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Acta Crystallogr Sect E Struct Rep Online. 2009 October 1; 65(Pt 10): o2478.
Published online 2009 September 16. doi:  10.1107/S1600536809036551
PMCID: PMC2970503

1,10-Phenanthrolinium 2′-carboxy­biphenyl-2-carboxyl­ate

Abstract

The title complex, C12H9N2 +·C14H9O4 or (Hphen)+(Hbptc) [H2btc = 2,2′-biphenyl­dicarboxylic acid and phen = 1,10-phenanthroline], has been synthesized under hydro­thermal conditions. The compound is composed of discrete cations (Hphen)+ and anions (Hbptc), which are linked by electrovalent bonding; the molecular and crystal structures are further strengthened by intra­molecular O—H(...)O and inter­molecular N—H(...)O hydrogen bonds.

Related literature

For the applications of the metal-organic coordination compounds constructed from biphenydicarboxylic acid, see: Gao & Cheng (2004 [triangle]).

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Object name is e-65-o2478-scheme1.jpg

Experimental

Crystal data

  • C12H9N2 +·C14H9O4
  • M r = 422.42
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2478-efi1.jpg
  • a = 12.1661 (13) Å
  • b = 7.389 (1) Å
  • c = 22.160 (2) Å
  • β = 91.061 (1)°
  • V = 1991.8 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 298 K
  • 0.48 × 0.45 × 0.37 mm

Data collection

  • Bruker SMART CCD area detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2007 [triangle]) T min = 0.955, T max = 0.965
  • 9415 measured reflections
  • 3479 independent reflections
  • 1771 reflections with I > 2σ(I)
  • R int = 0.102

Refinement

  • R[F 2 > 2σ(F 2)] = 0.076
  • wR(F 2) = 0.243
  • S = 1.01
  • 3479 reflections
  • 289 parameters
  • H-atom parameters constrained
  • Δρmax = 0.30 e Å−3
  • Δρmin = −0.29 e Å−3

Data collection: SMART (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809036551/ez2179sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809036551/ez2179Isup2.hkl

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

Acknowledgments

The author gratefully acknowledges the financial support of the Research Fund of Beijing University of Civil Engineering and Architecture, the Funding Project for Academic Human Resources Development in Institutions of Higher Learning Under the Jurisdiction of the Beijing Municipality.

supplementary crystallographic information

Comment

1,10-phenanthroline and 2,2'-biphenyldicarboxylic acid are both versatile ligands, which have been used in the self-assembly of various coordination compounds. The crystals of the title compound were obtained unintentionally as the harvested product of the hydrothermal reaction between Ce2O3 and 1,10-phenanthroline in the presence of 2,2'-biphenyldicarboxylic acid.

In the crystal of the title compound, 1,10-phenanthroline is protonated into the cation 1,10-phenanthrolinium [(Hphen)+], as indicated by the presence of a peak of electron density on the difference Fourier map at an appropriate distance from N1. The 2,2'-biphenydicarboxylic acid has been deprotonated into the anion biphenyldicarboxylate [(Hbptc)-], with the similar C—O distances on the deprotonated carboxylate indicating delocalisation (O1—C1=1.274 (5); O2—C1=1.221 (5)Å), whereas the C—O distances in the carboxylic acid group (O3—C14=1.315 (5); O4—C14=1.197 (5) Å) correspond to single and double bonds, respectively. The discrete cations (Hphen)+ and anions (Hbptc)- are linked by an electrovalent bond, and further strengthened by intermolecular N1—H1···O1i(Symmetry operator, i: -x + 1, y + 1/2, -z + 1/2) and intramolecular O3—H3···O1 hydrogen bonds.

The phenyl rings of the 2,2'-biphenyldicarboxylate are not coplanar, but twisted almost perpendicular to each other with a dihedral angle between the planes through the two rings of 86.06(0.13) °.

Experimental

The mixture of 2,2'-biphenydicarboxylic acid (0.04884 g), 1,10-phenanthroline (0.0360 g), Ce2O3 (0.0702 g) and deionized water (15 ml) was heated in a 23 ml teflon-lined reaction vessel at 433 K for 120 h to carry out the hydrothermal reaction. After slow cooling to room temperature the mixture was filtered, and the clear solution obtained was allowed to evaporate slowly at room temperature. After about 10 days, yellow block-like crystals of the title compound were harvested.

Refinement

The positions of the hydrogen atoms on O3 and N1 were identified from a difference Fourier map. All H atoms were then fixed geometrically and allowed to ride on their parent carbon atoms, with C—H distances of 0.93 Å, an N—H distance of 0.86 Å and an O—H distance of 0.82 Å; and with Uiso(H) = 1.2Ueq(C, N) or 1.5Ueq(O).

Figures

Fig. 1.
ORTEP drawing of the title compound showing the atom labelling scheme. Ellipsoids are drawn at the 30% level.
Fig. 2.
The crystal packing of the title complex. Hydrogen bonds are indicated by dashed lines.

Crystal data

C12H9N2+·C14H9O4F(000) = 880
Mr = 422.42Dx = 1.409 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 12.1661 (13) ÅCell parameters from 1541 reflections
b = 7.389 (1) Åθ = 2.5–21.4°
c = 22.160 (2) ŵ = 0.10 mm1
β = 91.061 (1)°T = 298 K
V = 1991.8 (4) Å3Block, brown
Z = 40.48 × 0.45 × 0.37 mm

Data collection

Bruker SMART CCD area detector diffractometer3479 independent reflections
Radiation source: fine-focus sealed tube1771 reflections with I > 2σ(I)
graphiteRint = 0.102
phi and ω scansθmax = 25.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2007)h = −14→14
Tmin = 0.955, Tmax = 0.965k = −8→7
9415 measured reflectionsl = −22→26

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.076Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.243H-atom parameters constrained
S = 1.01w = 1/[σ2(Fo2) + (0.0849P)2 + 0.7223P] where P = (Fo2 + 2Fc2)/3
3479 reflections(Δ/σ)max < 0.001
289 parametersΔρmax = 0.30 e Å3
0 restraintsΔρmin = −0.29 e Å3

Special details

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)

xyzUiso*/Ueq
N10.4893 (3)0.7686 (4)0.46216 (17)0.0382 (9)
H10.54620.81700.44640.046*
N20.6719 (3)0.8548 (5)0.52863 (18)0.0486 (11)
O10.3597 (2)0.4014 (4)0.10974 (14)0.0472 (8)
O20.4735 (2)0.3641 (5)0.18797 (16)0.0674 (11)
O30.1925 (2)0.5887 (4)0.07606 (14)0.0491 (9)
H30.24190.52100.08780.074*
O40.0140 (3)0.5855 (4)0.06817 (18)0.0685 (11)
C10.3850 (3)0.4087 (6)0.1657 (2)0.0411 (11)
C20.3001 (3)0.4868 (5)0.20651 (19)0.0349 (10)
C30.3300 (3)0.6209 (6)0.2472 (2)0.0447 (12)
H3A0.40310.65730.24980.054*
C40.2558 (4)0.7001 (6)0.2831 (2)0.0493 (12)
H40.27800.79160.30950.059*
C50.1464 (4)0.6457 (6)0.2811 (2)0.0505 (13)
H50.09500.70020.30570.061*
C60.1159 (3)0.5112 (6)0.2422 (2)0.0438 (11)
H60.04330.47140.24170.053*
C70.1900 (3)0.4322 (5)0.20367 (19)0.0344 (10)
C80.1484 (3)0.2851 (5)0.1628 (2)0.0347 (10)
C90.1496 (3)0.1076 (6)0.1828 (2)0.0442 (12)
H90.18200.07870.21990.053*
C100.1030 (4)−0.0250 (6)0.1479 (2)0.0505 (13)
H100.1074−0.14470.16070.061*
C110.0497 (4)0.0149 (6)0.0943 (2)0.0548 (13)
H110.0156−0.07620.07180.066*
C120.0474 (3)0.1894 (6)0.0745 (2)0.0466 (12)
H120.01160.21770.03830.056*
C130.0983 (3)0.3256 (5)0.1082 (2)0.0358 (10)
C140.0970 (3)0.5087 (6)0.0828 (2)0.0413 (11)
C150.4040 (3)0.7289 (6)0.4267 (2)0.0461 (12)
H150.40630.75340.38560.055*
C160.3115 (3)0.6510 (6)0.4508 (3)0.0526 (14)
H160.25070.62480.42630.063*
C170.3104 (4)0.6130 (6)0.5107 (3)0.0517 (13)
H170.24850.55920.52700.062*
C180.4003 (3)0.6533 (5)0.5482 (2)0.0417 (11)
C190.4904 (3)0.7367 (5)0.5213 (2)0.0371 (11)
C200.5865 (3)0.7782 (6)0.5575 (2)0.0421 (11)
C210.5874 (4)0.7370 (6)0.6186 (2)0.0503 (13)
C220.6842 (5)0.7747 (7)0.6519 (2)0.0632 (15)
H220.68930.74970.69300.076*
C230.7701 (4)0.8488 (7)0.6223 (3)0.0667 (16)
H230.83540.87360.64310.080*
C240.7609 (4)0.8868 (7)0.5623 (2)0.0568 (14)
H240.82110.93860.54360.068*
C250.4055 (4)0.6151 (7)0.6106 (3)0.0570 (14)
H250.34500.56220.62870.068*
C260.4940 (4)0.6525 (7)0.6443 (3)0.0590 (14)
H260.49510.62310.68510.071*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0245 (18)0.044 (2)0.046 (3)−0.0031 (15)0.0015 (16)0.0019 (18)
N20.033 (2)0.061 (3)0.052 (3)−0.0009 (18)−0.0029 (18)0.0035 (19)
O10.0283 (16)0.074 (2)0.039 (2)0.0077 (14)0.0005 (14)−0.0034 (17)
O20.0330 (18)0.106 (3)0.063 (3)0.0231 (18)−0.0067 (16)0.001 (2)
O30.0361 (17)0.0474 (18)0.064 (2)0.0008 (14)−0.0022 (15)0.0129 (16)
O40.0416 (19)0.052 (2)0.111 (3)0.0062 (16)−0.0257 (19)0.004 (2)
C10.026 (2)0.047 (3)0.050 (3)0.0011 (19)0.005 (2)0.001 (2)
C20.029 (2)0.037 (2)0.038 (3)0.0025 (18)−0.0028 (18)0.001 (2)
C30.031 (2)0.053 (3)0.050 (3)−0.005 (2)−0.009 (2)0.003 (2)
C40.056 (3)0.047 (3)0.045 (3)0.007 (2)−0.009 (2)−0.008 (2)
C50.041 (3)0.059 (3)0.051 (3)0.007 (2)0.001 (2)−0.012 (2)
C60.032 (2)0.052 (3)0.047 (3)0.004 (2)0.003 (2)−0.002 (2)
C70.027 (2)0.038 (2)0.038 (3)0.0013 (18)−0.0018 (18)0.0033 (19)
C80.024 (2)0.034 (2)0.046 (3)0.0014 (17)0.0036 (19)−0.004 (2)
C90.038 (2)0.042 (3)0.053 (3)0.001 (2)0.003 (2)0.001 (2)
C100.055 (3)0.034 (3)0.063 (4)0.000 (2)0.012 (3)0.001 (2)
C110.055 (3)0.044 (3)0.065 (4)−0.010 (2)0.002 (3)−0.014 (3)
C120.038 (3)0.043 (3)0.059 (4)−0.004 (2)−0.002 (2)−0.011 (2)
C130.026 (2)0.037 (2)0.044 (3)0.0005 (18)−0.0017 (19)−0.001 (2)
C140.033 (3)0.042 (3)0.049 (3)0.002 (2)−0.009 (2)−0.007 (2)
C150.033 (2)0.051 (3)0.055 (3)0.001 (2)−0.005 (2)0.000 (2)
C160.026 (2)0.059 (3)0.073 (4)−0.007 (2)0.000 (2)−0.011 (3)
C170.038 (3)0.046 (3)0.072 (4)−0.005 (2)0.016 (3)−0.008 (3)
C180.038 (3)0.035 (2)0.053 (3)0.0052 (19)0.013 (2)−0.001 (2)
C190.032 (2)0.035 (2)0.044 (3)0.0055 (18)0.005 (2)0.001 (2)
C200.039 (3)0.038 (2)0.049 (3)0.011 (2)0.004 (2)−0.002 (2)
C210.061 (3)0.045 (3)0.045 (3)0.010 (2)0.000 (2)0.000 (2)
C220.073 (4)0.072 (4)0.045 (4)0.010 (3)−0.009 (3)0.002 (3)
C230.055 (3)0.083 (4)0.062 (4)0.000 (3)−0.012 (3)−0.001 (3)
C240.038 (3)0.073 (4)0.059 (4)−0.002 (2)−0.009 (2)0.002 (3)
C250.055 (3)0.056 (3)0.061 (4)0.007 (3)0.021 (3)0.009 (3)
C260.068 (4)0.060 (3)0.050 (4)0.015 (3)0.016 (3)0.012 (3)

Geometric parameters (Å, °)

N1—C151.324 (5)C10—H100.9300
N1—C191.332 (5)C11—C121.363 (6)
N1—H10.8600C11—H110.9300
N2—C241.324 (6)C12—C131.392 (6)
N2—C201.354 (5)C12—H120.9300
O1—C11.274 (5)C13—C141.465 (6)
O2—C11.221 (5)C15—C161.380 (6)
O3—C141.315 (5)C15—H150.9300
O3—H30.8200C16—C171.356 (7)
O4—C141.197 (5)C16—H160.9300
C1—C21.501 (6)C17—C181.395 (6)
C2—C31.384 (6)C17—H170.9300
C2—C71.399 (5)C18—C191.401 (6)
C3—C41.348 (6)C18—C251.412 (7)
C3—H3A0.9300C19—C201.437 (6)
C4—C51.391 (6)C20—C211.390 (7)
C4—H40.9300C21—C221.406 (7)
C5—C61.361 (6)C21—C261.424 (7)
C5—H50.9300C22—C231.359 (7)
C6—C71.383 (6)C22—H220.9300
C6—H60.9300C23—C241.363 (7)
C7—C81.497 (6)C23—H230.9300
C8—C131.379 (6)C24—H240.9300
C8—C91.384 (6)C25—C261.328 (7)
C9—C101.364 (6)C25—H250.9300
C9—H90.9300C26—H260.9300
C10—C111.376 (7)
C15—N1—C19122.6 (4)C8—C13—C14122.6 (4)
C15—N1—H1118.7C12—C13—C14117.4 (4)
C19—N1—H1118.7O4—C14—O3119.9 (4)
C24—N2—C20115.8 (4)O4—C14—C13123.0 (4)
C14—O3—H3109.5O3—C14—C13117.1 (4)
O2—C1—O1125.2 (4)N1—C15—C16119.9 (5)
O2—C1—C2118.2 (4)N1—C15—H15120.1
O1—C1—C2116.5 (4)C16—C15—H15120.1
C3—C2—C7118.4 (4)C17—C16—C15119.3 (4)
C3—C2—C1119.5 (4)C17—C16—H16120.4
C7—C2—C1122.1 (4)C15—C16—H16120.4
C4—C3—C2121.7 (4)C16—C17—C18121.1 (4)
C4—C3—H3A119.2C16—C17—H17119.4
C2—C3—H3A119.2C18—C17—H17119.4
C3—C4—C5120.4 (4)C17—C18—C19116.9 (5)
C3—C4—H4119.8C17—C18—C25124.2 (5)
C5—C4—H4119.8C19—C18—C25118.9 (4)
C6—C5—C4118.8 (4)N1—C19—C18120.2 (4)
C6—C5—H5120.6N1—C19—C20120.3 (4)
C4—C5—H5120.6C18—C19—C20119.4 (4)
C5—C6—C7121.7 (4)N2—C20—C21124.1 (4)
C5—C6—H6119.2N2—C20—C19116.7 (4)
C7—C6—H6119.2C21—C20—C19119.2 (4)
C6—C7—C2119.0 (4)C20—C21—C22117.4 (5)
C6—C7—C8117.6 (3)C20—C21—C26119.6 (5)
C2—C7—C8123.4 (4)C22—C21—C26123.0 (5)
C13—C8—C9119.2 (4)C23—C22—C21118.1 (5)
C13—C8—C7120.8 (4)C23—C22—H22121.0
C9—C8—C7119.6 (4)C21—C22—H22121.0
C10—C9—C8119.9 (5)C22—C23—C24120.3 (5)
C10—C9—H9120.1C22—C23—H23119.9
C8—C9—H9120.1C24—C23—H23119.9
C9—C10—C11121.3 (4)N2—C24—C23124.4 (5)
C9—C10—H10119.4N2—C24—H24117.8
C11—C10—H10119.4C23—C24—H24117.8
C12—C11—C10119.2 (4)C26—C25—C18122.0 (5)
C12—C11—H11120.4C26—C25—H25119.0
C10—C11—H11120.4C18—C25—H25119.0
C11—C12—C13120.3 (5)C25—C26—C21120.8 (5)
C11—C12—H12119.8C25—C26—H26119.6
C13—C12—H12119.8C21—C26—H26119.6
C8—C13—C12120.0 (4)
O2—C1—C2—C347.2 (6)C12—C13—C14—O3−123.8 (4)
O1—C1—C2—C3−130.0 (4)C19—N1—C15—C16−0.1 (6)
O2—C1—C2—C7−134.7 (5)N1—C15—C16—C17−1.3 (7)
O1—C1—C2—C748.1 (6)C15—C16—C17—C180.8 (7)
C7—C2—C3—C4−0.8 (7)C16—C17—C18—C190.9 (6)
C1—C2—C3—C4177.4 (4)C16—C17—C18—C25−179.0 (4)
C2—C3—C4—C51.3 (7)C15—N1—C19—C181.9 (6)
C3—C4—C5—C60.1 (7)C15—N1—C19—C20178.3 (4)
C4—C5—C6—C7−2.2 (7)C17—C18—C19—N1−2.2 (6)
C5—C6—C7—C22.7 (7)C25—C18—C19—N1177.7 (4)
C5—C6—C7—C8179.9 (4)C17—C18—C19—C20−178.7 (4)
C3—C2—C7—C6−1.2 (6)C25—C18—C19—C201.2 (6)
C1—C2—C7—C6−179.4 (4)C24—N2—C20—C211.4 (6)
C3—C2—C7—C8−178.2 (4)C24—N2—C20—C19−177.9 (4)
C1—C2—C7—C83.7 (6)N1—C19—C20—N21.9 (6)
C6—C7—C8—C1384.8 (5)C18—C19—C20—N2178.4 (4)
C2—C7—C8—C13−98.2 (5)N1—C19—C20—C21−177.4 (4)
C6—C7—C8—C9−88.3 (5)C18—C19—C20—C21−0.9 (6)
C2—C7—C8—C988.7 (5)N2—C20—C21—C22−1.2 (7)
C13—C8—C9—C101.1 (6)C19—C20—C21—C22178.1 (4)
C7—C8—C9—C10174.3 (4)N2—C20—C21—C26−178.5 (4)
C8—C9—C10—C11−3.2 (7)C19—C20—C21—C260.8 (6)
C9—C10—C11—C122.8 (7)C20—C21—C22—C230.0 (7)
C10—C11—C12—C13−0.1 (7)C26—C21—C22—C23177.2 (5)
C9—C8—C13—C121.5 (6)C21—C22—C23—C240.9 (8)
C7—C8—C13—C12−171.6 (4)C20—N2—C24—C23−0.4 (7)
C9—C8—C13—C14−177.7 (4)C22—C23—C24—N2−0.7 (8)
C7—C8—C13—C149.2 (6)C17—C18—C25—C26178.5 (4)
C11—C12—C13—C8−2.0 (6)C19—C18—C25—C26−1.4 (7)
C11—C12—C13—C14177.2 (4)C18—C25—C26—C211.3 (7)
C8—C13—C14—O4−124.9 (5)C20—C21—C26—C25−1.0 (7)
C12—C13—C14—O455.9 (6)C22—C21—C26—C25−178.2 (5)
C8—C13—C14—O355.4 (6)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.861.822.643 (4)161
O3—H3···O10.821.752.559 (4)172

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: EZ2179).

References

  • Bruker (2007). SMART, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Gao, H.-W. & Cheng, P. (2004). Chin. J. Inorg. Chem.20, 1145–1149.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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