Lamotriginium dihydrogen phosphate–4-(dimethyl­amino)­benzaldehyde (1/1)

Razzaq, S.N.; Khan, I.U.; Şahin, O.; Büyükgüngör, O.

doi:10.1107/S1600536810034884

organic compounds

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ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page o2558

doi:10.1107/S1600536810034884

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Lamotriginium dihydrogen phosphate–4-(dimethylamino)benzaldehyde (1/1)

Syed Naeem Razzaq,^a Islam Ullah Khan,^a ^* Onur Şahin ^b ^* and Orhan Büyükgüngör ^b

^aMaterials Chemistry Laboratry, Department of Chemistry, GC University, Lahore 54000, Pakistan, and ^bDepartment of Physics, Ondokuz Mayıs University, TR-55139 Samsun, Turkey
^*Correspondence e-mail: onurs@omu.edu.tr, iukhan.gcu@gmail.com

(Received 25 August 2010; accepted 30 August 2010; online 15 September 2010)

In the title compound, C₉H₈Cl₂N₅⁺·H₂PO₄⁻·C₉H₁₁NO [systematic name: 3,5-diamino-6-(2,3-dichlorophenyl)-1,2,4-triazin-2-ium dihydrogen phosphate–4-(dimethylamino)benzaldehyde (1/1)], intermolecular N—H⋯O and O—H⋯O hydrogen bonds produce R₂²(8) and R₃²(8) rings, generating a layer. Intermolecular N—H⋯N interactions also occur. The dihedral angle between the rings in the cation is 71.73 (12)°.

Related literature

For the graph-set analysis of hydrogen-bond patterns, see: Bernstein et al. (1995 ). For related structures, see: Sridhar & Ravikumar (2006 ). For bond-valence calculations, see: Brese & O'Keeffe (1991 ).

Experimental

Crystal data

C₉H₈Cl₂N₅⁺·H₂PO₄⁻·C₉H₁₁NO
M_r = 503.28
Triclinic, $[P \overline 1]$
a = 8.1586 (4) Å
b = 10.5206 (6) Å
c = 13.6359 (7) Å
α = 98.665 (3)°
β = 98.131 (4)°
γ = 99.746 (3)°
V = 1123.49 (10) Å³
Z = 2
Mo Kα radiation
μ = 0.40 mm⁻¹
T = 296 K
0.31 × 0.27 × 0.25 mm

Data collection

Bruker Kappa APEXII CCD area detector diffractometer
19715 measured reflections
4310 independent reflections
3219 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.068
wR(F²) = 0.240
S = 1.07
4310 reflections
315 parameters
8 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.82 e Å⁻³
Δρ_min = −0.54 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2ⁱ	0.82 (6)	1.82 (5)	2.627 (5)	171 (7)
O3—H3⋯O4ⁱⁱ	0.81 (2)	1.80 (2)	2.602 (4)	169 (7)
N4—H4A⋯O5ⁱⁱⁱ	0.87 (4)	2.08 (3)	2.888 (5)	155 (5)
N4—H4B⋯O4	0.86 (2)	1.86 (2)	2.719 (4)	177 (5)
N5—H5A⋯N3^iv	0.89 (5)	2.21 (5)	3.088 (5)	171 (6)
N5—H5B⋯O5^v	0.87 (2)	2.14 (5)	2.799 (5)	132 (5)
N2—H2⋯O2	0.87 (2)	1.81 (2)	2.663 (4)	170 (6)
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) -x+2, -y+2, -z+1; (iii) x+1, y, z; (iv) -x+1, -y+1, -z; (v) -x, -y+1, -z.

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2002 ); 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 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810034884/jh2198sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810034884/jh2198Isup2.hkl

checkCIF report

Comment top

The title compound is a salt of Lamotrigine (Sridhar et al., 2006) an anticonvulsant drug used in the treatment of epilepsy and bipolar disorder. Herein we report the synthesis and crystal structure of title compound (I).

The molecular structure and atom-labelling scheme are shown in Fig. 1. Selected bond distances and angles are given in Table 1. The P1—O2 and P1—O4 bond lengths [1.506 (3)Å and 1.496 (3) Å] indicate significant single-bond character, whereas the P1—O1 and P1—O3 bond lengths [1.567 (4)Å and 1.559 (3) Å] are indicative of significant double-bond character. The O—P—O angles lie in the range 107.15 (19)–114.31 (16)°. Linkages P1—O1 and P1—O3 constitute POH groups, as confirmed both by the location of H atoms in the difference Fourier maps and by bond-valence calculations (Brese & O'Keeffe, 1991).

The amino atom N5 in the molecule at (x, y, z) acts as a hydrogen-bond donor (Table 2) to atom N3^iv so forming a centrosymmetric R₂²(8) ring (Bernstein et al., 1995) centred at (1/2, 1/2, 0). Similarly, atom O3 in the molecule at (x, y, z) acts as a hydrogen-bond donor to atom O4ⁱⁱ so forming a centrosymmetric R₂²(8) ring centred at (1, 1, 1/2). The combination of N—H···O and O—H···O hydrogen bonds generates R₃²(8) and R₂²(8) rings parallel to the [111] direction (Fig. 2).

Related literature top

For the graph-set analysis of hydrogen-bond patterns, see: Bernstein et al. (1995). For related structures, see: Sridhar & Ravikumar (2006). For bond-valence calculations, see: Brese & O'Keeffe (1991).

Experimental top

15 ml (0.06M) Methanolic solution of Lamotrigine is mixed with 15 ml (0.06M) Methanolic solution of 4-dimethylaminobenzaldehyde in glass beaker on hot plate stirrer for 10 minutes. Then add 3–4 drops of (85%) phosphoric acid and again mix for 4–5 h on hot plate stirrer. Yellow prisms of (I) were obtained by slow evaporation from methanol.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. A view of one molecule of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. Hydrogen bonds are indicated by dashed lines.
	Fig. 2. Part of the crystal structure of (I), showing the formation of a hydrogen-bonded sheet built from R₂²(8) and R₃²(8) rings. For the sake of clarity, H atoms not involved in the motif shown have been omitted.

3,5-diamino-6-(2,3-dichlorophenyl)-1,2,4-triazin-2-ium dihydrogen phosphate–4-(dimethylamino)benzaldehyde (1/1) top

Crystal data top

C₉H₈Cl₂N₅⁺·H₂PO₄⁻·C₉H₁₁NO	Z = 2
M_r = 503.28	F(000) = 520
Triclinic, P1	D_x = 1.488 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.1586 (4) Å	Cell parameters from 8437 reflections
b = 10.5206 (6) Å	θ = 2.3–28.0°
c = 13.6359 (7) Å	µ = 0.40 mm⁻¹
α = 98.665 (3)°	T = 296 K
β = 98.131 (4)°	Prism, yellow
γ = 99.746 (3)°	0.31 × 0.27 × 0.25 mm
V = 1123.49 (10) Å³

Data collection top

Bruker Kappa APEXII CCD area detector diffractometer	3219 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.031
Graphite monochromator	θ_max = 26.0°, θ_min = 1.5°
phi and ω scans	h = −10→9
19715 measured reflections	k = −12→12
4310 independent reflections	l = −16→16

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)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.240	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.1269P)² + 2.426P] where P = (F_o² + 2F_c²)/3
4310 reflections	(Δ/σ)_max = 0.011
315 parameters	Δρ_max = 1.82 e Å⁻³
8 restraints	Δρ_min = −0.54 e Å⁻³

Crystal data top

C₉H₈Cl₂N₅⁺·H₂PO₄⁻·C₉H₁₁NO	γ = 99.746 (3)°
M_r = 503.28	V = 1123.49 (10) Å³
Triclinic, P1	Z = 2
a = 8.1586 (4) Å	Mo Kα radiation
b = 10.5206 (6) Å	µ = 0.40 mm⁻¹
c = 13.6359 (7) Å	T = 296 K
α = 98.665 (3)°	0.31 × 0.27 × 0.25 mm
β = 98.131 (4)°

Data collection top

Bruker Kappa APEXII CCD area detector diffractometer	3219 reflections with I > 2σ(I)
19715 measured reflections	R_int = 0.031
4310 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.068	8 restraints
wR(F²) = 0.240	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 1.82 e Å⁻³
4310 reflections	Δρ_min = −0.54 e Å⁻³
315 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
C1	0.1434 (6)	0.8025 (4)	0.0052 (3)	0.0389 (10)
C2	0.1627 (6)	0.8530 (4)	−0.0804 (3)	0.0431 (10)
C3	0.0246 (7)	0.8825 (5)	−0.1405 (4)	0.0511 (12)
C4	−0.1267 (7)	0.8634 (5)	−0.1102 (4)	0.0529 (13)
H4	−0.2188	0.8840	−0.1487	0.064*
C5	−0.1487 (7)	0.8146 (6)	−0.0248 (4)	0.0577 (13)
H5	−0.2550	0.8049	−0.0065	0.069*
C6	−0.0185 (6)	0.7787 (5)	0.0361 (5)	0.0570 (14)
H6	−0.0353	0.7419	0.0926	0.068*
C7	0.2925 (6)	0.7763 (4)	0.0699 (3)	0.0378 (9)
C8	0.3738 (5)	0.6668 (4)	0.0404 (3)	0.0372 (9)
C9	0.5728 (5)	0.7406 (4)	0.1818 (3)	0.0301 (8)
C10	0.2160 (5)	0.5795 (4)	0.2953 (3)	0.0366 (9)
C11	0.2531 (7)	0.4619 (5)	0.2513 (4)	0.0506 (12)
H11	0.1751	0.4067	0.1995	0.061*
C12	0.4023 (7)	0.4262 (5)	0.2830 (4)	0.0578 (14)
H12	0.4235	0.3466	0.2530	0.069*
C13	0.5258 (6)	0.5084 (5)	0.3607 (3)	0.0421 (10)
C14	0.4861 (5)	0.6265 (4)	0.4056 (3)	0.0388 (10)
H14	0.5626	0.6817	0.4581	0.047*
C15	0.3367 (5)	0.6605 (4)	0.3728 (3)	0.0380 (9)
H15	0.3142	0.7397	0.4027	0.046*
C16	0.0600 (6)	0.6187 (4)	0.2665 (3)	0.0416 (10)
H16	0.0468	0.6993	0.2997	0.050*
C17	0.8050 (7)	0.5653 (6)	0.4645 (5)	0.0649 (15)
H17A	0.7933	0.6538	0.4610	0.097*
H17B	0.9142	0.5534	0.4510	0.097*
H17C	0.7933	0.5480	0.5306	0.097*
C18	0.7119 (9)	0.3496 (7)	0.3527 (6)	0.080 (2)
H18A	0.6212	0.2815	0.3586	0.120*
H18B	0.8149	0.3387	0.3913	0.120*
H18C	0.7238	0.3447	0.2833	0.120*
N1	0.3508 (5)	0.8558 (3)	0.1537 (3)	0.0387 (8)
N2	0.4890 (4)	0.8348 (3)	0.2110 (2)	0.0348 (8)
H2	0.525 (7)	0.894 (4)	0.265 (3)	0.062 (17)*
N3	0.5143 (4)	0.6533 (3)	0.0951 (2)	0.0351 (8)
N4	0.7119 (5)	0.7329 (4)	0.2380 (3)	0.0386 (8)
H4A	0.752 (6)	0.662 (3)	0.225 (4)	0.046*
H4B	0.755 (6)	0.784 (4)	0.294 (2)	0.046*
N5	0.3095 (6)	0.5793 (4)	−0.0417 (3)	0.0549 (12)
H5A	0.358 (7)	0.514 (4)	−0.064 (4)	0.066*
H5B	0.207 (4)	0.574 (6)	−0.073 (4)	0.066*
N6	0.6754 (6)	0.4756 (4)	0.3905 (4)	0.0564 (11)
Cl1	0.36141 (18)	0.88738 (17)	−0.11201 (11)	0.0679 (5)
Cl2	0.0485 (3)	0.9446 (2)	−0.24770 (12)	0.0872 (6)
P1	0.73789 (13)	0.97774 (10)	0.46306 (8)	0.0335 (3)
O1	0.6763 (4)	0.9254 (4)	0.5559 (2)	0.0525 (9)
H1	0.600 (6)	0.955 (6)	0.578 (5)	0.07 (2)*
O2	0.5893 (4)	0.9922 (3)	0.3893 (2)	0.0387 (7)
O3	0.8488 (4)	1.1173 (3)	0.5014 (3)	0.0515 (9)
H3	0.949 (3)	1.122 (6)	0.521 (5)	0.07 (2)*
O4	0.8423 (3)	0.8862 (3)	0.4206 (2)	0.0380 (7)
O5	−0.0585 (4)	0.5567 (3)	0.2023 (3)	0.0540 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.042 (2)	0.035 (2)	0.036 (2)	0.0089 (17)	−0.0034 (18)	0.0011 (17)
C2	0.043 (3)	0.043 (2)	0.038 (2)	0.0045 (19)	0.0011 (19)	−0.0010 (19)
C3	0.061 (3)	0.044 (3)	0.042 (3)	0.007 (2)	−0.008 (2)	0.006 (2)
C4	0.055 (3)	0.046 (3)	0.052 (3)	0.013 (2)	−0.009 (2)	0.003 (2)
C5	0.043 (3)	0.066 (3)	0.065 (3)	0.016 (2)	0.005 (2)	0.012 (3)
C6	0.032 (2)	0.060 (3)	0.073 (4)	0.018 (2)	−0.003 (2)	−0.005 (3)
C7	0.042 (2)	0.036 (2)	0.032 (2)	0.0090 (18)	−0.0045 (17)	0.0000 (16)
C8	0.038 (2)	0.036 (2)	0.033 (2)	0.0109 (17)	−0.0067 (17)	−0.0009 (16)
C9	0.029 (2)	0.033 (2)	0.0252 (18)	0.0041 (15)	0.0014 (15)	0.0032 (15)
C10	0.036 (2)	0.036 (2)	0.035 (2)	0.0088 (17)	−0.0029 (17)	0.0038 (17)
C11	0.053 (3)	0.041 (2)	0.048 (3)	0.013 (2)	−0.013 (2)	−0.005 (2)
C12	0.061 (3)	0.044 (3)	0.064 (3)	0.025 (2)	−0.006 (3)	−0.006 (2)
C13	0.037 (2)	0.049 (3)	0.043 (2)	0.0137 (19)	0.0019 (18)	0.012 (2)
C14	0.031 (2)	0.040 (2)	0.041 (2)	0.0042 (17)	−0.0025 (17)	0.0046 (18)
C15	0.037 (2)	0.035 (2)	0.039 (2)	0.0071 (17)	0.0007 (17)	0.0016 (17)
C16	0.041 (2)	0.045 (2)	0.037 (2)	0.0151 (19)	−0.0046 (18)	0.0030 (19)
C17	0.041 (3)	0.080 (4)	0.076 (4)	0.020 (3)	−0.007 (3)	0.029 (3)
C18	0.075 (5)	0.080 (4)	0.094 (5)	0.051 (4)	0.005 (4)	0.015 (4)
N1	0.040 (2)	0.0405 (19)	0.0329 (18)	0.0127 (15)	−0.0031 (15)	0.0026 (15)
N2	0.0364 (19)	0.0372 (19)	0.0262 (17)	0.0101 (15)	−0.0037 (14)	−0.0035 (14)
N3	0.0362 (19)	0.0362 (18)	0.0286 (17)	0.0111 (14)	−0.0045 (14)	−0.0028 (14)
N4	0.036 (2)	0.045 (2)	0.0290 (17)	0.0139 (16)	−0.0065 (14)	−0.0063 (15)
N5	0.056 (3)	0.049 (2)	0.046 (2)	0.023 (2)	−0.0238 (19)	−0.0178 (18)
N6	0.049 (3)	0.062 (3)	0.063 (3)	0.025 (2)	0.001 (2)	0.019 (2)
Cl1	0.0536 (8)	0.0924 (11)	0.0575 (8)	0.0018 (7)	0.0109 (6)	0.0257 (7)
Cl2	0.0991 (13)	0.1090 (14)	0.0548 (9)	0.0153 (10)	−0.0059 (8)	0.0430 (9)
P1	0.0261 (5)	0.0405 (6)	0.0291 (5)	0.0093 (4)	−0.0027 (4)	−0.0049 (4)
O1	0.042 (2)	0.083 (3)	0.0402 (18)	0.0265 (18)	0.0094 (15)	0.0162 (17)
O2	0.0304 (15)	0.0498 (17)	0.0313 (15)	0.0123 (12)	−0.0043 (11)	−0.0031 (12)
O3	0.0325 (18)	0.0419 (18)	0.068 (2)	0.0122 (14)	−0.0107 (15)	−0.0153 (15)
O4	0.0284 (15)	0.0406 (16)	0.0378 (15)	0.0082 (12)	−0.0023 (11)	−0.0094 (12)
O5	0.046 (2)	0.060 (2)	0.0463 (19)	0.0173 (16)	−0.0176 (15)	−0.0037 (16)

Geometric parameters (Å, º) top

C1—C2	1.371 (6)	C13—C14	1.409 (6)
C1—C6	1.436 (7)	C14—C15	1.362 (6)
C1—C7	1.489 (6)	C14—H14	0.9300
C2—C3	1.404 (7)	C15—H15	0.9300
C2—Cl1	1.730 (5)	C16—O5	1.225 (5)
C3—C4	1.349 (8)	C16—H16	0.9300
C3—Cl2	1.711 (5)	C17—N6	1.449 (7)
C4—C5	1.363 (8)	C17—H17A	0.9600
C4—H4	0.9300	C17—H17B	0.9600
C5—C6	1.393 (7)	C17—H17C	0.9600
C5—H5	0.9300	C18—N6	1.443 (7)
C6—H6	0.9300	C18—H18A	0.9600
C7—N1	1.286 (5)	C18—H18B	0.9600
C7—C8	1.458 (6)	C18—H18C	0.9600
C8—N5	1.317 (5)	N1—N2	1.347 (5)
C8—N3	1.318 (5)	N2—H2	0.87 (2)
C9—N4	1.298 (5)	N4—H4A	0.87 (4)
C9—N2	1.341 (5)	N4—H4B	0.857 (19)
C9—N3	1.353 (5)	N5—H5A	0.89 (5)
C10—C11	1.392 (6)	N5—H5B	0.87 (2)
C10—C15	1.401 (6)	P1—O4	1.496 (3)
C10—C16	1.424 (6)	P1—O2	1.506 (3)
C11—C12	1.366 (7)	P1—O3	1.559 (3)
C11—H11	0.9300	P1—O1	1.567 (4)
C12—C13	1.419 (7)	O1—H1	0.82 (6)
C12—H12	0.9300	O3—H3	0.81 (2)
C13—N6	1.348 (6)

C2—C1—C6	120.9 (4)	C13—C14—H14	119.7
C2—C1—C7	120.1 (4)	C14—C15—C10	121.9 (4)
C6—C1—C7	118.9 (4)	C14—C15—H15	119.1
C1—C2—C3	120.9 (4)	C10—C15—H15	119.1
C1—C2—Cl1	119.6 (4)	O5—C16—C10	126.5 (4)
C3—C2—Cl1	119.4 (4)	O5—C16—H16	116.8
C4—C3—C2	118.2 (5)	C10—C16—H16	116.8
C4—C3—Cl2	120.9 (4)	N6—C17—H17A	109.5
C2—C3—Cl2	120.9 (4)	N6—C17—H17B	109.5
C3—C4—C5	121.9 (5)	H17A—C17—H17B	109.5
C3—C4—H4	119.0	N6—C17—H17C	109.5
C5—C4—H4	119.0	H17A—C17—H17C	109.5
C4—C5—C6	122.8 (5)	H17B—C17—H17C	109.5
C4—C5—H5	118.6	N6—C18—H18A	109.5
C6—C5—H5	118.6	N6—C18—H18B	109.5
C5—C6—C1	115.1 (5)	H18A—C18—H18B	109.5
C5—C6—H6	122.4	N6—C18—H18C	109.5
C1—C6—H6	122.4	H18A—C18—H18C	109.5
N1—C7—C8	120.0 (4)	H18B—C18—H18C	109.5
N1—C7—C1	117.6 (4)	C7—N1—N2	117.8 (3)
C8—C7—C1	122.3 (3)	C9—N2—N1	123.0 (3)
N5—C8—N3	118.3 (4)	C9—N2—H2	123 (4)
N5—C8—C7	121.0 (4)	N1—N2—H2	113 (4)
N3—C8—C7	120.7 (4)	C8—N3—C9	117.1 (3)
N4—C9—N2	119.3 (3)	C9—N4—H4A	118 (3)
N4—C9—N3	119.7 (4)	C9—N4—H4B	124 (4)
N2—C9—N3	121.1 (3)	H4A—N4—H4B	117 (5)
C11—C10—C15	118.0 (4)	C8—N5—H5A	124 (4)
C11—C10—C16	122.8 (4)	C8—N5—H5B	121 (4)
C15—C10—C16	119.2 (4)	H5A—N5—H5B	114 (6)
C12—C11—C10	121.0 (4)	C13—N6—C18	121.9 (5)
C12—C11—H11	119.5	C13—N6—C17	120.8 (4)
C10—C11—H11	119.5	C18—N6—C17	117.2 (5)
C11—C12—C13	121.3 (4)	O4—P1—O2	114.31 (16)
C11—C12—H12	119.4	O4—P1—O3	109.93 (18)
C13—C12—H12	119.4	O2—P1—O3	107.15 (19)
N6—C13—C14	121.1 (4)	O4—P1—O1	107.16 (19)
N6—C13—C12	121.6 (4)	O2—P1—O1	110.19 (18)
C14—C13—C12	117.3 (4)	O3—P1—O1	107.9 (2)
C15—C14—C13	120.6 (4)	P1—O1—H1	118 (5)
C15—C14—H14	119.7	P1—O3—H3	118 (5)

C6—C1—C2—C3	−0.1 (7)	C10—C11—C12—C13	−0.9 (9)
C7—C1—C2—C3	−177.8 (4)	C11—C12—C13—N6	−178.1 (5)
C6—C1—C2—Cl1	177.0 (4)	C11—C12—C13—C14	1.6 (8)
C7—C1—C2—Cl1	−0.6 (6)	N6—C13—C14—C15	177.9 (4)
C1—C2—C3—C4	1.8 (7)	C12—C13—C14—C15	−1.8 (7)
Cl1—C2—C3—C4	−175.4 (4)	C13—C14—C15—C10	1.2 (7)
C1—C2—C3—Cl2	−179.6 (3)	C11—C10—C15—C14	−0.4 (7)
Cl1—C2—C3—Cl2	3.2 (6)	C16—C10—C15—C14	178.1 (4)
C2—C3—C4—C5	−1.2 (7)	C11—C10—C16—O5	0.5 (8)
Cl2—C3—C4—C5	−179.7 (4)	C15—C10—C16—O5	−177.9 (5)
C3—C4—C5—C6	−1.3 (8)	C8—C7—N1—N2	0.9 (6)
C4—C5—C6—C1	2.9 (8)	C1—C7—N1—N2	−178.0 (4)
C2—C1—C6—C5	−2.1 (7)	N4—C9—N2—N1	174.9 (4)
C7—C1—C6—C5	175.6 (4)	N3—C9—N2—N1	−5.4 (6)
C2—C1—C7—N1	105.5 (5)	C7—N1—N2—C9	4.1 (6)
C6—C1—C7—N1	−72.2 (6)	N5—C8—N3—C9	−176.6 (4)
C2—C1—C7—C8	−73.4 (6)	C7—C8—N3—C9	3.7 (6)
C6—C1—C7—C8	108.9 (5)	N4—C9—N3—C8	−179.1 (4)
N1—C7—C8—N5	175.3 (5)	N2—C9—N3—C8	1.2 (6)
C1—C7—C8—N5	−5.8 (7)	C14—C13—N6—C18	173.7 (5)
N1—C7—C8—N3	−4.9 (7)	C12—C13—N6—C18	−6.7 (8)
C1—C7—C8—N3	173.9 (4)	C14—C13—N6—C17	−4.5 (7)
C15—C10—C11—C12	0.3 (8)	C12—C13—N6—C17	175.2 (5)
C16—C10—C11—C12	−178.2 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.82 (6)	1.82 (5)	2.627 (5)	171 (7)
O3—H3···O4ⁱⁱ	0.81 (2)	1.80 (2)	2.602 (4)	169 (7)
N4—H4A···O5ⁱⁱⁱ	0.87 (4)	2.08 (3)	2.888 (5)	155 (5)
N4—H4B···O4	0.86 (2)	1.86 (2)	2.719 (4)	177 (5)
N5—H5A···N3^iv	0.89 (5)	2.21 (5)	3.088 (5)	171 (6)
N5—H5B···O5^v	0.87 (2)	2.14 (5)	2.799 (5)	132 (5)
N2—H2···O2	0.87 (2)	1.81 (2)	2.663 (4)	170 (6)

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

Experimental details

Crystal data
Chemical formula	C₉H₈Cl₂N₅⁺·H₂PO₄⁻·C₉H₁₁NO
M_r	503.28
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	8.1586 (4), 10.5206 (6), 13.6359 (7)
α, β, γ (°)	98.665 (3), 98.131 (4), 99.746 (3)
V (Å³)	1123.49 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.40
Crystal size (mm)	0.31 × 0.27 × 0.25

Data collection
Diffractometer	Bruker Kappa APEXII CCD area detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	19715, 4310, 3219
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.068, 0.240, 1.07
No. of reflections	4310
No. of parameters	315
No. of restraints	8
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.82, −0.54

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top

C7—N1	1.286 (5)	P1—O2	1.506 (3)
C16—O5	1.225 (5)	P1—O3	1.559 (3)
P1—O4	1.496 (3)	P1—O1	1.567 (4)

O4—P1—O2	114.31 (16)	O4—P1—O1	107.16 (19)
O4—P1—O3	109.93 (18)	O2—P1—O1	110.19 (18)
O2—P1—O3	107.15 (19)	O3—P1—O1	107.9 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.82 (6)	1.82 (5)	2.627 (5)	171 (7)
O3—H3···O4ⁱⁱ	0.81 (2)	1.80 (2)	2.602 (4)	169 (7)
N4—H4A···O5ⁱⁱⁱ	0.87 (4)	2.08 (3)	2.888 (5)	155 (5)
N4—H4B···O4	0.857 (19)	1.86 (2)	2.719 (4)	177 (5)
N5—H5A···N3^iv	0.89 (5)	2.21 (5)	3.088 (5)	171 (6)
N5—H5B···O5^v	0.87 (2)	2.14 (5)	2.799 (5)	132 (5)
N2—H2···O2	0.87 (2)	1.81 (2)	2.663 (4)	170 (6)

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

Acknowledgements

IUK thanks the Higher Education Commission of Pakistan for its financial support under the project `Strengthening of the Materials Chemistry Laboratory' at GCUL.

References

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