![](/logos/buttonlogos/cross.png)
![](/logos/buttonlogos/cross.png)
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)
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
The 14H13N2+·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].
of the title 2CRelated literature
For salt formation with benzene-1,2,4,5-tetracarboxylic acid, see: Arman & Tiekink (2013). For a 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
|
|
Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2005); cell 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
10.1107/S1600536813022691/xu5731sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536813022691/xu5731Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536813022691/xu5731Isup3.cml
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.
C-bound H-atoms were placed in calculated positions (C—H = 0.95–0.98 Å) and were included in the
in the riding model approximation with Uiso(H) set to 1.2–1.5Ueq(C). The O-and N-bound H-atoms were located in a difference Fourier map and were refined with a distance restraints of O—H = 0.84±0.01 Å and N—H = 0.88±0.01 Å, and with Uiso(H) = 1.2Ueq(N) and 1.5Ueq(O). Owing to being affected by the beam-stop, three reflections, i.e. (0 0 1), (1 0 1) and (-6 0 2), were omitted from the final cycles of refinement.Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2005); cell
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).2C14H13N2+·C10H4O82−·2C14H12N2·C10H6O8 | F(000) = 1400 |
Mr = 1341.32 | Dx = 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 |
Rigaku AFC12K/SATURN724 diffractometer | 7181 independent reflections |
Radiation source: fine-focus sealed tube | 6007 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.056 |
ω scans | θmax = 27.5°, θmin = 2.1° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −15→15 |
Tmin = 0.723, Tmax = 1.000 | k = −18→18 |
22006 measured reflections | l = −18→24 |
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(Fo2) + (0.0555P)2 + 1.3348P] where P = (Fo2 + 2Fc2)/3 |
7181 reflections | (Δ/σ)max < 0.001 |
467 parameters | Δρmax = 0.29 e Å−3 |
4 restraints | Δρmin = −0.25 e Å−3 |
2C14H13N2+·C10H4O82−·2C14H12N2·C10H6O8 | V = 3138.8 (16) Å3 |
Mr = 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)° |
Rigaku AFC12K/SATURN724 diffractometer | 7181 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 6007 reflections with I > 2σ(I) |
Tmin = 0.723, Tmax = 1.000 | Rint = 0.056 |
22006 measured reflections |
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 | Δρmax = 0.29 e Å−3 |
7181 reflections | Δρmin = −0.25 e Å−3 |
467 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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. |
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···N4iv | 0.85 (2) | 1.79 (2) | 2.636 (2) | 173 (2) |
N1—H1n···O3v | 0.89 (2) | 2.41 (2) | 3.257 (2) | 161 (2) |
N1—H1n···O4v | 0.89 (2) | 2.35 (2) | 2.957 (2) | 126 (2) |
C13—H13···O7vi | 0.95 | 2.28 | 3.225 (3) | 171 |
C28—H28···O5vii | 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. |
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···O7iv | 0.95 | 2.28 | 3.225 (3) | 171 |
C28—H28···O5v | 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
Arman, H. D., Kaulgud, T. & Tiekink, E. R. T. (2010). Acta Cryst. E66, o2602. Web of Science CSD CrossRef IUCr Journals Google Scholar
Arman, H. D. & Tiekink, E. R. T. (2013). Z. Kristallogr. Cryst. Mat. 228, 289–294. Web of Science CSD CrossRef CAS Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Derikvand, Z. & Olmstead, M. M. (2011). Acta Cryst. E67, o87–o88. Web of Science CrossRef CAS IUCr Journals Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Molecular Structure Corporation & Rigaku (2005). CrystalClear. MSC, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
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 LH22- 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+:LH22- 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 LH22- 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 LH22- 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.