Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827011005167X/sq3272sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827011005167X/sq3272Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827011005167X/sq3272IIsup3.hkl |
CCDC references: 813472; 813473
For related literature, see: Fu et al. (2008); Fuhr & Fenske (1999); Granifo et al. (2004); Lu et al. (2005); Marandi et al. (2005); Marlin et al. (2006); Planta & Unruh (1993); Sharma & Clearfield (2000); Thorn et al. (2005); Ye et al. (2010); Zhang et al. (2009, 2010); Zhu et al. (2000).
Bromoacetonitrile (0.1 mol, 12.00 g) was added to a CH3CN solution of 1,4-diazabicyclo[2.2.2]octane (DABCO) (0.05 mol, 5.6 g) with stirring for 1 h at room temperature. 1-Cyanomethyl-4-aza-1-azoniabicyclo[2.2.2]octane bromide which quickly formed as a white solid was filtered off, washed with acetonitrile and dried (yield: 80%). The compounds (I) and (II) were prepared from aqueous solutions containing 1-carboxymethyl-4-aza-1-azoniabicyclo[2.2.2]octane bromide [for (I)], or 1-cyanomethyl-4-aza-1-azoniabicyclo[2.2.2]octane bromide [for (II)] (0.01 mol, 2.32 g), CdSO4 (0.01 mol, 2.08 g), Ba(NO2)2 (0.01 mol, 2.29 g) and, additionally, imidazole (0.01 mol, 0.68 g) for (I). After removal of the precipitated BaSO4, the resulting solution was allowed to evaporate for 18 d [for (I)] or 6 d [for (II)] at room temperature, and colourless crystals suitable for X-ray analysis were obtained.
For (I), the carbon-bound H atoms were positioned with idealized geometry and treated as riding atoms, with C—H = 0.97 Å and Uiso(H) = 1.2Ueq(C). The H atoms for water and carboxyl were found in the difference Fourier maps; however, they were placed at idealized positions with O—H = 0.85 Å and Uiso(H) = 1.5Ueq(O) and refined using a rotating model with restraints for O(water)—H distances of 0.850 (1) Å. Carboxyl atoms O4 and O5 showed significantly larger anisotropic displacement parameters than C8 that were elongated perpendicular to the carboxyl plane suggesting possible disorder of the carboxylic acid group. Our attempt to model such disorder with two orientations did not afford reasonable results. Considering that the carboxylic acid is a terminal group in the structure, this can be understood as dynamical disorder in a single potential well corresponding to the rotation of the carboxyl group around C7—C8 bond. In the end, we used a SIMU command with an s.u. of 0.005 and a DELU command with an s.u. of 0.01 to maintain reasonable geometry and displacement parameters.
For (II), positional parameters of all the carbon-bound H atoms were calculated geometrically and the atoms were allowed to ride with C—H = 0.97 Å and Uiso(H) = 1.2Ueq(C). All the water H atoms were found in the difference Fourier maps; however, they were placed at ideal positions with O—H = 0.85 Å and Uiso(H) = 1.5Ueq(O) and refined using a rotating model with restraints for the O5—H5WA and O5—H5WB distances of 0.850 (1) Å. The O atoms in the nitrito groups showed large anisotropic displacement parameters that were elongated along the N—O bonds. The origin of this phenomenon is unknown; however, we do not believe it was caused by disorder because trying to model such disorder with two orientations did not afford an acceptable result. To maintain reasonable geometries as observed in similar known nitrito compounds, the N—O bonds were constrained to be 1.25 (1) by using DFIX and the atoms were restrained to have the same Uij components and the components of Uij in the direction of the bond by using SIMU with an s.u. of 0.01 and DELU with an s.u. of 0.003 (0.002 for O2—N4).
For both compounds, data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
[Cd2Br4(C8H15N2O2)2(NO2)2]·2H2O | F(000) = 976 |
Mr = 507.47 | Dx = 2.238 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 3824 reflections |
a = 8.7790 (18) Å | θ = 2.5–27.5° |
b = 13.374 (3) Å | µ = 6.77 mm−1 |
c = 13.113 (3) Å | T = 293 K |
β = 101.99 (3)° | Block, colourless |
V = 1505.9 (5) Å3 | 0.2 × 0.2 × 0.2 mm |
Z = 4 |
Rigaku Mercury CCD diffractometer | 3461 independent reflections |
Radiation source: fine-focus sealed tube | 2877 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.049 |
Detector resolution: 28.3714 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
ω scans | h = −11→11 |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −17→17 |
Tmin = 0.631, Tmax = 1.000 | l = −17→17 |
15299 measured reflections |
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)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.118 | w = 1/[σ2(Fo2) + (0.0391P)2 + 10.3781P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.001 |
3461 reflections | Δρmax = 1.30 e Å−3 |
172 parameters | Δρmin = −1.10 e Å−3 |
15 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008) |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0055 (11) |
[Cd2Br4(C8H15N2O2)2(NO2)2]·2H2O | V = 1505.9 (5) Å3 |
Mr = 507.47 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.7790 (18) Å | µ = 6.77 mm−1 |
b = 13.374 (3) Å | T = 293 K |
c = 13.113 (3) Å | 0.2 × 0.2 × 0.2 mm |
β = 101.99 (3)° |
Rigaku Mercury CCD diffractometer | 3461 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 2877 reflections with I > 2σ(I) |
Tmin = 0.631, Tmax = 1.000 | Rint = 0.049 |
15299 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 15 restraints |
wR(F2) = 0.118 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0391P)2 + 10.3781P] where P = (Fo2 + 2Fc2)/3 |
3461 reflections | Δρmax = 1.30 e Å−3 |
172 parameters | Δρmin = −1.10 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.4707 (8) | 0.3433 (5) | 0.6601 (6) | 0.0376 (15) | |
H1A | 0.4338 | 0.3653 | 0.7212 | 0.045* | |
H1B | 0.4906 | 0.4023 | 0.6219 | 0.045* | |
C2 | 0.6221 (7) | 0.2850 (5) | 0.6946 (5) | 0.0333 (14) | |
H2A | 0.7087 | 0.3237 | 0.6803 | 0.040* | |
H2B | 0.6406 | 0.2725 | 0.7690 | 0.040* | |
C3 | 0.3348 (7) | 0.1867 (5) | 0.6485 (6) | 0.0357 (15) | |
H3A | 0.2506 | 0.1479 | 0.6073 | 0.043* | |
H3B | 0.3079 | 0.2010 | 0.7151 | 0.043* | |
C4 | 0.4832 (8) | 0.1250 (5) | 0.6668 (6) | 0.0350 (14) | |
H4A | 0.5128 | 0.1063 | 0.7397 | 0.042* | |
H4B | 0.4665 | 0.0644 | 0.6253 | 0.042* | |
C5 | 0.4028 (8) | 0.2576 (6) | 0.4961 (5) | 0.0386 (16) | |
H5A | 0.4042 | 0.3179 | 0.4551 | 0.046* | |
H5B | 0.3301 | 0.2111 | 0.4551 | 0.046* | |
C6 | 0.5645 (8) | 0.2114 (6) | 0.5200 (5) | 0.0392 (16) | |
H6A | 0.6391 | 0.2579 | 0.5014 | 0.047* | |
H6B | 0.5653 | 0.1510 | 0.4792 | 0.047* | |
C7 | 0.7660 (7) | 0.1368 (5) | 0.6647 (6) | 0.0361 (15) | |
H7B | 0.7908 | 0.1267 | 0.7396 | 0.043* | |
H7C | 0.8438 | 0.1815 | 0.6475 | 0.043* | |
C8 | 0.7781 (11) | 0.0379 (7) | 0.6126 (8) | 0.064 (2) | |
N1 | 0.3496 (6) | 0.2826 (4) | 0.5939 (4) | 0.0270 (11) | |
N2 | 0.6105 (5) | 0.1866 (4) | 0.6362 (4) | 0.0241 (10) | |
N3 | 0.1119 (8) | 0.3897 (5) | 0.7770 (5) | 0.0488 (17) | |
O1 | 0.1730 (7) | 0.4519 (4) | 0.7289 (5) | 0.0544 (14) | |
O2 | 0.0559 (7) | 0.3195 (4) | 0.7278 (4) | 0.0541 (14) | |
O3 | 0.0808 (7) | 0.1201 (5) | 0.8226 (5) | 0.0656 (17) | |
H3D | 0.1004 | 0.1787 | 0.8036 | 0.098* | |
H3C | 0.0712 | 0.0745 | 0.7766 | 0.098* | |
O4 | 0.6879 (10) | −0.0053 (6) | 0.5509 (7) | 0.099 (2) | |
O5 | 0.9314 (11) | 0.0053 (7) | 0.6358 (8) | 0.109 (3) | |
H5C | 0.9382 | −0.0507 | 0.6064 | 0.163* | |
Br1 | 0.19513 (9) | 0.51062 (6) | 0.44617 (6) | 0.0458 (2) | |
Br2 | −0.04630 (9) | 0.23381 (6) | 0.44286 (6) | 0.0447 (2) | |
Cd1 | 0.10110 (6) | 0.37215 (4) | 0.56215 (4) | 0.03276 (15) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.038 (4) | 0.027 (3) | 0.047 (4) | 0.000 (3) | 0.006 (3) | −0.006 (3) |
C2 | 0.032 (3) | 0.024 (3) | 0.042 (4) | −0.003 (3) | 0.002 (3) | −0.009 (3) |
C3 | 0.031 (3) | 0.031 (3) | 0.046 (4) | −0.005 (3) | 0.012 (3) | 0.014 (3) |
C4 | 0.036 (3) | 0.026 (3) | 0.043 (4) | −0.008 (3) | 0.008 (3) | 0.010 (3) |
C5 | 0.044 (4) | 0.046 (4) | 0.027 (3) | 0.009 (3) | 0.008 (3) | 0.004 (3) |
C6 | 0.041 (4) | 0.054 (5) | 0.025 (3) | 0.004 (3) | 0.011 (3) | 0.005 (3) |
C7 | 0.027 (3) | 0.032 (3) | 0.047 (4) | 0.003 (3) | 0.002 (3) | 0.000 (3) |
C8 | 0.058 (4) | 0.051 (5) | 0.074 (5) | 0.010 (4) | −0.006 (4) | −0.013 (4) |
N1 | 0.029 (3) | 0.027 (3) | 0.026 (2) | 0.001 (2) | 0.008 (2) | 0.005 (2) |
N2 | 0.025 (2) | 0.020 (2) | 0.026 (2) | −0.0005 (19) | 0.0021 (19) | 0.000 (2) |
N3 | 0.058 (4) | 0.048 (4) | 0.045 (4) | 0.023 (3) | 0.023 (3) | 0.008 (3) |
O1 | 0.056 (3) | 0.048 (3) | 0.059 (4) | 0.008 (3) | 0.010 (3) | −0.011 (3) |
O2 | 0.069 (4) | 0.045 (3) | 0.049 (3) | 0.007 (3) | 0.014 (3) | 0.010 (3) |
O3 | 0.061 (4) | 0.059 (4) | 0.073 (4) | 0.004 (3) | 0.008 (3) | 0.005 (3) |
O4 | 0.094 (5) | 0.083 (5) | 0.114 (6) | −0.005 (4) | 0.012 (5) | −0.043 (5) |
O5 | 0.109 (5) | 0.087 (5) | 0.123 (6) | 0.031 (5) | 0.010 (5) | −0.005 (5) |
Br1 | 0.0407 (4) | 0.0409 (4) | 0.0579 (5) | 0.0031 (3) | 0.0154 (3) | 0.0171 (3) |
Br2 | 0.0401 (4) | 0.0490 (5) | 0.0446 (4) | −0.0023 (3) | 0.0078 (3) | −0.0109 (3) |
Cd1 | 0.0361 (3) | 0.0299 (3) | 0.0313 (2) | −0.0018 (2) | 0.00475 (19) | 0.0037 (2) |
C1—N1 | 1.471 (8) | C6—H6B | 0.9700 |
C1—C2 | 1.527 (9) | C7—N2 | 1.495 (8) |
C1—H1A | 0.9700 | C7—C8 | 1.503 (11) |
C1—H1B | 0.9700 | C7—H7B | 0.9700 |
C2—N2 | 1.515 (8) | C7—H7C | 0.9700 |
C2—H2A | 0.9700 | C8—O4 | 1.161 (11) |
C2—H2B | 0.9700 | C8—O5 | 1.387 (12) |
C3—N1 | 1.487 (8) | N1—Cd1 | 2.447 (5) |
C3—C4 | 1.519 (9) | N3—O2 | 1.185 (9) |
C3—H3A | 0.9700 | N3—O1 | 1.233 (9) |
C3—H3B | 0.9700 | O1—Cd1 | 2.397 (6) |
C4—N2 | 1.509 (8) | O2—Cd1 | 2.393 (6) |
C4—H4A | 0.9700 | O3—H3D | 0.8500 |
C4—H4B | 0.9700 | O3—H3C | 0.8501 |
C5—N1 | 1.491 (8) | O5—H5C | 0.8500 |
C5—C6 | 1.520 (10) | Br1—Cd1 | 2.6354 (9) |
C5—H5A | 0.9700 | Br1—Cd1i | 3.0191 (10) |
C5—H5B | 0.9700 | Br2—Cd1 | 2.5890 (10) |
C6—N2 | 1.529 (8) | Cd1—Br1i | 3.0191 (10) |
C6—H6A | 0.9700 | ||
N1—C1—C2 | 111.7 (5) | N2—C7—H7C | 108.6 |
N1—C1—H1A | 109.3 | C8—C7—H7C | 108.6 |
C2—C1—H1A | 109.3 | H7B—C7—H7C | 107.5 |
N1—C1—H1B | 109.3 | O4—C8—O5 | 118.4 (12) |
C2—C1—H1B | 109.3 | O4—C8—C7 | 132.0 (12) |
H1A—C1—H1B | 107.9 | O5—C8—C7 | 109.0 (10) |
N2—C2—C1 | 109.3 (5) | C1—N1—C3 | 108.4 (5) |
N2—C2—H2A | 109.8 | C1—N1—C5 | 108.5 (5) |
C1—C2—H2A | 109.8 | C3—N1—C5 | 107.1 (5) |
N2—C2—H2B | 109.8 | C1—N1—Cd1 | 109.9 (4) |
C1—C2—H2B | 109.8 | C3—N1—Cd1 | 109.8 (4) |
H2A—C2—H2B | 108.3 | C5—N1—Cd1 | 113.0 (4) |
N1—C3—C4 | 112.8 (5) | C7—N2—C4 | 112.3 (5) |
N1—C3—H3A | 109.0 | C7—N2—C2 | 107.3 (5) |
C4—C3—H3A | 109.0 | C4—N2—C2 | 108.5 (5) |
N1—C3—H3B | 109.0 | C7—N2—C6 | 112.5 (5) |
C4—C3—H3B | 109.0 | C4—N2—C6 | 109.1 (5) |
H3A—C3—H3B | 107.8 | C2—N2—C6 | 106.9 (5) |
N2—C4—C3 | 108.6 (5) | O2—N3—O1 | 115.6 (7) |
N2—C4—H4A | 110.0 | N3—O1—Cd1 | 96.0 (5) |
C3—C4—H4A | 110.0 | N3—O2—Cd1 | 97.7 (5) |
N2—C4—H4B | 110.0 | H3D—O3—H3C | 116.7 |
C3—C4—H4B | 110.0 | C8—O5—H5C | 109.4 |
H4A—C4—H4B | 108.3 | Cd1—Br1—Cd1i | 90.87 (3) |
N1—C5—C6 | 111.0 (5) | O2—Cd1—O1 | 50.5 (2) |
N1—C5—H5A | 109.4 | O2—Cd1—N1 | 90.73 (19) |
C6—C5—H5A | 109.4 | O1—Cd1—N1 | 90.37 (19) |
N1—C5—H5B | 109.4 | O2—Cd1—Br2 | 100.51 (16) |
C6—C5—H5B | 109.4 | O1—Cd1—Br2 | 150.81 (16) |
H5A—C5—H5B | 108.0 | N1—Cd1—Br2 | 93.99 (13) |
C5—C6—N2 | 109.6 (5) | O2—Cd1—Br1 | 149.41 (16) |
C5—C6—H6A | 109.7 | O1—Cd1—Br1 | 99.16 (16) |
N2—C6—H6A | 109.7 | N1—Cd1—Br1 | 93.80 (12) |
C5—C6—H6B | 109.7 | Br2—Cd1—Br1 | 109.31 (3) |
N2—C6—H6B | 109.7 | O2—Cd1—Br1i | 83.17 (15) |
H6A—C6—H6B | 108.2 | O1—Cd1—Br1i | 82.11 (14) |
N2—C7—C8 | 114.8 (7) | N1—Cd1—Br1i | 172.29 (12) |
N2—C7—H7B | 108.6 | Br2—Cd1—Br1i | 91.75 (3) |
C8—C7—H7B | 108.6 | Br1—Cd1—Br1i | 89.13 (3) |
Symmetry code: (i) −x, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5C···Br2ii | 0.85 | 2.75 | 3.569 (9) | 162 |
O3—H3D···O2 | 0.85 | 2.13 | 2.932 (9) | 158 |
O3—H3C···O5iii | 0.85 | 2.20 | 2.957 (12) | 149 |
Symmetry codes: (ii) −x+1, −y, −z+1; (iii) x−1, y, z. |
[CdBr(C8H14N3)(NO2)2(H2O)]·H2O | F(000) = 928 |
Mr = 472.58 | Dx = 2.075 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4571 reflections |
a = 7.343 (2) Å | θ = 3.0–27.5° |
b = 16.254 (5) Å | µ = 4.12 mm−1 |
c = 12.850 (4) Å | T = 293 K |
β = 99.505 (5)° | Block, colourless |
V = 1512.6 (8) Å3 | 0.2 × 0.2 × 0.2 mm |
Z = 4 |
Rigaku Mercury CCD diffractometer | 3458 independent reflections |
Radiation source: fine-focus sealed tube | 3110 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.047 |
Detector resolution: 28.2714 pixels mm-1 | θmax = 27.5°, θmin = 2.0° |
ω scans | h = −9→9 |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −21→21 |
Tmin = 0.663, Tmax = 1.000 | l = −16→16 |
16104 measured reflections |
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)] = 0.035 | H-atom parameters constrained |
wR(F2) = 0.123 | w = 1/[σ2(Fo2) + (0.0736P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.13 | (Δ/σ)max = 0.001 |
3458 reflections | Δρmax = 1.47 e Å−3 |
190 parameters | Δρmin = −0.86 e Å−3 |
34 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008) |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0055 (11) |
[CdBr(C8H14N3)(NO2)2(H2O)]·H2O | V = 1512.6 (8) Å3 |
Mr = 472.58 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.343 (2) Å | µ = 4.12 mm−1 |
b = 16.254 (5) Å | T = 293 K |
c = 12.850 (4) Å | 0.2 × 0.2 × 0.2 mm |
β = 99.505 (5)° |
Rigaku Mercury CCD diffractometer | 3458 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 3110 reflections with I > 2σ(I) |
Tmin = 0.663, Tmax = 1.000 | Rint = 0.047 |
16104 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 34 restraints |
wR(F2) = 0.123 | H-atom parameters constrained |
S = 1.13 | Δρmax = 1.47 e Å−3 |
3458 reflections | Δρmin = −0.86 e Å−3 |
190 parameters |
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 F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > \s(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ 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 | ||
C1 | 0.2992 (7) | 0.6297 (3) | 0.7637 (4) | 0.0275 (10) | |
H1A | 0.3909 | 0.6630 | 0.8079 | 0.033* | |
H1B | 0.2320 | 0.6651 | 0.7098 | 0.033* | |
C2 | 0.3962 (7) | 0.5613 (3) | 0.7113 (4) | 0.0284 (10) | |
H2A | 0.3997 | 0.5753 | 0.6383 | 0.034* | |
H2B | 0.5220 | 0.5547 | 0.7476 | 0.034* | |
C3 | 0.2665 (7) | 0.5296 (3) | 0.8967 (4) | 0.0307 (11) | |
H3A | 0.1902 | 0.5114 | 0.9471 | 0.037* | |
H3B | 0.3802 | 0.5518 | 0.9358 | 0.037* | |
C4 | 0.3108 (8) | 0.4564 (3) | 0.8309 (4) | 0.0324 (11) | |
H4A | 0.4363 | 0.4380 | 0.8552 | 0.039* | |
H4B | 0.2277 | 0.4111 | 0.8384 | 0.039* | |
C5 | 0.0147 (6) | 0.5555 (3) | 0.7566 (4) | 0.0298 (11) | |
H5A | −0.0631 | 0.5977 | 0.7189 | 0.036* | |
H5B | −0.0601 | 0.5232 | 0.7970 | 0.036* | |
C6 | 0.0902 (6) | 0.4996 (3) | 0.6775 (4) | 0.0280 (10) | |
H6A | 0.0212 | 0.4484 | 0.6692 | 0.034* | |
H6B | 0.0769 | 0.5264 | 0.6092 | 0.034* | |
C7 | 0.3627 (8) | 0.4154 (3) | 0.6535 (4) | 0.0316 (11) | |
H7A | 0.4950 | 0.4107 | 0.6759 | 0.038* | |
H7B | 0.3073 | 0.3633 | 0.6678 | 0.038* | |
C8 | 0.3254 (7) | 0.4310 (3) | 0.5413 (4) | 0.0295 (10) | |
N1 | 0.1689 (5) | 0.5945 (2) | 0.8292 (3) | 0.0202 (7) | |
N2 | 0.2893 (5) | 0.4822 (2) | 0.7169 (3) | 0.0219 (8) | |
N3 | 0.2950 (7) | 0.4459 (3) | 0.4532 (4) | 0.0422 (11) | |
N4 | −0.3010 (5) | 0.6625 (2) | 0.9524 (3) | 0.0259 (8) | |
N5 | 0.2563 (5) | 0.8420 (2) | 0.9520 (3) | 0.0269 (8) | |
O1 | −0.2233 (6) | 0.6158 (3) | 0.9155 (4) | 0.0497 (10) | |
O2 | −0.2363 (6) | 0.7303 (3) | 0.9817 (4) | 0.0515 (11) | |
O3 | 0.3111 (6) | 0.7861 (3) | 0.9084 (4) | 0.0496 (10) | |
O4 | 0.1159 (6) | 0.8418 (3) | 0.9881 (4) | 0.0526 (10) | |
O5 | −0.0829 (5) | 0.7616 (2) | 0.7690 (3) | 0.0405 (9) | |
H5WA | −0.0188 | 0.7869 | 0.7298 | 0.061* | |
H5WB | −0.1732 | 0.7296 | 0.7485 | 0.061* | |
O6 | 0.5766 (6) | 0.7698 (3) | 1.1547 (3) | 0.0488 (10) | |
H6WA | 0.5076 | 0.7313 | 1.1706 | 0.073* | |
H6WB | 0.5543 | 0.7781 | 1.0885 | 0.073* | |
Br1 | 0.19401 (7) | 0.63980 (3) | 1.12733 (4) | 0.03482 (17) | |
Cd1 | 0.05508 (4) | 0.700406 (19) | 0.93323 (2) | 0.02336 (14) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.028 (2) | 0.026 (2) | 0.031 (2) | −0.0057 (19) | 0.0115 (19) | −0.0026 (19) |
C2 | 0.026 (2) | 0.027 (2) | 0.034 (2) | −0.0033 (19) | 0.0098 (19) | −0.0042 (19) |
C3 | 0.041 (3) | 0.029 (2) | 0.022 (2) | 0.010 (2) | 0.006 (2) | 0.0023 (19) |
C4 | 0.046 (3) | 0.029 (2) | 0.022 (2) | 0.010 (2) | 0.005 (2) | 0.0021 (18) |
C5 | 0.019 (2) | 0.032 (3) | 0.038 (3) | −0.0030 (19) | 0.0027 (19) | −0.015 (2) |
C6 | 0.023 (2) | 0.031 (2) | 0.030 (2) | −0.0008 (19) | 0.0022 (18) | −0.0120 (19) |
C7 | 0.042 (3) | 0.025 (2) | 0.028 (2) | 0.010 (2) | 0.009 (2) | −0.0008 (19) |
C8 | 0.026 (2) | 0.030 (2) | 0.033 (3) | 0.0023 (19) | 0.0078 (19) | −0.011 (2) |
N1 | 0.0180 (17) | 0.0213 (18) | 0.0214 (18) | −0.0005 (14) | 0.0035 (14) | 0.0003 (14) |
N2 | 0.0233 (19) | 0.0210 (18) | 0.0221 (18) | 0.0011 (14) | 0.0057 (14) | −0.0022 (14) |
N3 | 0.039 (3) | 0.057 (3) | 0.030 (2) | 0.004 (2) | 0.0071 (19) | −0.010 (2) |
N4 | 0.0222 (18) | 0.0355 (19) | 0.0168 (17) | −0.0076 (15) | −0.0058 (13) | 0.0073 (14) |
N5 | 0.0254 (18) | 0.0256 (18) | 0.0257 (19) | 0.0004 (15) | −0.0077 (14) | 0.0064 (14) |
O1 | 0.041 (2) | 0.051 (2) | 0.056 (3) | −0.0120 (18) | 0.0054 (18) | 0.001 (2) |
O2 | 0.041 (2) | 0.049 (2) | 0.066 (3) | −0.0003 (18) | 0.013 (2) | −0.016 (2) |
O3 | 0.042 (2) | 0.045 (2) | 0.062 (3) | −0.0062 (18) | 0.008 (2) | −0.0025 (19) |
O4 | 0.054 (2) | 0.039 (2) | 0.064 (3) | 0.003 (2) | 0.009 (2) | −0.012 (2) |
O5 | 0.035 (2) | 0.049 (2) | 0.036 (2) | −0.0009 (17) | 0.0028 (16) | 0.0143 (17) |
O6 | 0.038 (2) | 0.065 (3) | 0.043 (2) | 0.003 (2) | 0.0035 (18) | −0.006 (2) |
Br1 | 0.0400 (3) | 0.0389 (3) | 0.0252 (3) | 0.0049 (2) | 0.0043 (2) | 0.00038 (19) |
Cd1 | 0.0233 (2) | 0.0231 (2) | 0.0240 (2) | −0.00063 (12) | 0.00500 (14) | −0.00251 (11) |
C1—N1 | 1.489 (5) | C7—C8 | 1.444 (7) |
C1—C2 | 1.535 (6) | C7—N2 | 1.510 (6) |
C1—H1A | 0.9700 | C7—H7A | 0.9700 |
C1—H1B | 0.9699 | C7—H7B | 0.9700 |
C2—N2 | 1.514 (6) | C8—N3 | 1.144 (7) |
C2—H2A | 0.9700 | N1—Cd1 | 2.413 (4) |
C2—H2B | 0.9700 | N4—O1 | 1.102 (5) |
C3—N1 | 1.474 (6) | N4—O2 | 1.234 (5) |
C3—C4 | 1.526 (6) | N5—O3 | 1.172 (5) |
C3—H3A | 0.9700 | N5—O4 | 1.199 (5) |
C3—H3B | 0.9701 | O1—Cd1 | 2.443 (4) |
C4—N2 | 1.506 (6) | O2—Cd1 | 2.376 (4) |
C4—H4A | 0.9701 | O3—Cd1 | 2.403 (4) |
C4—H4B | 0.9701 | O4—Cd1 | 2.424 (4) |
C5—N1 | 1.485 (5) | O5—Cd1 | 2.401 (4) |
C5—C6 | 1.533 (6) | O5—H5WA | 0.8500 |
C5—H5A | 0.9700 | O5—H5WB | 0.8500 |
C5—H5B | 0.9699 | O6—H6WA | 0.8501 |
C6—N2 | 1.493 (6) | O6—H6WB | 0.8500 |
C6—H6A | 0.9702 | Br1—Cd1 | 2.7187 (9) |
C6—H6B | 0.9699 | ||
N1—C1—C2 | 110.9 (4) | C3—N1—C5 | 108.1 (4) |
N1—C1—H1A | 109.4 | C3—N1—C1 | 108.2 (4) |
C2—C1—H1A | 109.4 | C5—N1—C1 | 107.7 (3) |
N1—C1—H1B | 109.5 | C3—N1—Cd1 | 111.3 (3) |
C2—C1—H1B | 109.5 | C5—N1—Cd1 | 110.8 (3) |
H1A—C1—H1B | 108.1 | C1—N1—Cd1 | 110.6 (3) |
N2—C2—C1 | 108.2 (4) | C6—N2—C4 | 108.8 (4) |
N2—C2—H2A | 110.0 | C6—N2—C7 | 111.7 (4) |
C1—C2—H2A | 110.1 | C4—N2—C7 | 109.5 (3) |
N2—C2—H2B | 110.1 | C6—N2—C2 | 108.0 (4) |
C1—C2—H2B | 110.1 | C4—N2—C2 | 108.2 (4) |
H2A—C2—H2B | 108.4 | C7—N2—C2 | 110.5 (4) |
N1—C3—C4 | 111.1 (4) | O1—N4—O2 | 123.1 (5) |
N1—C3—H3A | 109.4 | O3—N5—O4 | 124.6 (4) |
C4—C3—H3A | 109.4 | N4—O1—Cd1 | 93.3 (3) |
N1—C3—H3B | 109.4 | N4—O2—Cd1 | 93.1 (3) |
C4—C3—H3B | 109.4 | N5—O3—Cd1 | 92.8 (3) |
H3A—C3—H3B | 108.0 | N5—O4—Cd1 | 91.1 (3) |
N2—C4—C3 | 108.9 (4) | Cd1—O5—H5WA | 121.8 |
N2—C4—H4A | 109.9 | Cd1—O5—H5WB | 102.3 |
C3—C4—H4A | 109.9 | H5WA—O5—H5WB | 126.3 |
N2—C4—H4B | 110.0 | H6WA—O6—H6WB | 109.5 |
C3—C4—H4B | 109.9 | O2—Cd1—O5 | 83.00 (15) |
H4A—C4—H4B | 108.3 | O2—Cd1—O3 | 132.41 (14) |
N1—C5—C6 | 110.3 (4) | O5—Cd1—O3 | 82.45 (15) |
N1—C5—H5A | 109.7 | O2—Cd1—N1 | 134.50 (13) |
C6—C5—H5A | 109.7 | O5—Cd1—N1 | 86.75 (13) |
N1—C5—H5B | 109.5 | O3—Cd1—N1 | 89.43 (13) |
C6—C5—H5B | 109.5 | O2—Cd1—O4 | 81.96 (15) |
H5A—C5—H5B | 108.1 | O5—Cd1—O4 | 83.89 (16) |
N2—C6—C5 | 109.1 (3) | O3—Cd1—O4 | 51.57 (14) |
N2—C6—H6A | 109.8 | N1—Cd1—O4 | 140.72 (14) |
C5—C6—H6A | 109.9 | O2—Cd1—O1 | 50.46 (15) |
N2—C6—H6B | 109.8 | O5—Cd1—O1 | 85.77 (14) |
C5—C6—H6B | 109.8 | O3—Cd1—O1 | 167.12 (16) |
H6A—C6—H6B | 108.3 | N1—Cd1—O1 | 84.71 (14) |
C8—C7—N2 | 112.7 (4) | O4—Cd1—O1 | 132.21 (15) |
C8—C7—H7A | 109.0 | O2—Cd1—Br1 | 92.94 (12) |
N2—C7—H7A | 109.0 | O5—Cd1—Br1 | 175.22 (10) |
C8—C7—H7B | 109.1 | O3—Cd1—Br1 | 98.55 (11) |
N2—C7—H7B | 109.1 | N1—Cd1—Br1 | 97.92 (9) |
H7A—C7—H7B | 107.8 | O4—Cd1—Br1 | 93.06 (12) |
N3—C8—C7 | 177.9 (5) | O1—Cd1—Br1 | 93.61 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5WA···Br1i | 0.85 | 2.50 | 3.352 (4) | 175 |
O5—H5WB···O6ii | 0.85 | 2.02 | 2.731 (6) | 140 |
O6—H6WA···Br1 | 0.85 | 2.72 | 3.486 (5) | 151 |
O6—H6WB···O2iii | 0.85 | 2.36 | 2.872 (6) | 120 |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) x−1, −y+3/2, z−1/2; (iii) x+1, y, z. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Cd2Br4(C8H15N2O2)2(NO2)2]·2H2O | [CdBr(C8H14N3)(NO2)2(H2O)]·H2O |
Mr | 507.47 | 472.58 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21/c |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 8.7790 (18), 13.374 (3), 13.113 (3) | 7.343 (2), 16.254 (5), 12.850 (4) |
β (°) | 101.99 (3) | 99.505 (5) |
V (Å3) | 1505.9 (5) | 1512.6 (8) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 6.77 | 4.12 |
Crystal size (mm) | 0.2 × 0.2 × 0.2 | 0.2 × 0.2 × 0.2 |
Data collection | ||
Diffractometer | Rigaku Mercury CCD diffractometer | Rigaku Mercury CCD diffractometer |
Absorption correction | Multi-scan (CrystalClear; Rigaku, 2005) | Multi-scan (CrystalClear; Rigaku, 2005) |
Tmin, Tmax | 0.631, 1.000 | 0.663, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15299, 3461, 2877 | 16104, 3458, 3110 |
Rint | 0.049 | 0.047 |
(sin θ/λ)max (Å−1) | 0.649 | 0.649 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.118, 1.07 | 0.035, 0.123, 1.13 |
No. of reflections | 3461 | 3458 |
No. of parameters | 172 | 190 |
No. of restraints | 15 | 34 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0391P)2 + 10.3781P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.0736P)2] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 1.30, −1.10 | 1.47, −0.86 |
Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005).
N1—Cd1 | 2.447 (5) | Br1—Cd1 | 2.6354 (9) |
O1—Cd1 | 2.397 (6) | Br1—Cd1i | 3.0191 (10) |
O2—Cd1 | 2.393 (6) | Br2—Cd1 | 2.5890 (10) |
Cd1—Br1—Cd1i | 90.87 (3) | N1—Cd1—Br1 | 93.80 (12) |
O2—Cd1—N1 | 90.73 (19) | N1—Cd1—Br1i | 172.29 (12) |
O1—Cd1—N1 | 90.37 (19) | Br1—Cd1—Br1i | 89.13 (3) |
N1—Cd1—Br2 | 93.99 (13) |
Symmetry code: (i) −x, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5C···Br2ii | 0.85 | 2.75 | 3.569 (9) | 161.9 |
O3—H3D···O2 | 0.85 | 2.13 | 2.932 (9) | 157.5 |
O3—H3C···O5iii | 0.85 | 2.20 | 2.957 (12) | 148.7 |
Symmetry codes: (ii) −x+1, −y, −z+1; (iii) x−1, y, z. |
N1—Cd1 | 2.413 (4) | O4—Cd1 | 2.424 (4) |
O1—Cd1 | 2.443 (4) | O5—Cd1 | 2.401 (4) |
O2—Cd1 | 2.376 (4) | Br1—Cd1 | 2.7187 (9) |
O3—Cd1 | 2.403 (4) | ||
O5—Cd1—N1 | 86.75 (13) | O3—Cd1—O1 | 167.12 (16) |
O3—Cd1—N1 | 89.43 (13) | N1—Cd1—O1 | 84.71 (14) |
O3—Cd1—O4 | 51.57 (14) | O5—Cd1—Br1 | 175.22 (10) |
O2—Cd1—O1 | 50.46 (15) | N1—Cd1—Br1 | 97.92 (9) |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5WA···Br1i | 0.85 | 2.50 | 3.352 (4) | 174.9 |
O5—H5WB···O6ii | 0.85 | 2.02 | 2.731 (6) | 140.1 |
O6—H6WA···Br1 | 0.85 | 2.72 | 3.486 (5) | 150.5 |
O6—H6WB···O2iii | 0.85 | 2.36 | 2.872 (6) | 119.6 |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) x−1, −y+3/2, z−1/2; (iii) x+1, y, z. |
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Certain metal–organic hybrid materials are of interest for their electric properties, such as ferroelectricity, piezoelectricity and dielectricity (Planta & Unruh, 1993; Fu et al., 2008; Ye et al., 2009; Zhang et al., 2010). A large variety of multifunctional ligands, such as 1,2,4-triazine, carboxylates and bipyridyl, have been used in order to prepare new metal–organic hybrid materials. Extended structures of cadmium(II) nitrate–organic ligand materials have been reported (Marlin et al., 2006; Sharma & Clearfield, 2000; Lu et al., 2005), but cadmium(II) nitrite–organic ligand materials are very rare. Additionally, previous studies have reported that 1,4-diaza-bicyclo[2.2.2]octane (DABCO) derivatives can go through phase transitions (Zhang et al., 2009; Ye et al., 2010). As part of an exploration of new metal–organic hybrid materials, we produced a new DABCO derivative, namely 1-cyanomethyl-4-aza-1-azoniabicyclo[2.2.2]octane bromide, and then obtained novel cadmium(II) complexes with this ligand and the related 1-carboxymethyl-4-aza-1-azoniabicyclo[2.2.2]octane ligand, together with nitrite and bromide.
Cadmium(II) complexes have rich coordination numbers and geometries because of the d10 configuration of the CdII ions. The structural diversity observed includes monomers (Choudhury et al., 2003), dimers (Fuhr & Fenske, 1999) and coordination polymers (Thorn et al., 2005). The title compounds are a cadmium(II) dimer with bromide bridges, di-µ-bromido-bis[bromido(1-carboxymethyl-4-aza-1-azoniabicyclo[2.2.2]octane-κN4)(nitrito-κ2O,O')cadmium(II)] dihydrate, (I), and a cadmium(II) monomer, aquabromido(1-cyanomethyl-4-aza-1-azoniabicyclo[2.2.2]octane-κN4)bis(nitrito-κ2O,O')cadmium(II) monohydrate, (II), both of which are the first structurally examined cadmium complexes with these organic ligands.
Compound (I) consists of discrete neutral [Cd2(1-carboxymethyl-4-aza-1-azoniabicyclo[2.2.2]octane)2(µ2-Br)2Br2(NO2)2] molecules and interstitial water molecules (Fig. 1). The dinuclear complex is distributed across a centre of inversion so that the asymmetric unit consists of one CdII cation, two bromide anions, one nitrite anion, one organic ligand and one lattice water molecule. Each CdII ion takes a sixfold coordination of two O atoms from a bidentate nitrite ion, one N atom from the organic ligand and three bromide ions, which can be regarded as a somewhat distorted octahedral coordination geometry. One of the three bromide ligands is monodentate, while the other two are bridging, thus producing a tetranuclear [Cd2Br2] dimeric unit. The two terminal bromide ligands are trans oriented with respect to the four-membered bridge ring, and the two bridging bromide ligands and two CdII ions form a rectangular plane whose centre is located on a crystallographic centre of inversion. The Cd2Br2 rings in reported cadmium(II) dimers (Pickardt & Staub, 1999) are almost square because the CdII atom only has one kind of ligand other than Br, while in (I) the Cd2Br2 ring is rectangular since there are two quite different ligands besides Br, resulting in asymmetry of the Cd—Br bonds (Table 1). A similar [Cd2Br2] unit with a terminal Br on each Cd has been observed previously in the compound di-µ-bromo-bis[bromo(di-2-pyridylmethanediol)cadmium(II)] trihydrate (Zhu et al., 2000). The Cd—O bond distances within the nitrite ligand are slightly shorter than the Cd—N distance, which is the opposite of what is observed in the related complex [Cd(pyterpy)(H2O)(NO3)2] [pyterpy is 4'-(4-pyridyl)-2,2':6',2''-terpyridine; Granifo et al., 2004]. The two Br ligands and bidentate nitrite at the equatorial positions are almost coplanar, with a dihedral angle between the Cd1/Br1/Br2 and Cd1/O1/O2 planes of 7.33 (34)°. The apical N1—Cd1—Br1i angle [symmetry code: (i) -x, -y + 1, -z + 1] deviates only modestly from 180°.
Molecules are linked into two-dimensional sheets parallel to the crystallographic ab plane through O—H···Br and O—H···O interactions which also form centrosymmetric R66(16) rings (Fig. 2). Carboxyl atom O5 of the organic ligand forms one donor hydrogen bond with a monodentate Br ligand from an adjacent dimer and also one acceptor hydrogen bond with a water molecule from another adjacent dimer. The intermolecular O—H···Br hydrogen bonds (Table 2) serve to link the complexes into zigzag chains, some of which run along [110] and others along [110] depending on which layer one is in. Meanwhile, water molecules act as hydrogen-bond donors to O2 atoms of the coordinated nitrite. The hydrogen bonds produced by the water molecules extend the zigzag chains into two-dimensional hydrogen-bonded layers which then stack along [001], with no obvious interactions.
Although compound (II) has similar ligands, the structure of (II) is a CdII monomer with quite different coordination geometry. The CdII ion in (II) is seven-coordinate and the distorted pentagonal–bipyramidal coordination environment consists of one monodentate Br atom, one N atom of the organic ligand, four O atoms from two bidentate nitrite groups and one coordinated water molecule (Fig. 3). The asymmetric unit also includes one non-coordinated water molecule. The two coordinated nitrite groups at the equatorial positions are not coplanar, with a dihedral angle between the Cd1/O1/O2 and Cd1/O3/O4 planes of 12.70 (33)°, which is different from what is found in a related complex containing two nitrite ligands (Marandi et al., 2005), though the ligands at the apical positions in the two complexes are quite different.
While the molecular structures of the Cd complexes in (I) and (II) are dissimilar, they do have similar intermolecular interactions. For both complexes, the uncoordinated water molecule is decisive for the crystal packing. In (II), intermolecular O—H···Br hydrogen bonds link discrete neutral molecules into chains along the c axis (Fig. 4). The free water atom (O6) acts as a hydrogen-bond donor, via atoms H6WA and H6WB, respectively, to atoms O2iii and Br1, and also as a hydrogen-bond acceptor with O5ii via atom H5WB [symmetry codes: (ii) x + 1, -y - 3/2, z + 1/2; (iii) x + 1, y, z]. The combination of the O—H···O and O—H···Br hydrogen bonds generates alternating R54(14) and R33(8) rings, resulting in two-dimensional layers parallel to ac plane.
Dielectric measurements of both compounds show no dielectric anomaly from 93 to 363 K, indicating no structural phase transitions in the measured temperature range.