In the title complex, pyromellitic acid–dimethyl sulfoxide (1/2), C
10H
6O
8·2C
2H
6OS, molecules of pyromellitic acid (1,2,4,5-benzenetetracarboxylic acid) and dimethyl sulfoxide, the latter being well ordered, are linked to each other by O—H
O hydrogen bonds. The formula unit displays crystallographic inversion symmetry. The packing consists of ribbons of hydrogen-bonded rings that can be described by graph set
C(10)
R(18).
Supporting information
CCDC reference: 196228
PMA (0.0 1 mol), DMSO (0.04 mol) and water (0.02 mol) were mixed and heated to form a clear solution. Crystals of the title complex formed by gradual concentration over a period of one week at 293 K.
The O—H distances of the hydroxyl groups, the H atoms of which were located in difference Fourier maps, were restrained; otherwise these H atoms were refined freely. The other H atoms were placed in calculated positions, with their Uiso values set at 1.2Ueq of the parent atoms.
Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: SHELXTL-Plus (Sheldrick, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus; software used to prepare material for publication: SHELXTL-Plus.
Pyromellitic acid–dimethyl sulfoxide (1/2)
top
Crystal data top
C10H6O8·2C2H6OS | Z = 1 |
Mr = 410.40 | F(000) = 214 |
Triclinic, P1 | Dx = 1.467 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.377 (1) Å | Cell parameters from 25 reflections |
b = 7.424 (1) Å | θ = 3.4–14.2° |
c = 8.934 (1) Å | µ = 0.34 mm−1 |
α = 80.07 (1)° | T = 296 K |
β = 80.97 (1)° | Prism, colorless |
γ = 76.15 (1)° | 0.50 × 0.50 × 0.44 mm |
V = 464.51 (10) Å3 | |
Data collection top
Siemens P4 diffractometer | Rint = 0.013 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 2.3° |
Graphite monochromator | h = 0→8 |
ω scans | k = −8→8 |
1775 measured reflections | l = −10→10 |
1634 independent reflections | 3 standard reflections every 97 reflections |
1413 reflections with I > 2σ(I) | intensity decay: 3.6% |
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)] = 0.032 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.086 | w = 1/[σ2(Fo2) + (0.0447P)2 + 0.1816P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
1634 reflections | Δρmax = 0.26 e Å−3 |
129 parameters | Δρmin = −0.24 e Å−3 |
2 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.129 (10) |
Crystal data top
C10H6O8·2C2H6OS | γ = 76.15 (1)° |
Mr = 410.40 | V = 464.51 (10) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.377 (1) Å | Mo Kα radiation |
b = 7.424 (1) Å | µ = 0.34 mm−1 |
c = 8.934 (1) Å | T = 296 K |
α = 80.07 (1)° | 0.50 × 0.50 × 0.44 mm |
β = 80.97 (1)° | |
Data collection top
Siemens P4 diffractometer | Rint = 0.013 |
1775 measured reflections | 3 standard reflections every 97 reflections |
1634 independent reflections | intensity decay: 3.6% |
1413 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.032 | 2 restraints |
wR(F2) = 0.086 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.26 e Å−3 |
1634 reflections | Δρmin = −0.24 e Å−3 |
129 parameters | |
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 | Uiso*/Ueq | |
O1 | 0.2108 (2) | 0.5497 (3) | 0.69190 (18) | 0.0595 (5) | |
O2 | 0.4485 (2) | 0.6869 (2) | 0.59915 (16) | 0.0437 (4) | |
O3 | 0.3879 (2) | 0.9808 (2) | 0.8045 (2) | 0.0560 (5) | |
O4 | 0.6979 (2) | 0.8918 (2) | 0.80119 (19) | 0.0488 (4) | |
C1 | 0.4108 (3) | 0.3836 (2) | 0.9479 (2) | 0.0282 (4) | |
H1 | 0.3504 | 0.3054 | 0.9129 | 0.034* | |
C2 | 0.4291 (2) | 0.5529 (2) | 0.8586 (2) | 0.0263 (4) | |
C3 | 0.5194 (2) | 0.6711 (2) | 0.9120 (2) | 0.0262 (4) | |
C4 | 0.3499 (3) | 0.5982 (3) | 0.7087 (2) | 0.0308 (4) | |
C5 | 0.5259 (3) | 0.8645 (3) | 0.8311 (2) | 0.0291 (4) | |
S | 0.11370 (7) | 0.68265 (7) | 0.33963 (6) | 0.0348 (2) | |
O5 | 0.2693 (2) | 0.7812 (2) | 0.35311 (16) | 0.0396 (4) | |
C6 | −0.0921 (3) | 0.7997 (4) | 0.4438 (3) | 0.0492 (6) | |
H6A | −0.1130 | 0.9318 | 0.4084 | 0.059* | |
H6B | −0.0772 | 0.7774 | 0.5507 | 0.059* | |
H6C | −0.1979 | 0.7533 | 0.4288 | 0.059* | |
C7 | 0.0531 (3) | 0.7653 (5) | 0.1514 (3) | 0.0584 (7) | |
H7A | 0.1608 | 0.7298 | 0.0784 | 0.070* | |
H7B | 0.0129 | 0.8994 | 0.1388 | 0.070* | |
H7C | −0.0470 | 0.7114 | 0.1352 | 0.070* | |
H4O | 0.706 (4) | 1.006 (3) | 0.753 (3) | 0.074 (9)* | |
H2O | 0.394 (4) | 0.711 (4) | 0.514 (2) | 0.069 (8)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0586 (11) | 0.0859 (13) | 0.0451 (9) | −0.0436 (10) | −0.0268 (8) | 0.0187 (8) |
O2 | 0.0468 (9) | 0.0598 (10) | 0.0286 (8) | −0.0255 (7) | −0.0140 (7) | 0.0100 (7) |
O3 | 0.0408 (9) | 0.0333 (8) | 0.0896 (13) | −0.0053 (7) | −0.0199 (9) | 0.0100 (8) |
O4 | 0.0367 (8) | 0.0415 (9) | 0.0639 (10) | −0.0172 (7) | −0.0079 (7) | 0.0184 (8) |
C1 | 0.0296 (9) | 0.0286 (9) | 0.0297 (9) | −0.0109 (7) | −0.0074 (7) | −0.0037 (7) |
C2 | 0.0260 (9) | 0.0281 (9) | 0.0249 (9) | −0.0058 (7) | −0.0049 (7) | −0.0027 (7) |
C3 | 0.0241 (9) | 0.0270 (9) | 0.0271 (9) | −0.0058 (7) | −0.0035 (7) | −0.0019 (7) |
C4 | 0.0340 (10) | 0.0300 (10) | 0.0309 (10) | −0.0101 (8) | −0.0106 (8) | −0.0006 (8) |
C5 | 0.0338 (10) | 0.0284 (9) | 0.0268 (9) | −0.0083 (8) | −0.0085 (8) | −0.0022 (7) |
S | 0.0308 (3) | 0.0348 (3) | 0.0403 (3) | −0.0112 (2) | −0.0069 (2) | −0.0015 (2) |
O5 | 0.0396 (8) | 0.0463 (8) | 0.0368 (8) | −0.0230 (7) | −0.0141 (6) | 0.0116 (6) |
C6 | 0.0403 (13) | 0.0620 (15) | 0.0441 (13) | −0.0106 (11) | −0.0004 (10) | −0.0088 (11) |
C7 | 0.0398 (13) | 0.103 (2) | 0.0368 (12) | −0.0221 (13) | −0.0082 (10) | −0.0097 (13) |
Geometric parameters (Å, º) top
O1—C4 | 1.204 (2) | C3—C1i | 1.387 (3) |
O2—C4 | 1.306 (2) | C3—C5 | 1.500 (2) |
O2—H2O | 0.882 (17) | S—O5 | 1.5310 (14) |
O3—C5 | 1.192 (2) | S—C6 | 1.769 (2) |
O4—C5 | 1.312 (2) | S—C7 | 1.776 (2) |
O4—H4O | 0.891 (17) | C6—H6A | 0.9600 |
C1—C3i | 1.387 (3) | C6—H6B | 0.9600 |
C1—C2 | 1.391 (3) | C6—H6C | 0.9600 |
C1—H1 | 0.9300 | C7—H7A | 0.9600 |
C2—C3 | 1.402 (2) | C7—H7B | 0.9600 |
C2—C4 | 1.498 (2) | C7—H7C | 0.9600 |
| | | |
C4—O2—H2O | 110.2 (18) | O4—C5—C3 | 112.28 (15) |
C5—O4—H4O | 114.1 (19) | O5—S—C6 | 106.04 (10) |
C3i—C1—C2 | 121.54 (16) | O5—S—C7 | 104.63 (10) |
C3i—C1—H1 | 119.2 | C6—S—C7 | 98.92 (12) |
C2—C1—H1 | 119.2 | S—C6—H6A | 109.5 |
C1—C2—C3 | 119.17 (16) | S—C6—H6B | 109.5 |
C1—C2—C4 | 117.31 (15) | H6A—C6—H6B | 109.5 |
C3—C2—C4 | 123.52 (16) | S—C6—H6C | 109.5 |
C1i—C3—C2 | 119.29 (16) | H6A—C6—H6C | 109.5 |
C1i—C3—C5 | 118.11 (15) | H6B—C6—H6C | 109.5 |
C2—C3—C5 | 122.29 (16) | S—C7—H7A | 109.5 |
O1—C4—O2 | 123.88 (17) | S—C7—H7B | 109.5 |
O1—C4—C2 | 121.85 (17) | H7A—C7—H7B | 109.5 |
O2—C4—C2 | 114.21 (16) | S—C7—H7C | 109.5 |
O3—C5—O4 | 124.79 (18) | H7A—C7—H7C | 109.5 |
O3—C5—C3 | 122.84 (17) | H7B—C7—H7C | 109.5 |
| | | |
C3i—C1—C2—C3 | −0.3 (3) | C3—C2—C4—O1 | −146.5 (2) |
C3i—C1—C2—C4 | 179.62 (16) | C1—C2—C4—O2 | −143.98 (18) |
C1—C2—C3—C1i | 0.3 (3) | C3—C2—C4—O2 | 36.0 (3) |
C4—C2—C3—C1i | −179.63 (16) | C1i—C3—C5—O3 | −117.2 (2) |
C1—C2—C3—C5 | −173.10 (17) | C2—C3—C5—O3 | 56.3 (3) |
C4—C2—C3—C5 | 6.9 (3) | C1i—C3—C5—O4 | 59.5 (2) |
C1—C2—C4—O1 | 33.5 (3) | C2—C3—C5—O4 | −126.99 (19) |
Symmetry code: (i) −x+1, −y+1, −z+2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2O···O5 | 0.88 (2) | 1.77 (2) | 2.647 (2) | 174 (2) |
O4—H4O···O5ii | 0.89 (2) | 1.73 (2) | 2.622 (2) | 176 (2) |
C6—H6B···O1 | 0.96 | 2.71 | 3.391 (3) | 128 |
C6—H6C···O1iii | 0.96 | 2.68 | 3.386 (4) | 130 |
C7—H7C···O1iii | 0.96 | 2.67 | 3.379 (4) | 131 |
Symmetry codes: (ii) −x+1, −y+2, −z+1; (iii) −x, −y+1, −z+1. |
Experimental details
Crystal data |
Chemical formula | C10H6O8·2C2H6OS |
Mr | 410.40 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 7.377 (1), 7.424 (1), 8.934 (1) |
α, β, γ (°) | 80.07 (1), 80.97 (1), 76.15 (1) |
V (Å3) | 464.51 (10) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.34 |
Crystal size (mm) | 0.50 × 0.50 × 0.44 |
|
Data collection |
Diffractometer | Siemens P4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1775, 1634, 1413 |
Rint | 0.013 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.086, 1.05 |
No. of reflections | 1634 |
No. of parameters | 129 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.26, −0.24 |
Selected bond lengths (Å) topO1—C4 | 1.204 (2) | O4—C5 | 1.312 (2) |
O2—C4 | 1.306 (2) | C1—C3i | 1.387 (3) |
O3—C5 | 1.192 (2) | C2—C3 | 1.402 (2) |
Symmetry code: (i) −x+1, −y+1, −z+2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2O···O5 | 0.882 (17) | 1.769 (17) | 2.647 (2) | 174 (2) |
O4—H4O···O5ii | 0.891 (17) | 1.732 (17) | 2.622 (2) | 176 (2) |
C6—H6B···O1 | 0.96 | 2.71 | 3.391 (3) | 128 |
C6—H6C···O1iii | 0.96 | 2.68 | 3.386 (4) | 130 |
C7—H7C···O1iii | 0.96 | 2.67 | 3.379 (4) | 131 |
Symmetry codes: (ii) −x+1, −y+2, −z+1; (iii) −x, −y+1, −z+1. |
Until now, only a few supramolecular structures involving pyromellitic acid (PMA) have been determined (Mrvoš-Sermek et al., 1996; Biradha & Zaworotko 1998; Lough et al., 2000). From these known cases, it was impossible to predict the supramolecular hydrogen-bonding behaviour of PMA, even at the gross connectivity level (Lough et al., 2000). Thus, it is desirable to search for new examples of hydrogen-bonding motifs of PMA. Dimethyl sulfoxide (DMSO) is a versatile solvent which can dissolve various organic substances, and can form crystalline solvates in which it is either disordered (Deetz et al., 2000; Harper et al., 2001) or well ordered (Trangui, et al., 1998). In this context, the title complex, pyromellitic acid–dimethyl sulfoxide (1/2), (I), has been synthesized and its hydrogen-bonding pattern elucidated.
Fig. 1 shows the inversion symmetric formula unit of (I). The carboxyl groups display normal bond lengths and angles. It has been noted previously that the dihedral angles between the phenyl ring and carboxyl groups in PMA are disposed at random (Biradha & Zaworotko, 1998). In (I), these dihedral angles are 58.6 (2) and 35.0 (3)°, respectively, for the C5 and C4 carboxyl groups.
Disordered DMSO has been previously observed in cases where DMSO is held by a host molecule via only one O—H···O hydrogen bond (Deetz et al., 2000; Harper et al., 2001). In (I), where atom O5 is hydrogen bonded through both O2 and O4, the DMSO molecules are well ordered.
As seen in Fig. 2, molecules of DMSO and PMA are linked to each other by O2···O5 and O4···O5(1 − x, 2 − y, 1 − z) hydrogen bonds to form a hydrogen-bonded ring that can be described by graph set R42(18). The centre of the PMA molecule and the hydrogen-bonded rings are at (1/2, 1/2, 0) and (1/2, 1, 1/2), respectively. While the dihedral angle between the C7—S—O5 and O1—C4—O2 planes is 11.9 (1)°, that between the C6—S—O5 and O3—C5—O4 at (1 − x, −y, 1 − z) is 14.0 (3)°. This means that the methyl groups of DMSO are arranged so as to comply with the hydrogen-bonding requirements of both carboxyl groups.
A ribbon motif is formed by propagation of the hydrogen-bonded ring along the [011] direction, and may be depicted as graph set C21(10)R42(18). Such a ribbon is translated repeatedly for one unit along the b or c axis to generate a layer parallel to the (100) plane. The nearest face-to-face distance of benzene ring centroids between neighboring layers is 7.377 (1) Å, indicating no π–π-stacking interactions. There are many C—H···O hydrogen bonds playing subordinate roles in the crystal packing; some of the shorter ones are listed in Table 2.