Hydrogen-bonded supra­molecular motifs in pyrimethaminium 4-methyl­benzoate, pyrimethaminium 3-hydroxy­picolinate and pyri­meth­aminium 2,4-di­chloro­benzoate

In 2,4-diamino-5-(4-chloro­phenyl)-6-ethyl­pyrimidin-1-ium (pyri­methaminium, PMNH) 4-methyl­benzoate, C₁₂H₁₄ClN₄⁺·C₈H₇O₂⁻, (I), pyrimethaminium 3-hydroxy­picolinate, C₁₂H₁₄ClN₄⁺·C₆H₄NO₃⁻, (II), and pyrimethaminium 2,4-dichloro­benzoate, C₁₂H₁₄ClN₄⁺·C₇H₃Cl₂O₂⁻, (III), the PMNH cations inter­act with the carboxyl­ate groups of the corresponding anion via nearly parallel N—H...O hydrogen bonds, forming R₂²(8) ring motifs. A description of the observed arrays of quadruple hydrogen bonds in (I) and (II) in terms of hydrogen donors and acceptors (the DA model), their graph-set motifs and the resulting supra­molecular ladder is given. In (III), supra­molecular chains along the b axis and helical chains along the a axis are formed via N—H...O hydrogen bonds involving the 2-amino and 4-amino groups of the PMNH cation, respectively. Weak Cl...Cl inter­actions are also found in (III).

S1. Comment

Pyrimethamine (PMN) is an antifolate drug used in the treatment of malaria. In the chemotherapy of malaria and neoplastic diseases, substituted 2,4-diaminopyrimidines are widely employed as metabolic inhibitors of pathways leading to the synthesis of proteins and nucleic acids (Hitchings & Burchall, 1965). PMN acts against malarial parasites by selectively inhibiting their dihydrofolate reductase–thymidylate synthase (Sardarian et al., 2003). PMN is also used along with other drugs for the treatment of opportunistic infections in patients suffering from AIDS (Tanaka et al., 2004). 2-Aminopyrimidine and its derivatives form good adducts as they readily form hydrogen-bonded patterns through their stereochemically associated amine group and ring N atom (Lynch et al., 2000). The crystal structures of PMN (Sethuraman & Thomas Muthiah, 2002) and many of its salts have been reported from our laboratory (Sethuraman et al., 2003; Stanley et al., 2005). The present study of the title salts, pyrimethaminium 4-methylbenzoate, (I), pyrimethaminium 3-hydroxypicolinate, (II), and pyrimethaminium 2,4-dichlorobenzoate, (III), was undertaken to obtain more information regarding patterns of hydrogen bonding in these types of compounds.

Views of compounds (I)–(III) are shown in Figs. 1–3 and comparitive geometric parameters are given in Table 1. In these compounds, the asymmetric unit contains one pyrimethaminium cation, together with a 4-methylbenzoate anion in (I), a 3-hydroxypicolinate anion in (II) and a 2,4-dichlorobenzoate anion in (III). As expected, in all three crystal structures the PMNH cations are protonated at the N1 position. The dihedral angle between the 2,4-diaminopyrimidine and 4-chlorophenyl planes is 80.11 (14)° in (I), 68.28 (9)° in (II) and 72.50 (8)° in (III). These values are close to those observed in modelling studies of dihydrofolate reductase pyrimethamine (DHFR–PMN) complexes (Sansom et al., 1989). Such modelling studies of DHFR–PMN complexes indicate that this dihedral angle is important for the proper docking of the drug molecule at the active site of the enzyme (Sansom et al., 1989). By contrast, the value of the C5—C6—C7—C8 torsion angle (Table 1), representing the deviation of the ethyl group from the pyrimidine plane, is not very important, as it does not affect the overall binding energy of the enzyme–drug complex (Sansom et al., 1989).

In each of (I)–(III), the carboxylate group of the respective anion (4-methylbenzoate, 3-hydroxypicolinate and 2,4-dichlorobenzoate, respectively) interacts with the protonated pyrimidine moiety of PMNH in a linear fashion through a pair of N—H···O hydrogen bonds, to form an eight-membered R₂²(8) ring motif (Etter, 1990; Bernstein et al., 1995) (Figs. 1–3). This motif has been observed in modelling studies of DHFR–PMN complexes (Sansom et al., 1989), and it is one of the 24 most frequently observed motifs in organic crystal structures (Allen et al., 1998).

In (I), the R₂²(8) motifs are crosslinked via N—H···O hydrogen bonds to produce a DDAA array (where D is a hydrogen-bond donor and A is a hydrogen-bond acceptor) of quadruple hydrogen bonds (Table 1); this can be represented by the graph-set notations R₂²(8) and R₄²(8) (see Fig. 4). The inversion-centre-related PMNH cations are also base-paired via N—H···N hydrogen bonds involving the unprotonated pyrimidine N atom and the 4-amino group (Table 2). This type of base pairing, also with an R₂²(8) motif, has been observed in many diaminopyrimidinecarboxylate salts (Stanley et al., 2005). In addition to the base pairing, a hydrogen-bonded acceptor (O1) bridges the 4-amino and 2-amino groups on the sides of the pairing, leading to a complementary linear DADA array of quadruple hydrogen bonds with rings having graph-set notation R₂²(8) and R₃²(8). In general, only one of the motifs (DADA or DDAA array) has been identified at any one time in diaminopyrimidinecarboxylate salts. Here, both the DADA and DDAA array motifs co-exist in an alternating manner to form a hydrogen-bonded supramolecular ladder (Fig. 4).

In (II) (Table 3), inversion-related molecules are connected via N2—H···N5 hydrogen bonds to form an array with an R₄⁴(14) ring motif. This array is futher crosslinked via N—H···O hydrogen bonds (Fig. 5). A typical intramolecular hydrogen bond exists between the hydroxy and carboxylate groups of the 3-hydroxypicolinate anion to form a six-membered hydrogen-bonded ring [S(6), Fig. 2].

In (III), the 2-amino group of the PMNH cation interacts with one of the carboxylate O atoms (O1) through an N—H···O hydrogen bond, to form a supramolecular chain motif C₂¹(6) along the b axis (Fig. 6). In addition, the 4-amino group of the PMNH cation interacts with one of the carboxylate O atoms (O2) through an N—H···O hydrogen bond, to form a helical chain along the a axis (Fig. 7) with motif C₂¹(8). Details of these hydrogen bonds are given in Table 4. Further, the cations and anions are linked by weak Cl···Cl interactions (Table 5) which are not observed in compounds (I) and (II).

In conclusion, in all three crystal stuctures the PMNH cation interacts with the carboxylate O atoms via N—H···O hydrogen bonds to form the frequently observed hydrogen-bonded eight-membered R₂²(8) ring motif. In compound (I), the R₂²(8) motifs are further bridged by N—H···O hydrogen bonds on either side, forming a DDAA array of quadruple hydrogen bonds. In (I), N4—H···N3 base pairing is observed, while there is none in compounds (II) and (III). In (I), both DADA and DDAA array motifs co-exist in an alternating manner to form a hydrogen-bonded supramolecular ladder. Thus, it appears that the variation in supramolecular organization depends in part on the nature of the side chain attached to the anionic ring, viz. 4-methylbenzoate, 3-hydroxypicolinate or 2,4-dichlorobenzoate.

S2. Experimental

Compounds (I)–(III) were prepared by mixing hot methanol solutions (20 ml) of pyrimethamine (62 mg; Shah Pharma Chemicals, India) with hot aqueous solutions (Volume?) of the corresponding acid [4-methylbenzoic acid (34 mg, Loba Chemie) for (I), 3-hydroxypicolinic acid (34 mg, Loba Chemie) for (II) and 2,4-dichlorobenzoic acid (47 mg, Loba Chemie) for (III)] in a 1:1 molar ratio, and warming for 30 min over a water bath. Each solution was cooled slowly and kept at room temperature. After a few days, colourless crystals were obtained in each case.

S3. Refinement

All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93–0.97 Å and N—H = 0.86 Å in (I)–(III), and O—H = 0.82 Å in (II), and with U_iso(H) = 1.5U_eq(C,O) for OH groups in (II) and for all methyl groups, and U_iso(H) = 1.2U_eq(C,N) for all other H atoms.

Computing details

For all compounds, data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures

	Fig. 1. The asymmetric unit of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Dashed lines indicate hydrogen bonds.
	Fig. 2. The asymmetric unit of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Dashed lines indicate hydrogen bonds.
	Fig. 3. The asymmetric unit of (III), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Dashed lines indicate hydrogen bonds.
	Fig. 4. A view of the DADA and DDAA arrays of hydrogen bonds leading to a supramolecular ladder in (I). Dashed lines indicate hydrogen bonds and H atoms not involved in hydrogen bonding have been omitted. [Symmetry codes: (i) -x + 1, y, -z + 3/2; (ii) -x + 1/2, -y + 1/2, -z + 1; (iii) x - 1/2, -y + 1/2, z - 1/2.]
	Fig. 5. The crystal structure of (II). Dashed lines indicate hydrogen bonds and H atoms not involved in hydrogen bonding have been omitted. [Symmetry codes: (i) -x + 2, -y + 1, -z + 1; (ii) -x + 2, y + 1/2, -z + 3/2.]
	Fig. 6. N—H···O hydrogen-bonding patterns in the supramolecular chain of (III). Dashed lines indicate hydrogen bonds and H atoms not involved in hydrogen bonding have been omitted. [Symmetry code: (i) -x + 3/2, y + 1/2, z.]
	Fig. 7. View of the N—H···O hydrogen bonds responsible for the spiral type of hydrogen bonding in (III). Dashed lines indicate hydrogen bonds and H atoms not involved in hydrogen bonding have been omitted. [Symmetry code: (ii) x + 1/2, -y + 3/2, -z + 1.]

(I) 2,4-diamino-5-(4-chlorophenyl)-6-ethylpyrimidin-1-ium 4-methylbenzoate

Crystal data

C12H14ClN4^+·C8H7O2^−	F(000) = 1616
Mr = 384.86	Dx = 1.247 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3398 reflections
a = 17.1373 (3) Å	θ = 1.8–24.5°
b = 16.4776 (3) Å	µ = 0.21 mm^−1
c = 16.6127 (3) Å	T = 293 K
β = 119.080 (1)°	Prism, colourless
V = 4099.77 (13) Å^3	0.15 × 0.12 × 0.12 mm
Z = 8

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	3398 independent reflections
Radiation source: fine-focus sealed tube	2474 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
ϕ and ω scans	θmax = 24.5°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −19→19
Tmin = 0.970, Tmax = 0.975	k = −19→19
32486 measured reflections	l = −19→19

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.047	H-atom parameters constrained
wR(F^2) = 0.144	w = 1/[σ^2(Fo^2) + (0.0658P)^2 + 3.2788P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
3398 reflections	Δρmax = 0.42 e Å^−3
247 parameters	Δρmin = −0.39 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^* = kFc[1+0.001Fc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0027 (4)

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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
Cl1	0.30822 (8)	0.39451 (7)	0.04367 (7)	0.1284 (5)
N1	0.48427 (13)	0.14845 (13)	0.52582 (12)	0.0611 (7)
N2	0.44626 (15)	0.11987 (15)	0.63640 (14)	0.0813 (9)
N3	0.35105 (12)	0.19873 (12)	0.51388 (12)	0.0528 (6)
N4	0.26177 (13)	0.28077 (13)	0.39515 (13)	0.0667 (8)
C2	0.42561 (15)	0.15605 (15)	0.55722 (15)	0.0554 (8)
C4	0.33485 (14)	0.23610 (14)	0.43547 (15)	0.0506 (7)
C5	0.39374 (15)	0.22935 (14)	0.39751 (15)	0.0534 (8)
C6	0.46936 (15)	0.18496 (15)	0.44614 (15)	0.0576 (8)
C7	0.54004 (18)	0.17130 (18)	0.41872 (19)	0.0742 (10)
C8	0.5349 (3)	0.0906 (3)	0.3791 (3)	0.1290 (19)
C9	0.37267 (15)	0.27061 (15)	0.30981 (16)	0.0564 (8)
C10	0.41131 (18)	0.34358 (17)	0.30932 (19)	0.0703 (10)
C11	0.3911 (2)	0.38150 (18)	0.2270 (2)	0.0799 (11)
C12	0.3324 (2)	0.3462 (2)	0.1463 (2)	0.0776 (11)
C13	0.2929 (2)	0.2741 (2)	0.1443 (2)	0.0900 (11)
C14	0.3130 (2)	0.23686 (18)	0.22632 (18)	0.0759 (10)
O1	0.64302 (12)	0.09524 (12)	0.75217 (12)	0.0764 (7)
O2	0.61921 (13)	0.05308 (13)	0.61543 (13)	0.0884 (8)
C15	0.74092 (15)	−0.00252 (15)	0.74470 (16)	0.0580 (8)
C16	0.76369 (17)	−0.04889 (16)	0.68968 (19)	0.0667 (9)
C17	0.8389 (2)	−0.09686 (19)	0.7290 (3)	0.0904 (14)
C18	0.8935 (2)	−0.0998 (2)	0.8236 (3)	0.1095 (16)
C19	0.8693 (2)	−0.0547 (3)	0.8768 (2)	0.1027 (14)
C20	0.79429 (17)	−0.00652 (19)	0.83934 (18)	0.0764 (10)
C21	0.66182 (16)	0.05275 (16)	0.70211 (16)	0.0591 (8)
C22	0.9769 (3)	−0.1533 (4)	0.8658 (4)	0.192 (3)
H1	0.53190	0.12010	0.55650	0.0730*
H2A	0.41120	0.12410	0.65960	0.0980*
H2B	0.49470	0.09210	0.66460	0.0980*
H4A	0.22750	0.28470	0.41930	0.0800*
H4B	0.24850	0.30590	0.34470	0.0800*
H7A	0.53400	0.21220	0.37400	0.0890*
H7B	0.59840	0.17790	0.47250	0.0890*
H8A	0.53850	0.04980	0.42210	0.1930*
H8B	0.58350	0.08390	0.36640	0.1930*
H8C	0.47930	0.08530	0.32300	0.1930*
H10	0.45140	0.36780	0.36480	0.0840*
H11	0.41770	0.43070	0.22710	0.0960*
H13	0.25290	0.25040	0.08850	0.1080*
H14	0.28570	0.18780	0.22540	0.0910*
H16	0.72800	−0.04760	0.62600	0.0800*
H17	0.85340	−0.12790	0.69130	0.1090*
H19	0.90470	−0.05660	0.94050	0.1230*
H20	0.77950	0.02330	0.87750	0.0910*
H22A	0.96980	−0.19640	0.82390	0.2880*
H22B	0.98530	−0.17580	0.92270	0.2880*
H22C	1.02810	−0.12120	0.87720	0.2880*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.1810 (11)	0.1438 (9)	0.0940 (7)	0.0300 (7)	0.0932 (7)	0.0522 (6)
N1	0.0549 (11)	0.0839 (14)	0.0490 (11)	0.0213 (10)	0.0288 (9)	0.0102 (10)
N2	0.0817 (15)	0.1171 (19)	0.0622 (13)	0.0446 (14)	0.0484 (12)	0.0364 (13)
N3	0.0491 (11)	0.0684 (12)	0.0463 (10)	0.0099 (9)	0.0274 (9)	0.0073 (9)
N4	0.0601 (12)	0.0950 (16)	0.0580 (12)	0.0274 (11)	0.0389 (10)	0.0266 (11)
C2	0.0545 (13)	0.0689 (15)	0.0479 (13)	0.0099 (12)	0.0290 (11)	0.0040 (11)
C4	0.0480 (12)	0.0623 (14)	0.0456 (12)	0.0039 (11)	0.0259 (10)	0.0035 (10)
C5	0.0514 (13)	0.0672 (15)	0.0479 (12)	0.0050 (11)	0.0291 (11)	0.0042 (11)
C6	0.0554 (13)	0.0745 (16)	0.0494 (13)	0.0068 (12)	0.0306 (11)	0.0024 (11)
C7	0.0702 (16)	0.098 (2)	0.0689 (17)	0.0213 (15)	0.0451 (14)	0.0120 (15)
C8	0.142 (3)	0.149 (4)	0.138 (3)	0.000 (3)	0.101 (3)	−0.038 (3)
C9	0.0544 (13)	0.0725 (16)	0.0537 (14)	0.0113 (12)	0.0353 (12)	0.0078 (11)
C10	0.0693 (16)	0.0784 (18)	0.0685 (17)	0.0022 (14)	0.0377 (14)	0.0082 (14)
C11	0.084 (2)	0.0795 (19)	0.099 (2)	0.0102 (16)	0.0624 (19)	0.0246 (17)
C12	0.089 (2)	0.098 (2)	0.0673 (19)	0.0240 (17)	0.0550 (17)	0.0249 (16)
C13	0.110 (2)	0.107 (2)	0.0544 (17)	−0.003 (2)	0.0411 (17)	0.0100 (16)
C14	0.0881 (19)	0.0864 (19)	0.0568 (16)	−0.0091 (15)	0.0381 (15)	0.0066 (14)
O1	0.0703 (11)	0.1006 (14)	0.0644 (11)	0.0182 (10)	0.0375 (9)	−0.0077 (10)
O2	0.0814 (13)	0.1205 (17)	0.0544 (11)	0.0424 (12)	0.0261 (10)	0.0025 (10)
C15	0.0539 (13)	0.0667 (15)	0.0588 (14)	0.0059 (11)	0.0317 (12)	0.0124 (11)
C16	0.0681 (16)	0.0658 (16)	0.0751 (17)	0.0087 (13)	0.0419 (14)	0.0075 (13)
C17	0.097 (2)	0.081 (2)	0.124 (3)	0.0313 (17)	0.078 (2)	0.0307 (19)
C18	0.090 (2)	0.132 (3)	0.130 (3)	0.056 (2)	0.072 (2)	0.078 (3)
C19	0.075 (2)	0.157 (3)	0.080 (2)	0.035 (2)	0.0407 (17)	0.061 (2)
C20	0.0655 (16)	0.107 (2)	0.0627 (16)	0.0114 (15)	0.0359 (14)	0.0235 (15)
C21	0.0543 (13)	0.0722 (16)	0.0533 (15)	0.0071 (12)	0.0281 (12)	0.0016 (12)
C22	0.150 (4)	0.246 (6)	0.214 (6)	0.136 (4)	0.116 (4)	0.146 (5)

Geometric parameters (Å, º)

Cl1—C12	1.739 (3)	C7—H7B	0.9700
O1—C21	1.243 (3)	C7—H7A	0.9700
O2—C21	1.259 (3)	C8—H8C	0.9600
N1—C6	1.360 (3)	C8—H8A	0.9600
N1—C2	1.345 (4)	C8—H8B	0.9600
N2—C2	1.326 (3)	C10—H10	0.9300
N3—C4	1.342 (3)	C11—H11	0.9300
N3—C2	1.323 (3)	C13—H13	0.9300
N4—C4	1.320 (3)	C14—H14	0.9300
N1—H1	0.8600	C15—C16	1.385 (4)
N2—H2B	0.8600	C15—C20	1.384 (4)
N2—H2A	0.8600	C15—C21	1.495 (4)
N4—H4A	0.8600	C16—C17	1.376 (5)
N4—H4B	0.8600	C17—C18	1.385 (6)
C4—C5	1.431 (4)	C18—C19	1.364 (6)
C5—C9	1.485 (3)	C18—C22	1.529 (7)
C5—C6	1.360 (4)	C19—C20	1.376 (5)
C6—C7	1.504 (4)	C16—H16	0.9300
C7—C8	1.467 (6)	C17—H17	0.9300
C9—C14	1.378 (4)	C19—H19	0.9300
C9—C10	1.375 (4)	C20—H20	0.9300
C10—C11	1.386 (4)	C22—H22A	0.9600
C11—C12	1.355 (4)	C22—H22B	0.9600
C12—C13	1.360 (5)	C22—H22C	0.9600
C13—C14	1.377 (4)
Cl1···C19^i	3.507 (4)	C14···H4B	2.9100
Cl1···H19^i	3.0100	C16···H14^xi	3.0200
Cl1···H13^ii	3.0600	C16···H11^iii	3.0900
O1···N4^iii	3.043 (3)	C17···H11^iii	3.0600
O1···N2	2.988 (3)	C17···H14^xi	2.9900
O1···N2^iv	2.947 (3)	C21···H1	2.6100
O2···N1	2.586 (3)	C21···H2B	2.7000
O1···H2B	2.2300	H1···O1	2.8900
O1···H20	2.5400	H1···O2	1.7300
O1···H2A^iv	2.1400	H1···C8	3.0100
O1···H4B^iii	2.3600	H1···H2B	2.2300
O1···H1	2.8900	H1···H7B	2.3900
O2···H1	1.7300	H1···H8A	2.5700
O2···H16	2.4400	H1···C21	2.6100
O2···H2B	2.7100	H2A···H4A^v	2.5700
O2···H8A	2.8100	H2A···O1^iv	2.1400
N1···O2	2.586 (3)	H2B···O1	2.2300
N1···C21	3.415 (3)	H2B···H1	2.2300
N2···O1^iv	2.947 (3)	H2B···C8^xi	3.0800
N2···O1	2.988 (3)	H2B···O2	2.7100
N2···N2^iv	3.299 (3)	H2B···C21	2.7000
N3···N4^v	2.996 (3)	H4A···N3^v	2.1400
N4···N3^v	2.996 (3)	H4A···H2A^v	2.5700
N4···O1^vi	3.043 (3)	H4A···C2^v	3.0000
N4···C14	3.399 (4)	H4A···C4^v	3.1000
N1···H8A	2.8300	H4B···C14	2.9100
N3···H4A^v	2.1400	H4B···O1^vi	2.3600
C2···C22^vii	3.496 (7)	H4B···C9	2.5300
C7···C10	3.512 (4)	H7A···C9	2.6200
C10···C7	3.512 (4)	H7A···C10	2.8400
C10···C20^vi	3.529 (4)	H7B···H1	2.3900
C11···C16^vi	3.383 (4)	H8A···O2	2.8100
C11···C11^viii	3.427 (5)	H8A···H1	2.5700
C11···C15^vi	3.380 (4)	H8A···N1	2.8300
C14···N4	3.399 (4)	H11···C16^vi	3.0900
C15···C11^iii	3.380 (4)	H11···C17^vi	3.0600
C16···C11^iii	3.383 (4)	H11···H11^viii	2.5400
C19···Cl1^ix	3.507 (4)	H11···C11^viii	3.0900
C20···C10^iii	3.529 (4)	H13···Cl1^ii	3.0600
C21···N1	3.415 (3)	H14···C16^xi	3.0200
C22···C2^x	3.496 (7)	H14···C17^xi	2.9900
C2···H22A^vii	3.1000	H16···O2	2.4400
C2···H4A^v	3.0000	H17···H22A	2.4200
C4···H4A^v	3.1000	H19···H22B	2.5000
C6···H22B^vii	2.9900	H19···Cl1^ix	3.0100
C8···H1	3.0100	H20···O1	2.5400
C8···H2B^xi	3.0800	H22A···H17	2.4200
C9···H7A	2.6200	H22A···C2^x	3.1000
C9···H4B	2.5300	H22B···H19	2.5000
C10···H7A	2.8400	H22B···C6^x	2.9900
C11···H11^viii	3.0900
C2—N1—C6	120.9 (2)	C7—C8—H8C	109.00
C2—N3—C4	117.5 (2)	H8A—C8—H8B	110.00
C2—N1—H1	120.00	H8A—C8—H8C	109.00
C6—N1—H1	119.00	H8B—C8—H8C	110.00
C2—N2—H2A	120.00	C9—C10—H10	120.00
C2—N2—H2B	120.00	C11—C10—H10	120.00
H2A—N2—H2B	120.00	C10—C11—H11	120.00
H4A—N4—H4B	120.00	C12—C11—H11	120.00
C4—N4—H4A	120.00	C12—C13—H13	121.00
C4—N4—H4B	120.00	C14—C13—H13	121.00
N1—C2—N3	123.0 (2)	C9—C14—H14	119.00
N2—C2—N3	120.0 (3)	C13—C14—H14	119.00
N1—C2—N2	117.0 (2)	C16—C15—C20	118.7 (3)
N3—C4—N4	116.5 (2)	C16—C15—C21	120.4 (2)
N3—C4—C5	122.3 (2)	C20—C15—C21	120.9 (2)
N4—C4—C5	121.2 (2)	C15—C16—C17	120.2 (3)
C4—C5—C6	116.9 (2)	C16—C17—C18	121.3 (3)
C4—C5—C9	120.7 (2)	C17—C18—C19	117.7 (4)
C6—C5—C9	122.4 (2)	C17—C18—C22	120.4 (4)
N1—C6—C5	119.3 (2)	C19—C18—C22	121.9 (4)
N1—C6—C7	115.5 (2)	C18—C19—C20	122.2 (3)
C5—C6—C7	125.2 (2)	C15—C20—C19	119.9 (3)
C6—C7—C8	113.0 (3)	O1—C21—O2	124.6 (3)
C5—C9—C10	121.2 (2)	O1—C21—C15	119.8 (2)
C5—C9—C14	120.7 (2)	O2—C21—C15	115.6 (2)
C10—C9—C14	118.1 (2)	C15—C16—H16	120.00
C9—C10—C11	120.7 (3)	C17—C16—H16	120.00
C10—C11—C12	119.5 (3)	C16—C17—H17	119.00
Cl1—C12—C11	118.8 (3)	C18—C17—H17	119.00
Cl1—C12—C13	119.8 (2)	C18—C19—H19	119.00
C11—C12—C13	121.4 (3)	C20—C19—H19	119.00
C12—C13—C14	118.9 (3)	C15—C20—H20	120.00
C9—C14—C13	121.5 (3)	C19—C20—H20	120.00
C6—C7—H7A	109.00	C18—C22—H22A	109.00
C6—C7—H7B	109.00	C18—C22—H22B	110.00
C8—C7—H7A	109.00	C18—C22—H22C	109.00
C8—C7—H7B	109.00	H22A—C22—H22B	110.00
H7A—C7—H7B	108.00	H22A—C22—H22C	109.00
C7—C8—H8A	109.00	H22B—C22—H22C	109.00
C7—C8—H8B	109.00
C6—N1—C2—N2	−178.6 (2)	C14—C9—C10—C11	−0.5 (5)
C6—N1—C2—N3	−0.1 (4)	C5—C9—C14—C13	−179.8 (3)
C2—N1—C6—C5	−0.4 (4)	C10—C9—C14—C13	0.7 (5)
C2—N1—C6—C7	−179.8 (2)	C9—C10—C11—C12	0.2 (5)
C4—N3—C2—N1	−0.5 (3)	C10—C11—C12—Cl1	−179.7 (3)
C4—N3—C2—N2	178.0 (2)	C10—C11—C12—C13	−0.1 (6)
C2—N3—C4—N4	−177.6 (2)	Cl1—C12—C13—C14	180.0 (3)
C2—N3—C4—C5	1.6 (3)	C11—C12—C13—C14	0.4 (6)
N3—C4—C5—C6	−2.0 (3)	C12—C13—C14—C9	−0.7 (5)
N3—C4—C5—C9	179.0 (2)	C20—C15—C16—C17	−1.0 (4)
N4—C4—C5—C6	177.1 (2)	C21—C15—C16—C17	177.0 (3)
N4—C4—C5—C9	−1.9 (3)	C16—C15—C20—C19	1.3 (5)
C4—C5—C6—N1	1.3 (3)	C21—C15—C20—C19	−176.7 (3)
C4—C5—C6—C7	−179.3 (2)	C16—C15—C21—O1	−178.6 (3)
C9—C5—C6—N1	−179.7 (2)	C16—C15—C21—O2	0.4 (4)
C9—C5—C6—C7	−0.4 (4)	C20—C15—C21—O1	−0.7 (4)
C4—C5—C9—C10	99.0 (3)	C20—C15—C21—O2	178.3 (3)
C4—C5—C9—C14	−80.5 (3)	C15—C16—C17—C18	−0.3 (5)
C6—C5—C9—C10	−79.9 (3)	C16—C17—C18—C19	1.3 (6)
C6—C5—C9—C14	100.6 (3)	C16—C17—C18—C22	−179.8 (4)
N1—C6—C7—C8	76.8 (3)	C17—C18—C19—C20	−1.0 (6)
C5—C6—C7—C8	−102.6 (3)	C22—C18—C19—C20	−179.9 (4)
C5—C9—C10—C11	−180.0 (3)	C18—C19—C20—C15	−0.3 (6)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.86	1.73	2.586 (3)	173
N2—H2A···O1^iv	0.86	2.14	2.947 (3)	157
N2—H2B···O1	0.86	2.23	2.988 (3)	147
N4—H4A···N3^v	0.86	2.14	2.996 (3)	176
N4—H4B···O1^vi	0.86	2.36	3.043 (3)	136

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

(II) 2,4-diamino-(p-chlorophenyl)-6-ethylpyrimidinium 3-hydroxypicolinate'

Crystal data

C12H14ClN4^+·C6H4NO3^−	F(000) = 808
Mr = 387.82	Dx = 1.387 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5622 reflections
a = 11.2563 (3) Å	θ = 1.9–30.4°
b = 14.3968 (4) Å	µ = 0.24 mm^−1
c = 11.7902 (3) Å	T = 293 K
β = 103.625 (1)°	Prism, colourless
V = 1856.89 (9) Å^3	0.22 × 0.20 × 0.18 mm
Z = 4

Data collection

Bruker SMART APEX II CCD area detector diffractometer	5622 independent reflections
Radiation source: fine-focus sealed tube	3927 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
ϕ and ω scans	θmax = 30.4°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −15→15
Tmin = 0.950, Tmax = 0.959	k = −20→20
21858 measured reflections	l = −15→16

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) = 0.153	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0709P)^2 + 0.5158P] where P = (Fo^2 + 2Fc^2)/3
5622 reflections	(Δ/σ)max = 0.001
246 parameters	Δρmax = 0.39 e Å^−3
0 restraints	Δρmin = −0.35 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > 2sigma(F²) is used only for calculating -R-factor-obs 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
Cl1	0.66240 (6)	0.62306 (4)	1.38986 (4)	0.0694 (2)
N1	0.82081 (12)	0.54460 (9)	0.75791 (11)	0.0375 (4)
N2	0.96003 (13)	0.58674 (10)	0.65198 (12)	0.0423 (4)
N3	0.96070 (12)	0.66575 (9)	0.82133 (13)	0.0416 (4)
N4	0.95778 (15)	0.74277 (11)	0.98868 (15)	0.0585 (6)
C2	0.91478 (14)	0.59983 (10)	0.74512 (13)	0.0352 (4)
C4	0.91457 (14)	0.67436 (11)	0.91553 (15)	0.0401 (5)
C5	0.82281 (14)	0.61243 (11)	0.93933 (14)	0.0369 (4)
C6	0.77637 (14)	0.54923 (11)	0.85573 (13)	0.0357 (4)
C7	0.68328 (16)	0.47616 (12)	0.86360 (16)	0.0464 (5)
C8	0.7442 (3)	0.38982 (17)	0.9185 (3)	0.0912 (12)
C9	0.78431 (14)	0.61809 (11)	1.05183 (13)	0.0371 (4)
C10	0.86250 (18)	0.59219 (16)	1.15633 (17)	0.0577 (7)
C11	0.8264 (2)	0.59431 (17)	1.26033 (17)	0.0626 (7)
C12	0.71056 (17)	0.62210 (12)	1.26052 (15)	0.0450 (5)
C13	0.63071 (18)	0.64809 (18)	1.15934 (17)	0.0623 (7)
C14	0.66868 (18)	0.64717 (17)	1.05624 (16)	0.0604 (7)
O1	0.89470 (11)	0.40927 (9)	0.54067 (11)	0.0504 (4)
O2	0.71175 (11)	0.43050 (9)	0.57770 (10)	0.0477 (4)
O3	0.51752 (11)	0.39159 (12)	0.42491 (13)	0.0606 (5)
N5	0.79256 (12)	0.33747 (10)	0.32772 (12)	0.0414 (4)
C15	0.71958 (14)	0.36663 (10)	0.39545 (13)	0.0348 (4)
C16	0.59211 (14)	0.36258 (12)	0.35892 (15)	0.0416 (5)
C17	0.54154 (17)	0.32534 (15)	0.24937 (16)	0.0550 (6)
C18	0.61739 (19)	0.29373 (17)	0.18254 (17)	0.0613 (7)
C19	0.74202 (18)	0.30191 (15)	0.22363 (16)	0.0552 (6)
C20	0.78153 (14)	0.40452 (10)	0.51336 (13)	0.0361 (4)
H1	0.78890	0.50620	0.70340	0.0450*
H2A	1.01900	0.62100	0.64120	0.0510*
H2B	0.93040	0.54400	0.60240	0.0510*
H4A	1.01310	0.77930	0.97460	0.0700*
H4B	0.93060	0.75070	1.05030	0.0700*
H7A	0.62870	0.49950	0.90960	0.0560*
H7B	0.63480	0.46210	0.78600	0.0560*
H8A	0.80480	0.37060	0.87800	0.1370*
H8B	0.68440	0.34160	0.91380	0.1370*
H8C	0.78280	0.40180	0.99880	0.1370*
H10	0.94140	0.57290	1.15640	0.0690*
H11	0.88050	0.57700	1.32960	0.0750*
H13	0.55160	0.66620	1.15990	0.0750*
H14	0.61490	0.66670	0.98790	0.0730*
H3	0.55830	0.41250	0.48660	0.0910*
H17	0.45720	0.32200	0.22180	0.0660*
H18	0.58500	0.26700	0.11010	0.0740*
H19	0.79270	0.28180	0.17670	0.0660*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0910 (4)	0.0813 (4)	0.0453 (3)	0.0149 (3)	0.0348 (3)	0.0063 (2)
N1	0.0422 (7)	0.0389 (7)	0.0336 (6)	−0.0089 (5)	0.0133 (5)	−0.0064 (5)
N2	0.0446 (7)	0.0464 (7)	0.0403 (7)	−0.0052 (6)	0.0191 (6)	−0.0020 (6)
N3	0.0420 (7)	0.0364 (7)	0.0514 (8)	−0.0057 (5)	0.0208 (6)	−0.0068 (6)
N4	0.0592 (10)	0.0552 (9)	0.0695 (11)	−0.0239 (7)	0.0323 (8)	−0.0289 (8)
C2	0.0372 (7)	0.0331 (7)	0.0374 (7)	0.0008 (6)	0.0129 (6)	0.0027 (6)
C4	0.0371 (8)	0.0379 (8)	0.0476 (9)	−0.0035 (6)	0.0147 (7)	−0.0085 (7)
C5	0.0367 (7)	0.0387 (8)	0.0379 (8)	−0.0028 (6)	0.0140 (6)	−0.0041 (6)
C6	0.0382 (7)	0.0358 (7)	0.0354 (7)	−0.0031 (6)	0.0132 (6)	−0.0017 (6)
C7	0.0496 (9)	0.0480 (9)	0.0463 (9)	−0.0161 (7)	0.0208 (7)	−0.0087 (7)
C8	0.0942 (19)	0.0500 (12)	0.128 (3)	−0.0174 (12)	0.0234 (17)	0.0184 (14)
C9	0.0390 (8)	0.0388 (8)	0.0347 (7)	−0.0011 (6)	0.0113 (6)	−0.0047 (6)
C10	0.0469 (10)	0.0817 (14)	0.0449 (10)	0.0213 (9)	0.0114 (8)	0.0027 (9)
C11	0.0654 (12)	0.0847 (15)	0.0368 (9)	0.0300 (11)	0.0100 (8)	0.0077 (9)
C12	0.0557 (10)	0.0462 (9)	0.0364 (8)	0.0040 (7)	0.0174 (7)	−0.0011 (7)
C13	0.0453 (10)	0.1000 (17)	0.0438 (10)	0.0204 (10)	0.0149 (8)	−0.0011 (10)
C14	0.0477 (10)	0.0974 (16)	0.0351 (9)	0.0231 (10)	0.0075 (7)	0.0031 (9)
O1	0.0370 (6)	0.0601 (8)	0.0513 (7)	0.0040 (5)	0.0046 (5)	−0.0165 (6)
O2	0.0473 (7)	0.0586 (7)	0.0405 (6)	−0.0020 (5)	0.0167 (5)	−0.0113 (5)
O3	0.0372 (6)	0.0900 (11)	0.0571 (8)	0.0004 (6)	0.0162 (6)	−0.0172 (7)
N5	0.0393 (7)	0.0477 (7)	0.0392 (7)	−0.0016 (6)	0.0133 (5)	−0.0068 (6)
C15	0.0365 (7)	0.0340 (7)	0.0343 (7)	−0.0004 (6)	0.0094 (6)	−0.0008 (6)
C16	0.0372 (8)	0.0470 (9)	0.0412 (8)	0.0011 (6)	0.0104 (6)	0.0008 (7)
C17	0.0394 (9)	0.0755 (14)	0.0461 (10)	−0.0024 (8)	0.0018 (7)	−0.0070 (9)
C18	0.0573 (11)	0.0815 (15)	0.0412 (9)	−0.0047 (10)	0.0041 (8)	−0.0170 (9)
C19	0.0527 (10)	0.0729 (13)	0.0418 (9)	−0.0012 (9)	0.0147 (8)	−0.0159 (9)
C20	0.0394 (8)	0.0333 (7)	0.0359 (7)	0.0020 (6)	0.0095 (6)	−0.0013 (6)

Geometric parameters (Å, º)

Cl1—C12	1.7347 (19)	C9—C10	1.386 (3)
O1—C20	1.240 (2)	C9—C14	1.380 (3)
O2—C20	1.270 (2)	C10—C11	1.380 (3)
O3—C16	1.339 (2)	C11—C12	1.364 (3)
O3—H3	0.8200	C12—C13	1.366 (3)
N1—C6	1.363 (2)	C13—C14	1.380 (3)
N1—C2	1.360 (2)	C7—H7B	0.9700
N2—C2	1.328 (2)	C7—H7A	0.9700
N3—C4	1.338 (2)	C8—H8B	0.9600
N3—C2	1.325 (2)	C8—H8A	0.9600
N4—C4	1.324 (2)	C8—H8C	0.9600
N1—H1	0.8600	C10—H10	0.9300
N2—H2A	0.8600	C11—H11	0.9300
N2—H2B	0.8600	C13—H13	0.9300
N4—H4A	0.8600	C14—H14	0.9300
N4—H4B	0.8600	C15—C16	1.399 (2)
N5—C15	1.341 (2)	C15—C20	1.503 (2)
N5—C19	1.328 (2)	C16—C17	1.391 (3)
C4—C5	1.441 (2)	C17—C18	1.369 (3)
C5—C6	1.353 (2)	C18—C19	1.377 (3)
C5—C9	1.492 (2)	C17—H17	0.9300
C6—C7	1.503 (2)	C18—H18	0.9300
C7—C8	1.492 (3)	C19—H19	0.9300
Cl1···C20^i	3.5913 (16)	C19···H2A^iv	3.0000
Cl1···O3^ii	3.3165 (15)	C19···H8A^xii	3.0600
O1···N4^iii	2.982 (2)	C20···H1	2.6600
O1···N5	2.7082 (19)	C20···H4A^iii	2.9100
O1···N2^iv	3.0962 (19)	C20···H2B	2.6700
O1···N2	2.8873 (19)	C20···H3	2.4600
O2···O3	2.5462 (19)	H1···O1	2.8500
O2···N1	2.7370 (18)	H1···O2	1.8800
O3···O2	2.5462 (19)	H1···C20	2.6600
O3···Cl1^ii	3.3165 (15)	H1···H2B	2.2700
O1···H4A^iii	2.1700	H1···H7B	2.2700
O1···H2A^iv	2.5900	H2A···C15^iv	3.0800
O1···H2B	2.0800	H2A···N4^vi	2.6400
O1···H11^v	2.6400	H2A···H4A^vi	2.4200
O1···H1	2.8500	H2A···C19^iv	3.0000
O2···H3	1.8200	H2A···O1^iv	2.5900
O2···H1	1.8800	H2A···N5^iv	2.1500
O2···H7B	2.8300	H2A···H4B^vi	2.2500
O2···H2B	2.9100	H2B···C20	2.6700
N1···O2	2.7370 (18)	H2B···O2	2.9100
N2···O1	2.8873 (19)	H2B···H1	2.2700
N2···N4^vi	3.116 (2)	H2B···O1	2.0800
N2···O1^iv	3.0962 (19)	H3···O2	1.8200
N2···N5^iv	2.948 (2)	H3···C20	2.4600
N4···N2^vii	3.116 (2)	H4A···H2A^vii	2.4200
N4···C10	3.280 (3)	H4A···O1^viii	2.1700
N4···O1^viii	2.982 (2)	H4A···C20^viii	2.9100
N5···N2^iv	2.948 (2)	H4A···N5^viii	2.9200
N5···O1	2.7082 (19)	H4B···C9	2.5200
N1···H8A	2.9000	H4B···H2A^vii	2.2500
N2···H4B^vi	2.6100	H4B···C10	2.7900
N2···H11^v	2.9400	H4B···N2^vii	2.6100
N3···H19^iv	2.8700	H7A···H14	2.6000
N4···H2A^vii	2.6400	H7A···C9	2.7200
N5···H2A^iv	2.1500	H7A···C14	2.7100
N5···H4A^iii	2.9200	H7B···O2	2.8300
C7···C14	3.380 (3)	H7B···H1	2.2700
C8···C19^ix	3.588 (4)	H8A···N1	2.9000
C10···N4	3.280 (3)	H8A···C19^ix	3.0600
C13···C17^x	3.523 (3)	H8B···C15^ix	3.0400
C14···C7	3.380 (3)	H8B···H13^ii	2.6000
C17···C13^xi	3.523 (3)	H10···C2^v	3.0400
C19···C8^xii	3.588 (4)	H11···N2^v	2.9400
C20···Cl1^xiii	3.5913 (16)	H11···O1^v	2.6400
C2···H10^v	3.0400	H13···C17^x	2.8300
C9···H7A	2.7200	H13···H8B^ii	2.6000
C9···H4B	2.5200	H14···H18^xiv	2.4700
C10···H4B	2.7900	H14···H7A	2.6000
C14···H7A	2.7100	H14···C17^xiv	2.9400
C15···H8B^xii	3.0400	H14···C18^xiv	2.9500
C15···H2A^iv	3.0800	H14···H17^xiv	2.4200
C17···H13^xi	2.8300	H17···H14^xiv	2.4200
C17···H14^xiv	2.9400	H18···H14^xiv	2.4700
C18···H14^xiv	2.9500	H19···N3^iv	2.8700
C16—O3—H3	109.00	C8—C7—H7A	109.00
C2—N1—C6	121.03 (13)	C8—C7—H7B	110.00
C2—N3—C4	117.61 (14)	H7A—C7—H7B	108.00
C2—N1—H1	119.00	C6—C7—H7B	109.00
C6—N1—H1	119.00	C7—C8—H8B	109.00
C2—N2—H2A	120.00	H8A—C8—H8B	109.00
C2—N2—H2B	120.00	H8A—C8—H8C	109.00
H2A—N2—H2B	120.00	C7—C8—H8C	109.00
C4—N4—H4A	120.00	H8B—C8—H8C	110.00
C4—N4—H4B	120.00	C7—C8—H8A	109.00
H4A—N4—H4B	120.00	C11—C10—H10	119.00
C15—N5—C19	118.82 (15)	C9—C10—H10	119.00
N2—C2—N3	119.86 (15)	C10—C11—H11	120.00
N1—C2—N2	117.94 (14)	C12—C11—H11	120.00
N1—C2—N3	122.20 (14)	C12—C13—H13	120.00
N3—C4—C5	122.71 (15)	C14—C13—H13	120.00
N3—C4—N4	117.05 (15)	C13—C14—H14	119.00
N4—C4—C5	120.24 (16)	C9—C14—H14	119.00
C4—C5—C6	116.48 (15)	N5—C15—C16	122.11 (14)
C4—C5—C9	120.73 (14)	N5—C15—C20	116.65 (14)
C6—C5—C9	122.78 (15)	C16—C15—C20	121.24 (14)
N1—C6—C7	114.73 (14)	O3—C16—C15	123.11 (15)
C5—C6—C7	125.53 (15)	O3—C16—C17	118.98 (16)
N1—C6—C5	119.59 (15)	C15—C16—C17	117.90 (16)
C6—C7—C8	110.74 (18)	C16—C17—C18	119.24 (18)
C5—C9—C14	121.62 (14)	C17—C18—C19	119.40 (19)
C5—C9—C10	121.28 (15)	N5—C19—C18	122.50 (18)
C10—C9—C14	117.08 (16)	O1—C20—C15	118.98 (14)
C9—C10—C11	121.72 (19)	O2—C20—C15	116.22 (14)
C10—C11—C12	119.31 (19)	O1—C20—O2	124.80 (14)
Cl1—C12—C13	119.21 (15)	C16—C17—H17	120.00
Cl1—C12—C11	120.03 (14)	C18—C17—H17	120.00
C11—C12—C13	120.76 (18)	C17—C18—H18	120.00
C12—C13—C14	119.34 (19)	C19—C18—H18	120.00
C9—C14—C13	121.78 (18)	N5—C19—H19	119.00
C6—C7—H7A	110.00	C18—C19—H19	119.00
C6—N1—C2—N2	174.80 (14)	N1—C6—C7—C8	87.0 (2)
C6—N1—C2—N3	−5.8 (2)	C5—C9—C10—C11	−177.86 (19)
C2—N1—C6—C5	2.8 (2)	C14—C9—C10—C11	0.7 (3)
C2—N1—C6—C7	−172.89 (14)	C5—C9—C14—C13	176.7 (2)
C4—N3—C2—N1	2.6 (2)	C10—C9—C14—C13	−1.8 (3)
C4—N3—C2—N2	−178.01 (15)	C9—C10—C11—C12	0.4 (3)
C2—N3—C4—N4	−177.41 (15)	C10—C11—C12—C13	−0.3 (3)
C2—N3—C4—C5	3.2 (2)	C10—C11—C12—Cl1	178.72 (17)
C19—N5—C15—C20	178.81 (15)	Cl1—C12—C13—C14	−179.84 (18)
C15—N5—C19—C18	−0.1 (3)	C11—C12—C13—C14	−0.8 (3)
C19—N5—C15—C16	−1.4 (2)	C12—C13—C14—C9	1.9 (4)
N3—C4—C5—C6	−5.9 (2)	N5—C15—C16—O3	−179.76 (16)
N3—C4—C5—C9	173.08 (15)	N5—C15—C16—C17	1.2 (2)
N4—C4—C5—C6	174.78 (16)	C20—C15—C16—O3	0.0 (3)
N4—C4—C5—C9	−6.3 (2)	C20—C15—C16—C17	−179.05 (16)
C4—C5—C6—C7	177.89 (15)	N5—C15—C20—O1	1.9 (2)
C4—C5—C9—C10	−69.3 (2)	N5—C15—C20—O2	−178.84 (14)
C9—C5—C6—N1	−176.28 (14)	C16—C15—C20—O1	−177.92 (15)
C9—C5—C6—C7	−1.0 (3)	C16—C15—C20—O2	1.4 (2)
C4—C5—C6—N1	2.7 (2)	O3—C16—C17—C18	−178.61 (19)
C6—C5—C9—C14	−68.9 (2)	C15—C16—C17—C18	0.5 (3)
C4—C5—C9—C14	112.3 (2)	C16—C17—C18—C19	−1.9 (3)
C6—C5—C9—C10	109.6 (2)	C17—C18—C19—N5	1.7 (3)
C5—C6—C7—C8	−88.4 (2)

Symmetry codes: (i) x, y, z+1; (ii) −x+1, −y+1, −z+2; (iii) −x+2, y−1/2, −z+3/2; (iv) −x+2, −y+1, −z+1; (v) −x+2, −y+1, −z+2; (vi) x, −y+3/2, z−1/2; (vii) x, −y+3/2, z+1/2; (viii) −x+2, y+1/2, −z+3/2; (ix) x, −y+1/2, z+1/2; (x) −x+1, y+1/2, −z+3/2; (xi) −x+1, y−1/2, −z+3/2; (xii) x, −y+1/2, z−1/2; (xiii) x, y, z−1; (xiv) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.86	1.88	2.7370 (18)	175
N2—H2A···O1^iv	0.86	2.59	3.0962 (19)	119
N2—H2A···N5^iv	0.86	2.15	2.948 (2)	154
N2—H2B···O1	0.86	2.08	2.8873 (19)	157
O3—H3···O2	0.82	1.82	2.5462 (19)	146
N4—H4A···O1^viii	0.86	2.17	2.982 (2)	158
N4—H4B···N2^vii	0.86	2.61	3.116 (2)	118

Symmetry codes: (iv) −x+2, −y+1, −z+1; (vii) x, −y+3/2, z+1/2; (viii) −x+2, y+1/2, −z+3/2.

(III) 2,4-diamino-(4-chlorophenyl)-6-ethylpyrimidinium 2,4-dichlorobenzoate

Crystal data

C12H14ClN4^+·C7H3Cl2O2^−	F(000) = 1808
Mr = 439.72	Dx = 1.430 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 5639 reflections
a = 14.3808 (2) Å	θ = 1.8–29.4°
b = 12.6799 (2) Å	µ = 0.47 mm^−1
c = 22.4021 (3) Å	T = 293 K
V = 4084.96 (10) Å^3	Prism, colourless
Z = 8	0.25 × 0.22 × 0.20 mm

Data collection

Bruker SMART APEX II CCD area-detector diffractometer	5639 independent reflections
Radiation source: fine-focus sealed tube	3791 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
ϕ and ω scans	θmax = 29.4°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −11→19
Tmin = 0.891, Tmax = 0.912	k = −12→17
26496 measured reflections	l = −30→30

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.042	H-atom parameters constrained
wR(F^2) = 0.118	w = 1/[σ^2(Fo^2) + (0.0442P)^2 + 1.8433P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.001
5639 reflections	Δρmax = 0.48 e Å^−3
255 parameters	Δρmin = −0.51 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^* = kFc[1+0.001Fc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0016 (3)

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > 2sigma(F²) is used only for calculating -R-factor-obs 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
Cl1	1.16200 (5)	0.33814 (6)	0.20424 (3)	0.0878 (3)
N1	0.83136 (10)	0.58234 (10)	0.46549 (6)	0.0349 (4)
N2	0.80363 (11)	0.73723 (12)	0.51484 (7)	0.0462 (5)
N3	0.92006 (10)	0.73383 (11)	0.44467 (6)	0.0386 (4)
N4	1.03918 (11)	0.72461 (12)	0.37804 (7)	0.0504 (5)
C2	0.85241 (11)	0.68540 (13)	0.47439 (7)	0.0348 (5)
C4	0.96752 (12)	0.67725 (13)	0.40467 (8)	0.0371 (5)
C5	0.94500 (11)	0.57010 (13)	0.39029 (7)	0.0354 (5)
C6	0.87640 (11)	0.52406 (12)	0.42301 (7)	0.0331 (5)
C7	0.84999 (12)	0.40996 (13)	0.41939 (8)	0.0394 (5)
C8	0.90786 (17)	0.34450 (17)	0.46207 (11)	0.0662 (8)
C9	0.99831 (12)	0.51108 (13)	0.34432 (7)	0.0372 (5)
C10	1.08977 (13)	0.48089 (15)	0.35500 (9)	0.0484 (6)
C11	1.14047 (14)	0.42735 (16)	0.31203 (10)	0.0547 (7)
C12	1.09873 (15)	0.40420 (15)	0.25855 (9)	0.0514 (7)
C13	1.00845 (15)	0.43143 (16)	0.24713 (8)	0.0521 (6)
C14	0.95886 (13)	0.48576 (15)	0.28998 (8)	0.0448 (6)
Cl2	0.69947 (4)	0.35207 (5)	0.65836 (3)	0.0674 (2)
Cl3	0.33345 (6)	0.32074 (7)	0.69141 (5)	0.1177 (4)
O1	0.70611 (9)	0.46896 (10)	0.53099 (6)	0.0513 (4)
O2	0.66023 (10)	0.61880 (10)	0.57229 (7)	0.0623 (5)
C15	0.57511 (11)	0.46659 (13)	0.59459 (7)	0.0363 (5)
C16	0.58815 (13)	0.38883 (14)	0.63712 (8)	0.0422 (6)
C17	0.51428 (16)	0.34230 (15)	0.66646 (10)	0.0570 (7)
C18	0.42618 (15)	0.37455 (18)	0.65230 (12)	0.0638 (8)
C19	0.40979 (14)	0.45014 (18)	0.60983 (11)	0.0625 (8)
C20	0.48434 (13)	0.49682 (16)	0.58148 (9)	0.0486 (6)
C21	0.65385 (12)	0.52255 (13)	0.56385 (8)	0.0378 (5)
H1	0.78900	0.55310	0.48690	0.0420*
H2A	0.81560	0.80250	0.52200	0.0550*
H2B	0.75990	0.70570	0.53400	0.0550*
H4A	1.05290	0.78870	0.38690	0.0600*
H4B	1.07160	0.69100	0.35200	0.0600*
H7A	0.85930	0.38480	0.37890	0.0470*
H7B	0.78460	0.40200	0.42910	0.0470*
H8A	0.97250	0.35180	0.45220	0.0990*
H8B	0.89010	0.27170	0.45890	0.0990*
H8C	0.89770	0.36850	0.50220	0.0990*
H10	1.11730	0.49690	0.39150	0.0580*
H11	1.20170	0.40750	0.31930	0.0660*
H13	0.98080	0.41360	0.21100	0.0620*
H14	0.89780	0.50570	0.28210	0.0540*
H17	0.52420	0.29040	0.69510	0.0680*
H19	0.34930	0.46970	0.60030	0.0750*
H20	0.47380	0.54920	0.55320	0.0580*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.1036 (5)	0.0906 (5)	0.0691 (4)	0.0491 (4)	0.0325 (4)	−0.0026 (3)
N1	0.0362 (7)	0.0280 (7)	0.0405 (7)	−0.0031 (6)	0.0069 (6)	−0.0021 (5)
N2	0.0525 (9)	0.0296 (7)	0.0564 (9)	−0.0025 (7)	0.0152 (7)	−0.0075 (7)
N3	0.0412 (8)	0.0296 (7)	0.0449 (8)	−0.0041 (6)	0.0036 (6)	−0.0020 (6)
N4	0.0505 (9)	0.0386 (8)	0.0620 (10)	−0.0132 (7)	0.0177 (8)	−0.0076 (7)
C2	0.0363 (8)	0.0284 (8)	0.0396 (8)	0.0003 (7)	−0.0012 (6)	−0.0012 (6)
C4	0.0373 (8)	0.0325 (8)	0.0414 (8)	−0.0038 (7)	0.0009 (7)	0.0012 (7)
C5	0.0347 (8)	0.0325 (8)	0.0390 (8)	−0.0020 (7)	0.0016 (7)	−0.0036 (7)
C6	0.0335 (8)	0.0294 (8)	0.0364 (8)	−0.0004 (6)	−0.0022 (6)	−0.0028 (6)
C7	0.0431 (9)	0.0305 (8)	0.0445 (9)	−0.0048 (7)	0.0052 (7)	−0.0055 (7)
C8	0.0732 (15)	0.0431 (11)	0.0823 (16)	0.0058 (11)	−0.0038 (13)	0.0134 (11)
C9	0.0365 (9)	0.0320 (8)	0.0431 (9)	−0.0030 (7)	0.0061 (7)	−0.0012 (7)
C10	0.0412 (10)	0.0493 (11)	0.0547 (11)	−0.0004 (8)	−0.0008 (8)	−0.0080 (9)
C11	0.0393 (10)	0.0507 (11)	0.0740 (14)	0.0086 (8)	0.0094 (10)	−0.0012 (10)
C12	0.0619 (13)	0.0417 (10)	0.0506 (11)	0.0148 (9)	0.0212 (9)	0.0036 (8)
C13	0.0662 (13)	0.0520 (11)	0.0380 (9)	0.0120 (10)	0.0043 (9)	−0.0013 (8)
C14	0.0436 (10)	0.0488 (10)	0.0419 (9)	0.0083 (8)	0.0026 (8)	−0.0008 (8)
Cl2	0.0547 (3)	0.0690 (4)	0.0784 (4)	0.0048 (3)	−0.0097 (3)	0.0230 (3)
Cl3	0.0870 (5)	0.0880 (5)	0.1782 (9)	−0.0426 (4)	0.0789 (6)	−0.0259 (5)
O1	0.0563 (8)	0.0334 (7)	0.0642 (8)	−0.0011 (6)	0.0258 (7)	−0.0041 (6)
O2	0.0612 (9)	0.0311 (7)	0.0946 (11)	−0.0042 (6)	0.0317 (8)	−0.0089 (7)
C15	0.0349 (8)	0.0320 (8)	0.0419 (8)	−0.0021 (7)	0.0040 (7)	−0.0068 (7)
C16	0.0421 (10)	0.0336 (9)	0.0509 (10)	−0.0020 (7)	0.0051 (8)	−0.0017 (7)
C17	0.0668 (14)	0.0374 (10)	0.0669 (13)	−0.0107 (9)	0.0211 (11)	0.0014 (9)
C18	0.0489 (12)	0.0490 (12)	0.0935 (17)	−0.0204 (10)	0.0317 (12)	−0.0228 (12)
C19	0.0344 (10)	0.0610 (13)	0.0921 (17)	−0.0033 (9)	0.0055 (10)	−0.0252 (13)
C20	0.0404 (10)	0.0467 (10)	0.0588 (11)	0.0038 (8)	−0.0023 (8)	−0.0088 (9)
C21	0.0378 (9)	0.0311 (8)	0.0444 (9)	0.0018 (7)	0.0045 (7)	0.0007 (7)

Geometric parameters (Å, º)

Cl1—C12	1.735 (2)	C10—C11	1.385 (3)
Cl2—C16	1.7339 (19)	C11—C12	1.372 (3)
Cl3—C18	1.735 (3)	C12—C13	1.368 (3)
O1—C21	1.252 (2)	C13—C14	1.380 (3)
O2—C21	1.238 (2)	C7—H7A	0.9700
N1—C6	1.368 (2)	C7—H7B	0.9700
N1—C2	1.356 (2)	C8—H8A	0.9600
N2—C2	1.321 (2)	C8—H8B	0.9600
N3—C2	1.329 (2)	C8—H8C	0.9600
N3—C4	1.336 (2)	C10—H10	0.9300
N4—C4	1.334 (2)	C11—H11	0.9300
N1—H1	0.8600	C13—H13	0.9300
N2—H2A	0.8600	C14—H14	0.9300
N2—H2B	0.8600	C15—C16	1.384 (2)
N4—H4A	0.8600	C15—C20	1.392 (2)
N4—H4B	0.8600	C15—C21	1.503 (2)
C4—C5	1.433 (2)	C16—C17	1.382 (3)
C5—C9	1.486 (2)	C17—C18	1.369 (3)
C5—C6	1.361 (2)	C18—C19	1.371 (3)
C6—C7	1.498 (2)	C19—C20	1.380 (3)
C7—C8	1.515 (3)	C17—H17	0.9300
C9—C10	1.391 (3)	C19—H19	0.9300
C9—C14	1.381 (2)	C20—H20	0.9300
Cl1···C19^i	3.570 (2)	C2···H8A^viii	3.0400
Cl1···Cl3^ii	3.1969 (11)	C4···H8C^viii	2.9100
Cl2···O1	3.2168 (15)	C9···H4B	2.5200
Cl3···Cl1^iii	3.1969 (11)	C9···H7A	2.6800
Cl2···H2A^iv	3.1300	C10···H4B	2.6800
Cl3···H7A^v	3.0700	C12···H17^xi	2.8800
O1···N1	2.7321 (19)	C14···H7A	2.7700
O1···C7	3.330 (2)	C15···H2A^iv	3.0700
O1···Cl2	3.2168 (15)	C20···H4A^vi	2.9800
O1···N2^iv	2.964 (2)	C21···H1	2.6300
O2···N4^vi	2.866 (2)	C21···H2B	2.8600
O2···N2	2.857 (2)	C21···H4A^vi	3.0100
O1···H1	1.8800	C21···H2A^iv	2.9800
O1···H2A^iv	2.1400	H1···H7B	2.3100
O1···H7B	2.6800	H1···O1	1.8800
O2···H4A^vi	2.1400	H1···O2	2.7900
O2···H1	2.7900	H1···C21	2.6300
O2···H2B	2.0000	H1···H2B	2.2400
O2···H20	2.8500	H2A···O1^vii	2.1400
N1···O1	2.7321 (19)	H2A···C15^vii	3.0700
N2···O2	2.857 (2)	H2A···Cl2^vii	3.1300
N2···O1^vii	2.964 (2)	H2A···C21^vii	2.9800
N3···C8^viii	3.388 (3)	H2B···H1	2.2400
N4···C10	3.217 (2)	H2B···O2	2.0000
N4···O2^ix	2.866 (2)	H2B···C21	2.8600
N3···H20^ix	2.8600	H4A···O2^ix	2.1400
C4···C8^viii	3.493 (3)	H4A···C20^ix	2.9800
C7···C14	3.432 (3)	H4A···C21^ix	3.0100
C7···O1	3.330 (2)	H4B···C9	2.5200
C8···C4^viii	3.493 (3)	H4B···C10	2.6800
C8···N3^viii	3.388 (3)	H7A···Cl3^xi	3.0700
C10···N4	3.217 (2)	H7A···C9	2.6800
C13···C18^i	3.384 (3)	H7A···C14	2.7700
C13···C17^i	3.407 (3)	H7B···O1	2.6800
C14···C17^i	3.544 (3)	H7B···H1	2.3100
C14···C7	3.432 (3)	H8A···C2^viii	3.0400
C17···C14^x	3.544 (3)	H8C···C4^viii	2.9100
C17···C13^x	3.407 (3)	H17···C12^v	2.8800
C18···C13^x	3.384 (3)	H20···O2	2.8500
C19···Cl1^x	3.570 (2)	H20···N3^vi	2.8600
C2—N1—C6	121.14 (14)	H7A—C7—H7B	108.00
C2—N3—C4	117.51 (14)	C7—C8—H8A	109.00
C2—N1—H1	119.00	C7—C8—H8B	110.00
C6—N1—H1	119.00	C7—C8—H8C	109.00
C2—N2—H2A	120.00	H8A—C8—H8B	109.00
C2—N2—H2B	120.00	H8A—C8—H8C	109.00
H2A—N2—H2B	120.00	H8B—C8—H8C	109.00
H4A—N4—H4B	120.00	C9—C10—H10	120.00
C4—N4—H4A	120.00	C11—C10—H10	120.00
C4—N4—H4B	120.00	C10—C11—H11	121.00
N1—C2—N3	122.34 (15)	C12—C11—H11	121.00
N2—C2—N3	120.16 (15)	C12—C13—H13	120.00
N1—C2—N2	117.50 (15)	C14—C13—H13	120.00
N3—C4—N4	116.95 (15)	C9—C14—H14	119.00
N3—C4—C5	122.99 (15)	C13—C14—H14	119.00
N4—C4—C5	120.06 (15)	C16—C15—C20	117.94 (16)
C4—C5—C6	116.71 (15)	C16—C15—C21	123.34 (15)
C4—C5—C9	121.10 (14)	C20—C15—C21	118.67 (15)
C6—C5—C9	122.09 (15)	Cl2—C16—C15	120.37 (14)
N1—C6—C5	119.10 (14)	Cl2—C16—C17	117.68 (15)
N1—C6—C7	116.06 (14)	C15—C16—C17	121.85 (17)
C5—C6—C7	124.68 (15)	C16—C17—C18	118.3 (2)
C6—C7—C8	110.83 (15)	Cl3—C18—C17	118.48 (19)
C5—C9—C10	120.49 (15)	Cl3—C18—C19	119.55 (17)
C5—C9—C14	121.07 (15)	C17—C18—C19	121.9 (2)
C10—C9—C14	118.44 (16)	C18—C19—C20	119.07 (19)
C9—C10—C11	120.87 (18)	C15—C20—C19	120.90 (18)
C10—C11—C12	118.78 (19)	O1—C21—O2	125.45 (17)
Cl1—C12—C11	119.10 (16)	O1—C21—C15	117.72 (15)
Cl1—C12—C13	119.25 (15)	O2—C21—C15	116.81 (16)
C11—C12—C13	121.65 (19)	C16—C17—H17	121.00
C12—C13—C14	119.11 (18)	C18—C17—H17	121.00
C9—C14—C13	121.13 (17)	C18—C19—H19	120.00
C6—C7—H7A	109.00	C20—C19—H19	120.00
C6—C7—H7B	110.00	C15—C20—H20	120.00
C8—C7—H7A	110.00	C19—C20—H20	120.00
C8—C7—H7B	110.00
C6—N1—C2—N2	177.74 (15)	C10—C9—C14—C13	0.3 (3)
C6—N1—C2—N3	−3.1 (2)	C9—C10—C11—C12	−0.2 (3)
C2—N1—C6—C5	1.6 (2)	C10—C11—C12—Cl1	179.47 (15)
C2—N1—C6—C7	177.30 (14)	C10—C11—C12—C13	−0.9 (3)
C4—N3—C2—N1	0.4 (2)	Cl1—C12—C13—C14	−178.77 (15)
C2—N3—C4—C5	3.8 (2)	C11—C12—C13—C14	1.6 (3)
C2—N3—C4—N4	−175.64 (15)	C12—C13—C14—C9	−1.2 (3)
C4—N3—C2—N2	179.46 (16)	C20—C15—C16—Cl2	−176.73 (14)
N3—C4—C5—C9	178.42 (15)	C20—C15—C16—C17	−0.5 (3)
N3—C4—C5—C6	−5.1 (2)	C21—C15—C16—Cl2	0.8 (2)
N4—C4—C5—C6	174.30 (16)	C21—C15—C16—C17	177.04 (17)
N4—C4—C5—C9	−2.2 (2)	C16—C15—C20—C19	−0.4 (3)
C4—C5—C6—N1	2.2 (2)	C21—C15—C20—C19	−178.01 (18)
C9—C5—C6—C7	3.4 (3)	C16—C15—C21—O1	64.5 (2)
C4—C5—C9—C10	69.9 (2)	C16—C15—C21—O2	−117.1 (2)
C4—C5—C9—C14	−109.5 (2)	C20—C15—C21—O1	−118.03 (19)
C6—C5—C9—C10	−106.3 (2)	C20—C15—C21—O2	60.5 (2)
C6—C5—C9—C14	74.3 (2)	Cl2—C16—C17—C18	176.69 (17)
C4—C5—C6—C7	−173.04 (15)	C15—C16—C17—C18	0.4 (3)
C9—C5—C6—N1	178.65 (14)	C16—C17—C18—Cl3	−177.10 (16)
N1—C6—C7—C8	−87.32 (19)	C16—C17—C18—C19	0.7 (3)
C5—C6—C7—C8	88.1 (2)	Cl3—C18—C19—C20	176.24 (18)
C5—C9—C10—C11	−178.95 (17)	C17—C18—C19—C20	−1.5 (4)
C14—C9—C10—C11	0.5 (3)	C18—C19—C20—C15	1.3 (3)
C5—C9—C14—C13	179.66 (17)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.86	1.88	2.7321 (19)	171
N2—H2A···O1^vii	0.86	2.14	2.964 (2)	159
N2—H2B···O2	0.86	2.00	2.857 (2)	174
N4—H4A···O2^ix	0.86	2.14	2.866 (2)	141

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