1,10-Phenanthrolin-1-ium 2-carb-oxy-4,5-dichloro-benzoate.

In the structure of the 1:1 proton-transfer compound of 1,10-phenanthroline with 4,5-dichloro-phthalic acid, C(12)H(9)N(2) (+)·C(8)H(3)Cl(2)O(4) (-), determined at 130 K, the 1,10-phenanthrolinium cation and the hydrogen 4,5-dichloro-phthalate anion associate through a single N-H⋯O(carbox-yl) 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 inter-actions [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 intra-molecular O-H⋯O(carbox-yl) 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 = 415.22

Monoclinic,

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 (; 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[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.085

S = 1.04

3734 reflections

261 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.30 e Å−3

Δρmin = −0.19 e Å−3

Absolute structure: Flack (1983 ▶), 1564 Friedel pairs

Flack parameter: 0.00 (4)

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.

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C12H9N2+·C8H3Cl2O4−	F(000) = 424
Mr = 415.22	Dx = 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

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

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(Fo2) + (0.053P)2 + 0.0522P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.001
3734 reflections	Δρmax = 0.30 e Å−3
261 parameters	Δρmin = −0.19 e Å−3
1 restraint	Absolute structure: Flack (1983), 1564 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.00 (4)

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.

	x	y	z	Uiso*/Ueq
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)*

	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)

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)

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

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) ; (ii) ; (iii) .