1,10-Phenanthrolin-1-ium 2-carb­oxy-4,5-dichloro­benzoate

Smith, G.; Wermuth, U.D.; White, J.M.

doi:10.1107/S1600536809034448

organic compounds

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Volume 65| Part 10| October 2009| Page o2333

doi:10.1107/S1600536809034448

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1,10-Phenanthrolin-1-ium 2-carboxy-4,5-dichlorobenzoate

Graham Smith,^a ^* Urs D. Wermuth ^a and Jonathan M. White ^b

^aSchool of Physical and Chemical Sciences, Queensland University of Technology, GPO Box 2434, Brisbane, Queensland 4001, Australia, and ^bBIO-21 Molecular Science and Biotechnology, University of Melbourne, Parkville, Victoria 3052, Australia
^*Correspondence e-mail: g.smith@qut.edu.au

(Received 8 August 2009; accepted 27 August 2009; online 5 September 2009)

In the structure of the 1:1 proton-transfer compound of 1,10-phenanthroline with 4,5-dichlorophthalic acid, C₁₂H₉N₂⁺·C₈H₃Cl₂O₄⁻, determined at 130 K, the 1,10-phenanthrolinium cation and the hydrogen 4,5-dichlorophthalate anion associate through a single N—H⋯O_carboxyl hydrogen bond giving discrete units which have no extension except through a number of weak cation C—H⋯O_anion associations and weak cation–anion aromatic ring π–π interactions [minimum centroid–centroid separation = 3.6815 (12) Å]. The anions are essentially planar "[maximum deviation 0.214 (1) Å (a carboxyl O)] with the syn-related H atom of the carboxyl group, forming a short intramolecular O—H⋯O_carboxyl hydrogen bond.

Related literature

For the structures of other hydrogen 4,5-dichlorophthalate salts, see: Mallinson et al. (2003 ); Bozkurt et al. (2006 ); Smith et al. (2007 , 2008a ,b , 2009a ,b ). For hydrogen-bond motifs, see: Etter et al. (1990 ).

Experimental

Crystal data

C₁₂H₉N₂⁺·C₈H₃Cl₂O₄⁻
M_r = 415.22
Monoclinic, P 2₁
a = 6.4598 (11) Å
b = 7.3696 (12) Å
c = 18.302 (3) Å
β = 94.978 (3)°
V = 868.0 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.41 mm⁻¹
T = 130 K
0.55 × 0.45 × 0.05 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.81, T_max = 0.98
5464 measured reflections
3734 independent reflections
3629 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.085
S = 1.04
3734 reflections
261 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.19 e Å⁻³
Absolute structure: Flack (1983 ), 1564 Friedel pairs
Flack parameter: 0.00 (4)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1A⋯O22	0.90 (2)	1.83 (2)	2.6926 (19)	158 (2)
N1A—H1A⋯N10A	0.90 (2)	2.38 (2)	2.749 (2)	104.3 (15)
O12—H12⋯O21	0.98 (3)	1.43 (3)	2.4054 (19)	179 (4)
C2A—H2A⋯O21	0.93	2.52	3.279 (2)	140
C3—H3⋯O22	0.93	2.26	2.647 (2)	104
C3A—H3A⋯O11ⁱ	0.93	2.44	3.355 (2)	168
C4A—H4A⋯O21ⁱⁱ	0.93	2.49	3.252 (2)	139
C6—H6⋯O11	0.93	2.29	2.668 (2)	103
C6A—H6A⋯O11ⁱⁱⁱ	0.93	2.59	3.270 (2)	130
Symmetry codes: (i) $[-x+2, y+{\script{1\over 2}}, -z]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z]$ ; (iii) x-2, y+1, z.

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT (Bruker, 1999 ); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809034448/fl2261sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809034448/fl2261Isup2.hkl

checkCIF report

Comment top

The 1:1 proton-transfer compounds of 4,5-dichlorophthalic acid (DCPA) with the aromatic nitrogen Lewis bases commonly have low-dimensional hydrogen-bonded structures (Smith et al., 2007, 2008a, 2008b, 2009a, 2009b; Bozkurt et al., 2006; Mallinson et al., 2003). In the two-dimensional examples the DCPA anions assume non-planar conformations and form into sheet substructures which in the case of the compounds with the meta- and para-aminobenzoic acids (Smith et al., 2008b) are extended into three-dimensional frameworks through peripheral cyclic head-to-head carboxylic acid hydrogen-bonding associations. However, with the majority of the structures, e.g. the brucinium salt (Smith et al., 2007), the DCPA anions are essentially planar with short intramolecular carboxylic acid O–H···O_carboxyl hydrogen bonds. These features were therefore expected and found in the 1:1 proton-transfer compound of DCPA with 1,10-phenanthroline, (I), reported here.

In (I), a single N⁺–H···O_carboxyl hydrogen bond links the phenanthroline cation and the DCPA anion (Fig. 1). A weak aromatic ring C–H···O_carboxyl interaction (Table 1) completes an asymmetric R²₂(7) cyclic association (Etter et al., 1990). Three additional anion C–H···O interactions represent the only structure extensions present. Some overlap is present between the anion aromatic ring (C1–C6) and one six-membered ring of the cation (N10A, C9A, C8A, C7A, C6A, C14A) [minimum ring centroid separation, 3.6815 (12) Å] (Fig. 2), giving weak π–π stacking interactions (Fig. 3). The DCPA anion is essentially planar [torsion angles C2–C1–C11–O11, -168.30 (16)°: C1–C2–C21–O22, -179.53 (16)°], and exhibits a short intramolecular O–H···O_carboxyl hydrogen bond [2.4054 (19) Å]. Associated with this bond is a significant distortion of the exo-C1 and C2 bond angles [C1–C2–C21, 128.55 (15) ° and C2–C1–C11, 129.18 (16) °]. This and a lengthening of the C1–C11 and C2–C21 bonds [1.538 (3) and 1.536 (3) Å] is common to the planar DCPA anions in the series of 1:1 proton-transfer compounds [angle range: 127.88 (16)° in the nicotinamide salt (Smith et al., 2009a) to 129.27 (14)° in the 8-aminoquinoline salt (Smith et al., 2008a); bond length range: 1.523 (3)–1.535 (3) Å, both in the brucinium salt (Smith et al., 2007).

Related literature top

For the structures of other hydrogen 4,5-dichlorophthalate salts, see: Mallinson et al. (2003); Bozkurt et al. (2006); Smith et al. (2007, 2008a,b, 2009a,b). For hydrogen-bond motifs, see: Etter et al. (1990).

Experimental top

The title compound (I) was synthesized by heating 1 mmol quantities of 1,10-phenanthroline and 4,5-dichlorophthalic acid in 50 ml of 95% ethanol for 10 min under reflux. After concentration to ca. 30 ml, partial room-temperature evaporation of the hot-filtered solution gave colourless plates (m.p. 464–465 K) suitable for data collection.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 1999); 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 top

	Fig. 1. Molecular configuration and atom numbering scheme for the 1,10-phenanthrolin-1-ium cation and the hydrogen 4,5-dichlorophthalate anion in (I). Non-H atoms are shown as 50% probability displacement ellipsoids. The inter-species hydrogen bond is shown as a dashed line.
	Fig. 2. Cation–anion aromatic ring overlap in (I) viewed down the approximate b direction in the unit cell. For symmetry code (iv): x + 1, y - 1, z.
	Fig. 3. Aromatic ring π–π interactions in a perspective view of part of the unit cell. Non-interactive H atoms are omitted. For symmetry code (v): x - 1, y, z.

1,10-Phenanthrolin-1-ium 2-carboxy-4,5-dichlorobenzoate top

Crystal data top

C₁₂H₉N₂⁺·C₈H₃Cl₂O₄⁻	F(000) = 424
M_r = 415.22	D_x = 1.589 Mg m⁻³
Monoclinic, P2₁	Melting point = 464–465 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 6.4598 (11) Å	Cell parameters from 3630 reflections
b = 7.3696 (12) Å	θ = 2.2–27.5°
c = 18.302 (3) Å	µ = 0.41 mm⁻¹
β = 94.978 (3)°	T = 130 K
V = 868.0 (2) Å³	Plate, colourless
Z = 2	0.55 × 0.45 × 0.05 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	3734 independent reflections
Radiation source: sealed tube	3629 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
ϕ and ω scans	θ_max = 27.6°, θ_min = 1.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −5→8
T_min = 0.81, T_max = 0.98	k = −9→9
5464 measured reflections	l = −23→21

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)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.085	w = 1/[σ²(F_o²) + (0.053P)² + 0.0522P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
3734 reflections	Δρ_max = 0.30 e Å⁻³
261 parameters	Δρ_min = −0.19 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1564 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (4)

Crystal data top

C₁₂H₉N₂⁺·C₈H₃Cl₂O₄⁻	V = 868.0 (2) Å³
M_r = 415.22	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 6.4598 (11) Å	µ = 0.41 mm⁻¹
b = 7.3696 (12) Å	T = 130 K
c = 18.302 (3) Å	0.55 × 0.45 × 0.05 mm
β = 94.978 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3734 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3629 reflections with I > 2σ(I)
T_min = 0.81, T_max = 0.98	R_int = 0.017
5464 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.085	Δρ_max = 0.30 e Å⁻³
S = 1.04	Δρ_min = −0.19 e Å⁻³
3734 reflections	Absolute structure: Flack (1983), 1564 Friedel pairs
261 parameters	Absolute structure parameter: 0.00 (4)
1 restraint

Special details top

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 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
N1A	0.4667 (2)	0.7304 (2)	0.14863 (8)	0.0192 (4)
N10A	0.4177 (2)	0.7715 (2)	0.29542 (8)	0.0212 (4)
C2A	0.5046 (3)	0.7149 (3)	0.07881 (10)	0.0232 (5)
C3A	0.3645 (3)	0.7828 (3)	0.02322 (10)	0.0277 (5)
C4A	0.1845 (3)	0.8641 (3)	0.04213 (10)	0.0268 (5)
C5A	−0.0459 (3)	0.9562 (3)	0.13825 (11)	0.0233 (5)
C6A	−0.0804 (3)	0.9634 (2)	0.20961 (11)	0.0246 (5)
C7A	0.0442 (3)	0.9113 (2)	0.34093 (10)	0.0259 (6)
C8A	0.2013 (3)	0.8540 (3)	0.39058 (10)	0.0286 (5)
C9A	0.3857 (3)	0.7854 (3)	0.36523 (10)	0.0253 (5)
C11A	0.2617 (3)	0.8274 (2)	0.24641 (9)	0.0184 (4)
C12A	0.2916 (3)	0.8115 (2)	0.16952 (10)	0.0178 (4)
C13A	0.1421 (3)	0.8783 (2)	0.11565 (10)	0.0207 (4)
C14A	0.0717 (3)	0.9002 (2)	0.26564 (10)	0.0207 (5)
Cl4	1.15820 (7)	0.37080 (8)	0.46649 (2)	0.0332 (1)
Cl5	1.59276 (7)	0.22144 (8)	0.42219 (2)	0.0316 (1)
O11	1.5052 (2)	0.18688 (18)	0.14604 (7)	0.0251 (4)
O12	1.2404 (2)	0.34157 (19)	0.09355 (7)	0.0265 (4)
O21	0.9277 (2)	0.4836 (2)	0.12771 (7)	0.0271 (4)
O22	0.76248 (19)	0.53666 (18)	0.22655 (7)	0.0254 (4)
C1	1.2820 (3)	0.3211 (2)	0.22748 (9)	0.0179 (5)
C2	1.0928 (3)	0.3971 (2)	0.24707 (9)	0.0178 (4)
C3	1.0603 (3)	0.4092 (2)	0.32117 (10)	0.0206 (5)
C4	1.2096 (3)	0.3536 (3)	0.37559 (9)	0.0215 (5)
C5	1.3983 (3)	0.2862 (2)	0.35636 (10)	0.0207 (5)
C6	1.4314 (3)	0.2693 (2)	0.28333 (10)	0.0196 (4)
C11	1.3502 (3)	0.2788 (2)	0.15083 (9)	0.0195 (5)
C21	0.9127 (3)	0.4764 (2)	0.19673 (9)	0.0193 (4)
H1A	0.556 (3)	0.683 (3)	0.1842 (12)	0.021 (5)*
H2A	0.62580	0.65840	0.06680	0.0280*
H3A	0.39190	0.77330	−0.02570	0.0330*
H4A	0.09010	0.91030	0.00560	0.0320*
H5A	−0.14490	1.00210	0.10310	0.0280*
H6A	−0.20540	1.01040	0.22290	0.0300*
H7A	−0.07860	0.95670	0.35670	0.0310*
H8A	0.18650	0.86030	0.44060	0.0340*
H9A	0.49080	0.74780	0.39980	0.0300*
H3	0.93520	0.45580	0.33450	0.0250*
H6	1.55700	0.22200	0.27080	0.0230*
H12	1.113 (5)	0.400 (4)	0.1072 (17)	0.035 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1A	0.0167 (6)	0.0212 (7)	0.0195 (7)	−0.0015 (6)	0.0013 (5)	0.0001 (6)
N10A	0.0217 (7)	0.0224 (7)	0.0193 (7)	0.0012 (6)	0.0005 (6)	−0.0004 (6)
C2A	0.0222 (8)	0.0261 (8)	0.0222 (8)	−0.0047 (8)	0.0078 (7)	−0.0028 (7)
C3A	0.0292 (10)	0.0360 (10)	0.0182 (8)	−0.0077 (8)	0.0036 (7)	0.0005 (7)
C4A	0.0268 (9)	0.0298 (9)	0.0230 (8)	−0.0069 (8)	−0.0029 (7)	0.0060 (8)
C5A	0.0176 (8)	0.0211 (8)	0.0302 (9)	−0.0004 (7)	−0.0040 (7)	0.0041 (7)
C6A	0.0164 (8)	0.0202 (9)	0.0375 (10)	0.0014 (7)	0.0033 (7)	−0.0017 (8)
C7A	0.0242 (9)	0.0253 (10)	0.0295 (10)	0.0011 (8)	0.0104 (7)	−0.0027 (7)
C8A	0.0358 (10)	0.0308 (10)	0.0203 (8)	0.0001 (9)	0.0096 (7)	−0.0023 (8)
C9A	0.0295 (9)	0.0263 (9)	0.0197 (8)	0.0025 (8)	−0.0007 (7)	0.0020 (7)
C11A	0.0182 (8)	0.0164 (7)	0.0207 (8)	−0.0009 (6)	0.0026 (6)	0.0009 (6)
C12A	0.0163 (7)	0.0166 (7)	0.0204 (8)	−0.0040 (6)	0.0005 (6)	0.0001 (6)
C13A	0.0186 (7)	0.0188 (7)	0.0241 (8)	−0.0039 (7)	−0.0020 (6)	0.0027 (7)
C14A	0.0195 (8)	0.0181 (8)	0.0248 (8)	−0.0031 (7)	0.0039 (6)	−0.0021 (7)
Cl4	0.0291 (2)	0.0541 (3)	0.0169 (2)	0.0014 (2)	0.0045 (2)	−0.0034 (2)
Cl5	0.0251 (2)	0.0463 (3)	0.0221 (2)	0.0067 (2)	−0.0046 (2)	−0.0001 (2)
O11	0.0227 (6)	0.0297 (7)	0.0236 (6)	0.0044 (6)	0.0058 (5)	−0.0029 (5)
O12	0.0260 (6)	0.0354 (7)	0.0187 (6)	0.0056 (6)	0.0052 (5)	0.0018 (5)
O21	0.0264 (7)	0.0343 (7)	0.0204 (6)	0.0068 (6)	0.0009 (5)	0.0030 (5)
O22	0.0200 (6)	0.0284 (7)	0.0277 (7)	0.0044 (5)	0.0023 (5)	0.0012 (5)
C1	0.0189 (8)	0.0157 (8)	0.0192 (8)	−0.0027 (6)	0.0029 (6)	0.0006 (6)
C2	0.0188 (8)	0.0149 (7)	0.0197 (8)	−0.0012 (6)	0.0024 (6)	0.0007 (6)
C3	0.0189 (8)	0.0215 (9)	0.0215 (8)	−0.0012 (7)	0.0032 (7)	−0.0034 (6)
C4	0.0229 (8)	0.0263 (9)	0.0161 (7)	−0.0035 (7)	0.0057 (6)	−0.0019 (7)
C5	0.0188 (8)	0.0231 (8)	0.0196 (8)	−0.0005 (7)	−0.0019 (6)	0.0019 (7)
C6	0.0155 (7)	0.0207 (8)	0.0229 (8)	0.0010 (6)	0.0040 (6)	−0.0014 (7)
C11	0.0202 (8)	0.0197 (8)	0.0192 (8)	−0.0041 (7)	0.0055 (6)	−0.0012 (6)
C21	0.0168 (7)	0.0173 (8)	0.0233 (8)	−0.0023 (6)	−0.0005 (6)	−0.0004 (6)

Geometric parameters (Å, º) top

Cl4—C4	1.7291 (17)	C11A—C12A	1.442 (2)
Cl5—C5	1.7305 (19)	C11A—C14A	1.412 (3)
O11—C11	1.218 (2)	C12A—C13A	1.408 (3)
O12—C11	1.299 (2)	C2A—H2A	0.9300
O21—C21	1.276 (2)	C3A—H3A	0.9300
O22—C21	1.236 (2)	C4A—H4A	0.9300
O12—H12	0.98 (3)	C5A—H5A	0.9300
N1A—C12A	1.363 (2)	C6A—H6A	0.9300
N1A—C2A	1.327 (2)	C7A—H7A	0.9300
N10A—C11A	1.354 (2)	C8A—H8A	0.9300
N10A—C9A	1.316 (2)	C9A—H9A	0.9300
N1A—H1A	0.90 (2)	C1—C2	1.419 (3)
C2A—C3A	1.395 (3)	C1—C11	1.538 (2)
C3A—C4A	1.379 (3)	C1—C6	1.397 (3)
C4A—C13A	1.400 (3)	C2—C21	1.536 (3)
C5A—C6A	1.345 (3)	C2—C3	1.393 (2)
C5A—C13A	1.436 (3)	C3—C4	1.387 (3)
C6A—C14A	1.435 (3)	C4—C5	1.390 (3)
C7A—C14A	1.407 (3)	C5—C6	1.377 (3)
C7A—C8A	1.369 (3)	C3—H3	0.9300
C8A—C9A	1.409 (3)	C6—H6	0.9300

C11—O12—H12	111 (2)	C14A—C6A—H6A	119.00
C2A—N1A—C12A	122.34 (16)	C5A—C6A—H6A	119.00
C9A—N10A—C11A	116.68 (15)	C8A—C7A—H7A	121.00
C12A—N1A—H1A	117.5 (13)	C14A—C7A—H7A	121.00
C2A—N1A—H1A	120.1 (13)	C9A—C8A—H8A	120.00
N1A—C2A—C3A	120.63 (18)	C7A—C8A—H8A	120.00
C2A—C3A—C4A	118.74 (17)	C8A—C9A—H9A	118.00
C3A—C4A—C13A	120.89 (17)	N10A—C9A—H9A	118.00
C6A—C5A—C13A	120.73 (18)	C2—C1—C11	129.18 (16)
C5A—C6A—C14A	121.35 (18)	C2—C1—C6	118.60 (15)
C8A—C7A—C14A	118.87 (17)	C6—C1—C11	112.19 (16)
C7A—C8A—C9A	119.43 (17)	C1—C2—C21	128.55 (15)
N10A—C9A—C8A	123.79 (17)	C1—C2—C3	118.51 (16)
N10A—C11A—C14A	124.31 (15)	C3—C2—C21	112.92 (16)
C12A—C11A—C14A	117.85 (16)	C2—C3—C4	121.74 (17)
N10A—C11A—C12A	117.83 (16)	Cl4—C4—C5	121.05 (14)
C11A—C12A—C13A	120.89 (17)	C3—C4—C5	119.63 (16)
N1A—C12A—C11A	119.61 (16)	Cl4—C4—C3	119.32 (15)
N1A—C12A—C13A	119.50 (16)	C4—C5—C6	119.44 (17)
C5A—C13A—C12A	118.94 (17)	Cl5—C5—C4	121.47 (14)
C4A—C13A—C5A	123.19 (17)	Cl5—C5—C6	119.09 (15)
C4A—C13A—C12A	117.87 (17)	C1—C6—C5	122.00 (17)
C6A—C14A—C7A	122.97 (17)	O11—C11—C1	118.72 (15)
C7A—C14A—C11A	116.91 (16)	O12—C11—C1	118.97 (15)
C6A—C14A—C11A	120.09 (16)	O11—C11—O12	122.32 (16)
C3A—C2A—H2A	120.00	O22—C21—C2	117.04 (15)
N1A—C2A—H2A	120.00	O21—C21—O22	123.49 (17)
C2A—C3A—H3A	121.00	O21—C21—C2	119.41 (16)
C4A—C3A—H3A	121.00	C2—C3—H3	119.00
C3A—C4A—H4A	120.00	C4—C3—H3	119.00
C13A—C4A—H4A	120.00	C1—C6—H6	119.00
C6A—C5A—H5A	120.00	C5—C6—H6	119.00
C13A—C5A—H5A	120.00

C12A—N1A—C2A—C3A	0.2 (3)	N1A—C12A—C13A—C5A	177.27 (16)
C2A—N1A—C12A—C11A	−178.71 (17)	C11A—C12A—C13A—C4A	177.79 (16)
C2A—N1A—C12A—C13A	1.4 (3)	C11A—C12A—C13A—C5A	−2.6 (2)
C11A—N10A—C9A—C8A	0.0 (3)	C6—C1—C2—C3	−2.9 (2)
C9A—N10A—C11A—C12A	−179.22 (16)	C6—C1—C2—C21	175.21 (15)
C9A—N10A—C11A—C14A	0.8 (2)	C11—C1—C2—C3	174.90 (15)
N1A—C2A—C3A—C4A	−0.9 (3)	C11—C1—C2—C21	−7.0 (3)
C2A—C3A—C4A—C13A	−0.1 (3)	C2—C1—C6—C5	1.5 (2)
C3A—C4A—C13A—C5A	−177.89 (19)	C11—C1—C6—C5	−176.68 (14)
C3A—C4A—C13A—C12A	1.7 (3)	C2—C1—C11—O11	−168.30 (16)
C13A—C5A—C6A—C14A	2.4 (3)	C2—C1—C11—O12	11.4 (3)
C6A—C5A—C13A—C4A	178.76 (18)	C6—C1—C11—O11	9.6 (2)
C6A—C5A—C13A—C12A	−0.8 (3)	C6—C1—C11—O12	−170.67 (15)
C5A—C6A—C14A—C7A	177.74 (17)	C1—C2—C3—C4	1.7 (2)
C5A—C6A—C14A—C11A	−0.5 (2)	C21—C2—C3—C4	−176.64 (16)
C14A—C7A—C8A—C9A	−0.1 (3)	C1—C2—C21—O21	−2.2 (3)
C8A—C7A—C14A—C6A	−177.47 (17)	C1—C2—C21—O22	−179.53 (16)
C8A—C7A—C14A—C11A	0.8 (2)	C3—C2—C21—O21	175.96 (15)
C7A—C8A—C9A—N10A	−0.3 (3)	C3—C2—C21—O22	−1.4 (2)
N10A—C11A—C12A—N1A	4.5 (2)	C2—C3—C4—Cl4	−179.50 (14)
N10A—C11A—C12A—C13A	−175.62 (15)	C2—C3—C4—C5	0.9 (3)
C14A—C11A—C12A—N1A	−175.47 (15)	Cl4—C4—C5—Cl5	−1.6 (2)
C14A—C11A—C12A—C13A	4.4 (2)	Cl4—C4—C5—C6	178.04 (14)
N10A—C11A—C14A—C6A	177.13 (15)	C3—C4—C5—Cl5	178.02 (14)
N10A—C11A—C14A—C7A	−1.2 (2)	C3—C4—C5—C6	−2.4 (3)
C12A—C11A—C14A—C6A	−2.9 (2)	Cl5—C5—C6—C1	−179.20 (12)
C12A—C11A—C14A—C7A	178.83 (14)	C4—C5—C6—C1	1.2 (2)
N1A—C12A—C13A—C4A	−2.4 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···O22	0.90 (2)	1.83 (2)	2.6926 (19)	158 (2)
N1A—H1A···N10A	0.90 (2)	2.38 (2)	2.749 (2)	104.3 (15)
O12—H12···O21	0.98 (3)	1.43 (3)	2.4054 (19)	179 (4)
C2A—H2A···O21	0.93	2.52	3.279 (2)	140
C3—H3···O22	0.93	2.26	2.647 (2)	104
C3A—H3A···O11ⁱ	0.93	2.44	3.355 (2)	168
C4A—H4A···O21ⁱⁱ	0.93	2.49	3.252 (2)	139
C6—H6···O11	0.93	2.29	2.668 (2)	103
C6A—H6A···O11ⁱⁱⁱ	0.93	2.59	3.270 (2)	130

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

Experimental details

Crystal data
Chemical formula	C₁₂H₉N₂⁺·C₈H₃Cl₂O₄⁻
M_r	415.22
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	130
a, b, c (Å)	6.4598 (11), 7.3696 (12), 18.302 (3)
β (°)	94.978 (3)
V (Å³)	868.0 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.41
Crystal size (mm)	0.55 × 0.45 × 0.05

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.81, 0.98
No. of measured, independent and observed [I > 2σ(I)] reflections	5464, 3734, 3629
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.652

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.085, 1.04
No. of reflections	3734
No. of parameters	261
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.19
Absolute structure	Flack (1983), 1564 Friedel pairs
Absolute structure parameter	0.00 (4)

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···O22	0.90 (2)	1.83 (2)	2.6926 (19)	158 (2)
N1A—H1A···N10A	0.90 (2)	2.38 (2)	2.749 (2)	104.3 (15)
O12—H12···O21	0.98 (3)	1.43 (3)	2.4054 (19)	179 (4)
C2A—H2A···O21	0.93	2.52	3.279 (2)	140
C3—H3···O22	0.93	2.26	2.647 (2)	104
C3A—H3A···O11ⁱ	0.93	2.44	3.355 (2)	168
C4A—H4A···O21ⁱⁱ	0.93	2.49	3.252 (2)	139
C6—H6···O11	0.93	2.29	2.668 (2)	103
C6A—H6A···O11ⁱⁱⁱ	0.93	2.59	3.270 (2)	130

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

Acknowledgements

The authors acknowledge financial support from the School of Physical and Chemical Sciences, Queensland University of Technology, and the School of Chemistry, University of Melbourne.

References

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