Bis(2,9-dimethyl-1,10-phenanthrolin-1-ium) 2,5-di­carb­oxy­benzene-1,4-di­carb­oxyl­ate–2,9-dimethyl-1,10-phenanthroline–benzene-1,2,4,5-tetra­carb­oxy­lic acid (1/2/1)

Arman, H.D.; Kaulgud, T.; Tiekink, E.R.T.

doi:10.1107/S1600536813022691

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 9| September 2013| Pages o1445-o1446

doi:10.1107/S1600536813022691

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Bis(2,9-dimethyl-1,10-phenanthrolin-1-ium) 2,5-dicarboxybenzene-1,4-dicarboxylate–2,9-dimethyl-1,10-phenanthroline–benzene-1,2,4,5-tetracarboxylic acid (1/2/1)

Hadi D. Arman,^a Trupta Kaulgud ^a and Edward R. T. Tiekink ^b ^*

^aDepartment of Chemistry, The University of Texas at San Antonio, One UTSA Circle, San Antonio, Texas 78249-0698, USA, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 10 August 2013; accepted 12 August 2013; online 17 August 2013)

The asymmetric unit of the title co-crystal, 2C₁₄H₁₃N₂⁺·C₁₀H₄O₈²⁻·2C₁₄H₁₂N₂·C₁₀H₆O₈, comprises a 2,9-dimethyl-1,10-phenanthrolin-1-ium cation (Me₂PhenH⁺) and a 2,9-dimethyl-1,10-phenanthroline molecule (Me₂Phen), each in a general position, and half each of a 2,5-dicarboxybenzene-1,4-dicarboxylate dianion (LH₂²⁻) and a benzene-1,2,4,5-tetracarboxylic acid molecule (LH₄), each being disposed about a centre of inversion. Small twists are evident in the dianion [the C—C—C—O torsion angles are 168.41 (18) and 16.2 (3)°], whereas a major twist is found for one carboxylic acid group in the neutral molecule [C—C—C—O = 66.3 (2) and 18.2 (3)°]. The most prominent feature of the crystal packing is the formation of linear supramolecular chains along [001] mediated by charge-assisted O—H⋯O⁻ hydrogen bonding between alternating LH₄ and LH₂²⁻. These are connected to the Me₂PhenH⁺ and Me₂Phen species by N—H⋯O and O—H⋯N hydrogen bonds, respectively. A three-dimensional architecture is formed by C—H⋯O and π–π interactions [inter-centroid distance = 3.5337 (17) Å].

Related literature

For salt formation with benzene-1,2,4,5-tetracarboxylic acid, see: Arman & Tiekink (2013 ). For a co-crystal involving 2,9-dimethyl-1,10-phenanthroline, see: Arman et al. (2010 ). For the structure of a 2,9-dimethyl-1,10-phenanthrolin-1-ium carboxylate salt, see: Derikvand & Olmstead (2011 ).

Experimental

Crystal data

2C₁₄H₁₃N₂⁺·C₁₀H₄O₈²⁻·2C₁₄H₁₂N₂·C₁₀H₆O₈
M_r = 1341.32
Monoclinic, P 2₁ /n
a = 11.798 (4) Å
b = 13.893 (4) Å
c = 19.163 (6) Å
β = 92.216 (5)°
V = 3138.8 (16) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 98 K
0.48 × 0.37 × 0.09 mm

Data collection

Rigaku AFC12/SATURN724 diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.723, T_max = 1.000
22006 measured reflections
7181 independent reflections
6007 reflections with I > 2σ(I)
R_int = 0.056

Refinement

R[F² > 2σ(F²)] = 0.062
wR(F²) = 0.148
S = 1.11
7181 reflections
467 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H1o⋯O1	0.85 (2)	1.55 (2)	2.403 (2)	176 (3)
O6—H2o⋯O2ⁱ	0.85 (1)	1.74 (1)	2.577 (2)	168 (2)
O8—H3o⋯N4ⁱⁱ	0.85 (2)	1.79 (2)	2.636 (2)	173 (2)
N1—H1n⋯O3ⁱⁱⁱ	0.89 (2)	2.41 (2)	3.257 (2)	161 (2)
N1—H1n⋯O4ⁱⁱⁱ	0.89 (2)	2.35 (2)	2.957 (2)	126 (2)
C13—H13⋯O7^iv	0.95	2.28	3.225 (3)	171
C28—H28⋯O5^v	0.95	2.40	3.320 (3)	162
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x+1, -y, -z+1; (iii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (v) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2005 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813022691/xu5731sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813022691/xu5731Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813022691/xu5731Isup3.cml

checkCIF report

Comment top

In continuation of on-going structural studies of salts/co-crystals formed between carboxylic acids and various pyridyl derivatives (Arman et al., 2010; Arman & Tiekink, 2013), the title salt co-crystal, (I), was isolated from the 2:3 co-crystallization of benzene-1,2,4,5-tetracarboxylic acid (LH₄) and 2,9-dimethyl-1,10-phenanthroline (Me₂Phen).

The asymmetric unit of (I) comprises a centrosymmetric, doubly deprotonated LH₂^2- dianion, a centrosymmetric neutral LH₄ molecule, a protonated Me₂PhenH⁺ cation and a neutral Me₂Phen molecule, Fig. 1, and is formulated as a combination of a 2:1 Me₂Phen⁺:LH₂^2- salt combined with a 2:1 Me₂Phen:HL₄ co-crystal. A salt formed between Me₂PhenH⁺ and a hydrogen(S,S)-tartrate has been reported (Derikvand & Olmstead, 2011).

Small twists are evident in the LH₂^2- dianion as seen in the C2—C1—C4—O2 and C1—C2—C5—O4 torsion angles of 168.41 (18) and 16.2 (3)°, respectively. This arrangement is stabilized by intramolecular O—H···O hydrogen bonds, Table 1. By contrast, a considerable twist is evident in LH₄ with the C7—C6—C9—O6 and C6—C7—C10—O7 torsion angles being 66.3 (2) and 18.2 (3)°, respectively. Such variations in conformation have been discussed in some detail (Arman & Tiekink, 2013). The Me₂Phen molecule and Me₂PhenH⁺ cation are each planar with the r.m.s. deviation for the 16 non-hydrogen atoms being 0.037 and 0.036 Å, respectively.

The prominent feature of the crystal packing is the formation of linear supramolecular chains along [0 0 1] comprising alternating LH₄ and LH₂^2- species connected via charge-assisted O6—H···O2 hydrogen bonding, Table 1. The hydroxyl-O8 forms an O—H···N4 hydrogen bond with the neutral Me₂Phen molecules, one to either side of the carboxylic acid/carboxylate chain. The O3,O4 carboxylic acid residue accepts hydrogen bonds from the N1—H1n atom of the Me₂PhenH⁺ cation, again, from symmetry, one to either side, leading to the supramolecular chain shown in Fig. 2a; an end-on view is shown in Fig. 2b. The Me₂Phen and Me₂PhenH⁺ cations inter-digitate along the c axis and are connected by π—π [Cg(C15–C20)···Cg(C29—C34)ⁱ = 3.5337 (17) Å for i: x, 1 + y, z] interactions between Me₂PhenH⁺ and Me₂Phen. Additional contacts are of the type C—H···O, Table 1, as illustrated in the crystal packing diagram, Fig. 3.

Related literature top

For salt formation with benzene-1,2,4,5-tetracarboxylic acid, see: Arman & Tiekink (2013). For a co-crystal involving 2,9-dimethyl-1,10-phenanthroline, see: Arman et al. (2010). For a structure of a 2,9-dimethyl-1,10-phenanthrolin-1-ium carboxylate salt, see: Derikvand & Olmstead (2011).

Experimental top

Crystals of (I) were obtained by the co-crystallization of benzene-1,2,4,5-tetracarboxylic acid (Sigma-Aldrich), 0.06 mmol) and 2,9-dimethylphenanthroline (ACROS, 0.09 mmol) in ethanol solution. Crystals were obtained by slow evaporation.

Computing details top

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2005); cell refinement: CrystalClear (Molecular Structure Corporation & Rigaku, 2005); data reduction: CrystalClear (Molecular Structure Corporation & Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Molecular structures of the components of (I), showing atom-labelling scheme and displacement ellipsoids at the 50% probability level: (a) LH₂^2-, (b) LH₄, (c) Me₂PhenH⁺ and (d) Me₂Phen.
	Fig. 2. Views (a) side-on and (b) end-on of the supramolecular chain in (I). The O—H···O (orange), O—H···N (blue) and N—H···O (blue) hydrogen bonds are shown as dashed lines.
	Fig. 3. Unit-cell contents in (I) viewed in projection down the c axis. The C—H···O interactions are shown green dashed lines.

Bis(2,9-dimethyl-1,10-phenanthrolin-1-ium) 2,5-dicarboxybenzene-1,4-dicarboxylate–2,9-dimethyl-1,10-phenanthroline–benzene-1,2,4,5-tetracarboxylic acid (1/2/1) top

Crystal data top

2C₁₄H₁₃N₂⁺·C₁₀H₄O₈²⁻·2C₁₄H₁₂N₂·C₁₀H₆O₈	F(000) = 1400
M_r = 1341.32	D_x = 1.419 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2yn	Cell parameters from 12762 reflections
a = 11.798 (4) Å	θ = 2.0–40.7°
b = 13.893 (4) Å	µ = 0.10 mm⁻¹
c = 19.163 (6) Å	T = 98 K
β = 92.216 (5)°	Prism, colourless
V = 3138.8 (16) Å³	0.48 × 0.37 × 0.09 mm
Z = 2

Data collection top

Rigaku AFC12K/SATURN724 diffractometer	7181 independent reflections
Radiation source: fine-focus sealed tube	6007 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.056
ω scans	θ_max = 27.5°, θ_min = 2.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −15→15
T_min = 0.723, T_max = 1.000	k = −18→18
22006 measured reflections	l = −18→24

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.148	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ²(F_o²) + (0.0555P)² + 1.3348P] where P = (F_o² + 2F_c²)/3
7181 reflections	(Δ/σ)_max < 0.001
467 parameters	Δρ_max = 0.29 e Å⁻³
4 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

2C₁₄H₁₃N₂⁺·C₁₀H₄O₈²⁻·2C₁₄H₁₂N₂·C₁₀H₆O₈	V = 3138.8 (16) Å³
M_r = 1341.32	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.798 (4) Å	µ = 0.10 mm⁻¹
b = 13.893 (4) Å	T = 98 K
c = 19.163 (6) Å	0.48 × 0.37 × 0.09 mm
β = 92.216 (5)°

Data collection top

Rigaku AFC12K/SATURN724 diffractometer	7181 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	6007 reflections with I > 2σ(I)
T_min = 0.723, T_max = 1.000	R_int = 0.056
22006 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	4 restraints
wR(F²) = 0.148	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	Δρ_max = 0.29 e Å⁻³
7181 reflections	Δρ_min = −0.25 e Å⁻³
467 parameters

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
O1	0.60101 (12)	0.56642 (11)	0.32029 (7)	0.0298 (3)
O2	0.42698 (12)	0.50799 (11)	0.31498 (7)	0.0271 (3)
O3	0.80815 (11)	0.52832 (11)	0.50668 (7)	0.0276 (3)
O4	0.75764 (12)	0.58534 (11)	0.40310 (7)	0.0275 (3)
H1O	0.7039 (17)	0.5802 (19)	0.3723 (11)	0.041*
O5	1.04388 (12)	0.10773 (11)	0.67551 (7)	0.0279 (3)
O6	0.93416 (12)	−0.02423 (10)	0.68129 (6)	0.0225 (3)
H2O	0.941 (2)	−0.0150 (17)	0.7251 (5)	0.034*
O7	0.78053 (11)	0.10681 (9)	0.60744 (6)	0.0217 (3)
O8	0.69585 (11)	0.03734 (10)	0.51309 (7)	0.0225 (3)
H3O	0.6399 (14)	0.0441 (18)	0.5394 (10)	0.034*
N1	0.49493 (13)	1.05719 (11)	0.10595 (8)	0.0216 (3)
H1N	0.5525 (13)	1.0368 (16)	0.0816 (10)	0.026*
N2	0.59146 (14)	0.87982 (12)	0.11607 (8)	0.0242 (4)
N3	0.38546 (15)	0.11239 (12)	0.39446 (8)	0.0251 (4)
N4	0.48691 (13)	−0.06451 (12)	0.41450 (8)	0.0212 (3)
C1	0.51592 (16)	0.51633 (13)	0.42769 (9)	0.0183 (4)
C2	0.61045 (15)	0.52086 (13)	0.47597 (9)	0.0174 (3)
C3	0.59041 (15)	0.50468 (13)	0.54626 (9)	0.0185 (4)
H3	0.6533	0.5082	0.5787	0.022*
C4	0.51495 (16)	0.53048 (14)	0.34896 (9)	0.0206 (4)
C5	0.73412 (16)	0.54460 (14)	0.46160 (10)	0.0215 (4)
C6	0.99235 (15)	0.02306 (12)	0.57069 (9)	0.0172 (3)
C7	0.89506 (15)	0.02660 (12)	0.52636 (9)	0.0170 (3)
C8	0.90372 (15)	0.00341 (13)	0.45593 (9)	0.0177 (4)
H8	0.8380	0.0057	0.4257	0.021*
C9	0.99120 (15)	0.04220 (13)	0.64807 (9)	0.0191 (4)
C10	0.78392 (15)	0.06034 (13)	0.55334 (9)	0.0182 (4)
C11	0.51318 (18)	1.21161 (15)	0.04831 (11)	0.0287 (4)
H11A	0.5737	1.2474	0.0733	0.043*
H11B	0.4577	1.2569	0.0277	0.043*
H11C	0.5457	1.1731	0.0112	0.043*
C12	0.45601 (16)	1.14676 (14)	0.09806 (10)	0.0234 (4)
C13	0.36476 (17)	1.17594 (14)	0.13837 (10)	0.0261 (4)
H13	0.3340	1.2388	0.1328	0.031*
C14	0.32018 (17)	1.11385 (15)	0.18567 (10)	0.0258 (4)
H14	0.2590	1.1343	0.2128	0.031*
C15	0.36416 (16)	1.01985 (14)	0.19451 (10)	0.0220 (4)
C16	0.45351 (16)	0.99289 (13)	0.15246 (10)	0.0206 (4)
C17	0.32532 (16)	0.95298 (15)	0.24508 (10)	0.0245 (4)
H17	0.2658	0.9708	0.2744	0.029*
C18	0.37276 (17)	0.86434 (15)	0.25149 (10)	0.0253 (4)
H18	0.3459	0.8209	0.2854	0.030*
C19	0.46257 (16)	0.83521 (13)	0.20811 (10)	0.0225 (4)
C20	0.50465 (16)	0.89957 (13)	0.15806 (10)	0.0214 (4)
C21	0.51552 (18)	0.74414 (15)	0.21224 (11)	0.0284 (4)
H21	0.4910	0.6975	0.2446	0.034*
C22	0.60207 (18)	0.72363 (15)	0.16957 (11)	0.0301 (5)
H22	0.6371	0.6621	0.1717	0.036*
C23	0.64006 (17)	0.79384 (15)	0.12197 (11)	0.0271 (4)
C24	0.73845 (19)	0.77429 (16)	0.07645 (12)	0.0353 (5)
H24A	0.7311	0.8138	0.0342	0.053*
H24B	0.7389	0.7061	0.0635	0.053*
H24C	0.8095	0.7903	0.1020	0.053*
C25	0.2311 (2)	0.21602 (17)	0.42569 (13)	0.0394 (6)
H25A	0.1657	0.1888	0.3995	0.059*
H25B	0.2202	0.2855	0.4314	0.059*
H25C	0.2385	0.1854	0.4717	0.059*
C26	0.3371 (2)	0.19826 (15)	0.38637 (11)	0.0310 (5)
C27	0.3831 (2)	0.27008 (16)	0.34338 (12)	0.0391 (6)
H27	0.3487	0.3318	0.3400	0.047*
C28	0.4769 (2)	0.24996 (18)	0.30682 (12)	0.0421 (6)
H28	0.5070	0.2973	0.2769	0.051*
C29	0.5297 (2)	0.15893 (17)	0.31328 (11)	0.0347 (5)
C30	0.48077 (17)	0.09257 (15)	0.35951 (9)	0.0253 (4)
C31	0.6265 (2)	0.1311 (2)	0.27508 (11)	0.0434 (7)
H31	0.6579	0.1756	0.2435	0.052*
C32	0.6740 (2)	0.0432 (2)	0.28292 (11)	0.0418 (6)
H32	0.7377	0.0265	0.2566	0.050*
C33	0.62883 (17)	−0.02531 (18)	0.33100 (11)	0.0322 (5)
C34	0.53289 (16)	−0.00081 (15)	0.36943 (10)	0.0239 (4)
C35	0.67628 (18)	−0.11709 (18)	0.34117 (12)	0.0379 (6)
H35	0.7416	−0.1353	0.3169	0.045*
C36	0.62834 (18)	−0.18028 (17)	0.38602 (12)	0.0342 (5)
H36	0.6598	−0.2427	0.3929	0.041*
C37	0.53169 (17)	−0.15191 (14)	0.42193 (11)	0.0256 (4)
C38	0.47268 (19)	−0.22145 (15)	0.46823 (12)	0.0326 (5)
H38A	0.4480	−0.1877	0.5099	0.049*
H38B	0.5250	−0.2734	0.4822	0.049*
H38C	0.4065	−0.2487	0.4428	0.049*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0286 (8)	0.0431 (9)	0.0180 (7)	−0.0085 (6)	0.0034 (6)	0.0057 (6)
O2	0.0271 (8)	0.0398 (8)	0.0145 (6)	−0.0042 (6)	0.0010 (5)	−0.0001 (6)
O3	0.0188 (7)	0.0367 (8)	0.0272 (7)	0.0001 (6)	−0.0012 (6)	0.0025 (6)
O4	0.0218 (7)	0.0401 (8)	0.0208 (7)	−0.0060 (6)	0.0042 (5)	0.0038 (6)
O5	0.0260 (7)	0.0373 (8)	0.0204 (7)	−0.0079 (6)	0.0032 (5)	−0.0083 (6)
O6	0.0290 (7)	0.0263 (7)	0.0122 (6)	−0.0009 (5)	0.0024 (5)	0.0003 (5)
O7	0.0234 (7)	0.0229 (7)	0.0191 (6)	−0.0006 (5)	0.0035 (5)	−0.0034 (5)
O8	0.0170 (6)	0.0313 (7)	0.0193 (7)	−0.0010 (5)	0.0029 (5)	−0.0039 (5)
N1	0.0181 (8)	0.0210 (8)	0.0256 (8)	0.0010 (6)	0.0007 (6)	−0.0010 (6)
N2	0.0229 (8)	0.0232 (8)	0.0264 (8)	0.0045 (6)	−0.0002 (6)	−0.0027 (6)
N3	0.0280 (9)	0.0243 (9)	0.0229 (8)	0.0006 (7)	−0.0024 (7)	0.0001 (6)
N4	0.0174 (7)	0.0246 (8)	0.0215 (8)	−0.0004 (6)	−0.0010 (6)	−0.0052 (6)
C1	0.0231 (9)	0.0168 (8)	0.0152 (8)	0.0017 (7)	0.0010 (7)	0.0004 (6)
C2	0.0190 (9)	0.0181 (8)	0.0152 (8)	0.0010 (6)	0.0022 (6)	−0.0010 (6)
C3	0.0190 (9)	0.0212 (9)	0.0152 (8)	0.0024 (7)	0.0002 (6)	0.0006 (7)
C4	0.0229 (9)	0.0235 (9)	0.0155 (8)	0.0028 (7)	0.0027 (7)	0.0003 (7)
C5	0.0211 (9)	0.0223 (9)	0.0212 (9)	−0.0010 (7)	0.0027 (7)	−0.0035 (7)
C6	0.0208 (9)	0.0177 (8)	0.0133 (8)	−0.0016 (7)	0.0036 (6)	−0.0010 (6)
C7	0.0188 (8)	0.0166 (8)	0.0156 (8)	−0.0012 (6)	0.0026 (6)	0.0005 (6)
C8	0.0164 (8)	0.0204 (9)	0.0160 (8)	−0.0008 (6)	−0.0018 (6)	−0.0004 (6)
C9	0.0170 (8)	0.0252 (9)	0.0153 (8)	0.0024 (7)	0.0013 (6)	−0.0013 (7)
C10	0.0205 (9)	0.0172 (8)	0.0172 (8)	0.0000 (7)	0.0020 (7)	0.0016 (6)
C11	0.0310 (11)	0.0250 (10)	0.0300 (11)	0.0021 (8)	0.0003 (8)	0.0029 (8)
C12	0.0221 (9)	0.0220 (9)	0.0257 (10)	0.0010 (7)	−0.0033 (7)	−0.0006 (7)
C13	0.0245 (10)	0.0218 (10)	0.0318 (11)	0.0062 (7)	−0.0020 (8)	−0.0048 (8)
C14	0.0216 (9)	0.0276 (10)	0.0283 (10)	0.0037 (7)	0.0022 (8)	−0.0062 (8)
C15	0.0187 (9)	0.0249 (9)	0.0221 (9)	0.0004 (7)	−0.0027 (7)	−0.0041 (7)
C16	0.0173 (9)	0.0228 (9)	0.0213 (9)	−0.0015 (7)	−0.0029 (7)	−0.0016 (7)
C17	0.0205 (9)	0.0316 (11)	0.0214 (9)	−0.0034 (8)	−0.0002 (7)	−0.0025 (8)
C18	0.0268 (10)	0.0267 (10)	0.0222 (9)	−0.0051 (8)	−0.0023 (8)	0.0012 (7)
C19	0.0241 (9)	0.0206 (9)	0.0223 (9)	−0.0021 (7)	−0.0049 (7)	−0.0026 (7)
C20	0.0212 (9)	0.0207 (9)	0.0222 (9)	0.0010 (7)	−0.0036 (7)	−0.0032 (7)
C21	0.0315 (11)	0.0226 (10)	0.0303 (11)	−0.0020 (8)	−0.0085 (8)	0.0010 (8)
C22	0.0328 (11)	0.0211 (10)	0.0357 (11)	0.0050 (8)	−0.0072 (9)	−0.0024 (8)
C23	0.0249 (10)	0.0258 (10)	0.0302 (10)	0.0035 (8)	−0.0038 (8)	−0.0056 (8)
C24	0.0323 (12)	0.0307 (11)	0.0432 (13)	0.0112 (9)	0.0034 (10)	−0.0051 (9)
C25	0.0454 (14)	0.0277 (11)	0.0444 (13)	0.0117 (10)	−0.0056 (11)	−0.0029 (10)
C26	0.0396 (12)	0.0256 (10)	0.0268 (10)	−0.0002 (9)	−0.0113 (9)	−0.0008 (8)
C27	0.0559 (16)	0.0267 (11)	0.0334 (12)	−0.0054 (10)	−0.0178 (11)	0.0059 (9)
C28	0.0616 (17)	0.0373 (13)	0.0263 (11)	−0.0224 (12)	−0.0150 (11)	0.0104 (9)
C29	0.0425 (13)	0.0411 (13)	0.0202 (10)	−0.0199 (10)	−0.0035 (9)	0.0016 (9)
C30	0.0283 (10)	0.0304 (10)	0.0168 (9)	−0.0091 (8)	−0.0024 (7)	−0.0017 (7)
C31	0.0448 (14)	0.0651 (18)	0.0203 (10)	−0.0326 (13)	0.0019 (9)	−0.0003 (10)
C32	0.0334 (12)	0.0664 (18)	0.0265 (11)	−0.0236 (12)	0.0105 (9)	−0.0155 (11)
C33	0.0211 (10)	0.0505 (14)	0.0252 (10)	−0.0123 (9)	0.0036 (8)	−0.0151 (9)
C34	0.0183 (9)	0.0321 (11)	0.0215 (9)	−0.0074 (8)	0.0015 (7)	−0.0055 (8)
C35	0.0176 (10)	0.0558 (15)	0.0404 (13)	−0.0023 (9)	0.0035 (9)	−0.0252 (11)
C36	0.0228 (10)	0.0381 (12)	0.0412 (12)	0.0078 (9)	−0.0039 (9)	−0.0193 (10)
C37	0.0200 (9)	0.0268 (10)	0.0297 (10)	0.0030 (7)	−0.0044 (8)	−0.0090 (8)
C38	0.0321 (11)	0.0244 (10)	0.0408 (12)	0.0035 (8)	−0.0062 (9)	−0.0006 (9)

Geometric parameters (Å, º) top

O1—C4	1.275 (2)	C15—C16	1.402 (3)
O2—C4	1.244 (2)	C15—C17	1.431 (3)
O3—C5	1.226 (2)	C16—C20	1.432 (3)
O4—C5	1.295 (2)	C17—C18	1.356 (3)
O4—H1O	0.853 (10)	C17—H17	0.9500
O5—C9	1.211 (2)	C18—C19	1.430 (3)
O6—C9	1.320 (2)	C18—H18	0.9500
O6—H2O	0.850 (10)	C19—C21	1.412 (3)
O7—C10	1.223 (2)	C19—C20	1.415 (3)
O8—C10	1.309 (2)	C21—C22	1.363 (3)
O8—H3O	0.851 (10)	C21—H21	0.9500
N1—C12	1.333 (2)	C22—C23	1.420 (3)
N1—C16	1.366 (2)	C22—H22	0.9500
N1—H1N	0.886 (10)	C23—C24	1.503 (3)
N2—C23	1.328 (3)	C24—H24A	0.9800
N2—C20	1.355 (3)	C24—H24B	0.9800
N3—C26	1.329 (3)	C24—H24C	0.9800
N3—C30	1.359 (3)	C25—C26	1.505 (3)
N4—C37	1.330 (3)	C25—H25A	0.9800
N4—C34	1.364 (3)	C25—H25B	0.9800
C1—C3ⁱ	1.399 (3)	C25—H25C	0.9800
C1—C2	1.423 (2)	C26—C27	1.415 (3)
C1—C4	1.521 (2)	C27—C28	1.362 (4)
C2—C3	1.395 (2)	C27—H27	0.9500
C2—C5	1.531 (3)	C28—C29	1.413 (4)
C3—C1ⁱ	1.399 (3)	C28—H28	0.9500
C3—H3	0.9500	C29—C30	1.417 (3)
C6—C8ⁱⁱ	1.396 (3)	C29—C31	1.433 (4)
C6—C7	1.402 (2)	C30—C34	1.445 (3)
C6—C9	1.507 (2)	C31—C32	1.349 (4)
C7—C8	1.395 (2)	C31—H31	0.9500
C7—C10	1.503 (3)	C32—C33	1.442 (3)
C8—C6ⁱⁱ	1.396 (3)	C32—H32	0.9500
C8—H8	0.9500	C33—C35	1.403 (3)
C11—C12	1.492 (3)	C33—C34	1.415 (3)
C11—H11A	0.9800	C35—C36	1.366 (3)
C11—H11B	0.9800	C35—H35	0.9500
C11—H11C	0.9800	C36—C37	1.411 (3)
C12—C13	1.409 (3)	C36—H36	0.9500
C13—C14	1.371 (3)	C37—C38	1.501 (3)
C13—H13	0.9500	C38—H38A	0.9800
C14—C15	1.413 (3)	C38—H38B	0.9800
C14—H14	0.9500	C38—H38C	0.9800

C5—O4—H1O	112.6 (18)	C20—C19—C18	120.15 (17)
C9—O6—H2O	109.7 (17)	N2—C20—C19	124.58 (18)
C10—O8—H3O	103.9 (16)	N2—C20—C16	117.70 (18)
C12—N1—C16	123.66 (17)	C19—C20—C16	117.71 (18)
C12—N1—H1N	120.4 (15)	C22—C21—C19	119.6 (2)
C16—N1—H1N	115.9 (15)	C22—C21—H21	120.2
C23—N2—C20	117.74 (18)	C19—C21—H21	120.2
C26—N3—C30	118.95 (19)	C21—C22—C23	120.28 (19)
C37—N4—C34	119.62 (18)	C21—C22—H22	119.9
C3ⁱ—C1—C2	117.94 (16)	C23—C22—H22	119.9
C3ⁱ—C1—C4	114.11 (15)	N2—C23—C22	121.8 (2)
C2—C1—C4	127.95 (17)	N2—C23—C24	116.98 (19)
C3—C2—C1	117.58 (17)	C22—C23—C24	121.24 (19)
C3—C2—C5	114.00 (15)	C23—C24—H24A	109.5
C1—C2—C5	128.39 (16)	C23—C24—H24B	109.5
C2—C3—C1ⁱ	124.48 (16)	H24A—C24—H24B	109.5
C2—C3—H3	117.8	C23—C24—H24C	109.5
C1ⁱ—C3—H3	117.8	H24A—C24—H24C	109.5
O2—C4—O1	122.35 (17)	H24B—C24—H24C	109.5
O2—C4—C1	117.46 (17)	C26—C25—H25A	109.5
O1—C4—C1	120.17 (16)	C26—C25—H25B	109.5
O3—C5—O4	121.32 (18)	H25A—C25—H25B	109.5
O3—C5—C2	119.44 (17)	C26—C25—H25C	109.5
O4—C5—C2	119.17 (16)	H25A—C25—H25C	109.5
C8ⁱⁱ—C6—C7	119.87 (16)	H25B—C25—H25C	109.5
C8ⁱⁱ—C6—C9	116.60 (15)	N3—C26—C27	121.9 (2)
C7—C6—C9	123.48 (16)	N3—C26—C25	116.8 (2)
C8—C7—C6	119.28 (17)	C27—C26—C25	121.4 (2)
C8—C7—C10	120.16 (15)	C28—C27—C26	119.5 (2)
C6—C7—C10	120.47 (16)	C28—C27—H27	120.3
C7—C8—C6ⁱⁱ	120.85 (16)	C26—C27—H27	120.3
C7—C8—H8	119.6	C27—C28—C29	120.2 (2)
C6ⁱⁱ—C8—H8	119.6	C27—C28—H28	119.9
O5—C9—O6	125.37 (17)	C29—C28—H28	119.9
O5—C9—C6	122.40 (17)	C28—C29—C30	116.7 (2)
O6—C9—C6	112.04 (15)	C28—C29—C31	123.6 (2)
O7—C10—O8	125.23 (17)	C30—C29—C31	119.7 (2)
O7—C10—C7	120.91 (16)	N3—C30—C29	122.7 (2)
O8—C10—C7	113.84 (15)	N3—C30—C34	118.23 (18)
C12—C11—H11A	109.5	C29—C30—C34	119.0 (2)
C12—C11—H11B	109.5	C32—C31—C29	121.5 (2)
H11A—C11—H11B	109.5	C32—C31—H31	119.2
C12—C11—H11C	109.5	C29—C31—H31	119.2
H11A—C11—H11C	109.5	C31—C32—C33	120.4 (2)
H11B—C11—H11C	109.5	C31—C32—H32	119.8
N1—C12—C13	118.27 (18)	C33—C32—H32	119.8
N1—C12—C11	118.29 (18)	C35—C33—C34	118.0 (2)
C13—C12—C11	123.41 (18)	C35—C33—C32	122.3 (2)
C14—C13—C12	120.16 (18)	C34—C33—C32	119.8 (2)
C14—C13—H13	119.9	N4—C34—C33	121.3 (2)
C12—C13—H13	119.9	N4—C34—C30	119.23 (18)
C13—C14—C15	120.83 (18)	C33—C34—C30	119.49 (19)
C13—C14—H14	119.6	C36—C35—C33	119.9 (2)
C15—C14—H14	119.6	C36—C35—H35	120.0
C16—C15—C14	117.30 (18)	C33—C35—H35	120.0
C16—C15—C17	118.90 (18)	C35—C36—C37	119.3 (2)
C14—C15—C17	123.76 (19)	C35—C36—H36	120.4
N1—C16—C15	119.75 (17)	C37—C36—H36	120.4
N1—C16—C20	118.73 (18)	N4—C37—C36	121.9 (2)
C15—C16—C20	121.51 (18)	N4—C37—C38	117.36 (18)
C18—C17—C15	120.61 (19)	C36—C37—C38	120.71 (19)
C18—C17—H17	119.7	C37—C38—H38A	109.5
C15—C17—H17	119.7	C37—C38—H38B	109.5
C17—C18—C19	121.10 (19)	H38A—C38—H38B	109.5
C17—C18—H18	119.4	C37—C38—H38C	109.5
C19—C18—H18	119.4	H38A—C38—H38C	109.5
C21—C19—C20	115.99 (19)	H38B—C38—H38C	109.5
C21—C19—C18	123.85 (19)

C3ⁱ—C1—C2—C3	−0.5 (3)	C18—C19—C20—N2	177.97 (17)
C4—C1—C2—C3	−179.62 (17)	C21—C19—C20—C16	−179.72 (16)
C3ⁱ—C1—C2—C5	−178.40 (17)	C18—C19—C20—C16	−0.6 (3)
C4—C1—C2—C5	2.4 (3)	N1—C16—C20—N2	−0.6 (2)
C1—C2—C3—C1ⁱ	0.5 (3)	C15—C16—C20—N2	−179.19 (16)
C5—C2—C3—C1ⁱ	178.73 (17)	N1—C16—C20—C19	178.12 (15)
C3ⁱ—C1—C4—O2	−10.8 (2)	C15—C16—C20—C19	−0.5 (3)
C2—C1—C4—O2	168.41 (18)	C20—C19—C21—C22	0.4 (3)
C3ⁱ—C1—C4—O1	167.52 (17)	C18—C19—C21—C22	−178.69 (18)
C2—C1—C4—O1	−13.3 (3)	C19—C21—C22—C23	1.0 (3)
C3—C2—C5—O3	15.2 (3)	C20—N2—C23—C22	1.1 (3)
C1—C2—C5—O3	−166.75 (18)	C20—N2—C23—C24	−178.25 (17)
C3—C2—C5—O4	−161.82 (17)	C21—C22—C23—N2	−1.8 (3)
C1—C2—C5—O4	16.2 (3)	C21—C22—C23—C24	177.49 (19)
C8ⁱⁱ—C6—C7—C8	0.0 (3)	C30—N3—C26—C27	−1.1 (3)
C9—C6—C7—C8	−177.05 (16)	C30—N3—C26—C25	179.39 (17)
C8ⁱⁱ—C6—C7—C10	−176.53 (16)	N3—C26—C27—C28	2.7 (3)
C9—C6—C7—C10	6.4 (3)	C25—C26—C27—C28	−177.8 (2)
C6—C7—C8—C6ⁱⁱ	0.0 (3)	C26—C27—C28—C29	−1.7 (3)
C10—C7—C8—C6ⁱⁱ	176.54 (16)	C27—C28—C29—C30	−0.8 (3)
C8ⁱⁱ—C6—C9—O5	64.4 (2)	C27—C28—C29—C31	178.0 (2)
C7—C6—C9—O5	−118.4 (2)	C26—N3—C30—C29	−1.5 (3)
C8ⁱⁱ—C6—C9—O6	−110.89 (18)	C26—N3—C30—C34	179.41 (16)
C7—C6—C9—O6	66.3 (2)	C28—C29—C30—N3	2.5 (3)
C8—C7—C10—O7	−158.38 (17)	C31—C29—C30—N3	−176.38 (18)
C6—C7—C10—O7	18.2 (3)	C28—C29—C30—C34	−178.51 (17)
C8—C7—C10—O8	20.0 (2)	C31—C29—C30—C34	2.7 (3)
C6—C7—C10—O8	−163.44 (16)	C28—C29—C31—C32	−180.0 (2)
C16—N1—C12—C13	−2.0 (3)	C30—C29—C31—C32	−1.2 (3)
C16—N1—C12—C11	176.50 (16)	C29—C31—C32—C33	−0.6 (3)
N1—C12—C13—C14	1.8 (3)	C31—C32—C33—C35	−179.5 (2)
C11—C12—C13—C14	−176.64 (18)	C31—C32—C33—C34	1.0 (3)
C12—C13—C14—C15	−0.4 (3)	C37—N4—C34—C33	−1.0 (3)
C13—C14—C15—C16	−0.8 (3)	C37—N4—C34—C30	177.42 (16)
C13—C14—C15—C17	176.99 (17)	C35—C33—C34—N4	−0.6 (3)
C12—N1—C16—C15	0.8 (3)	C32—C33—C34—N4	178.94 (17)
C12—N1—C16—C20	−177.88 (16)	C35—C33—C34—C30	−179.09 (17)
C14—C15—C16—N1	0.7 (3)	C32—C33—C34—C30	0.5 (3)
C17—C15—C16—N1	−177.25 (16)	N3—C30—C34—N4	−1.7 (3)
C14—C15—C16—C20	179.30 (16)	C29—C30—C34—N4	179.23 (16)
C17—C15—C16—C20	1.4 (3)	N3—C30—C34—C33	176.79 (16)
C16—C15—C17—C18	−1.1 (3)	C29—C30—C34—C33	−2.3 (3)
C14—C15—C17—C18	−178.89 (18)	C34—C33—C35—C36	1.3 (3)
C15—C17—C18—C19	0.0 (3)	C32—C33—C35—C36	−178.27 (19)
C17—C18—C19—C21	179.92 (18)	C33—C35—C36—C37	−0.4 (3)
C17—C18—C19—C20	0.9 (3)	C34—N4—C37—C36	2.0 (3)
C23—N2—C20—C19	0.4 (3)	C34—N4—C37—C38	−175.67 (16)
C23—N2—C20—C16	179.00 (16)	C35—C36—C37—N4	−1.4 (3)
C21—C19—C20—N2	−1.1 (3)	C35—C36—C37—C38	176.27 (18)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H1o···O1	0.85 (2)	1.55 (2)	2.403 (2)	176 (3)
O6—H2o···O2ⁱⁱⁱ	0.85 (1)	1.74 (1)	2.577 (2)	168 (2)
O8—H3o···N4^iv	0.85 (2)	1.79 (2)	2.636 (2)	173 (2)
N1—H1n···O3^v	0.89 (2)	2.41 (2)	3.257 (2)	161 (2)
N1—H1n···O4^v	0.89 (2)	2.35 (2)	2.957 (2)	126 (2)
C13—H13···O7^vi	0.95	2.28	3.225 (3)	171
C28—H28···O5^vii	0.95	2.40	3.320 (3)	162

Symmetry codes: (iii) x+1/2, −y+1/2, z+1/2; (iv) −x+1, −y, −z+1; (v) −x+3/2, y+1/2, −z+1/2; (vi) x−1/2, −y+3/2, z−1/2; (vii) x−1/2, −y+1/2, z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H1o···O1	0.85 (2)	1.55 (2)	2.403 (2)	176 (3)
O6—H2o···O2ⁱ	0.850 (10)	1.739 (10)	2.577 (2)	168 (2)
O8—H3o···N4ⁱⁱ	0.851 (18)	1.789 (17)	2.636 (2)	172.9 (18)
N1—H1n···O3ⁱⁱⁱ	0.885 (17)	2.407 (17)	3.257 (2)	160.9 (18)
N1—H1n···O4ⁱⁱⁱ	0.885 (17)	2.347 (16)	2.957 (2)	126.2 (16)
C13—H13···O7^iv	0.95	2.28	3.225 (3)	171
C28—H28···O5^v	0.95	2.40	3.320 (3)	162

Symmetry codes: (i) x+1/2, −y+1/2, z+1/2; (ii) −x+1, −y, −z+1; (iii) −x+3/2, y+1/2, −z+1/2; (iv) x−1/2, −y+3/2, z−1/2; (v) x−1/2, −y+1/2, z−1/2.

Acknowledgements

We gratefully thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM.C/HIR-MOHE/SC/03).

References

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 9| September 2013| Pages o1445-o1446

doi:10.1107/S1600536813022691

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Bis(2,9-di­methyl-1,10-phenanthrolin-1-ium) 2,5-di­carb­­oxy­benzene-1,4-di­carb­oxyl­ate–2,9-di­methyl-1,10-phenanthroline–benzene-1,2,4,5-tetra­carb­­oxy­lic acid (1/2/1)

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

Bis(2,9-dimethyl-1,10-phenanthrolin-1-ium) 2,5-dicarboxybenzene-1,4-dicarboxylate–2,9-dimethyl-1,10-phenanthroline–benzene-1,2,4,5-tetracarboxylic acid (1/2/1)