2,4-Diamino-5-(4-chloro­phen­yl)-6-ethyl­pyrimidin-1-ium 2-acet­amido­benzoate

Natarajan, S.; Mathews, R.

doi:10.1107/S1600536811032570

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 9| September 2011| Pages o2357-o2358

doi:10.1107/S1600536811032570

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2,4-Diamino-5-(4-chlorophenyl)-6-ethylpyrimidin-1-ium 2-acetamidobenzoate

Sampath Natarajan ^a ^* and Rita Mathews ^a

^aDepartment of Advanced Technology Fusion, Konkuk University, 1 Hwayang-dong, Gwangjin-gu, Seoul 143 701, Republic of Korea
^*Correspondence e-mail: sampath@konkuk.ac.kr, sams76@gmail.com

(Received 7 August 2011; accepted 11 August 2011; online 17 August 2011)

The title compound, C₁₂H₁₄ClN₄⁺·C₉H₈NO₃⁻, is a salt with a 1:1 ratio of cation and anion components interacting with each other forming an R₂²(8) ring motif. The crystal structure is stabilized by hydrogen bonds (N—H⋯O) involving two different eight-membered rings. One of them is formed between the pyrimidine ring (donor) and the carboxylate group (acceptor) from the benzoate, whereas the other ring is formed by N—H⋯O interactions, which help to form a dimer between two symmetry-related salts in the unit cell. In addition, an intramolecular C—H⋯N and intermolecular C—H⋯Cl interactions help to control the molecules in the unit-cell packing.

Related literature

For related literature on aminopyrimidine–carboxylate interactions, see: Baker & Santi (1965 ); Chinnakali et al. (1999 ); Desiraju (1989 ); Hunt et al. (1980 ); Lynch & Jones (2004 ); Stanley et al. (2005 ). For literature on aminopyrimidine and benzoic acid adducts, see: Thanigaimani et al. (2006 , 2007 ); Balasubramani et al. (2005 , 2006 ). For puckering parameters, see: Cremer & Pople, (1975 ); Nardelli (1995 ).

Experimental

Crystal data

C₁₂H₁₄ClN₄⁺·C₉H₈NO₃⁻
M_r = 427.89
Monoclinic, C 2/c
a = 25.226 (4) Å
b = 9.0666 (16) Å
c = 20.688 (4) Å
β = 113.400 (3)°
V = 4342.5 (13) Å³
Z = 8
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 293 K
0.4 × 0.35 × 0.32 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
14400 measured reflections
3937 independent reflections
3079 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.123
S = 1.04
3937 reflections
272 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5⋯O1	0.86	1.90	2.614 (2)	140
C9—H9B⋯N5	0.97	2.87	3.683 (3)	142
N1—H1⋯O1ⁱ	0.86	1.86	2.715 (2)	177
N3—H3B⋯O2ⁱ	0.86	1.96	2.802 (3)	165
N3—H3A⋯O2ⁱⁱ	0.86	2.16	2.897 (2)	143
N4—H4A⋯O3ⁱⁱⁱ	0.86	2.01	2.859 (2)	168
C10—H10B⋯Cl1^iv	0.96	2.95	3.864 (3)	160
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) -x, -y+1, -z+1; (iv) $[x, -y, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811032570/ng5209sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811032570/ng5209Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811032570/ng5209Isup3.cml

checkCIF report

Comment top

Aminopyrimidine-Carboxylate interactions are important since they are involved in protein-nucleic acids recognition and protein-drug binding. Hydrogen bonding plays a key role in molecular recognition and crystal engineering research (Desiraju, 1989). In general, aminopyrimidines posses self complementary hydrogen-bonded motifs forming a base pair which in itself is a unique property. The adducts of carboxylic acid with 2-aminopyrimidine system form a graph-set motif R₂²(8) (Lynch & Jones, 2004). This motif is very robust in aminopyrimidine-carboxylic acid/carboxylates systems. The crystal structures of many aminopyrimidine carboxylates (Stanley et al., 2005) and co-crystal structures (Chinnakali et al.,1999) have been reported. Many structures of aminopyrimidine and benzoic acid adducts have been reported. Few of them are 2-amino-4,6-dimethoxy pyrimidine: 4-aminobenzoic acid (Thanigaimani et al., 2006), 2-amino-4,6-dimethoxypyrimidine: phthalic acid (Thanigaimani et al., 2007), 2-amino-4,6-dimethylpyrimidine: cinnamic acid (Balasubramani et al., 2005) and 2-amino-4,6-dimethylpyrimidine: 4-hydroxybenzoic acid (Balasubramani et al., 2006). All these reported structures also have common features of heterosynthone formation. In the present study we report a salt (1:1) namely, 2,4-diamino-5-(4-chlorophenyl)-6-ethylpyrimidin-1-ium- 2-(acetylamino)benzoate and its interactions are studied extensively.

The asymmetric unit of crystal contains a single molecule of each component of salt (Fig. 1) and does not have any direct interactions each other. The interactions were found between the symmetry related molecules of aminopyrimidin-1-ium and benzoate salt via hydrogen bonds N1—H1···O1 and N3—H3B···O2 (-x + 1/2, -y + 1/2, -z + 1) (Fig. 2). Here the pyrimidine acts as a donor which donates two H atoms and carboxylate O atoms as acceptors. In addition dimeric interactions by the atoms O2 and N3 form an eight membered ring through the Hydrogen bonds N3—H3A···O2 (x - 1/2, -y + 1/2, z - 1/2) and N3—H3B···O2 (-x + 1/2, -y + 1/2, -z + 1) (Fig. 2). The dihedral angle between the rings, 4-chlorophenyl and 2,4-diaminopyrimidine is 80.6 (1)°. This value is higher than that in a biphenyl ring system. This may be due to the substitution of ethyl and amine groups at C4 and C6, respectively. An extended moiety of acetylamino group is coplanar with phenyl carboxylate and the dihedral angle between these two is 1.59 (1)° (Cremer & Pople, 1975; Nardelli, 1995).

In the crystal packing, the molecules are arranged as sheets along the a direction (Fig. 3). These sheets are organized as two layers in the unit cell and both layer molecules are connected to each other through N4—H4A···O3 hydrogen bond. In addition, a six membered ring is formed by an intra-molecular interaction (N5—H5···O1)in benzoate molecule which also controls the molecules in crystal packing. Molecular packing is stabilized by many N—H···O and a C—H···Cl (x, -y, z - 1/2) intra and intermolecular interactions (Table 1, Fig. 2).

Related literature top

For related literature on aminopyrimidine–carboxylate interactions, see: Baker & Santi (1965); Chinnakali et al. (1999); Desiraju (1989); Hunt et al. (1980); Lynch & Jones (2004); Stanley et al. (2005); . For literature on aminopyrimidine and benzoic acid adducts, see: Thanigaimani et al. (2006, 2007); Balasubramani et al. (2005, 2006). For puckering parameters, see: Cremer & Pople, (1975); Nardelli (1995).

Experimental top

A hot methanolic solution (20 ml) of 2,4-diamino-5-(4-chlorophenyl)-6- ethylpyrimidine and 2-(acetylamino)benzoic acid in the ratio of 1:1 was warmed for 0.5 h over a water bath. The mixture was cooled slowly and kept at room temperature and after a few days, colourless crystals were obtained

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SMART (Bruker, 2004); data reduction: SMART (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. ORTEP diagram of the title molecule with the atom numbering scheme. Displacement ellipsoid are drawn at 30% probability level.
	Fig. 2. Dimer interaction between the symmetry related salts of title compound. Dashed lines indicate the intra and intermolecular hydrogen bonds.
	Fig. 3. Packing diagram of the title compound viewed down the b axis. Dashed lines indicate the intra and intermolecular interactions between the molecules.

2,4-Diamino-5-(4-chlorophenyl)-6-ethylpyrimidin-1-ium 2-acetamidobenzoate top

Crystal data top

C₁₂H₁₄ClN₄⁺·C₉H₈NO₃⁻	F(000) = 1792
M_r = 427.89	D_x = 1.309 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 25.226 (4) Å	Cell parameters from 14400 reflections
b = 9.0666 (16) Å	θ = 1.8–26.2°
c = 20.688 (4) Å	µ = 0.21 mm⁻¹
β = 113.400 (3)°	T = 293 K
V = 4342.5 (13) Å³	Block, colourless
Z = 8	0.4 × 0.35 × 0.32 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	3079 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.019
Graphite monochromator	θ_max = 26.2°, θ_min = 1.8°
ω scans	h = −29→30
14400 measured reflections	k = −11→11
3937 independent reflections	l = −25→24

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.123	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.059P)² + 2.2497P] where P = (F_o² + 2F_c²)/3
3937 reflections	(Δ/σ)_max < 0.001
272 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₂H₁₄ClN₄⁺·C₉H₈NO₃⁻	V = 4342.5 (13) Å³
M_r = 427.89	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 25.226 (4) Å	µ = 0.21 mm⁻¹
b = 9.0666 (16) Å	T = 293 K
c = 20.688 (4) Å	0.4 × 0.35 × 0.32 mm
β = 113.400 (3)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	3079 reflections with I > 2σ(I)
14400 measured reflections	R_int = 0.019
3937 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.123	H-atom parameters constrained
S = 1.04	Δρ_max = 0.20 e Å⁻³
3937 reflections	Δρ_min = −0.19 e Å⁻³
272 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.09641 (3)	0.17665 (8)	0.85360 (3)	0.0916 (3)
O1	0.34974 (6)	0.30249 (17)	0.60241 (7)	0.0668 (4)
O2	0.40391 (6)	0.20074 (17)	0.70432 (7)	0.0651 (4)
O3	0.16543 (8)	0.5398 (3)	0.55466 (10)	0.1088 (7)
N1	0.06713 (6)	0.24269 (18)	0.44774 (7)	0.0487 (4)
H1	0.0925	0.2276	0.4304	0.058*
N5	0.25286 (7)	0.4296 (2)	0.58885 (9)	0.0691 (5)
H5	0.2795	0.4091	0.5742	0.083*
N2	−0.02695 (6)	0.31925 (17)	0.42880 (8)	0.0490 (4)
C2	0.01378 (8)	0.2902 (2)	0.40505 (9)	0.0473 (4)
C4	−0.01287 (7)	0.30452 (19)	0.49808 (9)	0.0449 (4)
C5	0.04201 (8)	0.2494 (2)	0.54570 (9)	0.0450 (4)
C6	0.08133 (8)	0.2183 (2)	0.51771 (9)	0.0458 (4)
N3	0.00325 (7)	0.3063 (2)	0.33758 (8)	0.0642 (5)
H3A	−0.0302	0.3358	0.3086	0.077*
H3B	0.0298	0.2873	0.3226	0.077*
N4	−0.05259 (7)	0.34253 (19)	0.52206 (8)	0.0573 (4)
H4A	−0.0856	0.3749	0.4934	0.069*
H4B	−0.0453	0.3347	0.5662	0.069*
C9	0.13931 (8)	0.1497 (2)	0.55671 (10)	0.0573 (5)
H9A	0.1505	0.1627	0.6069	0.069*
H9B	0.1678	0.1987	0.5437	0.069*
C10	0.13821 (12)	−0.0142 (3)	0.54001 (14)	0.0866 (8)
H10A	0.1758	−0.0557	0.5655	0.130*
H10B	0.1277	−0.0270	0.4904	0.130*
H10C	0.1105	−0.0630	0.5536	0.130*
C11	0.05491 (8)	0.2300 (2)	0.62204 (9)	0.0461 (4)
C12	0.05200 (10)	0.0934 (2)	0.65023 (10)	0.0615 (5)
H12	0.0415	0.0115	0.6208	0.074*
C13	0.06433 (10)	0.0761 (2)	0.72089 (11)	0.0672 (6)
H13	0.0625	−0.0165	0.7392	0.081*
C14	0.07937 (9)	0.1978 (2)	0.76379 (10)	0.0583 (5)
C15	0.08186 (10)	0.3350 (2)	0.73762 (10)	0.0624 (5)
H15	0.0916	0.4169	0.7672	0.075*
C16	0.06970 (9)	0.3503 (2)	0.66685 (10)	0.0565 (5)
H16	0.0715	0.4433	0.6489	0.068*
C17	0.26374 (9)	0.3814 (2)	0.65760 (11)	0.0597 (5)
C18	0.22574 (11)	0.4080 (3)	0.69018 (15)	0.0842 (7)
H18	0.1915	0.4589	0.6659	0.101*
C19	0.23812 (13)	0.3602 (4)	0.75731 (16)	0.0925 (8)
H19	0.2122	0.3790	0.7781	0.111*
C20	0.28810 (12)	0.2852 (3)	0.79432 (14)	0.0819 (7)
H20	0.2964	0.2536	0.8401	0.098*
C21	0.32583 (10)	0.2572 (3)	0.76267 (11)	0.0654 (6)
H21	0.3597	0.2059	0.7878	0.078*
C22	0.31507 (8)	0.3029 (2)	0.69465 (10)	0.0516 (5)
C23	0.35930 (8)	0.2663 (2)	0.66497 (10)	0.0498 (5)
C24	0.20715 (10)	0.5028 (3)	0.54250 (13)	0.0763 (7)
C25	0.21049 (12)	0.5345 (4)	0.47279 (14)	0.0992 (9)
H25A	0.1732	0.5193	0.4355	0.149*
H25B	0.2381	0.4696	0.4664	0.149*
H25C	0.2223	0.6350	0.4720	0.149*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.1155 (6)	0.1148 (6)	0.0436 (3)	0.0138 (4)	0.0307 (3)	0.0113 (3)
O1	0.0521 (8)	0.0950 (11)	0.0544 (9)	0.0212 (8)	0.0222 (7)	0.0160 (8)
O2	0.0497 (8)	0.0881 (11)	0.0533 (8)	0.0187 (7)	0.0158 (6)	0.0105 (7)
O3	0.0666 (11)	0.1441 (18)	0.0979 (13)	0.0506 (12)	0.0139 (10)	0.0016 (12)
N1	0.0421 (8)	0.0635 (10)	0.0400 (8)	0.0054 (7)	0.0159 (6)	0.0034 (7)
N5	0.0487 (9)	0.0840 (13)	0.0700 (12)	0.0178 (9)	0.0187 (8)	0.0095 (10)
N2	0.0410 (8)	0.0601 (10)	0.0426 (8)	0.0025 (7)	0.0131 (7)	0.0051 (7)
C2	0.0437 (10)	0.0538 (11)	0.0400 (9)	−0.0003 (8)	0.0118 (8)	0.0027 (8)
C4	0.0432 (10)	0.0455 (10)	0.0449 (10)	−0.0014 (8)	0.0164 (8)	0.0034 (8)
C5	0.0461 (10)	0.0441 (10)	0.0428 (9)	0.0009 (8)	0.0156 (8)	0.0028 (8)
C6	0.0445 (10)	0.0488 (10)	0.0391 (9)	−0.0005 (8)	0.0112 (8)	−0.0002 (8)
N3	0.0499 (9)	0.1003 (14)	0.0388 (9)	0.0151 (9)	0.0136 (7)	0.0090 (8)
N4	0.0454 (9)	0.0785 (12)	0.0478 (9)	0.0105 (8)	0.0183 (7)	0.0101 (8)
C9	0.0496 (11)	0.0754 (14)	0.0418 (10)	0.0112 (10)	0.0128 (8)	0.0048 (9)
C10	0.0947 (18)	0.0754 (16)	0.0860 (17)	0.0288 (14)	0.0320 (14)	0.0133 (13)
C11	0.0449 (10)	0.0496 (11)	0.0420 (9)	0.0060 (8)	0.0154 (8)	0.0035 (8)
C12	0.0830 (15)	0.0490 (12)	0.0509 (11)	−0.0012 (10)	0.0248 (10)	0.0001 (9)
C13	0.0921 (16)	0.0565 (13)	0.0550 (12)	0.0053 (11)	0.0314 (11)	0.0141 (10)
C14	0.0613 (12)	0.0722 (14)	0.0407 (10)	0.0115 (10)	0.0194 (9)	0.0065 (10)
C15	0.0770 (14)	0.0601 (13)	0.0473 (11)	0.0038 (11)	0.0218 (10)	−0.0065 (9)
C16	0.0703 (13)	0.0474 (11)	0.0512 (11)	0.0036 (9)	0.0235 (10)	0.0034 (9)
C17	0.0486 (11)	0.0663 (13)	0.0625 (12)	0.0024 (9)	0.0204 (9)	−0.0077 (10)
C18	0.0624 (14)	0.1020 (19)	0.0919 (19)	0.0213 (13)	0.0344 (13)	−0.0068 (15)
C19	0.0876 (19)	0.121 (2)	0.0872 (19)	0.0119 (17)	0.0543 (16)	−0.0122 (17)
C20	0.0856 (18)	0.104 (2)	0.0663 (14)	0.0015 (15)	0.0405 (13)	−0.0067 (14)
C21	0.0640 (13)	0.0748 (14)	0.0574 (12)	0.0038 (11)	0.0243 (10)	−0.0023 (11)
C22	0.0447 (10)	0.0536 (11)	0.0539 (11)	−0.0036 (8)	0.0169 (8)	−0.0081 (9)
C23	0.0430 (10)	0.0543 (11)	0.0475 (11)	0.0014 (8)	0.0129 (8)	−0.0032 (9)
C24	0.0526 (13)	0.0783 (16)	0.0795 (16)	0.0147 (12)	0.0065 (11)	−0.0024 (12)
C25	0.0818 (17)	0.111 (2)	0.0846 (18)	0.0232 (16)	0.0111 (14)	0.0237 (16)

Geometric parameters (Å, º) top

Cl1—C14	1.7433 (19)	C10—H10C	0.9600
O1—C23	1.262 (2)	C11—C12	1.383 (3)
O2—C23	1.247 (2)	C11—C16	1.383 (3)
O3—C24	1.222 (3)	C12—C13	1.377 (3)
N1—C2	1.354 (2)	C12—H12	0.9300
N1—C6	1.364 (2)	C13—C14	1.372 (3)
N1—H1	0.8600	C13—H13	0.9300
N5—C24	1.346 (3)	C14—C15	1.368 (3)
N5—C17	1.407 (3)	C15—C16	1.379 (3)
N5—H5	0.8600	C15—H15	0.9300
N2—C2	1.329 (2)	C16—H16	0.9300
N2—C4	1.339 (2)	C17—C18	1.395 (3)
C2—N3	1.321 (2)	C17—C22	1.408 (3)
C4—N4	1.328 (2)	C18—C19	1.367 (4)
C4—C5	1.433 (2)	C18—H18	0.9300
C5—C6	1.362 (3)	C19—C20	1.368 (4)
C5—C11	1.491 (2)	C19—H19	0.9300
C6—C9	1.497 (3)	C20—C21	1.376 (3)
N3—H3A	0.8600	C20—H20	0.9300
N3—H3B	0.8600	C21—C22	1.386 (3)
N4—H4A	0.8600	C21—H21	0.9300
N4—H4B	0.8600	C22—C23	1.509 (3)
C9—C10	1.523 (3)	C24—C25	1.505 (4)
C9—H9A	0.9700	C25—H25A	0.9600
C9—H9B	0.9700	C25—H25B	0.9600
C10—H10A	0.9600	C25—H25C	0.9600
C10—H10B	0.9600

C2—N1—C6	121.21 (16)	C14—C13—C12	118.9 (2)
C2—N1—H1	119.4	C14—C13—H13	120.6
C6—N1—H1	119.4	C12—C13—H13	120.6
C24—N5—C17	129.9 (2)	C15—C14—C13	121.32 (18)
C24—N5—H5	115.1	C15—C14—Cl1	119.43 (17)
C17—N5—H5	115.1	C13—C14—Cl1	119.25 (17)
C2—N2—C4	117.42 (14)	C14—C15—C16	119.05 (19)
N3—C2—N2	120.54 (16)	C14—C15—H15	120.5
N3—C2—N1	117.07 (17)	C16—C15—H15	120.5
N2—C2—N1	122.39 (16)	C15—C16—C11	121.32 (19)
N4—C4—N2	117.08 (15)	C15—C16—H16	119.3
N4—C4—C5	120.00 (16)	C11—C16—H16	119.3
N2—C4—C5	122.92 (16)	C18—C17—N5	122.7 (2)
C6—C5—C4	116.60 (16)	C18—C17—C22	119.0 (2)
C6—C5—C11	122.45 (16)	N5—C17—C22	118.38 (18)
C4—C5—C11	120.95 (16)	C19—C18—C17	120.8 (2)
C5—C6—N1	119.27 (16)	C19—C18—H18	119.6
C5—C6—C9	125.29 (16)	C17—C18—H18	119.6
N1—C6—C9	115.35 (16)	C18—C19—C20	120.9 (2)
C2—N3—H3A	120.0	C18—C19—H19	119.5
C2—N3—H3B	120.0	C20—C19—H19	119.5
H3A—N3—H3B	120.0	C19—C20—C21	118.9 (2)
C4—N4—H4A	120.0	C19—C20—H20	120.6
C4—N4—H4B	120.0	C21—C20—H20	120.6
H4A—N4—H4B	120.0	C20—C21—C22	122.3 (2)
C6—C9—C10	110.93 (18)	C20—C21—H21	118.8
C6—C9—H9A	109.5	C22—C21—H21	118.8
C10—C9—H9A	109.5	C21—C22—C17	118.07 (19)
C6—C9—H9B	109.5	C21—C22—C23	117.99 (17)
C10—C9—H9B	109.5	C17—C22—C23	123.93 (18)
H9A—C9—H9B	108.0	O2—C23—O1	123.28 (18)
C9—C10—H10A	109.5	O2—C23—C22	117.42 (17)
C9—C10—H10B	109.5	O1—C23—C22	119.29 (16)
H10A—C10—H10B	109.5	O3—C24—N5	123.6 (3)
C9—C10—H10C	109.5	O3—C24—C25	121.7 (2)
H10A—C10—H10C	109.5	N5—C24—C25	114.8 (2)
H10B—C10—H10C	109.5	C24—C25—H25A	109.5
C12—C11—C16	117.94 (17)	C24—C25—H25B	109.5
C12—C11—C5	121.79 (17)	H25A—C25—H25B	109.5
C16—C11—C5	120.26 (17)	C24—C25—H25C	109.5
C13—C12—C11	121.50 (19)	H25A—C25—H25C	109.5
C13—C12—H12	119.3	H25B—C25—H25C	109.5
C11—C12—H12	119.3

C4—N2—C2—N3	−178.21 (17)	C12—C13—C14—Cl1	−178.78 (17)
C4—N2—C2—N1	2.2 (3)	C13—C14—C15—C16	−0.9 (3)
C6—N1—C2—N3	−177.84 (17)	Cl1—C14—C15—C16	178.42 (17)
C6—N1—C2—N2	1.8 (3)	C14—C15—C16—C11	0.2 (3)
C2—N2—C4—N4	175.89 (16)	C12—C11—C16—C15	0.7 (3)
C2—N2—C4—C5	−4.6 (3)	C5—C11—C16—C15	−179.95 (19)
N4—C4—C5—C6	−177.47 (17)	C24—N5—C17—C18	−1.4 (4)
N2—C4—C5—C6	3.1 (3)	C24—N5—C17—C22	178.4 (2)
N4—C4—C5—C11	1.7 (3)	N5—C17—C18—C19	−179.5 (2)
N2—C4—C5—C11	−177.80 (16)	C22—C17—C18—C19	0.7 (4)
C4—C5—C6—N1	1.0 (3)	C17—C18—C19—C20	0.0 (5)
C11—C5—C6—N1	−178.14 (16)	C18—C19—C20—C21	−0.5 (5)
C4—C5—C6—C9	−175.26 (17)	C19—C20—C21—C22	0.2 (4)
C11—C5—C6—C9	5.6 (3)	C20—C21—C22—C17	0.5 (3)
C2—N1—C6—C5	−3.3 (3)	C20—C21—C22—C23	−179.9 (2)
C2—N1—C6—C9	173.28 (17)	C18—C17—C22—C21	−0.9 (3)
C5—C6—C9—C10	100.7 (2)	N5—C17—C22—C21	179.27 (19)
N1—C6—C9—C10	−75.7 (2)	C18—C17—C22—C23	179.5 (2)
C6—C5—C11—C12	−80.4 (2)	N5—C17—C22—C23	−0.3 (3)
C4—C5—C11—C12	100.5 (2)	C21—C22—C23—O2	−2.1 (3)
C6—C5—C11—C16	100.3 (2)	C17—C22—C23—O2	177.44 (19)
C4—C5—C11—C16	−78.8 (2)	C21—C22—C23—O1	177.81 (18)
C16—C11—C12—C13	−1.1 (3)	C17—C22—C23—O1	−2.7 (3)
C5—C11—C12—C13	179.58 (19)	C17—N5—C24—O3	−0.3 (4)
C11—C12—C13—C14	0.5 (3)	C17—N5—C24—C25	−179.4 (2)
C12—C13—C14—C15	0.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5···O1	0.86	1.90	2.614 (2)	140
C9—H9B···N5	0.97	2.87	3.683 (3)	142
N1—H1···O1ⁱ	0.86	1.86	2.715 (2)	177
N3—H3B···O2ⁱ	0.86	1.96	2.802 (3)	165
N3—H3A···O2ⁱⁱ	0.86	2.16	2.897 (2)	143
N4—H4A···O3ⁱⁱⁱ	0.86	2.01	2.859 (2)	168
C10—H10B···Cl1^iv	0.96	2.95	3.864 (3)	160

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₄ClN₄⁺·C₉H₈NO₃⁻
M_r	427.89
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	25.226 (4), 9.0666 (16), 20.688 (4)
β (°)	113.400 (3)
V (Å³)	4342.5 (13)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.21
Crystal size (mm)	0.4 × 0.35 × 0.32

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	14400, 3937, 3079
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.622

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.123, 1.04
No. of reflections	3937
No. of parameters	272
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.19

Computer programs: SMART (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5···O1	0.86	1.90	2.614 (2)	140
C9—H9B···N5	0.97	2.87	3.683 (3)	142
N1—H1···O1ⁱ	0.86	1.86	2.715 (2)	177
N3—H3B···O2ⁱ	0.86	1.96	2.802 (3)	165
N3—H3A···O2ⁱⁱ	0.86	2.16	2.897 (2)	143
N4—H4A···O3ⁱⁱⁱ	0.86	2.01	2.859 (2)	168
C10—H10B···Cl1^iv	0.96	2.95	3.864 (3)	160

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

References

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Volume 67| Part 9| September 2011| Pages o2357-o2358

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