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Acta Crystallogr Sect E Struct Rep Online. 2009 August 1; 65(Pt 8): o1851.
Published online 2009 July 15. doi:  10.1107/S1600536809025914
PMCID: PMC2977266

2,2′-(Biphenyl-4,4′-diyldi­oxy)diacetic acid N,N-dimethyl­formamide solvate

Abstract

In the crystal struture of the title compound, C16H14O6·C3H7NO, the two crystallographically independent benzene rings are coplanar [dihedral angle = 1.00 (2)°]. The crystal structure is stabilized by O—H(...)O hydrogen bonds between the diacid and the solvate dimethylformamide mol­ecule, resulting in the formation of a zigzag chain structure extending parallel to [001].

Related literature

For general background to biphenyl carbinols and their biological applications, see: Kamoda et al. (2006 [triangle]); Mikami & Yamanaka (2003 [triangle]); Sallam et al. (2006 [triangle]). For the crystal structures of related compounds, see: Rabnawaz et al. (2008 [triangle]); Tan et al. (2005 [triangle]). For the preparation of the title compound, see: Hayes & Branch (1943 [triangle]).

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Object name is e-65-o1851-scheme1.jpg

Experimental

Crystal data

  • C16H14O6·C3H7NO
  • M r = 375.37
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1851-efi1.jpg
  • a = 7.7471 (15) Å
  • b = 8.1758 (16) Å
  • c = 28.625 (6) Å
  • V = 1813.1 (6) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.11 mm−1
  • T = 298 K
  • 0.32 × 0.25 × 0.18 mm

Data collection

  • Bruker SMART APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2004 [triangle]) T min = 0.971, T max = 0.984
  • 9412 measured reflections
  • 2079 independent reflections
  • 1778 reflections with I > 2σ(I)
  • R int = 0.028

Refinement

  • R[F 2 > 2σ(F 2)] = 0.042
  • wR(F 2) = 0.116
  • S = 1.05
  • 2079 reflections
  • 246 parameters
  • H-atom parameters constrained
  • Δρmax = 0.22 e Å−3
  • Δρmin = −0.19 e Å−3

Data collection: APEX2 (Bruker, 2004 [triangle]); cell refinement: SAINT (Bruker, 2004 [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: XP in SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809025914/zl2216sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809025914/zl2216Isup2.hkl

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

supplementary crystallographic information

Comment

Biphenyl carbinols are valuable intermediates in the preparation of new ligands (Mikami et al., 2003; Rabnawaz et al., 2008; Tan et al., 2005) and have shown important biological activities (Kamoda et al., 2006; Sallam et al., 2006). As part of our ongoing study of such biphenyl carbinol compounds, the crystal structure of the title compound is reported in this work.

The molecular structure of the title compound is shown in Fig. 1. The two crystallographically independent benzene rings are coplanar (dihedral angle = 1.00 (2)°) and the two carboxylic acid groups are oriented in different directions. There are no unusual bonds lengths and angles. The C1—O1 and C16—O5 distances in the title compound are 1.197 (3)Å and 1.184 (4)Å, respectively, typical of double bonds.

The –OCH2COOH substituents show torsion angles of 176.0 (2)° (C2—O3—C3—C8) and 169.7 (2)° (C15—O4—C12—C11) with respect to the phenyl rings. Intermolecular O—H···O hydrogen bonds between the hydroxyl groups of the diacid and the carbonyl group of the DMF molecule (Table 1) are observed in this structure, thereby forming a one-dimensional zigzag chain structure along the c-axial direction (Fig. 2).

The crystal structure is further stabilized by weak intermolecular hydrogen bonding interactions between the diacids, thus forming a sandwich structure as represented in Fig. 3.

Experimental

The title compound was prepared according to the general procedure reported by Hayes & Branch (1943). 2-Chloroacetic acid (114 mg, 1.2 mmol) and sodium hydroxide (40 mg, 10 mmol) in 20 ml of N,N-dimethylformamide (DMF) were stirred for 10 min, followed by addition of 2,2'-dihydroxybiphenyl (186 mg, 1 mmol). The reaction mixture was stirred at 100 °C for 3 h. After cooling, the solution was acidified and extracted with ether. Slow evaporation of ether at room temperature yielded colorless crystals of the title compound. IR(KBr pellet, cm-1): 3428.47, 3042.21, 2905.29, 2787.94,1740.59, 1707.78, 1607.65, 1500.03, 1430.90, 1234.94, 830.29, 797.57.

Refinement

All H atoms were placed in calculated positions and were allowed to ride on their parent atoms; C—H = 0.93 (aromatic C—H), 0.97 (methylene) and 0.96 (methyl) and O—H = 0.82 (hydroxyl) Å; Uiso(H) = 1.2 Ueq (aromatic and methylene C), Uiso(H) = 1.5 Ueq (methyl C) and Uiso (H) = 1.5 Ueq (O). In the absence of anomalous scatterers and using Mo radiation Friedel pairs were merged prior to refinement.

Figures

Fig. 1.
The molecular structure of the title compound with displacement ellipsoids at the 50% probability level. All H atoms are drawn as spheres of arbitrary radius.
Fig. 2.
A one-dimensional zigzag chain generated by the hydrogen bonds along the c-axial direction in the title compound. All H atoms are omitted for clarity.
Fig. 3.
A crystallographic packing diagram of the title compound.

Crystal data

C16H14O6·C3H7NODx = 1.375 Mg m3
Mr = 375.37Melting point = 524.9–525.8 K
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 3913 reflections
a = 7.7471 (15) Åθ = 1.4–27.8°
b = 8.1758 (16) ŵ = 0.11 mm1
c = 28.625 (6) ÅT = 298 K
V = 1813.1 (6) Å3Block, colorless
Z = 40.32 × 0.25 × 0.18 mm
F(000) = 792

Data collection

Bruker SMART APEXII CCD area-detector diffractometer2079 independent reflections
Radiation source: fine-focus sealed tube1778 reflections with I > 2σ(I)
graphiteRint = 0.028
[var phi] and ω scansθmax = 26.0°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)h = −9→9
Tmin = 0.971, Tmax = 0.984k = −10→9
9412 measured reflectionsl = −29→35

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)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116H-atom parameters constrained
S = 1.05w = 1/[σ2(Fo2) + (0.0655P)2 + 0.2914P] where P = (Fo2 + 2Fc2)/3
2079 reflections(Δ/σ)max = 0.001
246 parametersΔρmax = 0.22 e Å3
0 restraintsΔρmin = −0.19 e Å3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C10.0567 (4)−0.7098 (3)0.65314 (10)0.0437 (7)
C20.0253 (4)−0.5895 (3)0.61484 (10)0.0480 (7)
H2A0.0508−0.64060.58500.058*
H2B−0.0957−0.55880.61480.058*
C30.1124 (3)−0.3291 (3)0.58665 (9)0.0385 (6)
C40.0138 (4)−0.3432 (4)0.54660 (10)0.0508 (8)
H4−0.0507−0.43720.54110.061*
C50.0120 (4)−0.2161 (4)0.51477 (10)0.0506 (8)
H5−0.0555−0.22680.48810.061*
C60.1058 (3)−0.0739 (3)0.52075 (9)0.0355 (6)
C70.2023 (4)−0.0632 (3)0.56174 (9)0.0415 (6)
H70.26640.03080.56750.050*
C80.2051 (4)−0.1875 (3)0.59386 (9)0.0427 (6)
H80.2705−0.17620.62090.051*
C90.1043 (3)0.0598 (3)0.48540 (9)0.0353 (6)
C100.0092 (3)0.0467 (3)0.44397 (9)0.0409 (6)
H10−0.0528−0.04860.43830.049*
C110.0048 (3)0.1697 (4)0.41162 (9)0.0434 (6)
H11−0.06010.15670.38450.052*
C120.0958 (3)0.3135 (3)0.41877 (8)0.0367 (6)
C130.1927 (4)0.3298 (3)0.45907 (9)0.0457 (7)
H130.25580.42480.46450.055*
C140.1950 (4)0.2043 (3)0.49115 (10)0.0481 (7)
H140.26090.21730.51810.058*
C150.1904 (4)0.5669 (3)0.38615 (9)0.0452 (7)
H15A0.30900.53260.39090.054*
H15B0.15790.63980.41140.054*
C160.1717 (4)0.6512 (4)0.33992 (10)0.0480 (7)
C170.8034 (4)0.4650 (3)0.76651 (10)0.0467 (7)
H170.87150.45200.79300.056*
C180.7724 (5)0.1739 (4)0.76798 (13)0.0648 (9)
H18A0.66660.13210.78070.097*
H18B0.85700.18270.79240.097*
H18C0.81390.10090.74420.097*
C190.6242 (5)0.3421 (4)0.70858 (11)0.0618 (9)
H19A0.67220.28330.68260.093*
H19B0.60640.45430.69990.093*
H19C0.51580.29390.71720.093*
N10.7419 (3)0.3344 (3)0.74773 (7)0.0437 (6)
O1−0.0176 (3)−0.8381 (3)0.65378 (8)0.0711 (7)
O20.1679 (3)−0.6642 (3)0.68480 (7)0.0616 (6)
H20.1823−0.73870.70360.092*
O30.1272 (3)−0.4482 (2)0.61989 (6)0.0458 (5)
O40.0795 (3)0.4294 (2)0.38492 (6)0.0468 (5)
O50.0680 (5)0.6151 (4)0.31136 (10)0.1098 (12)
O60.2858 (4)0.7658 (3)0.33427 (8)0.0768 (8)
H60.28340.79820.30720.115*
O70.7798 (3)0.6075 (2)0.75226 (6)0.0565 (6)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0502 (16)0.0377 (15)0.0433 (15)0.0007 (13)0.0004 (13)0.0008 (13)
C20.0553 (17)0.0427 (16)0.0461 (16)−0.0061 (14)−0.0045 (14)0.0050 (14)
C30.0408 (13)0.0347 (13)0.0399 (13)0.0016 (12)−0.0011 (11)0.0039 (12)
C40.0592 (18)0.0400 (16)0.0533 (16)−0.0170 (15)−0.0174 (14)0.0059 (14)
C50.0581 (18)0.0478 (16)0.0459 (16)−0.0142 (15)−0.0207 (14)0.0058 (14)
C60.0337 (12)0.0357 (13)0.0372 (13)0.0027 (11)0.0011 (11)−0.0001 (12)
C70.0457 (15)0.0375 (14)0.0411 (14)−0.0062 (12)−0.0066 (12)0.0010 (12)
C80.0468 (15)0.0463 (15)0.0350 (13)−0.0014 (14)−0.0063 (12)0.0008 (12)
C90.0333 (12)0.0365 (13)0.0361 (13)0.0013 (11)0.0018 (11)0.0003 (12)
C100.0419 (14)0.0407 (15)0.0400 (14)−0.0089 (13)−0.0011 (12)−0.0023 (12)
C110.0428 (14)0.0536 (17)0.0339 (13)−0.0037 (14)−0.0044 (11)0.0031 (13)
C120.0384 (13)0.0377 (14)0.0340 (13)0.0037 (12)0.0042 (11)0.0033 (11)
C130.0553 (16)0.0371 (14)0.0446 (15)−0.0066 (14)−0.0071 (13)0.0052 (13)
C140.0561 (16)0.0479 (17)0.0403 (15)−0.0079 (15)−0.0119 (13)0.0049 (13)
C150.0533 (16)0.0402 (15)0.0420 (14)0.0025 (14)0.0030 (13)0.0020 (13)
C160.0502 (16)0.0475 (16)0.0462 (16)0.0002 (15)−0.0003 (14)0.0065 (14)
C170.0606 (18)0.0434 (16)0.0360 (14)0.0003 (15)−0.0080 (14)0.0035 (13)
C180.082 (2)0.0402 (17)0.072 (2)0.0019 (17)0.003 (2)0.0110 (16)
C190.068 (2)0.058 (2)0.0588 (19)0.0028 (17)−0.0166 (16)−0.0103 (17)
N10.0493 (13)0.0403 (13)0.0413 (12)0.0008 (11)−0.0014 (11)−0.0021 (10)
O10.0894 (17)0.0499 (13)0.0740 (15)−0.0250 (14)−0.0256 (13)0.0132 (12)
O20.0847 (15)0.0422 (11)0.0579 (12)−0.0134 (12)−0.0230 (12)0.0114 (10)
O30.0523 (11)0.0415 (10)0.0436 (10)−0.0074 (9)−0.0085 (9)0.0107 (9)
O40.0498 (11)0.0469 (11)0.0436 (10)−0.0045 (9)−0.0043 (9)0.0110 (10)
O50.119 (2)0.123 (3)0.0881 (19)−0.058 (2)−0.0515 (19)0.060 (2)
O60.1004 (19)0.0726 (16)0.0573 (14)−0.0360 (16)−0.0152 (14)0.0243 (12)
O70.0860 (16)0.0393 (11)0.0444 (12)−0.0036 (11)−0.0131 (11)0.0042 (9)

Geometric parameters (Å, °)

C1—O11.197 (3)C12—O41.361 (3)
C1—O21.305 (4)C12—C131.383 (4)
C1—C21.493 (4)C13—C141.377 (4)
C2—O31.407 (3)C13—H130.9300
C2—H2A0.9700C14—H140.9300
C2—H2B0.9700C15—O41.415 (3)
C3—O31.366 (3)C15—C161.499 (4)
C3—C81.377 (4)C15—H15A0.9700
C3—C41.383 (4)C15—H15B0.9700
C4—C51.382 (4)C16—O51.184 (4)
C4—H40.9300C16—O61.298 (4)
C5—C61.382 (4)C17—O71.248 (3)
C5—H50.9300C17—N11.287 (4)
C6—C71.394 (4)C17—H170.9300
C6—C91.489 (4)C18—N11.454 (4)
C7—C81.371 (4)C18—H18A0.9600
C7—H70.9300C18—H18B0.9600
C8—H80.9300C18—H18C0.9600
C9—C141.385 (4)C19—N11.446 (4)
C9—C101.400 (3)C19—H19A0.9600
C10—C111.368 (4)C19—H19B0.9600
C10—H100.9300C19—H19C0.9600
C11—C121.386 (4)O2—H20.8201
C11—H110.9300O6—H60.8200
O1—C1—O2123.9 (3)C13—C12—C11118.8 (2)
O1—C1—C2120.7 (3)C14—C13—C12119.4 (3)
O2—C1—C2115.4 (2)C14—C13—H13120.3
O3—C2—C1112.0 (2)C12—C13—H13120.3
O3—C2—H2A109.2C13—C14—C9123.4 (3)
C1—C2—H2A109.2C13—C14—H14118.3
O3—C2—H2B109.2C9—C14—H14118.3
C1—C2—H2B109.2O4—C15—C16106.5 (2)
H2A—C2—H2B107.9O4—C15—H15A110.4
O3—C3—C8116.8 (2)C16—C15—H15A110.4
O3—C3—C4124.4 (2)O4—C15—H15B110.4
C8—C3—C4118.8 (2)C16—C15—H15B110.4
C5—C4—C3119.3 (3)H15A—C15—H15B108.6
C5—C4—H4120.3O5—C16—O6123.8 (3)
C3—C4—H4120.3O5—C16—C15124.1 (3)
C4—C5—C6123.1 (2)O6—C16—C15112.1 (3)
C4—C5—H5118.5O7—C17—N1125.7 (3)
C6—C5—H5118.5O7—C17—H17117.1
C5—C6—C7116.0 (2)N1—C17—H17117.1
C5—C6—C9121.9 (2)N1—C18—H18A109.5
C7—C6—C9122.0 (2)N1—C18—H18B109.5
C8—C7—C6121.8 (2)H18A—C18—H18B109.5
C8—C7—H7119.1N1—C18—H18C109.5
C6—C7—H7119.1H18A—C18—H18C109.5
C7—C8—C3120.9 (2)H18B—C18—H18C109.5
C7—C8—H8119.5N1—C19—H19A109.5
C3—C8—H8119.5N1—C19—H19B109.5
C14—C9—C10115.7 (2)H19A—C19—H19B109.5
C14—C9—C6122.8 (2)N1—C19—H19C109.5
C10—C9—C6121.6 (2)H19A—C19—H19C109.5
C11—C10—C9122.0 (2)H19B—C19—H19C109.5
C11—C10—H10119.0C17—N1—C19121.4 (2)
C9—C10—H10119.0C17—N1—C18121.4 (2)
C10—C11—C12120.7 (2)C19—N1—C18116.8 (3)
C10—C11—H11119.6C1—O2—H2109.4
C12—C11—H11119.6C3—O3—C2117.8 (2)
O4—C12—C13125.2 (2)C12—O4—C15118.6 (2)
O4—C12—C11116.0 (2)C16—O6—H6109.6
O1—C1—C2—O3−178.9 (3)C9—C10—C11—C120.2 (4)
O2—C1—C2—O31.4 (4)C10—C11—C12—O4−178.6 (2)
O3—C3—C4—C5−178.3 (3)C10—C11—C12—C130.6 (4)
C8—C3—C4—C50.6 (4)O4—C12—C13—C14178.4 (3)
C3—C4—C5—C60.4 (5)C11—C12—C13—C14−0.7 (4)
C4—C5—C6—C7−1.1 (4)C12—C13—C14—C90.0 (5)
C4—C5—C6—C9178.8 (3)C10—C9—C14—C130.8 (4)
C5—C6—C7—C80.7 (4)C6—C9—C14—C13−179.0 (3)
C9—C6—C7—C8−179.1 (3)O4—C15—C16—O57.5 (5)
C6—C7—C8—C30.2 (4)O4—C15—C16—O6−170.6 (2)
O3—C3—C8—C7178.1 (2)O7—C17—N1—C19−4.7 (5)
C4—C3—C8—C7−0.9 (4)O7—C17—N1—C18−178.0 (3)
C5—C6—C9—C14178.9 (3)C8—C3—O3—C2176.0 (2)
C7—C6—C9—C14−1.3 (4)C4—C3—O3—C2−5.0 (4)
C5—C6—C9—C10−0.9 (4)C1—C2—O3—C3179.1 (2)
C7—C6—C9—C10178.9 (2)C13—C12—O4—C1511.2 (4)
C14—C9—C10—C11−0.8 (4)C11—C12—O4—C15−169.7 (2)
C6—C9—C10—C11179.0 (2)C16—C15—O4—C12167.4 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O6—H6···O7i0.821.872.685 (3)174
O2—H2···O7ii0.821.812.626 (3)176
C15—H15a···O1iii0.972.443.149 (2)129.0
C17—H17···O1iv0.932.563.248 (3)131

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ZL2216).

References

  • Bruker (2004). SAINT, APEX2 and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Hayes, N. V. & Branch, G. E. K. (1943). J. Am. Chem. Soc.65, 1555–1564.
  • Kamoda, O., Anzai, K., Mizoguchi, J., Shiojiri, M., Yanagi, T., Nishino, T. & Kamiya, S. (2006). Antimicrob. Agents Chemother.50, 3062–3069. [PMC free article] [PubMed]
  • Mikami, K. & Yamanaka, M. (2003). Chem. Rev.103, 3369–3400. [PubMed]
  • Rabnawaz, M., Ali, Q., Shah, M. R. & Singh, K. (2008). Acta Cryst. E64, o1909. [PMC free article] [PubMed]
  • Sallam, M. M., El-Sayed, B. A. & Abdel-Shafi, A. A. (2006). Curr. Appl. Phys.6, 71–75.
  • Sheldrick, G. M. (2004). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Tan, T.-F., Zhang, J.-X. & Meng, J.-B. (2005). Acta Cryst. E61, o1210–o1211.

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