Hydrogen bonding in pyrimethamine hydrogen adipate

Devi, P.; Muthiah, P.T.; Row, T.N.G.; Thiruvenkatam, V.

doi:10.1107/S1600536807044364

Buy article online - an online subscription or single-article purchase is required to access this article.

Hydrogen bonding in pyrimethamine hydrogen adipate

P. Devi, P. T. Muthiah, T. N. G. Row and V. Thiruvenkatam

In 2,4-diamino-5-(p-chlorophenyl)-6-ethylpyrimidinium hydrogen adipate, C₁₂H₁₄ClN₄⁺·C₆H₉O₄⁻, the protonated pyrimethamine cation interacts with the carboxylate group of the adipate ion through N—H

O hydrogen bonds, forming a cyclic hydrogen-bonded R²₂(8) motif. The carboxyl and carboxylate groups of the adipate ions are linked through O—H

O hydrogen bonds in a head-to-tail fashion, forming a chain. Anions and cations are further connected by an extensive network of N—H

O hydrogen bonds.

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807044364/bt2499sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807044364/bt2499Isup2.hkl Contains datablock I

CCDC reference: 237224

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.004 Å
R factor = 0.054
wR factor = 0.155
Data-to-parameter ratio = 16.1

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low .......       0.89

Author Response: The crystals may be of poor quality.



Alert level B
REFLT03_ALERT_3_B  Reflection count < 90% complete (theta max?)
           From the CIF: _diffrn_reflns_theta_max           27.11
           From the CIF: _diffrn_reflns_theta_full          27.11
           From the CIF: _reflns_number_total               3988
           TEST2: Reflns within _diffrn_reflns_theta_max
           Count of symmetry unique reflns         4499
           Completeness (_total/calc)             88.64%
PLAT022_ALERT_3_B Ratio Unique / Expected Reflections too Low ....       0.89
PLAT031_ALERT_4_B Refined Extinction Parameter within Range ......       2.00 Sigma

Alert level C
CELLV02_ALERT_1_C  The supplied cell volume s.u. differs from that
            calculated from the cell parameter s.u.'s by > 2
            Calculated cell volume su =       0.32
            Cell volume su given      =       3.00
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.58
PLAT150_ALERT_1_C Volume as Calculated Differs from that Given ...    1016.00 Ang-3
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)       2000 Deg.
PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 =          3
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.69 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.14 Ratio
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C16
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C12
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C15
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C20
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.15
PLAT734_ALERT_1_C Contact Calc    2.581(2), Rep    2.581(5) ......       2.50 su-Ra
              O2   -O4      1.555   1.455
PLAT734_ALERT_1_C Contact Calc    2.698(2), Rep    2.698(5) ......       2.50 su-Ra
              O2   -N1      1.555   1.555
PLAT734_ALERT_1_C Contact Calc    2.581(2), Rep    2.581(5) ......       2.50 su-Ra
              O4   -O2      1.555   1.655
PLAT734_ALERT_1_C Contact Calc    2.698(2), Rep    2.698(5) ......       2.50 su-Ra
              N1   -O2      1.555   1.555
PLAT737_ALERT_1_C D...A   Calc    2.698(2), Rep    2.698(5) ......       2.50 su-Ra
              N1   -O2      1.555   1.555
PLAT737_ALERT_1_C D...A   Calc    2.581(2), Rep    2.581(5) ......       2.50 su-Ra
              O4   -O2      1.555   1.655
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              C6 H9 O4

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT804_ALERT_5_G ARU-Pack Problem in PLATON Analysis ............          1 Times

   1 ALERT level A = In general: serious problem
   3 ALERT level B = Potentially serious problem
  20 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

  12 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   7 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

Comment top

Pyrimethamine [PMN] is an antimalarial drug widely employed in the chemotherapy of malaria. The drug selectively binds to the bacterial Dihydrofolate reductase enzyme (DHFR) with greater affinity than to the human enzyme inhibiting the synthesis of proteins and nucleic acids (Hitchings & Burchall, 1965). PMN [2,4-diamino-5- (p-chlorophenyl)-6-ethyl-pyrimidine] also used in combination with other drugs for treatment of protozoan disease like toxoplasmosis, bacterial infections and some types of cancer (Zuccotto et al., 1998; Kraut & Matthews, 1987). Adipic acid is used as acidulant in baking powders, in beverages and as a gelatinizing agent. Supramolecular aggregates of adipic acid with amino acids like L– and DL-Lysine(Sharma et al., 2006) and L-and DL-arginine (Roy et al., 2005) have been reported in literature. Adipic acid also forms complexes with metals like Cu, Cd, Ni (Bakalbassis et al., 2001) and co-crystal with caffeine (Bucar et al., 2007). Pyrimidine and aminopyrimidines are biologically important compounds and occur in nature as components of nucleic acid. The diaminopyrimidines PMN and TMP (trimethoprim) are components of many drugs. The carboxyl group and carboxylate anion involve in hydrogen bonding interactions with aminopyrimidines (Vallee & Auld, 1993). These interactions play a vital role in protein-nucleic acid and drug-protein recognition processes (Kuyper, 1990). Crystal structures of pyrimethamine (Sethuraman & Thomas Muthiah, 2002), PMN salts (Sethuraman et al., 2003), PMN hydrogen glutarate and PMN formate (Stanley et al., 2002), PMN 3-chloro benzoate, PMN sulfosalicylate monohydrate (Hemamalini et al., 2005) have been reported in our laboratory. The present study has been undertaken to study the hydrogen bonding patterns involving hydrogen adipate anion with the pyrimethamine cation. An ORTEP (II) view of the compound (I) is shown in Fig (1). The asymmetric unit contains one PMN cation and a hydrogen adipate anion. PMN is protonated at N1 as it is evident from the enhancement of internal angle at N1 from 116.3 (2)° in neutral PMN molecule A and 116.09 (18)° in molecule B (Sethuraman & Thomas Muthiah, 2002) to 121.32 (18)°. The conformation of PMN is described two angles namely dihedral and torsion angles. The dihedral angle between 2, 4 diamino pyrimidine and p-chlorophenyl rings is found to be 79.47 (10)°. The torsion angle C5—C6—C7—C8, which represents the deviation of the ethyl group from the pyrimidine ring is found to be 99.3 (3)°. The values are close to the modeling studies of DHFR-PMN complexes (Sansom et al., 1989). The C5—C9 bond length connecting the pyrimidine and phenyl ring was found to be 1.504 (4) Å. This is in agreement with the reported value (De et al., 1989). Adipic acid tends to deviate from the standard trans (Vanier & Brisse, 1983) conformation. This may be dueto increasing chain length of the lower aliphatic dicarboxylic acids and the flexibility of the bonds to adopt twisted conformations. The actual values of the torsion angles are -174.9 (2)°, -170.8 (2)° and -69.4 (3)° for C15—C16—C17—C18, C16—C17—C18—C19 and C17—C18—C19—C20 respectively. The angles indicate that the hydrogen adipate anion exhibits trans-trans-gauche conformation (Zheng et al., 2000; Zheng et al., 2001), which has been confirmed from CSD search of 46 adipic acid fragments (Allen & Kennard, 1993). The various hydrogen-bonding interactions are shown in Table 1. The protonated N1 cation interacts with the carboxyl ate group of the adipate ion via N—H···O hydrogen bonds forming cyclic hydrogen bonded ring motif represented by graph-set notation R²₂(8) (Etter, 1990; Bernstein et al., 1995; Lynch & Jones, 2004). The ring motif further self assembles to form a complementary DDAA (D represents hydrogen bond donor and A represents hydrogen bond acceptor) array of quadruple hydrogen bonds. The graph set notation of three fused rings is designated as R²₂(8), R²₄(8), R²₂(8) shown in Fig(2). Similar type of interactions has also been observed in crystal structures of TMP hydrogen adipate (Muthiah et al., 2006), PMN m-chlorobenzoate (Devi et al., 2006), TMP hydrogen glutarate (Robert et al., 2001), and PMN hydrogen glutarate (Stanley et al., 2002). The carboxyl and carboxylate ends of hydrogen adipate anion adopts a folded syn conformation so as to tie the 2-amino and 4-amino groups of the paired PMN cation on either sides to form a large 15 membered ring[R²₂(15)]. Similar interactions are seen in crystal structure of TMP hydrogen adipate (Muthiah et al., 2006). The hydrogen adipate ions are linked through O—H···O hydrogen bonds with the carboxylate group forming the head and carboxyl group forming the tail portions respectively. The infinite supramolecular chain [graph set: C(9)] is shown in Fig (3). This type of head to tail arrangement of hydrogen bonding has been observed in PMN hydrogen glutarate (Stanley et al., 2002) and TMP hydrogen glutarate (Robert et al., 2001). In adipate ions, the carbonyl O3 atoms of the free carboxyl group interacts with 4-amino groups of the pyrimethamine cations through N—H···O hydrogen bonds forming a quadrilateral ring R²₄(8), shown in Fig(2). This ring formation has also been observed in the crystal structures of cytosine (Barker & Marsh, 1964), 1-methyl cytosine and 5-fluoro-uracil complex (Voet & Rich, 1970) and cytosine and 5-fluoro-uracil complex (Voet & Rich, 1969).

Related literature top

For related literature, see: Allen & Kennard (1993); Bakalbassis et al. (2001); Barker & Marsh (1964); Bernstein et al. (1995); Bucar et al. (2007); De et al. (1989); Devi et al. (2006); Etter (1990); Hemamalini et al. (2005); Kuyper (1990); Lynch & Jones (2004); Robert et al. (2001); Roy et al. (2005); Sansom et al. (1989); Sethuraman & Thomas Muthiah (2002); Sethuraman et al. (2003); Sharma et al. (2006); Stanley et al. (2002); Vallee & Auld (1993); Voet & Rich (1969, 1970); Zheng et al. (2000, 2001); Hitchings & Burchall (1965); Kraut & Matthews (1987); Muthiah et al. (2006); Vanier & Brisse (1983); Zuccotto et al. (1998).

Experimental top

Pyrimethamine (62 mg, Shah Pharma Chem, India), adipic acid (36 mg, Merck) were mixed in 1:1 molar ratio in hot methanolic solution. The mixtures were allowed to cool at room temperature. Colourless needle shaped crystals were obtained after a few days.

Structure description top

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SMART (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003) and ORTEPII (Johnson, 1976); software used to prepare material for publication: PLATON (Spek, 2003).

Figures top

	Fig. 1. An ORTEPII (Johnson, 1976) diagram of the asymmetric unit of (I), showing 50% probability displacement ellipsoids.
	Fig. 2. Hydrogen bonding pattern of complementary DDAA array and quadrilateral ring. [Symmetry codes: (i) -x + 3, -y, -z + 1; (iii) x - 2, y + 1, z].
	Fig. 3. Head-to-tail arrangement of supramolecular chain of adipate ions. [Symmetry code: (ii) x + 1, y, z].

2,4-diamino-5-(p-chlorophenyl)-6-ethylpyrimidinium hydrogen adipate top

Crystal data top

C₁₂H₁₄ClN₄⁺·C₆H₉O₄⁻	Z = 2
M_r = 394.85	F(000) = 416
Triclinic, P1	D_x = 1.291 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.154 (1) Å	Cell parameters from 25 reflections
b = 11.420 (2) Å	θ = 1.8–27.1°
c = 12.238 (2) Å	µ = 0.22 mm⁻¹
α = 79.38 (2)°	T = 293 K
β = 71.06 (2)°	Needle, colourless
γ = 71.20 (2)°	0.3 × 0.12 × 0.1 mm
V = 1016 (3) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	3265 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.017
Graphite monochromator	θ_max = 27.1°, θ_min = 1.8°
ω–scans	h = −10→10
9586 measured reflections	k = −14→14
3988 independent reflections	l = −14→15

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.054	H-atom parameters constrained
wR(F²) = 0.155	w = 1/[σ²(F_o²) + (0.0761P)² + 0.4803P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
3988 reflections	Δρ_max = 0.75 e Å⁻³
247 parameters	Δρ_min = −0.29 e Å⁻³
0 restraints	Extinction correction: SHELXL97
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.004 (2)

Crystal data top

C₁₂H₁₄ClN₄⁺·C₆H₉O₄⁻	γ = 71.20 (2)°
M_r = 394.85	V = 1016 (3) Å³
Triclinic, P1	Z = 2
a = 8.154 (1) Å	Mo Kα radiation
b = 11.420 (2) Å	µ = 0.22 mm⁻¹
c = 12.238 (2) Å	T = 293 K
α = 79.38 (2)°	0.3 × 0.12 × 0.1 mm
β = 71.06 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3265 reflections with I > 2σ(I)
9586 measured reflections	R_int = 0.017
3988 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.155	H-atom parameters constrained
S = 1.03	Δρ_max = 0.75 e Å⁻³
3988 reflections	Δρ_min = −0.29 e Å⁻³
247 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'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 (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.34022 (11)	0.32332 (8)	0.00817 (7)	0.0860 (3)
N1	1.1280 (2)	0.03254 (15)	0.34090 (15)	0.0420 (5)
N2	1.2397 (2)	0.07015 (18)	0.47705 (15)	0.0495 (6)
N3	0.9774 (2)	0.21031 (16)	0.44490 (14)	0.0436 (5)
N4	0.7145 (2)	0.34147 (17)	0.41299 (16)	0.0538 (6)
C2	1.1124 (3)	0.10668 (18)	0.42111 (16)	0.0391 (6)
C4	0.8543 (3)	0.24149 (18)	0.38477 (17)	0.0396 (6)
C5	0.8706 (3)	0.17170 (17)	0.29244 (17)	0.0389 (6)
C6	1.0088 (3)	0.06442 (18)	0.27514 (17)	0.0415 (6)
C7	1.0468 (3)	−0.0232 (2)	0.1858 (2)	0.0616 (9)
C8	1.1962 (5)	−0.0045 (4)	0.0776 (3)	0.1047 (16)
C9	0.7367 (3)	0.21222 (17)	0.22296 (17)	0.0396 (6)
C10	0.7511 (3)	0.3024 (2)	0.1302 (2)	0.0596 (8)
C11	0.6303 (4)	0.3365 (3)	0.0632 (2)	0.0671 (9)
C12	0.4946 (3)	0.2799 (2)	0.09055 (19)	0.0521 (7)
C13	0.4764 (3)	0.1909 (2)	0.1818 (2)	0.0597 (8)
C14	0.5978 (3)	0.1571 (2)	0.2481 (2)	0.0562 (8)
O1	1.5619 (2)	−0.13053 (15)	0.39195 (16)	0.0613 (6)
O2	1.3938 (2)	−0.18294 (14)	0.30789 (16)	0.0594 (6)
O3	2.3656 (3)	−0.48130 (16)	0.38775 (17)	0.0706 (7)
O4	2.2650 (2)	−0.33732 (15)	0.25569 (15)	0.0590 (6)
C15	1.5422 (3)	−0.1989 (2)	0.3318 (2)	0.0494 (7)
C16	1.7001 (3)	−0.3033 (3)	0.2752 (3)	0.0774 (10)
C17	1.8551 (3)	−0.3532 (2)	0.3244 (2)	0.0609 (8)
C18	2.0095 (3)	−0.4499 (2)	0.2505 (3)	0.0633 (9)
C19	2.1553 (4)	−0.5163 (2)	0.3095 (3)	0.0675 (9)
C20	2.2707 (3)	−0.4429 (2)	0.3223 (2)	0.0494 (7)
H1	1.21400	−0.03560	0.33110	0.0500*
H2A	1.23490	0.11370	0.52890	0.0590*
H2B	1.32630	0.00310	0.46110	0.0590*
H4A	0.70540	0.38320	0.46750	0.0650*
H4B	0.63330	0.36430	0.37670	0.0650*
H7A	0.93730	−0.01070	0.16440	0.0740*
H7B	1.08080	−0.10810	0.21960	0.0740*
H8A	1.16410	0.07980	0.04440	0.1570*
H8B	1.21240	−0.05990	0.02230	0.1570*
H8C	1.30670	−0.02140	0.09750	0.1570*
H10	0.84250	0.34080	0.11240	0.0710*
H11	0.64160	0.39670	0.00090	0.0810*
H13	0.38420	0.15340	0.19940	0.0720*
H14	0.58570	0.09670	0.31010	0.0670*
H4	2.32700	−0.30130	0.26990	0.0890*
H16A	1.65360	−0.37170	0.27590	0.0930*
H16B	1.74600	−0.27460	0.19450	0.0930*
H17A	1.81520	−0.39120	0.40240	0.0730*
H17B	1.89920	−0.28560	0.32940	0.0730*
H18A	1.96110	−0.51030	0.23500	0.0760*
H18B	2.06230	−0.40890	0.17670	0.0760*
H19A	2.09780	−0.54900	0.38640	0.0810*
H19B	2.23460	−0.58680	0.26670	0.0810*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0792 (5)	0.1157 (7)	0.0790 (5)	−0.0179 (4)	−0.0553 (4)	−0.0043 (4)
N1	0.0379 (9)	0.0389 (9)	0.0504 (10)	−0.0029 (7)	−0.0203 (7)	−0.0073 (7)
N2	0.0413 (9)	0.0595 (11)	0.0510 (10)	−0.0062 (8)	−0.0222 (8)	−0.0108 (8)
N3	0.0399 (9)	0.0492 (10)	0.0424 (9)	−0.0077 (7)	−0.0156 (7)	−0.0077 (7)
N4	0.0514 (10)	0.0517 (10)	0.0576 (11)	0.0059 (8)	−0.0268 (9)	−0.0198 (8)
C2	0.0358 (10)	0.0458 (11)	0.0361 (10)	−0.0134 (8)	−0.0111 (8)	0.0001 (8)
C4	0.0389 (10)	0.0405 (10)	0.0390 (10)	−0.0095 (8)	−0.0134 (8)	−0.0013 (8)
C5	0.0391 (10)	0.0387 (10)	0.0404 (10)	−0.0094 (8)	−0.0156 (8)	−0.0025 (8)
C6	0.0421 (10)	0.0399 (10)	0.0457 (11)	−0.0094 (8)	−0.0186 (9)	−0.0041 (8)
C7	0.0614 (14)	0.0495 (13)	0.0829 (17)	0.0056 (10)	−0.0428 (13)	−0.0257 (12)
C8	0.109 (3)	0.123 (3)	0.078 (2)	−0.014 (2)	−0.013 (2)	−0.058 (2)
C9	0.0392 (10)	0.0390 (10)	0.0410 (10)	−0.0055 (8)	−0.0160 (8)	−0.0063 (8)
C10	0.0587 (14)	0.0644 (15)	0.0657 (15)	−0.0290 (12)	−0.0318 (12)	0.0168 (12)
C11	0.0696 (16)	0.0763 (17)	0.0595 (15)	−0.0255 (14)	−0.0343 (13)	0.0221 (13)
C12	0.0475 (12)	0.0641 (14)	0.0466 (12)	−0.0047 (10)	−0.0231 (10)	−0.0117 (10)
C13	0.0497 (13)	0.0736 (16)	0.0654 (15)	−0.0265 (12)	−0.0242 (11)	0.0012 (12)
C14	0.0548 (13)	0.0641 (14)	0.0545 (13)	−0.0247 (11)	−0.0239 (11)	0.0128 (11)
O1	0.0521 (9)	0.0558 (9)	0.0875 (12)	−0.0026 (7)	−0.0383 (9)	−0.0230 (9)
O2	0.0432 (8)	0.0513 (9)	0.0935 (12)	−0.0013 (7)	−0.0377 (8)	−0.0186 (8)
O3	0.0766 (12)	0.0603 (10)	0.0788 (12)	0.0042 (9)	−0.0453 (10)	−0.0157 (9)
O4	0.0568 (10)	0.0590 (10)	0.0756 (11)	−0.0168 (8)	−0.0378 (9)	−0.0049 (8)
C15	0.0419 (11)	0.0457 (11)	0.0665 (14)	−0.0071 (9)	−0.0270 (10)	−0.0076 (10)
C16	0.0483 (14)	0.0833 (19)	0.111 (2)	0.0037 (13)	−0.0370 (15)	−0.0481 (17)
C17	0.0466 (13)	0.0659 (15)	0.0725 (16)	−0.0073 (11)	−0.0219 (12)	−0.0183 (12)
C18	0.0436 (12)	0.0645 (15)	0.0900 (19)	−0.0100 (11)	−0.0199 (12)	−0.0345 (14)
C19	0.0623 (15)	0.0556 (14)	0.0877 (19)	−0.0121 (12)	−0.0227 (14)	−0.0198 (13)
C20	0.0428 (11)	0.0449 (11)	0.0579 (13)	0.0024 (9)	−0.0163 (10)	−0.0213 (10)

Geometric parameters (Å, º) top

Cl1—C12	1.756 (4)	C11—C12	1.377 (5)
O1—C15	1.244 (3)	C12—C13	1.369 (4)
O2—C15	1.285 (4)	C13—C14	1.395 (4)
O3—C20	1.219 (4)	C7—H7A	0.9706
O4—C20	1.322 (3)	C7—H7B	0.9702
O4—H4	0.8201	C8—H8A	0.9606
N1—C6	1.377 (4)	C8—H8C	0.9599
N1—C2	1.361 (3)	C8—H8B	0.9600
N2—C2	1.341 (4)	C10—H10	0.9302
N3—C2	1.333 (3)	C11—H11	0.9298
N3—C4	1.352 (4)	C13—H13	0.9292
N4—C4	1.332 (3)	C14—H14	0.9293
N1—H1	0.8601	C15—C16	1.515 (5)
N2—H2A	0.8598	C16—C17	1.479 (5)
N2—H2B	0.8603	C17—C18	1.535 (4)
N4—H4A	0.8602	C18—C19	1.511 (5)
N4—H4B	0.8605	C19—C20	1.505 (5)
C4—C5	1.448 (4)	C16—H16A	0.9697
C5—C9	1.504 (4)	C16—H16B	0.9709
C5—C6	1.366 (4)	C17—H17A	0.9706
C6—C7	1.509 (4)	C17—H17B	0.9694
C7—C8	1.516 (5)	C18—H18A	0.9694
C9—C14	1.391 (4)	C18—H18B	0.9705
C9—C10	1.387 (4)	C19—H19A	0.9705
C10—C11	1.398 (5)	C19—H19B	0.9699

Cl1···C16ⁱ	3.642 (6)	C16···H4ⁱⁱⁱ	3.0566
Cl1···H16Bⁱ	2.9746	C20···H17B	2.9648
O1···N2	2.909 (5)	C20···H4Aⁱⁱ	2.8597
O1···N2ⁱⁱ	2.911 (5)	H1···O2	1.8377
O2···O4ⁱⁱⁱ	2.581 (5)	H1···H7B	2.3844
O2···C20ⁱⁱⁱ	3.386 (6)	H1···C15	2.7262
O2···N1	2.698 (5)	H1···H2B	2.2429
O3···N4ⁱⁱ	2.941 (5)	H2A···H17Bⁱⁱ	2.5878
O3···N4^iv	2.986 (5)	H2A···O1ⁱⁱ	2.2442
O4···O2^v	2.581 (5)	H2B···O2	2.8943
O4···C17	3.228 (6)	H2B···O1	2.0656
O1···H2Aⁱⁱ	2.2442	H2B···C15	2.8008
O1···H2B	2.0656	H2B···H1	2.2429
O1···H17B	2.6982	H4···H16A^v	2.5434
O1···H14^v	2.6486	H4···O2^v	1.7918
O2···H1	1.8377	H4···C15^v	2.7445
O2···H2B	2.8943	H4···C16^v	3.0566
O2···H7B	2.9078	H4···H7B^v	2.5930
O2···H4ⁱⁱⁱ	1.7918	H4A···O3ⁱⁱ	2.0919
O3···H17A^vi	2.9045	H4A···C20ⁱⁱ	2.8597
O3···H4B^iv	2.3038	H4B···C9	2.5491
O3···H16A^v	2.8515	H4B···O3^viii	2.3038
O3···H4Aⁱⁱ	2.0919	H4B···C10	2.9983
O4···H7B^v	2.6026	H7A···C14	2.8015
O4···H17B	2.7154	H7A···C9	2.6263
O4···H18B	2.5561	H7B···O4ⁱⁱⁱ	2.6026
N1···O2	2.698 (5)	H7B···O2	2.9078
N1···C2^vii	3.384 (6)	H7B···H1	2.3844
N2···O1	2.909 (5)	H7B···H4ⁱⁱⁱ	2.5930
N2···O1ⁱⁱ	2.911 (5)	H8B···C12ⁱ	3.0324
N4···O3^viii	2.986 (5)	H8C···N1	2.9421
N4···O3ⁱⁱ	2.941 (5)	H13···N1ⁱⁱⁱ	2.8102
N1···H8C	2.9421	H13···C2ⁱⁱⁱ	2.9805
N1···H13^v	2.8102	H14···O1ⁱⁱⁱ	2.6486
C2···C2^vii	3.446 (6)	H16A···O3ⁱⁱⁱ	2.8515
C2···N1^vii	3.384 (6)	H16A···H4ⁱⁱⁱ	2.5434
C7···C14	3.483 (6)	H16A···H18A	2.4417
C14···C7	3.483 (6)	H16B···H18B	2.5021
C16···Cl1ⁱ	3.642 (6)	H16B···Cl1ⁱ	2.9746
C17···O4	3.228 (6)	H17A···H19A	2.3993
C20···O2^v	3.386 (6)	H17A···O3^vi	2.9045
C2···H13^v	2.9805	H17B···O1	2.6982
C9···H7A	2.6263	H17B···O4	2.7154
C9···H4B	2.5491	H17B···C20	2.9648
C10···H4B	2.9983	H17B···H2Aⁱⁱ	2.5878
C12···H8Bⁱ	3.0324	H18A···H16A	2.4417
C12···H19B^viii	2.7608	H18B···O4	2.5561
C13···H19B^viii	2.7979	H18B···H16B	2.5021
C14···H7A	2.8015	H19A···H17A	2.3993
C15···H1	2.7262	H19B···C12^iv	2.7608
C15···H4ⁱⁱⁱ	2.7445	H19B···C13^iv	2.7979
C15···H2B	2.8008

C20—O4—H4	109.48	H8A—C8—H8C	109.42
C2—N1—C6	121.32 (18)	H8B—C8—H8C	109.49
C2—N3—C4	117.41 (18)	C7—C8—H8C	109.50
C2—N1—H1	119.34	C11—C10—H10	119.54
C6—N1—H1	119.34	C9—C10—H10	119.45
C2—N2—H2A	120.04	C10—C11—H11	120.32
C2—N2—H2B	120.03	C12—C11—H11	120.46
H2A—N2—H2B	119.93	C14—C13—H13	120.36
C4—N4—H4A	119.98	C12—C13—H13	120.36
H4A—N4—H4B	120.03	C9—C14—H14	119.43
C4—N4—H4B	120.00	C13—C14—H14	119.43
N2—C2—N3	120.72 (19)	O1—C15—C16	120.7 (2)
N1—C2—N2	116.74 (19)	O2—C15—C16	115.6 (2)
N1—C2—N3	122.5 (2)	O1—C15—O2	123.6 (2)
N3—C4—C5	122.70 (19)	C15—C16—C17	118.7 (3)
N3—C4—N4	117.24 (18)	C16—C17—C18	111.8 (2)
N4—C4—C5	120.1 (2)	C17—C18—C19	112.2 (3)
C4—C5—C9	121.56 (18)	C18—C19—C20	117.7 (2)
C4—C5—C6	116.7 (2)	O3—C20—C19	121.4 (2)
C6—C5—C9	121.72 (19)	O4—C20—C19	115.3 (2)
N1—C6—C7	115.77 (19)	O3—C20—O4	123.2 (2)
C5—C6—C7	125.1 (2)	C15—C16—H16A	107.65
N1—C6—C5	119.10 (19)	C15—C16—H16B	107.64
C6—C7—C8	112.5 (2)	C17—C16—H16A	107.68
C5—C9—C10	121.2 (2)	C17—C16—H16B	107.65
C5—C9—C14	120.59 (18)	H16A—C16—H16B	107.01
C10—C9—C14	118.2 (2)	C16—C17—H17A	109.25
C9—C10—C11	121.0 (2)	C16—C17—H17B	109.32
C10—C11—C12	119.2 (2)	C18—C17—H17A	109.22
Cl1—C12—C13	119.2 (2)	C18—C17—H17B	109.29
Cl1—C12—C11	119.66 (19)	H17A—C17—H17B	107.89
C11—C12—C13	121.2 (2)	C17—C18—H18A	109.18
C12—C13—C14	119.3 (2)	C17—C18—H18B	109.16
C9—C14—C13	121.1 (2)	C19—C18—H18A	109.20
C6—C7—H7B	109.14	C19—C18—H18B	109.11
C8—C7—H7A	109.07	H18A—C18—H18B	107.90
C8—C7—H7B	109.10	C18—C19—H19A	107.82
H7A—C7—H7B	107.83	C18—C19—H19B	107.88
C6—C7—H7A	109.10	C20—C19—H19A	107.88
C7—C8—H8A	109.47	C20—C19—H19B	107.92
C7—C8—H8B	109.50	H19A—C19—H19B	107.18
H8A—C8—H8B	109.44

C2—N1—C6—C5	−1.1 (3)	C5—C6—C7—C8	99.4 (3)
C2—N1—C6—C7	177.32 (19)	N1—C6—C7—C8	−78.9 (3)
C6—N1—C2—N2	−177.18 (19)	C5—C9—C10—C11	177.6 (2)
C6—N1—C2—N3	3.4 (3)	C5—C9—C14—C13	−177.8 (2)
C4—N3—C2—N1	−0.8 (3)	C14—C9—C10—C11	−0.4 (3)
C2—N3—C4—C5	−3.9 (3)	C10—C9—C14—C13	0.3 (3)
C4—N3—C2—N2	179.81 (19)	C9—C10—C11—C12	0.4 (4)
C2—N3—C4—N4	176.57 (19)	C10—C11—C12—C13	−0.1 (4)
N3—C4—C5—C6	6.0 (3)	C10—C11—C12—Cl1	179.2 (2)
N4—C4—C5—C9	2.6 (3)	C11—C12—C13—C14	0.0 (4)
N3—C4—C5—C9	−176.8 (2)	Cl1—C12—C13—C14	−179.37 (17)
N4—C4—C5—C6	−174.5 (2)	C12—C13—C14—C9	0.0 (3)
C9—C5—C6—N1	179.56 (19)	O2—C15—C16—C17	−161.3 (2)
C4—C5—C6—C7	178.5 (2)	O1—C15—C16—C17	22.4 (4)
C4—C5—C6—N1	−3.3 (3)	C15—C16—C17—C18	−174.9 (2)
C4—C5—C9—C14	−99.6 (2)	C16—C17—C18—C19	−170.8 (2)
C6—C5—C9—C10	−100.6 (3)	C17—C18—C19—C20	−69.4 (3)
C6—C5—C9—C14	77.5 (3)	C18—C19—C20—O4	−16.5 (4)
C4—C5—C9—C10	82.4 (3)	C18—C19—C20—O3	165.4 (3)
C9—C5—C6—C7	1.3 (3)

Symmetry codes: (i) −x+2, −y, −z; (ii) −x+3, −y, −z+1; (iii) x−1, y, z; (iv) x+2, y−1, z; (v) x+1, y, z; (vi) −x+4, −y−1, −z+1; (vii) −x+2, −y, −z+1; (viii) x−2, y+1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.86	1.84	2.698 (5)	178
N2—H2A···O1ⁱⁱ	0.86	2.24	2.911 (5)	134
N2—H2B···O1	0.86	2.07	2.909 (5)	166
O4—H4···O2^v	0.82	1.79	2.581 (5)	161
N4—H4A···O3ⁱⁱ	0.86	2.09	2.941 (5)	169
N4—H4B···O3^viii	0.86	2.30	2.986 (5)	136

Symmetry codes: (ii) −x+3, −y, −z+1; (v) x+1, y, z; (viii) x−2, y+1, z.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₄ClN₄⁺·C₆H₉O₄⁻
M_r	394.85
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	8.154 (1), 11.420 (2), 12.238 (2)
α, β, γ (°)	79.38 (2), 71.06 (2), 71.20 (2)
V (Å³)	1016 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.22
Crystal size (mm)	0.3 × 0.12 × 0.1

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	9586, 3988, 3265
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.641

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.155, 1.03
No. of reflections	3988
No. of parameters	247
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.75, −0.29

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003) and ORTEPII (Johnson, 1976), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.8600	1.8400	2.698 (5)	178.00
N2—H2A···O1ⁱ	0.8600	2.2400	2.911 (5)	134.00
N2—H2B···O1	0.8600	2.0700	2.909 (5)	166.00
O4—H4···O2ⁱⁱ	0.8200	1.7900	2.581 (5)	161.00
N4—H4A···O3ⁱ	0.8600	2.0900	2.941 (5)	169.00
N4—H4B···O3ⁱⁱⁱ	0.8600	2.3000	2.986 (5)	136.00

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

Subscribe to Acta Crystallographica Section E: Crystallographic Communications

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.

E-mail address*
Repeat e-mail address* (for error checking)

Format*	PDF (US $40)
	HTML (US $40)
	PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number (non-UK EC countries only)
Country*

Terms and conditions of use
Contact us

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page