1,10-Phenanthrolinium 4-chloro-2-hydroxy­benzoate–1,10-phenanthroline–4-chloro-2-hydroxy­benzoic acid (1/1/1)

Shen, H.; Nie, J.-J.; Xu, D.-J.

doi:10.1107/S1600536808015110

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Pages o1146-o1147

doi:10.1107/S1600536808015110

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1,10-Phenanthrolinium 4-chloro-2-hydroxybenzoate–1,10-phenanthroline–4-chloro-2-hydroxybenzoic acid (1/1/1)

Hong Shen,^a Jing-Jing Nie ^a and Duan-Jun Xu ^a ^*

^aDepartment of Chemistry, Zhejiang University, People's Republic of China
^*Correspondence e-mail: xudj@mail.hz.zj.cn

(Received 19 May 2008; accepted 19 May 2008; online 24 May 2008)

The title compound, C₁₂H₉N₂⁺·C₇H₄ClO₃⁻·C₁₂H₈N₂·C₇H₅ClO₃, contains one phenanthrolinium (Hphen) cation, one phenanthroline (phen) molecule, one 4-chloro-2-hydroxybenzoate anion (hcba) and one 4-chloro-2-hydroxybenzoic acid (Hhcba) molecule in the asymmetric unit. The phen molecule is approximately parallel to Hphen, making a dihedral angle of 1.98 (6)°. The centroid–centroid distance between pyridine rings of adjacent phen and Hphen species is 3.7718 (15) Å, and that between the benzene and pyridine rings of adjacent phen and Hphen species is 3.7922 (16) Å, indicative of π–π stacking interactions. The crystal structure contains an extensive network of classical (O—H⋯O, N—H⋯N and O—H⋯Cl) and weak (C—H⋯O and C—H⋯N) hydrogen bonds. Finally, C—H⋯π interactions are seen between Hphen and hcba and between phen and Hhcba in the crystal structure. The hydroxy group of the anion is disordered over the two sites ortho to the carboxylate group in a 0.75:0.25 ratio.

Related literature

For general background, see: Su & Xu (2004 ); Pan et al. (2006 ). For a related structure, see: Fu et al. (2005 ).

Experimental

Crystal data

C₁₂H₉N₂⁺·C₇H₄ClO₃⁻·C₁₂H₈N₂·C₇H₅ClO₃
M_r = 705.53
Orthorhombic, P 2₁ 2₁ 2₁
a = 8.0627 (6) Å
b = 19.6005 (15) Å
c = 20.7929 (17) Å
V = 3286.0 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 295 (2) K
0.43 × 0.37 × 0.32 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: none
37126 measured reflections
6394 independent reflections
4326 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.098
S = 0.98
6394 reflections
460 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.14 e Å⁻³
Absolute structure: Flack (1983 ), 2739 Friedel pairs
Flack parameter: −0.09 (5)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O5	0.88	1.61	2.484 (2)	173
N1—H1N⋯N3ⁱ	0.85	2.14	2.915 (3)	153
O3—H3A⋯Cl1ⁱⁱ	0.95	2.66	3.1714 (19)	114
O3—H3A⋯O2	0.95	1.86	2.603 (3)	133
O6A—H6A⋯O4	0.94	1.74	2.584 (3)	148
O6B—H6B⋯O5	0.82	1.80	2.494 (7)	142
C5—H5⋯O2ⁱⁱⁱ	0.93	2.50	3.404 (3)	164
C12—H12⋯O4ⁱⁱ	0.93	2.51	3.381 (3)	157
C21—H21⋯N2ⁱ	0.93	2.51	3.345 (4)	150
C22—H22⋯O1^iv	0.93	2.54	3.220 (4)	130
C37—H37⋯O4	0.93	2.60	3.430 (3)	150
C25—H25⋯Cg1	0.93	2.65	3.571 (3)	174
C40—H40⋯Cg2	0.93	2.63	3.489 (3)	154
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) x+1, y, z; (iii) x-1, y, z; (iv) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ . Cg1 is the centroid of the C8–C13 benzene ring and Cg2 is the centroid of the C1–C6 benzene ring.

Data collection: PROCESS-AUTO (Rigaku, 1998 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ); 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 I, global. DOI: 10.1107/S1600536808015110/hb2735sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808015110/hb2735Isup2.hkl

checkCIF report

Comment top

As part of our ongoing investigation on the nature of π-π stacking (Su & Xu, 2004; Pan et al. 2006), the title compound, (I), incorporating 1,10-phenanthroline (phen) has been prepared and its crystal structure is reported here.

The asymmetric unit of (I) contains two neutral molecules, one cation and one anion (Fig. 1), similar to the situation in 1,10-phenanthrolinium 6-carboxypyridine-2-carboxylate 1,10-phenanthroline pyridine-2,6-dicarboxylic acid (Fu et al., 2005). The significant difference in C-O bond distances [1.312 (3) and 1.239 (3)Å] suggests that the C7-carboxyl group is protonated in the crystal. The neutral 4-chloro-2-hydroxybenzoic acid (Hhcba) is hydrogen bonded with the 4-chloro-2-hydroxybenzoate anion (hcba) (Fig. 1 and Table 2). The neutral phenathroline (phen) molecule is approximately parallel to the protonated phenathroline cation (Hphen), with a dihedral angle of 1.98 (6)°. Fig. 2 shows the nearly parallel arrangement of phen and Hphen. The centroid-to-centroid distances between N2-pyridine and N4-pyridine rings is 3.7718 (15) Å; the centroid-to-centroid distance between N1-pyridine and C37ⁱ-benzene rings is 3.7922 (16) Å [symmetry code: (i) 1 + x,y,z]. They suggest the existence of π-π stacking between phen and Hphen.

The crystal structure contains C—H···π interactions between Hphen and hcba and between phen and Hhcba (Fig. 1). H25···Cg1 = 2.64 Å, C25—H25···Cg1 = 174° and C25···Cg1 = 3.571 (2) Å (where Cg1 is the centroid of the C8-benzene ring); H40···Cg2 = 2.63 Å, C40—H40···Cg2 = 153° and C40···Cg2 = 3.489 (3) Å (where Cg2 is the centroid of the C1-benzene ring).

Related literature top

For general background, see: Su & Xu (2004); Pan et al. (2006). For a related structure, see: Fu et al. (2005).

Experimental top

4-chloro-2-hydroxybenzoic acid (0.17 g, 1 mmol) and 1,10-phenanthroline (0.20 g, 1 mmol) were dissolved in ethanol-water (10 ml, 7:3 v/v) at room temperature. The solution was filtered and red-brown chunks of (I) were obtained from the filtrate after 3 d.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1993); 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. The molecular structure of (I) with 30% probability displacement ellipsoids (arbitrary spheres for H atoms). The minor component of the disordered 4-chloro-2-hydroxybenzoate has been omitted for clarity. Dashed lines indicate hydrogen bonding; dotted lines indicate C—H···π interaction.
	Fig. 2. A packing diagram for (I) showing π-π stacking between phen and Hphen ring systems [symmetry code: (i) 1 + x,y,z]. The H atoms are omitted for clarity.

1,10-Phenanthrolinium 4-chloro-2-hydroxybenzoate–1,10-phenanthroline– 4-chloro-2-hydroxybenzoic acid (1/1/1) top

Crystal data top

C₁₂H₉N₂⁺·C₇H₄ClO₃⁻·C₁₂H₈N₂·C₇H₅ClO₃	F(000) = 1456
M_r = 705.53	D_x = 1.426 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3820 reflections
a = 8.0627 (6) Å	θ = 2.0–25.0°
b = 19.6005 (15) Å	µ = 0.25 mm⁻¹
c = 20.7929 (17) Å	T = 295 K
V = 3286.0 (4) Å³	Chunk, red brown
Z = 4	0.43 × 0.37 × 0.32 mm

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	4326 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.054
Graphite monochromator	θ_max = 26.0°, θ_min = 1.4°
Detector resolution: 10.00 pixels mm^-1	h = −9→9
ω scans	k = −24→24
37126 measured reflections	l = −23→24
6394 independent 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)] = 0.039	H-atom parameters constrained
wR(F²) = 0.098	w = 1/[σ²(F_o²) + (0.051P)²] where P = (F_o² + 2F_c²)/3
S = 0.98	(Δ/σ)_max < 0.001
6394 reflections	Δρ_max = 0.24 e Å⁻³
460 parameters	Δρ_min = −0.15 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 2739 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.09 (5)

Crystal data top

C₁₂H₉N₂⁺·C₇H₄ClO₃⁻·C₁₂H₈N₂·C₇H₅ClO₃	V = 3286.0 (4) Å³
M_r = 705.53	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 8.0627 (6) Å	µ = 0.25 mm⁻¹
b = 19.6005 (15) Å	T = 295 K
c = 20.7929 (17) Å	0.43 × 0.37 × 0.32 mm

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	4326 reflections with I > 2σ(I)
37126 measured reflections	R_int = 0.054
6394 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.098	Δρ_max = 0.24 e Å⁻³
S = 0.98	Δρ_min = −0.15 e Å⁻³
6394 reflections	Absolute structure: Flack (1983), 2739 Friedel pairs
460 parameters	Absolute structure parameter: −0.09 (5)
0 restraints

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	Occ. (<1)
Cl1	−0.36861 (10)	0.67865 (4)	0.46601 (4)	0.0854 (2)
Cl2	1.02809 (9)	0.33001 (4)	0.13135 (4)	0.0900 (3)
N1	0.7137 (3)	0.28257 (9)	0.44997 (10)	0.0559 (5)
H1N	0.6923	0.2791	0.4897	0.084*
N2	0.5485 (3)	0.38638 (10)	0.51279 (11)	0.0633 (6)
N3	0.2373 (3)	0.26039 (11)	0.41612 (11)	0.0681 (6)
N4	0.0909 (3)	0.36501 (10)	0.48502 (10)	0.0666 (6)
O1	0.1928 (2)	0.60893 (10)	0.24138 (10)	0.0753 (5)
H1A	0.2861	0.5960	0.2236	0.113*
O2	0.3673 (3)	0.63537 (12)	0.32124 (11)	0.0952 (7)
O3	0.2480 (2)	0.66890 (12)	0.43318 (11)	0.0951 (6)
H3A	0.3418	0.6628	0.4062	0.143*
O4	0.2843 (2)	0.47959 (10)	0.15141 (10)	0.0746 (5)
O5	0.4445 (2)	0.56412 (9)	0.18697 (9)	0.0726 (5)
C1	0.0776 (3)	0.64335 (12)	0.33999 (13)	0.0547 (6)
C2	0.0958 (3)	0.66070 (12)	0.40499 (14)	0.0611 (7)
C3	−0.0418 (3)	0.67074 (13)	0.44405 (13)	0.0626 (7)
H3	−0.0291	0.6810	0.4874	0.075*
C4	−0.1972 (3)	0.66515 (12)	0.41731 (13)	0.0594 (7)
C5	−0.2199 (3)	0.64899 (13)	0.35319 (14)	0.0648 (7)
H5	−0.3261	0.6457	0.3360	0.078*
C6	−0.0819 (3)	0.63782 (13)	0.31511 (13)	0.0594 (7)
H6	−0.0961	0.6264	0.2720	0.071*
C7	0.2243 (4)	0.62942 (13)	0.30020 (16)	0.0648 (7)
C8	0.5737 (3)	0.46147 (12)	0.15467 (10)	0.0501 (6)
C9	0.5603 (3)	0.39317 (13)	0.13526 (12)	0.0595 (6)
H9	0.4564	0.3747	0.1267	0.071*	0.25
C10	0.7005 (3)	0.35299 (13)	0.12879 (13)	0.0656 (7)
H10	0.6912	0.3074	0.1168	0.079*
C11	0.8526 (3)	0.38097 (12)	0.14023 (13)	0.0589 (6)
C12	0.8724 (3)	0.44813 (13)	0.15866 (12)	0.0569 (6)
H12	0.9773	0.4663	0.1660	0.068*
C13	0.7316 (3)	0.48752 (13)	0.16586 (12)	0.0538 (6)
H13	0.7426	0.5328	0.1786	0.065*	0.75
C14	0.4216 (3)	0.50398 (14)	0.16457 (12)	0.0581 (7)
C21	0.7978 (4)	0.23170 (13)	0.42364 (13)	0.0662 (7)
H21	0.8293	0.1946	0.4487	0.079*
C22	0.8394 (3)	0.23341 (14)	0.35891 (15)	0.0700 (8)
H22	0.8981	0.1977	0.3403	0.084*
C23	0.7924 (4)	0.28875 (15)	0.32288 (13)	0.0673 (7)
H23	0.8182	0.2901	0.2793	0.081*
C24	0.7056 (3)	0.34341 (12)	0.35095 (12)	0.0560 (6)
C25	0.6560 (4)	0.40270 (15)	0.31662 (14)	0.0722 (8)
H25	0.6798	0.4059	0.2730	0.087*
C26	0.5762 (4)	0.45383 (15)	0.34530 (15)	0.0740 (8)
H26	0.5459	0.4920	0.3214	0.089*
C27	0.5366 (3)	0.45098 (12)	0.41213 (14)	0.0618 (7)
C28	0.4538 (4)	0.50332 (13)	0.44537 (19)	0.0791 (9)
H28	0.4206	0.5424	0.4236	0.095*
C29	0.4222 (4)	0.49694 (14)	0.50952 (18)	0.0839 (9)
H29	0.3688	0.5317	0.5318	0.101*
C30	0.4707 (4)	0.43793 (14)	0.54105 (15)	0.0779 (8)
H30	0.4472	0.4342	0.5847	0.093*
C31	0.5796 (3)	0.39333 (11)	0.44856 (12)	0.0520 (6)
C32	0.6662 (3)	0.33901 (11)	0.41681 (11)	0.0490 (6)
C33	0.3118 (4)	0.21255 (15)	0.38143 (17)	0.0835 (10)
H33	0.3379	0.1717	0.4019	0.100*
C34	0.3539 (4)	0.21872 (16)	0.31680 (16)	0.0803 (9)
H34	0.4077	0.1834	0.2954	0.096*
C35	0.3145 (4)	0.27756 (15)	0.28567 (15)	0.0737 (8)
H35	0.3409	0.2831	0.2424	0.088*
C36	0.2336 (3)	0.32990 (13)	0.31938 (12)	0.0565 (6)
C37	0.1823 (3)	0.39218 (13)	0.28871 (13)	0.0646 (7)
H37	0.2046	0.3987	0.2453	0.077*
C38	0.1031 (4)	0.44091 (13)	0.32165 (12)	0.0651 (7)
H38	0.0716	0.4807	0.3006	0.078*
C39	0.0659 (3)	0.43319 (11)	0.38807 (11)	0.0537 (6)
C40	−0.0182 (3)	0.48382 (13)	0.42393 (14)	0.0649 (7)
H40	−0.0584	0.5227	0.4036	0.078*
C41	−0.0399 (4)	0.47545 (13)	0.48783 (15)	0.0730 (8)
H41	−0.0913	0.5091	0.5122	0.088*
C42	0.0156 (4)	0.41596 (15)	0.51631 (14)	0.0760 (9)
H42	−0.0005	0.4110	0.5603	0.091*
C43	0.1165 (3)	0.37377 (11)	0.42085 (11)	0.0522 (6)
C44	0.1987 (3)	0.31975 (12)	0.38519 (11)	0.0532 (6)
O6A	0.4152 (3)	0.36325 (13)	0.12245 (13)	0.0825 (8)	0.75
H6A	0.3325	0.3958	0.1317	0.124*	0.75
O6B	0.7525 (8)	0.5525 (3)	0.1865 (4)	0.0664 (19)	0.25
H6B	0.6650	0.5674	0.2002	0.100*	0.25

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0676 (4)	0.0996 (5)	0.0890 (6)	−0.0008 (4)	0.0144 (4)	−0.0178 (4)
Cl2	0.0706 (5)	0.0762 (5)	0.1232 (7)	0.0177 (4)	−0.0119 (4)	−0.0287 (5)
N1	0.0713 (13)	0.0502 (11)	0.0463 (12)	0.0009 (10)	0.0083 (11)	0.0075 (9)
N2	0.0744 (16)	0.0533 (12)	0.0623 (15)	−0.0072 (11)	0.0111 (12)	−0.0037 (11)
N3	0.0927 (18)	0.0526 (12)	0.0590 (14)	0.0024 (12)	−0.0153 (13)	0.0074 (11)
N4	0.0941 (18)	0.0588 (12)	0.0469 (14)	−0.0156 (12)	−0.0046 (12)	0.0017 (10)
O1	0.0561 (11)	0.0960 (13)	0.0736 (14)	0.0172 (10)	0.0067 (10)	0.0066 (11)
O2	0.0512 (12)	0.1293 (18)	0.1050 (17)	0.0025 (12)	0.0000 (12)	−0.0156 (14)
O3	0.0612 (13)	0.1030 (15)	0.1212 (18)	0.0034 (12)	−0.0074 (12)	−0.0249 (14)
O4	0.0514 (11)	0.0909 (14)	0.0816 (14)	−0.0026 (10)	−0.0025 (10)	0.0044 (10)
O5	0.0605 (12)	0.0680 (12)	0.0893 (14)	0.0038 (10)	0.0147 (10)	−0.0033 (10)
C1	0.0466 (14)	0.0511 (13)	0.0666 (18)	0.0076 (11)	−0.0001 (13)	0.0036 (12)
C2	0.0502 (16)	0.0534 (14)	0.0796 (19)	−0.0007 (12)	−0.0112 (14)	−0.0017 (13)
C3	0.0628 (18)	0.0589 (14)	0.0660 (17)	−0.0047 (13)	−0.0036 (14)	−0.0064 (13)
C4	0.0600 (16)	0.0477 (13)	0.0705 (19)	0.0023 (12)	0.0074 (14)	−0.0026 (13)
C5	0.0496 (15)	0.0712 (17)	0.074 (2)	0.0037 (13)	−0.0044 (14)	0.0064 (14)
C6	0.0514 (16)	0.0653 (15)	0.0615 (16)	0.0066 (12)	−0.0045 (13)	0.0048 (13)
C7	0.0534 (18)	0.0607 (16)	0.080 (2)	0.0092 (13)	−0.0016 (16)	0.0094 (14)
C8	0.0544 (15)	0.0584 (14)	0.0376 (13)	−0.0047 (12)	0.0013 (11)	0.0080 (10)
C9	0.0557 (16)	0.0701 (16)	0.0525 (16)	−0.0088 (14)	−0.0026 (13)	−0.0023 (13)
C10	0.0682 (18)	0.0590 (15)	0.0695 (18)	−0.0043 (14)	−0.0047 (15)	−0.0086 (13)
C11	0.0594 (16)	0.0622 (15)	0.0551 (16)	0.0072 (13)	−0.0017 (13)	−0.0042 (12)
C12	0.0500 (14)	0.0604 (15)	0.0602 (16)	−0.0021 (12)	−0.0011 (12)	0.0003 (12)
C13	0.0563 (16)	0.0549 (14)	0.0502 (16)	−0.0038 (12)	0.0023 (12)	0.0025 (11)
C14	0.0563 (17)	0.0699 (17)	0.0481 (16)	−0.0007 (14)	0.0084 (13)	0.0161 (13)
C21	0.0786 (19)	0.0538 (15)	0.066 (2)	0.0058 (14)	0.0056 (16)	0.0057 (13)
C22	0.0707 (19)	0.0711 (17)	0.068 (2)	0.0066 (14)	0.0054 (15)	−0.0076 (15)
C23	0.0681 (17)	0.087 (2)	0.0469 (16)	−0.0143 (16)	0.0028 (14)	−0.0019 (14)
C24	0.0586 (15)	0.0609 (15)	0.0486 (16)	−0.0076 (12)	−0.0043 (12)	0.0065 (12)
C25	0.080 (2)	0.084 (2)	0.0525 (17)	−0.0113 (17)	−0.0129 (15)	0.0186 (15)
C26	0.079 (2)	0.0660 (17)	0.077 (2)	−0.0018 (16)	−0.0179 (17)	0.0259 (16)
C27	0.0569 (16)	0.0526 (14)	0.076 (2)	−0.0056 (12)	−0.0137 (14)	0.0085 (14)
C28	0.073 (2)	0.0495 (15)	0.114 (3)	0.0013 (14)	−0.017 (2)	0.0003 (16)
C29	0.084 (2)	0.0571 (17)	0.111 (3)	−0.0002 (16)	0.008 (2)	−0.0194 (18)
C30	0.090 (2)	0.0618 (17)	0.082 (2)	−0.0074 (16)	0.0166 (17)	−0.0185 (16)
C31	0.0497 (14)	0.0463 (12)	0.0598 (17)	−0.0098 (11)	−0.0022 (13)	0.0012 (12)
C32	0.0507 (14)	0.0503 (13)	0.0461 (15)	−0.0090 (11)	−0.0019 (11)	0.0062 (11)
C33	0.107 (3)	0.0593 (17)	0.084 (2)	0.0125 (17)	−0.023 (2)	0.0040 (16)
C34	0.085 (2)	0.0715 (19)	0.084 (2)	0.0115 (16)	−0.0041 (18)	−0.0114 (17)
C35	0.076 (2)	0.0766 (19)	0.0690 (19)	−0.0025 (15)	0.0000 (16)	−0.0024 (16)
C36	0.0614 (15)	0.0573 (15)	0.0508 (16)	−0.0067 (13)	−0.0046 (12)	0.0011 (13)
C37	0.078 (2)	0.0686 (17)	0.0472 (16)	−0.0104 (15)	−0.0025 (14)	0.0102 (13)
C38	0.086 (2)	0.0558 (15)	0.0536 (17)	−0.0028 (14)	−0.0090 (15)	0.0106 (13)
C39	0.0597 (16)	0.0522 (14)	0.0492 (16)	−0.0082 (12)	−0.0088 (12)	0.0023 (12)
C40	0.0722 (18)	0.0515 (14)	0.071 (2)	−0.0046 (13)	−0.0034 (15)	−0.0009 (13)
C41	0.085 (2)	0.0613 (16)	0.072 (2)	−0.0110 (15)	0.0050 (16)	−0.0137 (15)
C42	0.107 (2)	0.0732 (18)	0.0478 (17)	−0.0254 (18)	0.0091 (16)	−0.0070 (15)
C43	0.0641 (16)	0.0487 (13)	0.0437 (15)	−0.0140 (11)	−0.0106 (12)	0.0043 (11)
C44	0.0599 (14)	0.0501 (13)	0.0495 (15)	−0.0065 (12)	−0.0114 (12)	−0.0003 (12)
O6A	0.0541 (15)	0.0888 (17)	0.105 (2)	−0.0090 (14)	−0.0027 (15)	−0.0180 (16)
O6B	0.058 (4)	0.048 (4)	0.093 (5)	−0.006 (3)	−0.001 (4)	−0.022 (4)

Geometric parameters (Å, º) top

Cl1—C4	1.734 (3)	C21—H21	0.9300
Cl2—C11	1.742 (3)	C22—C23	1.372 (4)
N1—C21	1.324 (3)	C22—H22	0.9300
N1—C32	1.359 (3)	C23—C24	1.406 (4)
N1—H1N	0.8464	C23—H23	0.9300
N2—C30	1.327 (3)	C24—C32	1.408 (3)
N2—C31	1.366 (3)	C24—C25	1.421 (4)
N3—C33	1.327 (4)	C25—C26	1.332 (4)
N3—C44	1.365 (3)	C25—H25	0.9300
N4—C42	1.338 (4)	C26—C27	1.427 (4)
N4—C43	1.361 (3)	C26—H26	0.9300
C7—O1	1.312 (3)	C27—C31	1.404 (3)
C7—O2	1.239 (3)	C27—C28	1.405 (4)
O1—H1A	0.8758	C28—C29	1.364 (4)
O3—C2	1.370 (3)	C28—H28	0.9300
O3—H3A	0.9483	C29—C30	1.386 (4)
O4—C14	1.236 (3)	C29—H29	0.9300
O5—C14	1.281 (3)	C30—H30	0.9300
C1—C6	1.391 (3)	C31—C32	1.434 (3)
C1—C2	1.401 (4)	C33—C34	1.391 (4)
C1—C7	1.469 (4)	C33—H33	0.9300
C2—C3	1.389 (4)	C34—C35	1.360 (4)
C3—C4	1.375 (4)	C34—H34	0.9300
C3—H3	0.9300	C35—C36	1.403 (4)
C4—C5	1.382 (4)	C35—H35	0.9300
C5—C6	1.383 (4)	C36—C44	1.411 (3)
C5—H5	0.9300	C36—C37	1.438 (4)
C6—H6	0.9300	C37—C38	1.338 (4)
C8—C13	1.391 (3)	C37—H37	0.9300
C8—C9	1.402 (3)	C38—C39	1.421 (3)
C8—C14	1.496 (3)	C38—H38	0.9300
C9—O6A	1.336 (3)	C39—C43	1.410 (3)
C9—C10	1.384 (3)	C39—C40	1.415 (3)
C9—H9	0.9300	C40—C41	1.350 (4)
C10—C11	1.364 (3)	C40—H40	0.9300
C10—H10	0.9300	C41—C42	1.382 (4)
C11—C12	1.380 (3)	C41—H41	0.9300
C12—C13	1.381 (3)	C42—H42	0.9300
C12—H12	0.9300	C43—C44	1.453 (3)
C13—O6B	1.354 (6)	O6A—H6A	0.9422
C13—H13	0.9300	O6B—H6B	0.8159
C21—C22	1.388 (4)

C21—N1—C32	123.2 (2)	C23—C24—C25	123.7 (3)
C21—N1—H1N	116.6	C32—C24—C25	118.3 (2)
C32—N1—H1N	120.2	C26—C25—C24	121.8 (3)
C30—N2—C31	116.4 (2)	C26—C25—H25	119.1
C33—N3—C44	116.7 (2)	C24—C25—H25	119.1
C42—N4—C43	116.8 (2)	C25—C26—C27	121.0 (3)
C7—O1—H1A	108.4	C25—C26—H26	119.5
C2—O3—H3A	116.5	C27—C26—H26	119.5
C6—C1—C2	118.3 (2)	C31—C27—C28	116.1 (3)
C6—C1—C7	121.4 (3)	C31—C27—C26	120.1 (3)
C2—C1—C7	120.3 (2)	C28—C27—C26	123.8 (3)
O3—C2—C3	116.7 (2)	C29—C28—C27	120.2 (3)
O3—C2—C1	122.3 (3)	C29—C28—H28	119.9
C3—C2—C1	121.0 (2)	C27—C28—H28	119.9
C4—C3—C2	118.7 (3)	C28—C29—C30	119.1 (3)
C4—C3—H3	120.7	C28—C29—H29	120.4
C2—C3—H3	120.7	C30—C29—H29	120.4
C3—C4—C5	122.0 (3)	N2—C30—C29	124.0 (3)
C3—C4—Cl1	118.6 (2)	N2—C30—H30	118.0
C5—C4—Cl1	119.5 (2)	C29—C30—H30	118.0
C4—C5—C6	118.8 (3)	N2—C31—C27	124.2 (2)
C4—C5—H5	120.6	N2—C31—C32	117.7 (2)
C6—C5—H5	120.6	C27—C31—C32	118.0 (2)
C5—C6—C1	121.3 (3)	N1—C32—C24	118.7 (2)
C5—C6—H6	119.4	N1—C32—C31	120.5 (2)
C1—C6—H6	119.4	C24—C32—C31	120.8 (2)
O2—C7—O1	122.6 (3)	N3—C33—C34	125.0 (3)
O2—C7—C1	122.2 (3)	N3—C33—H33	117.5
O1—C7—C1	115.2 (3)	C34—C33—H33	117.5
C13—C8—C9	118.0 (2)	C35—C34—C33	118.4 (3)
C13—C8—C14	121.5 (2)	C35—C34—H34	120.8
C9—C8—C14	120.5 (2)	C33—C34—H34	120.8
O6A—C9—C10	116.5 (2)	C34—C35—C36	119.4 (3)
O6A—C9—C8	122.9 (3)	C34—C35—H35	120.3
C10—C9—C8	120.5 (2)	C36—C35—H35	120.3
C10—C9—H9	119.7	C35—C36—C44	118.3 (2)
C8—C9—H9	119.7	C35—C36—C37	122.2 (2)
C11—C10—C9	119.2 (2)	C44—C36—C37	119.5 (2)
C11—C10—H10	120.4	C38—C37—C36	121.1 (2)
C9—C10—H10	120.4	C38—C37—H37	119.5
C10—C11—C12	122.4 (2)	C36—C37—H37	119.5
C10—C11—Cl2	118.8 (2)	C37—C38—C39	121.5 (2)
C12—C11—Cl2	118.8 (2)	C37—C38—H38	119.3
C11—C12—C13	117.9 (2)	C39—C38—H38	119.3
C11—C12—H12	121.1	C43—C39—C40	117.6 (2)
C13—C12—H12	121.1	C43—C39—C38	119.8 (2)
O6B—C13—C12	117.2 (4)	C40—C39—C38	122.6 (2)
O6B—C13—C8	120.8 (4)	C41—C40—C39	119.7 (3)
C12—C13—C8	121.9 (2)	C41—C40—H40	120.1
C12—C13—H13	119.0	C39—C40—H40	120.1
C8—C13—H13	119.0	C40—C41—C42	118.8 (3)
O4—C14—O5	124.4 (3)	C40—C41—H41	120.6
O4—C14—C8	119.2 (2)	C42—C41—H41	120.6
O5—C14—C8	116.4 (2)	N4—C42—C41	124.6 (3)
N1—C21—C22	120.4 (2)	N4—C42—H42	117.7
N1—C21—H21	119.8	C41—C42—H42	117.7
C22—C21—H21	119.8	N4—C43—C39	122.3 (2)
C23—C22—C21	118.8 (3)	N4—C43—C44	118.5 (2)
C23—C22—H22	120.6	C39—C43—C44	119.2 (2)
C21—C22—H22	120.6	N3—C44—C36	122.1 (2)
C22—C23—C24	120.9 (3)	N3—C44—C43	119.0 (2)
C22—C23—H23	119.6	C36—C44—C43	118.9 (2)
C24—C23—H23	119.6	C9—O6A—H6A	106.4
C23—C24—C32	118.0 (2)	C13—O6B—H6B	109.9

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O5	0.88	1.61	2.484 (2)	173
N1—H1N···N3ⁱ	0.85	2.14	2.915 (3)	153
O3—H3A···Cl1ⁱⁱ	0.95	2.66	3.1714 (19)	114
O3—H3A···O2	0.95	1.86	2.603 (3)	133
O6A—H6A···O4	0.94	1.74	2.584 (3)	148
O6B—H6B···O5	0.82	1.80	2.494 (7)	142
C5—H5···O2ⁱⁱⁱ	0.93	2.50	3.404 (3)	164
C12—H12···O4ⁱⁱ	0.93	2.51	3.381 (3)	157
C21—H21···N2ⁱ	0.93	2.51	3.345 (4)	150
C22—H22···O1^iv	0.93	2.54	3.220 (4)	130
C37—H37···O4	0.93	2.60	3.430 (3)	150
C25—H25···Cg1	0.93	2.65	3.571 (3)	174
C40—H40···Cg2	0.93	2.63	3.489 (3)	154

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

Experimental details

Crystal data
Chemical formula	C₁₂H₉N₂⁺·C₇H₄ClO₃⁻·C₁₂H₈N₂·C₇H₅ClO₃
M_r	705.53
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	295
a, b, c (Å)	8.0627 (6), 19.6005 (15), 20.7929 (17)
V (Å³)	3286.0 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.43 × 0.37 × 0.32

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	37126, 6394, 4326
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.098, 0.98
No. of reflections	6394
No. of parameters	460
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.15
Absolute structure	Flack (1983), 2739 Friedel pairs
Absolute structure parameter	−0.09 (5)

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O5	0.88	1.61	2.484 (2)	173
N1—H1N···N3ⁱ	0.85	2.14	2.915 (3)	153
O3—H3A···Cl1ⁱⁱ	0.95	2.66	3.1714 (19)	114
O3—H3A···O2	0.95	1.86	2.603 (3)	133
O6A—H6A···O4	0.94	1.74	2.584 (3)	148
O6B—H6B···O5	0.82	1.80	2.494 (7)	142
C5—H5···O2ⁱⁱⁱ	0.93	2.50	3.404 (3)	164
C12—H12···O4ⁱⁱ	0.93	2.51	3.381 (3)	157
C21—H21···N2ⁱ	0.93	2.51	3.345 (4)	150
C22—H22···O1^iv	0.93	2.54	3.220 (4)	130
C37—H37···O4	0.93	2.60	3.430 (3)	150
C25—H25···Cg1	0.93	2.6462	3.571 (3)	174
C40—H40···Cg2	0.93	2.6324	3.489 (3)	154

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

Acknowledgements

The work was supported by the ZIJIN project of Zhejiang University, China.

References

Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343–350. CrossRef Web of Science IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Fu, A.-Y., Wang, D.-Q. & Zhang, C.-L. (2005). Acta Cryst. E61, o3119–o3121. Web of Science CSD CrossRef IUCr Journals Google Scholar
Pan, T.-T., Liu, J.-G. & Xu, D.-J. (2006). Acta Cryst. E62, m1597–m1599. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Su, J.-R. & Xu, D.-J. (2004). J. Coord. Chem. 57, 223–229. Web of Science CSD CrossRef CAS Google Scholar

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Volume 64| Part 6| June 2008| Pages o1146-o1147

doi:10.1107/S1600536808015110

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1,10-Phenanthrolinium 4-chloro-2-hy­droxy­benzoate–1,10-phenanthroline–4-chloro-2-hy­droxy­benzoic acid (1/1/1)

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

1,10-Phenanthrolinium 4-chloro-2-hydroxybenzoate–1,10-phenanthroline–4-chloro-2-hydroxybenzoic acid (1/1/1)