In the title complex, 1,4-diazoniabicyclo[2.2.2]octane bis(hydrogen maleate), C
6H
14N
22+·2C
4H
3O
4−, the C
4H
3O
4− and C
6H
14N
22+ ions, derived from maleic acid and 1,4-diazabicyclo[2.2.2]octane, respectively, are disordered across a mirror plane in space group
Cmc2
1, and they are linked by two nearly linear N—H
O hydrogen bonds, with N
O distances of 2.662 (3) and 2.614 (4) Å, and N—H
O angles of 173°. The crystal structure consists of sheets with reticulations of 3.3792 (4) Å in stratum and 7.3892 (8) Å in width. The sheets are linked by C—H
O hydrogen bonds.
Supporting information
CCDC reference: 197333
1,4-Diazabicyclo[2.2.2]octane (0.01 mol) and maleic acid (0.02 mol) were
dissolved in water by heating to a temperature where a clear solution was
obtained. Single crystals of the title complex, (I), were formed by standing
the resulting solution overnight at 293 K.
The DABCO unit and some of the atoms of the anion (O1, O3, C8 and C9, and their
associated H atoms) were disordered across pairs of sites slightly removed
from the mirror plane at x = 0. The remaining atoms lie on the mirror
plane. H atoms were placed on calculated positions, with Uiso(H) =
1.2Ueq of their parent atoms and with N—H = 0.91 Å, O—H = 0.82 Å and C—H = 0.93–0.98 Å. Are these added distances correct? In the
absence of significant anomalous scattering, Friedel pairs were merged; the
absolute structure could not be determined.
Data collection: XSCANS (Siemens, year?); 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.
1,4-diazoniabicyclo[2.2.2]octane bis(maleate)
top
Crystal data top
C6H14N22+·2C4H3O4− | F(000) = 728 |
Mr = 344.32 | Dx = 1.493 Mg m−3 |
Orthorhombic, Cmc21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C 2c -2 | Cell parameters from 25 reflections |
a = 6.7584 (8) Å | θ = 4.3–15.0° |
b = 20.145 (4) Å | µ = 0.12 mm−1 |
c = 11.255 (2) Å | T = 289 K |
V = 1532.3 (4) Å3 | Prism, colourless |
Z = 4 | 0.46 × 0.38 × 0.36 mm |
Data collection top
Siemens P4 diffractometer | Rint = 0.010 |
Radiation source: normal-focus sealed tube | θmax = 28.0°, θmin = 2.0° |
Graphite monochromator | h = 0→8 |
ω scans | k = 0→26 |
1194 measured reflections | l = −1→14 |
1044 independent reflections | 3 standard reflections every 97 reflections |
845 reflections with I > 2σ(I) | intensity decay: 1.9% |
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)] = 0.033 | H-atom parameters constrained |
wR(F2) = 0.078 | w = 1/[σ2(Fo2) + (0.0485P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.96 | (Δ/σ)max < 0.001 |
1044 reflections | Δρmax = 0.17 e Å−3 |
178 parameters | Δρmin = −0.16 e Å−3 |
10 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.026 (2) |
Crystal data top
C6H14N22+·2C4H3O4− | V = 1532.3 (4) Å3 |
Mr = 344.32 | Z = 4 |
Orthorhombic, Cmc21 | Mo Kα radiation |
a = 6.7584 (8) Å | µ = 0.12 mm−1 |
b = 20.145 (4) Å | T = 289 K |
c = 11.255 (2) Å | 0.46 × 0.38 × 0.36 mm |
Data collection top
Siemens P4 diffractometer | Rint = 0.010 |
1194 measured reflections | 3 standard reflections every 97 reflections |
1044 independent reflections | intensity decay: 1.9% |
845 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.033 | 10 restraints |
wR(F2) = 0.078 | H-atom parameters constrained |
S = 0.96 | Δρmax = 0.17 e Å−3 |
1044 reflections | Δρmin = −0.16 e Å−3 |
178 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 | Occ. (<1) |
O1 | −0.026 (4) | 0.57705 (14) | 0.2955 (2) | 0.038 (4) | 0.50 |
O2 | 0.0000 | 0.65294 (10) | 0.4369 (2) | 0.0436 (7) | |
O3 | 0.029 (4) | 0.45539 (14) | 0.2817 (2) | 0.047 (5) | 0.50 |
H3 | 0.0476 | 0.4955 | 0.2869 | 0.056* | 0.50 |
O4 | 0.0000 | 0.37082 (10) | 0.4034 (3) | 0.0480 (7) | |
O5 | 0.0000 | 0.83938 (10) | −0.2111 (2) | 0.0423 (7) | |
O6 | 0.0000 | 0.91495 (11) | −0.0687 (2) | 0.0472 (7) | |
O7 | 0.0000 | 0.83663 (12) | −0.4278 (2) | 0.0456 (7) | |
H7 | 0.0226 | 0.8365 | −0.3563 | 0.055* | 0.50 |
O8 | 0.0000 | 0.91015 (13) | −0.5729 (2) | 0.0578 (8) | |
N1 | 0.0000 | 0.74108 (11) | 0.2607 (2) | 0.0299 (6) | |
H1 | −0.0096 | 0.7107 | 0.3203 | 0.036* | 0.50 |
N2 | 0.0000 | 0.82516 (13) | 0.0990 (2) | 0.0362 (7) | |
H2 | 0.0096 | 0.8555 | 0.0394 | 0.043* | 0.50 |
C1 | −0.019 (5) | 0.70581 (17) | 0.1439 (3) | 0.028 (3) | 0.50 |
H1A | −0.1343 | 0.6770 | 0.1447 | 0.034* | 0.50 |
H1B | 0.0970 | 0.6789 | 0.1292 | 0.034* | 0.50 |
C2 | −0.0412 (12) | 0.75845 (15) | 0.0467 (3) | 0.038 (3) | 0.50 |
H2A | 0.0510 | 0.7495 | −0.0174 | 0.045* | 0.50 |
H2B | −0.1743 | 0.7574 | 0.0145 | 0.045* | 0.50 |
C3 | 0.180 (2) | 0.7825 (9) | 0.2808 (15) | 0.035 (3) | 0.50 |
H3A | 0.2978 | 0.7552 | 0.2871 | 0.042* | 0.50 |
H3B | 0.1673 | 0.8093 | 0.3520 | 0.042* | 0.50 |
C4 | 0.1862 (16) | 0.8258 (5) | 0.1694 (14) | 0.046 (3) | 0.50 |
H4A | 0.2148 | 0.8711 | 0.1928 | 0.056* | 0.50 |
H4B | 0.2938 | 0.8108 | 0.1191 | 0.056* | 0.50 |
C5 | −0.1777 (15) | 0.7850 (7) | 0.2641 (15) | 0.031 (3) | 0.50 |
H5A | −0.1925 | 0.8025 | 0.3440 | 0.037* | 0.50 |
H5B | −0.2941 | 0.7586 | 0.2467 | 0.037* | 0.50 |
C6 | −0.1693 (17) | 0.8431 (4) | 0.1770 (13) | 0.038 (2) | 0.50 |
H6A | −0.2911 | 0.8467 | 0.1318 | 0.046* | 0.50 |
H6B | −0.1452 | 0.8847 | 0.2180 | 0.046* | 0.50 |
C7 | 0.0000 | 0.59369 (14) | 0.4019 (3) | 0.0318 (7) | |
C8 | 0.021 (6) | 0.54210 (18) | 0.4978 (3) | 0.029 (4) | 0.50 |
H8 | 0.0405 | 0.5590 | 0.5738 | 0.035* | 0.50 |
C9 | 0.015 (11) | 0.47632 (17) | 0.4915 (4) | 0.031 (6) | 0.50 |
H9 | 0.0222 | 0.4551 | 0.5647 | 0.038* | 0.50 |
C10 | 0.0000 | 0.43055 (15) | 0.3884 (3) | 0.0346 (8) | |
C11 | 0.0000 | 0.89922 (16) | −0.1748 (3) | 0.0321 (7) | |
C12 | 0.0000 | 0.95505 (15) | −0.2623 (3) | 0.0390 (9) | |
H12 | 0.0000 | 0.9972 | −0.2286 | 0.047* | |
C13 | 0.0000 | 0.95418 (15) | −0.3805 (3) | 0.0364 (9) | |
H13 | 0.0000 | 0.9961 | −0.4153 | 0.044* | |
C14 | 0.0000 | 0.89827 (17) | −0.4673 (3) | 0.0355 (9) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.057 (13) | 0.0325 (12) | 0.0252 (12) | −0.001 (2) | −0.003 (2) | 0.0040 (10) |
O2 | 0.0756 (19) | 0.0237 (10) | 0.0315 (12) | 0.000 | 0.000 | 0.0030 (11) |
O3 | 0.081 (15) | 0.0306 (12) | 0.0290 (13) | 0.006 (3) | 0.002 (3) | −0.0020 (11) |
O4 | 0.0658 (19) | 0.0254 (11) | 0.0529 (17) | 0.000 | 0.000 | −0.0012 (12) |
O5 | 0.0673 (18) | 0.0219 (11) | 0.0375 (14) | 0.000 | 0.000 | 0.0033 (11) |
O6 | 0.0829 (19) | 0.0311 (11) | 0.0275 (12) | 0.000 | 0.000 | 0.0063 (11) |
O7 | 0.068 (2) | 0.0326 (13) | 0.0361 (14) | 0.000 | 0.000 | −0.0066 (11) |
O8 | 0.095 (2) | 0.0505 (15) | 0.0277 (13) | 0.000 | 0.000 | −0.0039 (13) |
N1 | 0.0473 (16) | 0.0220 (11) | 0.0204 (12) | 0.000 | 0.000 | 0.0047 (10) |
N2 | 0.061 (2) | 0.0268 (13) | 0.0207 (12) | 0.000 | 0.000 | 0.0051 (10) |
C1 | 0.035 (9) | 0.0264 (15) | 0.0242 (15) | 0.004 (3) | −0.005 (3) | −0.0048 (12) |
C2 | 0.057 (8) | 0.0296 (19) | 0.0264 (18) | −0.001 (2) | −0.002 (2) | −0.0037 (15) |
C3 | 0.042 (7) | 0.034 (6) | 0.027 (5) | −0.006 (4) | −0.006 (3) | 0.011 (3) |
C4 | 0.045 (4) | 0.023 (5) | 0.071 (5) | −0.009 (3) | 0.002 (4) | 0.011 (4) |
C5 | 0.034 (6) | 0.033 (6) | 0.027 (5) | −0.010 (4) | 0.011 (4) | −0.010 (4) |
C6 | 0.053 (5) | 0.015 (4) | 0.046 (3) | 0.009 (3) | 0.003 (4) | 0.007 (3) |
C7 | 0.045 (2) | 0.0239 (14) | 0.0265 (17) | 0.000 | 0.000 | 0.0037 (13) |
C8 | 0.038 (14) | 0.0313 (16) | 0.0184 (15) | 0.001 (3) | −0.001 (3) | 0.0012 (13) |
C9 | 0.040 (17) | 0.0301 (16) | 0.0242 (15) | 0.006 (6) | 0.000 (4) | 0.0045 (15) |
C10 | 0.040 (2) | 0.0285 (15) | 0.0351 (18) | 0.000 | 0.000 | −0.0019 (13) |
C11 | 0.0395 (19) | 0.0280 (16) | 0.0288 (17) | 0.000 | 0.000 | 0.0051 (14) |
C12 | 0.063 (3) | 0.0209 (15) | 0.0328 (17) | 0.000 | 0.000 | −0.0022 (15) |
C13 | 0.058 (2) | 0.0239 (17) | 0.0276 (17) | 0.000 | 0.000 | 0.0007 (15) |
C14 | 0.040 (2) | 0.0353 (18) | 0.0310 (19) | 0.000 | 0.000 | −0.0029 (14) |
Geometric parameters (Å, º) top
O1—C7 | 1.257 (6) | C4—H4A | 0.9700 |
O2—C7 | 1.257 (4) | C4—H4B | 0.9700 |
O3—C10 | 1.315 (6) | C5—C6 | 1.528 (4) |
O3—H3 | 0.8200 | C5—H5A | 0.9700 |
O4—C10 | 1.215 (4) | C5—H5B | 0.9700 |
O5—C11 | 1.273 (4) | C6—H6A | 0.9700 |
O6—C11 | 1.235 (4) | C6—H6B | 0.9700 |
O7—C14 | 1.319 (4) | C7—C8 | 1.505 (6) |
O7—H7 | 0.8200 | C8—C9 | 1.328 (5) |
O8—C14 | 1.212 (4) | C8—H8 | 0.9300 |
N1—C5 | 1.493 (4) | C9—C10 | 1.486 (7) |
N1—C3 | 1.493 (4) | C9—H9 | 0.9300 |
N1—C1 | 1.500 (3) | C10—O4i | 1.215 (4) |
N1—H1 | 0.9100 | C10—O3i | 1.315 (6) |
N2—C6 | 1.486 (4) | C10—C9i | 1.486 (7) |
N2—C4 | 1.487 (4) | C11—O6i | 1.235 (4) |
N2—C2 | 1.494 (3) | C11—O5i | 1.273 (4) |
N2—H2 | 0.9100 | C11—C12i | 1.495 (5) |
C1—C2 | 1.531 (4) | C11—C12 | 1.495 (5) |
C1—H1A | 0.9700 | C12—C13 | 1.331 (4) |
C1—H1B | 0.9700 | C12—H12 | 0.9300 |
C2—H2A | 0.9700 | C13—C14 | 1.491 (5) |
C2—H2B | 0.9700 | C13—H13 | 0.9300 |
C3—C4 | 1.528 (4) | C14—O8i | 1.212 (4) |
C3—H3A | 0.9700 | C14—O7i | 1.319 (4) |
C3—H3B | 0.9700 | C14—C13i | 1.491 (5) |
| | | |
C10—O3—H3 | 109.5 | O1—C7—C8 | 120.8 (4) |
C14—O7—H7 | 109.5 | O2—C7—C8 | 115.5 (3) |
C5—N1—C3 | 108.7 (3) | C9—C8—C7 | 130.4 (8) |
C5—N1—C1 | 103.5 (12) | C9—C8—H8 | 114.8 |
C3—N1—C1 | 117.9 (13) | C7—C8—H8 | 114.8 |
C5—N1—H1 | 108.8 | C8—C9—C10 | 131.6 (5) |
C3—N1—H1 | 108.8 | C8—C9—H9 | 114.2 |
C1—N1—H1 | 108.8 | C10—C9—H9 | 114.2 |
C6—N2—C4 | 109.6 (4) | O4i—C10—O3i | 120.2 (3) |
C6—N2—C2 | 107.9 (5) | O4—C10—O3i | 120.2 (3) |
C4—N2—C2 | 112.1 (5) | O4i—C10—O3 | 120.2 (3) |
C6—N2—H2 | 109.1 | O4—C10—O3 | 120.2 (3) |
C4—N2—H2 | 109.1 | O4i—C10—C9 | 120.4 (4) |
C2—N2—H2 | 109.1 | O4—C10—C9 | 120.4 (4) |
N1—C1—C2 | 107.9 (3) | O3i—C10—C9 | 119.2 (5) |
N1—C1—H1A | 110.1 | O3—C10—C9 | 117.8 (7) |
C2—C1—H1A | 110.1 | O4i—C10—C9i | 120.4 (4) |
N1—C1—H1B | 110.1 | O4—C10—C9i | 120.4 (4) |
C2—C1—H1B | 110.1 | O3i—C10—C9i | 117.8 (7) |
H1A—C1—H1B | 108.4 | O3—C10—C9i | 119.2 (5) |
N2—C2—C1 | 108.9 (4) | O6i—C11—O5 | 123.6 (3) |
N2—C2—H2A | 109.9 | O6—C11—O5 | 123.6 (3) |
C1—C2—H2A | 109.9 | O6i—C11—O5i | 123.6 (3) |
N2—C2—H2B | 109.9 | O6—C11—O5i | 123.6 (3) |
C1—C2—H2B | 109.9 | O6i—C11—C12i | 116.3 (3) |
H2A—C2—H2B | 108.3 | O6—C11—C12i | 116.3 (3) |
N1—C3—C4 | 102.5 (10) | O5—C11—C12i | 120.1 (3) |
N1—C3—H3A | 111.3 | O5i—C11—C12i | 120.1 (3) |
C4—C3—H3A | 111.3 | O6i—C11—C12 | 116.3 (3) |
N1—C3—H3B | 111.3 | O6—C11—C12 | 116.3 (3) |
C4—C3—H3B | 111.3 | O5—C11—C12 | 120.1 (3) |
H3A—C3—H3B | 109.2 | O5i—C11—C12 | 120.1 (3) |
N2—C4—C3 | 114.2 (11) | C13—C12—C11 | 130.4 (3) |
N2—C4—H4A | 108.7 | C13—C12—H12 | 114.8 |
C3—C4—H4A | 108.7 | C11—C12—H12 | 114.8 |
N2—C4—H4B | 108.7 | C12—C13—C14 | 131.7 (3) |
C3—C4—H4B | 108.7 | C12—C13—H13 | 114.1 |
H4A—C4—H4B | 107.6 | C14—C13—H13 | 114.1 |
N1—C5—C6 | 114.1 (10) | O8i—C14—O7 | 121.1 (3) |
N1—C5—H5A | 108.7 | O8—C14—O7 | 121.1 (3) |
C6—C5—H5A | 108.7 | O8i—C14—O7i | 121.1 (3) |
N1—C5—H5B | 108.7 | O8—C14—O7i | 121.1 (3) |
C6—C5—H5B | 108.7 | O8i—C14—C13i | 119.6 (3) |
H5A—C5—H5B | 107.6 | O8—C14—C13i | 119.6 (3) |
N2—C6—C5 | 102.8 (9) | O7—C14—C13i | 119.4 (3) |
N2—C6—H6A | 111.2 | O7i—C14—C13i | 119.4 (3) |
C5—C6—H6A | 111.2 | O8i—C14—C13 | 119.6 (3) |
N2—C6—H6B | 111.2 | O8—C14—C13 | 119.6 (3) |
C5—C6—H6B | 111.2 | O7—C14—C13 | 119.4 (3) |
H6A—C6—H6B | 109.1 | O7i—C14—C13 | 119.4 (3) |
O1—C7—O2 | 123.5 (3) | | |
| | | |
C5—N1—C1—C2 | 54.2 (19) | C7—C8—C9—C10 | 4 (11) |
C3—N1—C1—C2 | −66 (2) | C8—C9—C10—O4i | 179 (6) |
C6—N2—C2—C1 | −72.0 (15) | C8—C9—C10—O4 | 179 (6) |
C4—N2—C2—C1 | 48.8 (16) | C8—C9—C10—O3i | −6 (9) |
N1—C1—C2—N2 | 10 (2) | C8—C9—C10—O3 | 13 (9) |
C5—N1—C3—C4 | −66.7 (12) | C8—C9—C10—C9i | −89 (7) |
C1—N1—C3—C4 | 50.6 (17) | O6i—C11—C12—C13 | 180.000 (1) |
C6—N2—C4—C3 | 54.2 (13) | O6—C11—C12—C13 | 180.000 (1) |
C2—N2—C4—C3 | −65.6 (14) | O5—C11—C12—C13 | 0.000 (2) |
N1—C3—C4—N2 | 14.0 (17) | O5i—C11—C12—C13 | 0.000 (2) |
C3—N1—C5—C6 | 55.3 (11) | C12i—C11—C12—C13 | 0 (100) |
C1—N1—C5—C6 | −70.8 (14) | C11—C12—C13—C14 | 0.000 (2) |
C4—N2—C6—C5 | −65.7 (11) | C12—C13—C14—O8i | 180.000 (1) |
C2—N2—C6—C5 | 56.6 (11) | C12—C13—C14—O8 | 180.000 (1) |
N1—C5—C6—N2 | 12.6 (15) | C12—C13—C14—O7 | 0.000 (1) |
O1—C7—C8—C9 | 0 (6) | C12—C13—C14—O7i | 0.000 (1) |
O2—C7—C8—C9 | 176 (5) | C12—C13—C14—C13i | 0 (100) |
Symmetry code: (i) −x, y, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2 | 0.91 | 1.76 | 2.662 (3) | 174 |
N2—H2···O6 | 0.91 | 1.71 | 2.614 (4) | 173 |
O3—H3···O1 | 0.82 | 1.72 | 2.484 (7) | 154 |
O7—H7···O5 | 0.82 | 1.64 | 2.440 (4) | 164 |
C3—H3A···O5ii | 0.97 | 2.34 | 3.27 (2) | 160 |
C4—H4B···O2iii | 0.97 | 2.58 | 3.395 (19) | 141 |
C12—H12···O8iv | 0.93 | 2.56 | 3.452 (4) | 161 |
C13—H13···O6v | 0.93 | 2.49 | 3.382 (4) | 161 |
C3—H3B···O8vi | 0.97 | 2.47 | 3.288 (2) | 141 |
C8—H8···O3vii | 0.93 | 2.40 | 3.213 (7) | 145 |
C5—H5A···O8vi | 0.97 | 2.70 | 3.341 (2) | 124 |
C5—H5B···O5viii | 0.97 | 2.46 | 3.332 (4) | 149 |
Symmetry codes: (ii) −x+1/2, −y+3/2, z+1/2; (iii) −x+1/2, −y+3/2, z−1/2; (iv) −x, −y+2, z+1/2; (v) −x, −y+2, z−1/2; (vi) x, y, z+1; (vii) −x, −y+1, z+1/2; (viii) x−1/2, −y+3/2, z+1/2. |
Experimental details
Crystal data |
Chemical formula | C6H14N22+·2C4H3O4− |
Mr | 344.32 |
Crystal system, space group | Orthorhombic, Cmc21 |
Temperature (K) | 289 |
a, b, c (Å) | 6.7584 (8), 20.145 (4), 11.255 (2) |
V (Å3) | 1532.3 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.46 × 0.38 × 0.36 |
|
Data collection |
Diffractometer | Siemens P4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1194, 1044, 845 |
Rint | 0.010 |
(sin θ/λ)max (Å−1) | 0.661 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.078, 0.96 |
No. of reflections | 1044 |
No. of parameters | 178 |
No. of restraints | 10 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.17, −0.16 |
Selected geometric parameters (Å, º) topO1—C7 | 1.257 (6) | O8—C14 | 1.212 (4) |
O2—C7 | 1.257 (4) | N1—C5 | 1.493 (4) |
O3—C10 | 1.315 (6) | N1—C3 | 1.493 (4) |
O4—C10 | 1.215 (4) | N1—C1 | 1.500 (3) |
O5—C11 | 1.273 (4) | N2—C6 | 1.486 (4) |
O6—C11 | 1.235 (4) | N2—C4 | 1.487 (4) |
O7—C14 | 1.319 (4) | N2—C2 | 1.494 (3) |
| | | |
N1—C1—C2—N2 | 10 (2) | N1—C5—C6—N2 | 12.6 (15) |
N1—C3—C4—N2 | 14.0 (17) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2 | 0.91 | 1.76 | 2.662 (3) | 174 |
N2—H2···O6 | 0.91 | 1.71 | 2.614 (4) | 173 |
O3—H3···O1 | 0.82 | 1.72 | 2.484 (7) | 154 |
O7—H7···O5 | 0.82 | 1.64 | 2.440 (4) | 164 |
C3—H3A···O5i | 0.97 | 2.34 | 3.27 (2) | 160 |
C4—H4B···O2ii | 0.97 | 2.58 | 3.395 (19) | 141 |
C12—H12···O8iii | 0.93 | 2.56 | 3.452 (4) | 161 |
C13—H13···O6iv | 0.93 | 2.49 | 3.382 (4) | 161 |
C3—H3B···O8v | 0.97 | 2.47 | 3.288 (2) | 141 |
C8—H8···O3vi | 0.93 | 2.40 | 3.213 (7) | 145 |
C5—H5A···O8v | 0.97 | 2.70 | 3.341 (2) | 124 |
C5—H5B···O5vii | 0.97 | 2.46 | 3.332 (4) | 149 |
Symmetry codes: (i) −x+1/2, −y+3/2, z+1/2; (ii) −x+1/2, −y+3/2, z−1/2; (iii) −x, −y+2, z+1/2; (iv) −x, −y+2, z−1/2; (v) x, y, z+1; (vi) −x, −y+1, z+1/2; (vii) x−1/2, −y+3/2, z+1/2. |
Supramolecular aggregate design is an active field (Zaworotko, 2001). Some examples have been reported which use 1,4-diazabicyclo[2.2.2]octane (DABCO) as one of the building blocks (Ferguson et al., 1997; Glidewell et al., 1999) to build supramolecular architecture in two and three dimensions. We have used two simple building blocks, DABCO and maleic acid (MA), to synthesize the title complex, (I), and we report here its sheet-type structure. \sch
In the structure of (I) (Fig. 1), the C4H3O4- and C6H14N22+ ions are linked by two nearly linear hydrogen bonds (Table 2). Hydrogen maleate anions, C4H3O4-, have been reported with both symmetric and asymmetric intramolecular hydrogen bonds (Fillaux et al., 1999; James & Williams, 1974). Complex (I) contains two distinct hydrogen maleate ions, each with an asymmetric intramolecular hydrogen bond (Table 2), with O···O distances intermediate betwen those typical of symmetric (2.437 Å; Fillaux et al., 1999) and asymmetric [2.502 (1) Å; James & Williams, 1974] examples.
Viewed approximately along [100] (Fig. 2), the geometrical arrangement of (I) is characterized by a sheet-like structure of MA and DABCO moieties enclosing spaces measuring 3.3792 (4) × 7.3892 (8) Å. DABCO atoms N1, N2, C1 and C2, and the whole MA moiety, exhibit small deviations from the mirror plane and form a continuous sheet.
The C—H···O hydrogen bonds (Table 2) in (I) play an important role in linking the sheets. The methylene groups of the DABCO moieties take part in another C—H···O hydrogen bond to reinforce the structure. Zigzag and straight sheets in the same layer are coplanar with each other, forming the observed continuous structure.
It may be noted here that DABCO has been observed disordered across a centre of inversion in the 1:1 complex with 4,4'-biphenol (Ferguson et al., 1998) and perchloric acid (Katrusiak, 2000).