4-Carbamoylpyridin-1-ium 2,2,2-trichloro­acetate

Perdih, F.

doi:10.1107/S1600536812035507

organic compounds

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ISSN: 2056-9890

Volume 68| Part 9| September 2012| Page o2733

doi:10.1107/S1600536812035507

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4-Carbamoylpyridin-1-ium 2,2,2-trichloroacetate

Franc Perdih ^a ^*

^aFaculty of Chemistry and Chemical Technology, University of Ljubljana, Aškerčeva 5, P. O. Box 537, SI-1000 Ljubljana, Slovenia, and CO EN–FIST, Dunajska 156, SI-1000 Ljubljana, Slovenia
^*Correspondence e-mail: franc.perdih@fkkt.uni-lj.si

(Received 9 August 2012; accepted 11 August 2012; online 23 August 2012)

In the asymmetric unit of the title salt, C₆H₇N₂O⁺·C₂Cl₃O₂⁻, there are two crystallographic independent ion pairs. The amide groups of the 4-carbamoylpyridin-1-ium ions are slightly twisted out of the plane of the aromatic ring with C—C—C—N torsion angles of 8.8 (9)° and 4.6 (8)°. In the crystal, the 4-carbamoylpyridin-1-ium ion is N—H⋯O hydrogen bonded to the trichloroacetate ion via the pyridinium unit and amide group. Layers parallel to the ac plane are formed due to the N—H⋯O hydrogen bonding of the adjacent amide groups of 4-carbamoylpyridin-1-ium ions. Weak C—H⋯O interactions also occur.

Related literature

For applications of co-crystals, see: Karki et al. (2009 ); Friščić & Jones (2010 ). For related structures, see: Das & Baruah (2011 ).

Experimental

Crystal data

C₆H₇N₂O⁺·C₂Cl₃O₂⁻
M_r = 285.51
Monoclinic, P c
a = 9.8768 (3) Å
b = 9.4403 (3) Å
c = 12.5157 (3) Å
β = 90.240 (2)°
V = 1166.95 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.78 mm⁻¹
T = 293 K
0.2 × 0.2 × 0.2 mm

Data collection

Agilent SuperNova, Dual, Cu at zero, Atlas diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.860, T_max = 0.860
11114 measured reflections
5195 independent reflections
4452 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.069
wR(F²) = 0.199
S = 1.04
5195 reflections
289 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.47 e Å⁻³
Absolute structure: Flack (1983 ), 2512 Friedel pairs
Flack parameter: 0.08 (12)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2ⁱ	0.86	1.78	2.643 (5)	176
N2—H2A⋯O1ⁱⁱ	0.86	2.03	2.883 (6)	170
N2—H2B⋯O6ⁱⁱⁱ	0.86	2.06	2.854 (7)	152
N3—H3A⋯O3^iv	0.86	1.8	2.661 (5)	178
N4—H4A⋯O4^v	0.86	2.01	2.858 (6)	169
N4—H4B⋯O5^v	0.86	2.03	2.858 (7)	160
C2—H2⋯O6ⁱⁱⁱ	0.93	2.34	3.251 (7)	166
C5—H5⋯O3	0.93	2.6	3.422 (8)	148
C8—H8⋯O5^v	0.93	2.36	3.270 (6)	166
Symmetry codes: (i) x+1, y, z; (ii) x+1, y, z-1; (iii) $[x+1, -y+1, z-{\script{1\over 2}}]$ ; (iv) $[x, -y+1, z-{\script{1\over 2}}]$ ; (v) $[x, -y+1, z+{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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 ) and DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999 ) and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablock global. DOI: 10.1107/S1600536812035507/bq2374sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812035507/bq2374Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812035507/bq2374Isup3.cml

checkCIF report

Comment top

Salts or co-crystals represent two possible ways to produce functional pharmaceutical materials. The salt or co-crystal formation is dependent on a pK_a difference between the acid and the base (Karki et al., 2009; Friščić & Jones, 2010). Here we present the structure obtained by contacting isonicotinamide and trichloroacetic acid in 1:1 molar ratio.

The asymmetric unit of (I) consists of two crystallographic independent 4-carbamoylpyridin-1-ium cations and two trichloroacetate anions (Fig. 1). The amide groups of 4-carbamoylpyridin-1-ium ions are only slightly twisted out of the plane of the aromatic ring with a C—C—C—N torsion angle of 8.8 (9)° and 4.6 (8)°, respectively. The 4-carbamoylpyridin-1-ium ion is N—H···O hydrogen bonded to the trichloroacetate ion via the pyridinium unit and amide group (Fig. 2). Two-dimensional framework is formed due to the N—H···O hydrogen bonding of the adjacent amide groups of 4-carbamoylpyridin-1-ium ions. This layer formation is further stabilized by weak C—H···O interactions. In the structure of (I) typical amide-amide hydrogen-bonded homodimer is not present as is for example in the 4-carbamoylpyridin-1-ium 3-carboxypicolinate (Das & Baruah, 2011).

Related literature top

For applications of co-crystals, see: Karki et al. (2009); Friščić & Jones (2010). For related structures, see: Das & Baruah (2011).

Experimental top

Crystals of the title compound were obtained by slow evaporation of a 1:1 mol. mixture of isonicotinamide and trichloroacetic acid in methanol at room temperature.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); 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) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999) and publCIF (Westrip, 2010).

Figures top

Fig. 1. The asymmetric unit of the title compound with displacement ellipsoids drawn at the 50% probability level.

Fig. 2. Layer formation. Dashed lines indicate intermolecular N—H···O and C—H···O hydrogen bonding. For the sake of clarity, H atoms not involved in the motif shown have been omitted. Symmetry codes: ⁱ x + 1, y, z; ⁱⁱ x + 1, y, z – 1; ⁱⁱⁱ x + 1, –y + 1, z – 1/2; ^v x, –y + 1, z + 1/2.

4-Carbamoylpyridin-1-ium 2,2,2-trichloroacetate top

Crystal data top

C₆H₇N₂O⁺·C₂Cl₃O₂⁻	F(000) = 576
M_r = 285.51	D_x = 1.625 Mg m⁻³
Monoclinic, Pc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P -2yc	Cell parameters from 4989 reflections
a = 9.8768 (3) Å	θ = 3.0–30.3°
b = 9.4403 (3) Å	µ = 0.78 mm⁻¹
c = 12.5157 (3) Å	T = 293 K
β = 90.240 (2)°	Cube, colourless
V = 1166.95 (6) Å³	0.2 × 0.2 × 0.2 mm
Z = 4

Data collection top

Agilent SuperNova, Dual, Cu at zero, Atlas diffractometer	5195 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	4452 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.026
Detector resolution: 10.4933 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
ω scans	h = −12→12
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −12→12
T_min = 0.860, T_max = 0.860	l = −16→16
11114 measured reflections

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)] = 0.069	H-atom parameters constrained
wR(F²) = 0.199	w = 1/[σ²(F_o²) + (0.104P)² + 1.1455P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
5195 reflections	Δρ_max = 0.53 e Å⁻³
289 parameters	Δρ_min = −0.47 e Å⁻³
2 restraints	Absolute structure: Flack (1983), 2512 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.08 (12)

Crystal data top

C₆H₇N₂O⁺·C₂Cl₃O₂⁻	V = 1166.95 (6) Å³
M_r = 285.51	Z = 4
Monoclinic, Pc	Mo Kα radiation
a = 9.8768 (3) Å	µ = 0.78 mm⁻¹
b = 9.4403 (3) Å	T = 293 K
c = 12.5157 (3) Å	0.2 × 0.2 × 0.2 mm
β = 90.240 (2)°

Data collection top

Agilent SuperNova, Dual, Cu at zero, Atlas diffractometer	5195 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	4452 reflections with I > 2σ(I)
T_min = 0.860, T_max = 0.860	R_int = 0.026
11114 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.069	H-atom parameters constrained
wR(F²) = 0.199	Δρ_max = 0.53 e Å⁻³
S = 1.04	Δρ_min = −0.47 e Å⁻³
5195 reflections	Absolute structure: Flack (1983), 2512 Friedel pairs
289 parameters	Absolute structure parameter: 0.08 (12)
2 restraints

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	0.10761 (17)	0.0588 (2)	0.78518 (16)	0.0826 (5)
Cl2	−0.0364 (2)	0.03005 (15)	0.98391 (14)	0.0768 (5)
Cl3	−0.18351 (17)	0.0792 (2)	0.78632 (16)	0.0819 (5)
Cl4	0.3217 (3)	0.0487 (2)	0.5048 (3)	0.1287 (12)
Cl5	0.4613 (3)	0.04358 (18)	0.70263 (17)	0.0950 (7)
Cl6	0.6112 (3)	0.0464 (2)	0.5097 (3)	0.1206 (10)
N1	0.9738 (5)	0.3469 (4)	0.5899 (3)	0.0465 (9)
H1A	0.9911	0.3487	0.6573	0.07*
N2	0.9725 (5)	0.3126 (5)	0.1897 (3)	0.0545 (11)
H2A	0.9523	0.3112	0.1228	0.082*
H2B	1.0545	0.2975	0.21	0.082*
N3	0.4737 (5)	0.6594 (5)	0.3579 (3)	0.0489 (10)
H3A	0.4908	0.6608	0.2906	0.073*
N4	0.4753 (5)	0.6746 (5)	0.7577 (3)	0.0519 (10)
H4A	0.4549	0.6785	0.8243	0.078*
H4B	0.5587	0.6786	0.7384	0.078*
O1	−0.0643 (6)	0.3280 (4)	0.9614 (3)	0.0789 (15)
O2	0.0158 (5)	0.3511 (5)	0.7986 (3)	0.0713 (13)
O3	0.5208 (6)	0.3362 (5)	0.6487 (3)	0.0713 (12)
O4	0.4394 (7)	0.3324 (4)	0.4841 (3)	0.0834 (16)
O5	0.7614 (5)	0.3595 (9)	0.2357 (4)	0.116 (3)
O6	0.2588 (5)	0.6567 (10)	0.7106 (4)	0.138 (3)
C1	1.0769 (5)	0.3404 (6)	0.5206 (4)	0.0512 (12)
H1	1.1657	0.3372	0.5456	0.061*
C2	1.0507 (5)	0.3384 (6)	0.4112 (4)	0.0451 (10)
H2	1.1213	0.3352	0.3623	0.054*
C3	0.9178 (5)	0.3415 (5)	0.3768 (4)	0.0410 (9)
C4	0.8152 (5)	0.3479 (5)	0.4506 (4)	0.0471 (10)
H4	0.7253	0.3503	0.4283	0.057*
C5	0.8467 (6)	0.3506 (6)	0.5575 (4)	0.0555 (13)
H5	0.7775	0.3551	0.6076	0.067*
C6	0.8784 (6)	0.3376 (6)	0.2605 (4)	0.0538 (13)
C7	0.5779 (6)	0.6614 (6)	0.4269 (4)	0.0519 (12)
H7	0.6667	0.6613	0.4026	0.062*
C8	0.5502 (5)	0.6637 (5)	0.5346 (4)	0.0470 (11)
H8	0.6208	0.6664	0.5839	0.056*
C9	0.4176 (5)	0.6621 (5)	0.5696 (4)	0.0418 (10)
C10	0.3170 (6)	0.6561 (6)	0.4940 (4)	0.0543 (12)
H10	0.2271	0.6525	0.5155	0.065*
C11	0.3464 (6)	0.6552 (6)	0.3887 (4)	0.0556 (13)
H11	0.2771	0.6518	0.3382	0.067*
C12	0.3792 (5)	0.6626 (7)	0.6854 (4)	0.0558 (13)
C13	−0.0250 (5)	0.2831 (5)	0.8761 (3)	0.0436 (10)
C14	−0.0344 (5)	0.1177 (5)	0.8593 (4)	0.0481 (10)
C15	0.4722 (5)	0.2781 (5)	0.5682 (3)	0.0419 (9)
C16	0.4658 (5)	0.1124 (5)	0.5706 (4)	0.0463 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0647 (9)	0.0950 (12)	0.0882 (12)	0.0167 (8)	0.0213 (8)	−0.0217 (10)
Cl2	0.1036 (12)	0.0537 (7)	0.0730 (10)	0.0026 (8)	0.0071 (9)	0.0188 (7)
Cl3	0.0599 (8)	0.1001 (12)	0.0856 (11)	−0.0164 (8)	−0.0161 (7)	−0.0240 (10)
Cl4	0.1135 (16)	0.0708 (11)	0.201 (3)	−0.0082 (11)	−0.0941 (19)	−0.0250 (14)
Cl5	0.1471 (19)	0.0620 (9)	0.0760 (11)	−0.0091 (10)	0.0003 (12)	0.0210 (8)
Cl6	0.1032 (15)	0.0709 (12)	0.188 (3)	0.0098 (11)	0.0773 (17)	−0.0256 (14)
N1	0.066 (3)	0.049 (2)	0.0250 (16)	−0.0007 (19)	0.0018 (17)	0.0029 (14)
N2	0.059 (2)	0.083 (3)	0.0216 (17)	0.008 (2)	−0.0014 (16)	−0.0018 (19)
N3	0.065 (3)	0.053 (2)	0.0280 (18)	0.004 (2)	−0.0005 (17)	0.0013 (16)
N4	0.057 (2)	0.069 (3)	0.0296 (19)	0.003 (2)	−0.0002 (17)	−0.0002 (18)
O1	0.146 (5)	0.059 (2)	0.0319 (18)	0.012 (3)	0.008 (2)	0.0011 (16)
O2	0.116 (4)	0.071 (3)	0.0270 (16)	−0.017 (2)	0.002 (2)	0.0035 (16)
O3	0.117 (4)	0.065 (2)	0.0324 (18)	−0.017 (2)	0.004 (2)	−0.0052 (16)
O4	0.158 (5)	0.052 (2)	0.040 (2)	0.007 (3)	−0.014 (3)	0.0037 (17)
O5	0.049 (2)	0.251 (8)	0.047 (2)	0.012 (4)	−0.0102 (19)	0.015 (4)
O6	0.051 (3)	0.312 (11)	0.051 (3)	−0.018 (4)	0.011 (2)	0.008 (4)
C1	0.047 (2)	0.067 (3)	0.039 (2)	0.005 (2)	−0.005 (2)	0.001 (2)
C2	0.040 (2)	0.065 (3)	0.030 (2)	0.003 (2)	0.0028 (17)	0.0013 (19)
C3	0.043 (2)	0.052 (3)	0.0288 (18)	−0.0013 (19)	0.0020 (16)	0.0073 (16)
C4	0.040 (2)	0.057 (3)	0.044 (2)	0.001 (2)	0.0088 (19)	0.003 (2)
C5	0.061 (3)	0.065 (3)	0.041 (3)	0.000 (2)	0.018 (2)	0.004 (2)
C6	0.051 (3)	0.082 (4)	0.029 (2)	−0.007 (3)	−0.0046 (19)	0.010 (2)
C7	0.053 (3)	0.063 (3)	0.040 (2)	−0.008 (2)	0.010 (2)	0.004 (2)
C8	0.049 (3)	0.063 (3)	0.029 (2)	−0.008 (2)	−0.0054 (19)	0.0021 (19)
C9	0.047 (2)	0.051 (3)	0.0277 (19)	−0.0028 (19)	−0.0021 (17)	0.0005 (17)
C10	0.049 (3)	0.071 (3)	0.043 (2)	0.002 (2)	−0.005 (2)	−0.001 (2)
C11	0.056 (3)	0.065 (3)	0.046 (3)	0.012 (3)	−0.010 (2)	−0.001 (2)
C12	0.044 (2)	0.093 (4)	0.030 (2)	−0.004 (3)	0.0067 (19)	0.003 (2)
C13	0.056 (2)	0.046 (2)	0.028 (2)	−0.001 (2)	−0.0072 (18)	0.0027 (17)
C14	0.047 (2)	0.051 (3)	0.046 (2)	−0.002 (2)	0.0039 (19)	−0.006 (2)
C15	0.058 (2)	0.044 (2)	0.0239 (18)	−0.004 (2)	0.0062 (17)	−0.0036 (17)
C16	0.044 (2)	0.048 (2)	0.047 (2)	0.001 (2)	0.0028 (19)	−0.005 (2)

Geometric parameters (Å, º) top

Cl1—C14	1.774 (5)	O5—C6	1.213 (7)
Cl2—C14	1.766 (5)	O6—C12	1.233 (7)
Cl3—C14	1.768 (5)	C1—C2	1.393 (6)
Cl4—C16	1.748 (5)	C1—H1	0.93
Cl5—C16	1.777 (6)	C2—C3	1.380 (7)
Cl6—C16	1.743 (5)	C2—H2	0.93
N1—C5	1.318 (7)	C3—C4	1.375 (6)
N1—C1	1.342 (7)	C3—C6	1.505 (6)
N1—H1A	0.86	C4—C5	1.372 (8)
N2—C6	1.308 (7)	C4—H4	0.93
N2—H2A	0.86	C5—H5	0.93
N2—H2B	0.86	C7—C8	1.377 (7)
N3—C11	1.317 (7)	C7—H7	0.93
N3—C7	1.340 (7)	C8—C9	1.382 (7)
N3—H3A	0.86	C8—H8	0.93
N4—C12	1.314 (7)	C9—C10	1.371 (7)
N4—H4A	0.86	C9—C12	1.499 (6)
N4—H4B	0.86	C10—C11	1.350 (8)
O1—C13	1.213 (6)	C10—H10	0.93
O2—C13	1.233 (6)	C11—H11	0.93
O3—C15	1.242 (6)	C13—C14	1.578 (7)
O4—C15	1.215 (6)	C15—C16	1.566 (7)

C5—N1—C1	121.8 (4)	C7—C8—C9	120.2 (4)
C5—N1—H1A	119.1	C7—C8—H8	119.9
C1—N1—H1A	119.1	C9—C8—H8	119.9
C6—N2—H2A	120	C10—C9—C8	117.8 (4)
C6—N2—H2B	120	C10—C9—C12	118.8 (4)
H2A—N2—H2B	120	C8—C9—C12	123.4 (4)
C11—N3—C7	122.9 (4)	C11—C10—C9	121.1 (5)
C11—N3—H3A	118.6	C11—C10—H10	119.5
C7—N3—H3A	118.6	C9—C10—H10	119.5
C12—N4—H4A	120	N3—C11—C10	119.6 (5)
C12—N4—H4B	120	N3—C11—H11	120.2
H4A—N4—H4B	120	C10—C11—H11	120.2
N1—C1—C2	119.8 (5)	O6—C12—N4	121.5 (5)
N1—C1—H1	120.1	O6—C12—C9	119.7 (5)
C2—C1—H1	120.1	N4—C12—C9	118.8 (4)
C3—C2—C1	118.6 (4)	O1—C13—O2	128.1 (5)
C3—C2—H2	120.7	O1—C13—C14	116.4 (4)
C1—C2—H2	120.7	O2—C13—C14	115.4 (4)
C4—C3—C2	119.6 (4)	C13—C14—Cl2	110.3 (3)
C4—C3—C6	117.6 (4)	C13—C14—Cl3	108.7 (3)
C2—C3—C6	122.8 (4)	Cl2—C14—Cl3	110.3 (3)
C5—C4—C3	119.5 (5)	C13—C14—Cl1	109.5 (3)
C5—C4—H4	120.3	Cl2—C14—Cl1	109.1 (3)
C3—C4—H4	120.3	Cl3—C14—Cl1	108.9 (3)
N1—C5—C4	120.7 (5)	O4—C15—O3	128.1 (5)
N1—C5—H5	119.6	O4—C15—C16	115.3 (4)
C4—C5—H5	119.6	O3—C15—C16	116.2 (4)
O5—C6—N2	122.4 (5)	C15—C16—Cl6	108.4 (3)
O5—C6—C3	119.0 (5)	C15—C16—Cl4	111.6 (4)
N2—C6—C3	118.6 (5)	Cl6—C16—Cl4	110.0 (3)
N3—C7—C8	118.4 (5)	C15—C16—Cl5	112.6 (3)
N3—C7—H7	120.8	Cl6—C16—Cl5	107.4 (3)
C8—C7—H7	120.8	Cl4—C16—Cl5	106.8 (3)

C5—N1—C1—C2	0.5 (8)	C7—N3—C11—C10	1.5 (8)
N1—C1—C2—C3	−0.8 (8)	C9—C10—C11—N3	0.4 (9)
C1—C2—C3—C4	0.7 (8)	C10—C9—C12—O6	0.5 (10)
C1—C2—C3—C6	−179.1 (5)	C8—C9—C12—O6	−177.8 (7)
C2—C3—C4—C5	−0.3 (8)	C10—C9—C12—N4	−177.1 (6)
C6—C3—C4—C5	179.6 (5)	C8—C9—C12—N4	4.6 (8)
C1—N1—C5—C4	0.0 (8)	O1—C13—C14—Cl2	−23.3 (6)
C3—C4—C5—N1	−0.1 (8)	O2—C13—C14—Cl2	159.9 (4)
C4—C3—C6—O5	9.9 (9)	O1—C13—C14—Cl3	97.8 (5)
C2—C3—C6—O5	−170.3 (7)	O2—C13—C14—Cl3	−79.1 (5)
C4—C3—C6—N2	−171.0 (5)	O1—C13—C14—Cl1	−143.3 (5)
C2—C3—C6—N2	8.8 (9)	O2—C13—C14—Cl1	39.8 (6)
C11—N3—C7—C8	−2.1 (8)	O4—C15—C16—Cl6	80.2 (6)
N3—C7—C8—C9	0.8 (8)	O3—C15—C16—Cl6	−93.8 (5)
C7—C8—C9—C10	0.9 (8)	O4—C15—C16—Cl4	−41.1 (6)
C7—C8—C9—C12	179.2 (5)	O3—C15—C16—Cl4	145.0 (5)
C8—C9—C10—C11	−1.6 (9)	O4—C15—C16—Cl5	−161.2 (5)
C12—C9—C10—C11	−180.0 (5)	O3—C15—C16—Cl5	24.9 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.86	1.78	2.643 (5)	176
N2—H2A···O1ⁱⁱ	0.86	2.03	2.883 (6)	170
N2—H2B···O6ⁱⁱⁱ	0.86	2.06	2.854 (7)	152
N3—H3A···O3^iv	0.86	1.8	2.661 (5)	178
N4—H4A···O4^v	0.86	2.01	2.858 (6)	169
N4—H4B···O5^v	0.86	2.03	2.858 (7)	160
C2—H2···O6ⁱⁱⁱ	0.93	2.34	3.251 (7)	166
C5—H5···O3	0.93	2.6	3.422 (8)	148
C8—H8···O5^v	0.93	2.36	3.270 (6)	166

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

Experimental details

Crystal data
Chemical formula	C₆H₇N₂O⁺·C₂Cl₃O₂⁻
M_r	285.51
Crystal system, space group	Monoclinic, Pc
Temperature (K)	293
a, b, c (Å)	9.8768 (3), 9.4403 (3), 12.5157 (3)
β (°)	90.240 (2)
V (Å³)	1166.95 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.78
Crystal size (mm)	0.2 × 0.2 × 0.2

Data collection
Diffractometer	Agilent SuperNova, Dual, Cu at zero, Atlas diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.860, 0.860
No. of measured, independent and observed [I > 2σ(I)] reflections	11114, 5195, 4452
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.069, 0.199, 1.04
No. of reflections	5195
No. of parameters	289
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.47
Absolute structure	Flack (1983), 2512 Friedel pairs
Absolute structure parameter	0.08 (12)

Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 1999), WinGX publication routines (Farrugia, 1999) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.86	1.78	2.643 (5)	176.4
N2—H2A···O1ⁱⁱ	0.86	2.03	2.883 (6)	169.7
N2—H2B···O6ⁱⁱⁱ	0.86	2.06	2.854 (7)	152.4
N3—H3A···O3^iv	0.86	1.8	2.661 (5)	178.2
N4—H4A···O4^v	0.86	2.01	2.858 (6)	169.3
N4—H4B···O5^v	0.86	2.03	2.858 (7)	160.1
C2—H2···O6ⁱⁱⁱ	0.93	2.34	3.251 (7)	166.4
C5—H5···O3	0.93	2.6	3.422 (8)	148.3
C8—H8···O5^v	0.93	2.36	3.270 (6)	165.6

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

Acknowledgements

The author thanks the Ministry of Education, Science, Culture and Sport of the Republic of Slovenia and the Slovenian Research Agency for financial support through grants P1–0230–0175 as well as the EN–FIST Centre of Excellence, Dunajska 156, 1000 Ljubljana, Slovenia for use of the Supernova diffractometer.

References

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