21—C26—C25	−0.83 (19)
C14—C15—C16—N11	−3.90 (18)	C24—C25—C26—N21	0.67 (19)
C14—C15—C16—N161	175.68 (12)	C24—C25—C26—N261	180.00 (12)
N11—C16—N161—C162	−168.38 (11)	N21—C26—N261—C262	−173.24 (12)
C15—C16—N161—C162	12.03 (19)	C25—C26—N261—C262	7.4 (2)
N11—C16—N161—C166	−10.13 (18)	N21—C26—N261—C266	−24.78 (18)
C15—C16—N161—C166	170.29 (12)	C25—C26—N261—C266	155.87 (12)
C16—N161—C162—C163	95.88 (11)	C26—N261—C262—C263	−158.02 (13)
C166—N161—C162—C163	−64.39 (10)	C266—N261—C262—C263	52.21 (16)
N161—C162—C163—C164	59.36 (9)	N261—C262—C263—C264	−52.37 (17)
C162—C163—C164—C165	−53.16 (12)	C262—C263—C264—C265	54.62 (17)
C163—C164—C165—C166	50.16 (16)	C263—C264—C265—C266	−55.99 (17)
C16—N161—C166—C165	−99.61 (15)	C26—N261—C266—C265	155.60 (12)
C162—N161—C166—C165	60.74 (14)	C262—N261—C266—C265	−54.31 (15)
C164—C165—C166—N161	−52.69 (16)	C264—C265—C266—N261	55.86 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N12—H11···N23	0.88	2.19	3.0479 (16)	163
N22—H22···N11	0.88	2.40	3.2601 (17)	167
N12—H12···N13^i	0.88	2.12	2.9862 (16)	169

Symmetry code: (i) −x+2, −y+1, −z+1.