Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100016279/qa0409sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100016279/qa0409Isup2.hkl |
CCDC reference: 156200
The ligand tren (2 mmol) in water (5 ml) was added dropwise with stirring to Cd(NO3)2 (2 mmol) dissolved in water (15 ml) at room temperature, followed by the addition of solid phen (2 mmol). After the filtrate was allowed to stand in the air for several weeks, colourless prismatic crystals of the compound were obtained (yield 65.2%). Elemental analysis calculated for C18H28CdN8O7 (%): C 37.22, H 4.86, N 19.29; found: C 37.23, H 4.50, N 19.27.
All H atoms of organic ligands were placed in idealized positions and refined as riding atoms with isotropic displacement parameters. H atoms of the water molecule were found from the difference Fourier map and were also refined as riding atoms.
Data collection: SMART (Bruker, 1998); cell refinement: SMART (Bruker, 1998); data reduction: SAINT+ (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1998).
[Cd(C6H18N4)(C12H8N2)](NO3)2·H2O | F(000) = 1184 |
Mr = 580.88 | Dx = 1.644 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 11.385 (2) Å | Cell parameters from 4451 reflections |
b = 9.951 (2) Å | θ = 1.8–25.7° |
c = 20.745 (4) Å | µ = 0.99 mm−1 |
β = 92.72 (3)° | T = 293 K |
V = 2347.6 (8) Å3 | Prism, colourless |
Z = 4 | 0.21 × 0.13 × 0.07 mm |
Bruker SMART CCD area-detector diffractometer | 4451 independent reflections |
Radiation source: fine-focus sealed tube | 3857 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
ϕ and ω scans | θmax = 25.7°, θmin = 1.8° |
Absorption correction: empirical (using intensity measurements) (Blessing, 1995) | h = −13→12 |
Tmin = 0.820, Tmax = 0.934 | k = −12→9 |
12068 measured reflections | l = −25→25 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.087 | H-atom parameters constrained |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0547P)2 + 0.9055P] where P = (Fo2 + 2Fc2)/3 |
4451 reflections | (Δ/σ)max = 0.001 |
309 parameters | Δρmax = 0.77 e Å−3 |
0 restraints | Δρmin = −0.61 e Å−3 |
[Cd(C6H18N4)(C12H8N2)](NO3)2·H2O | V = 2347.6 (8) Å3 |
Mr = 580.88 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.385 (2) Å | µ = 0.99 mm−1 |
b = 9.951 (2) Å | T = 293 K |
c = 20.745 (4) Å | 0.21 × 0.13 × 0.07 mm |
β = 92.72 (3)° |
Bruker SMART CCD area-detector diffractometer | 4451 independent reflections |
Absorption correction: empirical (using intensity measurements) (Blessing, 1995) | 3857 reflections with I > 2σ(I) |
Tmin = 0.820, Tmax = 0.934 | Rint = 0.020 |
12068 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.087 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.77 e Å−3 |
4451 reflections | Δρmin = −0.61 e Å−3 |
309 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 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 | ||
Cd1 | 0.248243 (16) | 0.039206 (18) | 0.126790 (9) | 0.04151 (9) | |
C1 | −0.0036 (3) | 0.0198 (4) | 0.19340 (19) | 0.0657 (9) | |
H1A | −0.0116 | −0.0757 | 0.1882 | 0.080* | |
H1B | −0.0600 | 0.0489 | 0.2234 | 0.080* | |
C2 | −0.0297 (3) | 0.0862 (4) | 0.12899 (19) | 0.0704 (9) | |
H2A | −0.0265 | 0.1819 | 0.1345 | 0.080* | |
H2B | −0.1074 | 0.0628 | 0.1127 | 0.080* | |
C3 | 0.1558 (4) | −0.0503 (4) | 0.26795 (17) | 0.0651 (9) | |
H3A | 0.2133 | −0.0099 | 0.2972 | 0.080* | |
H3B | 0.0907 | −0.0788 | 0.2923 | 0.080* | |
C4 | 0.2098 (3) | −0.1706 (4) | 0.23619 (16) | 0.0610 (8) | |
H4A | 0.1523 | −0.2121 | 0.2073 | 0.080* | |
H4B | 0.2347 | −0.2355 | 0.2683 | 0.080* | |
C5 | 0.1243 (3) | 0.1878 (4) | 0.24519 (17) | 0.0675 (9) | |
H5A | 0.0752 | 0.2467 | 0.2190 | 0.080* | |
H5B | 0.0964 | 0.1890 | 0.2881 | 0.080* | |
C6 | 0.2486 (3) | 0.2394 (4) | 0.24602 (17) | 0.0718 (10) | |
H6A | 0.2977 | 0.1819 | 0.2729 | 0.080* | |
H6B | 0.2523 | 0.3284 | 0.2638 | 0.080* | |
N1 | 0.1152 (2) | 0.0502 (2) | 0.21959 (12) | 0.0516 (6) | |
N2 | 0.0575 (3) | 0.0442 (3) | 0.08272 (14) | 0.0615 (7) | |
H2C | 0.0383 | −0.0381 | 0.0677 | 0.080* | |
H2D | 0.0544 | 0.1013 | 0.0490 | 0.080* | |
N3 | 0.3110 (2) | −0.1269 (3) | 0.19972 (12) | 0.0560 (6) | |
H3C | 0.3676 | −0.0941 | 0.2271 | 0.080* | |
H3D | 0.3406 | −0.1969 | 0.1784 | 0.080* | |
N4 | 0.2922 (3) | 0.2388 (3) | 0.18040 (13) | 0.0661 (7) | |
H4C | 0.2588 | 0.3077 | 0.1582 | 0.080* | |
H4D | 0.3706 | 0.2513 | 0.1822 | 0.080* | |
C7 | 0.2495 (3) | −0.2588 (3) | 0.04878 (16) | 0.0568 (7) | |
H7A | 0.2199 | −0.2901 | 0.0887 | 0.080* | |
C8 | 0.2594 (3) | −0.3498 (3) | −0.00211 (19) | 0.0662 (9) | |
H8A | 0.2342 | −0.4412 | 0.0025 | 0.080* | |
C9 | 0.3042 (3) | −0.3074 (3) | −0.05794 (16) | 0.0621 (8) | |
H9A | 0.3129 | −0.3695 | −0.0928 | 0.080* | |
C10 | 0.3378 (2) | −0.1723 (3) | −0.06468 (14) | 0.0497 (6) | |
C11 | 0.3842 (3) | −0.1216 (4) | −0.12208 (14) | 0.0587 (8) | |
H11A | 0.3972 | −0.1817 | −0.1572 | 0.080* | |
C12 | 0.4106 (3) | 0.0088 (4) | −0.12776 (15) | 0.0583 (8) | |
H12A | 0.4402 | 0.0413 | −0.1675 | 0.080* | |
C13 | 0.3967 (2) | 0.1003 (3) | −0.07603 (14) | 0.0492 (7) | |
C14 | 0.3539 (2) | 0.0543 (3) | −0.01708 (13) | 0.0396 (6) | |
C15 | 0.3234 (2) | −0.0862 (3) | −0.01188 (13) | 0.0398 (5) | |
C16 | 0.4249 (3) | 0.2368 (4) | −0.07984 (16) | 0.0606 (8) | |
H16A | 0.4539 | 0.2726 | −0.1190 | 0.080* | |
C17 | 0.4110 (3) | 0.3180 (3) | −0.02844 (18) | 0.0657 (9) | |
H17A | 0.4319 | 0.4112 | −0.0307 | 0.080* | |
C18 | 0.3676 (3) | 0.2646 (3) | 0.02800 (16) | 0.0569 (7) | |
H18A | 0.3564 | 0.3236 | 0.0638 | 0.080* | |
N5 | 0.2803 (2) | −0.1295 (2) | 0.04431 (11) | 0.0464 (5) | |
N6 | 0.3395 (2) | 0.1355 (2) | 0.03419 (11) | 0.0451 (5) | |
N7 | 0.4578 (2) | 0.5269 (2) | 0.18674 (13) | 0.0529 (6) | |
N8 | −0.0600 (3) | −0.3059 (4) | 0.06637 (18) | 0.0812 (9) | |
O1 | 0.3787 (4) | 0.5471 (3) | 0.1476 (2) | 0.1318 (17) | |
O2 | 0.5128 (3) | 0.4226 (3) | 0.1868 (2) | 0.1090 (12) | |
O3 | 0.4841 (3) | 0.6132 (3) | 0.22606 (14) | 0.0994 (10) | |
O4 | 0.0084 (4) | −0.3047 (6) | 0.11431 (19) | 0.1492 (18) | |
O5 | −0.0695 (5) | −0.2191 (6) | 0.0332 (3) | 0.208 (3) | |
O6 | −0.1042 (6) | −0.4073 (5) | 0.0622 (4) | 0.227 (4) | |
O1W | 0.1023 (4) | 0.3954 (5) | 0.1001 (2) | 0.1296 (14) | |
H1W | 0.0230 | 0.4034 | 0.0893 | 0.115 (19)* | |
H2W | 0.0891 | 0.4750 | 0.1166 | 0.18 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.04632 (14) | 0.03935 (13) | 0.03893 (13) | −0.00235 (8) | 0.00268 (9) | −0.00182 (7) |
C1 | 0.0458 (17) | 0.072 (2) | 0.080 (2) | 0.0029 (15) | 0.0120 (16) | 0.0046 (18) |
C2 | 0.0476 (17) | 0.070 (2) | 0.092 (3) | 0.0078 (16) | −0.0091 (17) | 0.008 (2) |
C3 | 0.075 (2) | 0.072 (2) | 0.0494 (18) | 0.0030 (17) | 0.0108 (16) | 0.0114 (16) |
C4 | 0.068 (2) | 0.0590 (18) | 0.0558 (18) | 0.0057 (16) | −0.0010 (15) | 0.0189 (15) |
C5 | 0.076 (2) | 0.069 (2) | 0.0583 (19) | 0.0095 (18) | 0.0166 (17) | −0.0127 (17) |
C6 | 0.085 (2) | 0.069 (2) | 0.061 (2) | −0.0047 (19) | −0.0009 (18) | −0.0257 (17) |
N1 | 0.0532 (14) | 0.0541 (15) | 0.0480 (13) | 0.0032 (11) | 0.0079 (11) | 0.0007 (11) |
N2 | 0.0632 (17) | 0.0662 (19) | 0.0538 (15) | −0.0063 (13) | −0.0122 (13) | 0.0076 (12) |
N3 | 0.0537 (14) | 0.0566 (15) | 0.0572 (14) | 0.0089 (12) | −0.0027 (11) | 0.0027 (12) |
N4 | 0.0708 (17) | 0.0582 (16) | 0.0698 (18) | −0.0172 (14) | 0.0103 (14) | −0.0186 (14) |
C7 | 0.0641 (19) | 0.0410 (16) | 0.0661 (19) | −0.0081 (13) | 0.0102 (15) | −0.0006 (14) |
C8 | 0.073 (2) | 0.0400 (16) | 0.085 (2) | −0.0062 (15) | −0.0010 (18) | −0.0095 (16) |
C9 | 0.070 (2) | 0.0521 (18) | 0.0630 (19) | 0.0061 (15) | −0.0053 (16) | −0.0186 (15) |
C10 | 0.0461 (15) | 0.0535 (16) | 0.0489 (15) | 0.0074 (12) | −0.0051 (12) | −0.0084 (13) |
C11 | 0.0573 (17) | 0.079 (2) | 0.0400 (15) | 0.0135 (16) | 0.0009 (13) | −0.0088 (15) |
C12 | 0.0545 (17) | 0.079 (2) | 0.0418 (16) | 0.0093 (16) | 0.0063 (13) | 0.0072 (15) |
C13 | 0.0396 (13) | 0.0598 (18) | 0.0482 (15) | 0.0051 (13) | 0.0023 (11) | 0.0138 (14) |
C14 | 0.0361 (12) | 0.0414 (14) | 0.0411 (13) | 0.0019 (10) | −0.0003 (11) | 0.0046 (11) |
C15 | 0.0376 (13) | 0.0403 (13) | 0.0410 (13) | 0.0023 (11) | −0.0022 (10) | −0.0015 (11) |
C16 | 0.0558 (18) | 0.064 (2) | 0.0621 (19) | 0.0002 (15) | 0.0073 (15) | 0.0219 (17) |
C17 | 0.065 (2) | 0.0440 (16) | 0.088 (2) | −0.0078 (15) | 0.0015 (18) | 0.0186 (17) |
C18 | 0.0633 (19) | 0.0421 (15) | 0.0654 (19) | −0.0048 (14) | 0.0036 (15) | 0.0008 (14) |
N5 | 0.0537 (13) | 0.0369 (12) | 0.0488 (13) | −0.0034 (10) | 0.0058 (10) | −0.0012 (10) |
N6 | 0.0489 (12) | 0.0378 (12) | 0.0485 (12) | −0.0039 (10) | 0.0021 (10) | 0.0012 (10) |
N7 | 0.0587 (15) | 0.0430 (14) | 0.0563 (15) | −0.0114 (11) | −0.0034 (12) | 0.0110 (11) |
N8 | 0.096 (2) | 0.069 (2) | 0.077 (2) | −0.0229 (18) | −0.0186 (18) | 0.0038 (17) |
O1 | 0.128 (3) | 0.094 (3) | 0.164 (4) | −0.0122 (19) | −0.086 (3) | 0.033 (2) |
O2 | 0.091 (2) | 0.0598 (16) | 0.173 (4) | 0.0173 (16) | −0.026 (2) | −0.016 (2) |
O3 | 0.131 (3) | 0.088 (2) | 0.0803 (19) | −0.0179 (19) | 0.0133 (18) | −0.0254 (17) |
O4 | 0.121 (3) | 0.236 (6) | 0.092 (2) | −0.033 (3) | 0.015 (2) | −0.025 (3) |
O5 | 0.209 (6) | 0.175 (5) | 0.232 (6) | −0.047 (4) | −0.067 (5) | 0.129 (5) |
O6 | 0.218 (6) | 0.100 (3) | 0.349 (9) | −0.054 (4) | −0.125 (6) | 0.001 (5) |
O1W | 0.129 (3) | 0.108 (3) | 0.150 (4) | 0.012 (2) | −0.014 (3) | 0.040 (3) |
Cd1—N2 | 2.316 (3) | C10—C15 | 1.407 (4) |
Cd1—N4 | 2.320 (3) | C10—C11 | 1.419 (4) |
Cd1—N3 | 2.330 (3) | C11—C12 | 1.338 (5) |
Cd1—N6 | 2.424 (2) | C12—C13 | 1.422 (5) |
Cd1—N5 | 2.437 (2) | C13—C16 | 1.399 (5) |
Cd1—N1 | 2.508 (3) | C13—C14 | 1.413 (4) |
C1—N1 | 1.465 (4) | C14—N6 | 1.352 (3) |
C1—C2 | 1.507 (5) | C14—C15 | 1.446 (4) |
C2—N2 | 1.474 (5) | C15—N5 | 1.357 (4) |
C3—N1 | 1.475 (4) | C16—C17 | 1.353 (5) |
C3—C4 | 1.511 (5) | C17—C18 | 1.397 (5) |
C4—N3 | 1.473 (4) | C18—N6 | 1.332 (4) |
C5—N1 | 1.471 (4) | N7—O1 | 1.201 (4) |
C5—C6 | 1.505 (5) | N7—O3 | 1.212 (4) |
C6—N4 | 1.471 (4) | N7—O2 | 1.213 (4) |
C7—N5 | 1.337 (4) | N8—O5 | 1.107 (5) |
C7—C8 | 1.399 (5) | N8—O6 | 1.129 (5) |
C8—C9 | 1.354 (5) | N8—O4 | 1.233 (5) |
C9—C10 | 1.407 (5) | ||
N2—Cd1—N4 | 110.36 (11) | C9—C8—C7 | 119.4 (3) |
N2—Cd1—N3 | 121.62 (10) | C8—C9—C10 | 119.8 (3) |
N4—Cd1—N3 | 104.10 (10) | C15—C10—C9 | 117.6 (3) |
N2—Cd1—N6 | 96.18 (9) | C15—C10—C11 | 119.9 (3) |
N4—Cd1—N6 | 87.17 (9) | C9—C10—C11 | 122.5 (3) |
N3—Cd1—N6 | 131.70 (8) | C12—C11—C10 | 120.9 (3) |
N2—Cd1—N5 | 84.62 (9) | C11—C12—C13 | 121.4 (3) |
N4—Cd1—N5 | 152.94 (9) | C16—C13—C14 | 116.9 (3) |
N3—Cd1—N5 | 85.17 (9) | C16—C13—C12 | 123.0 (3) |
N6—Cd1—N5 | 68.40 (7) | C14—C13—C12 | 120.1 (3) |
N2—Cd1—N1 | 73.32 (10) | N6—C14—C13 | 123.2 (2) |
N4—Cd1—N1 | 73.69 (9) | N6—C14—C15 | 118.7 (2) |
N3—Cd1—N1 | 73.15 (9) | C13—C14—C15 | 118.1 (2) |
N6—Cd1—N1 | 152.65 (8) | N5—C15—C10 | 122.4 (3) |
N5—Cd1—N1 | 133.23 (8) | N5—C15—C14 | 118.0 (2) |
N1—C1—C2 | 112.2 (3) | C10—C15—C14 | 119.6 (2) |
N2—C2—C1 | 110.0 (3) | C17—C16—C13 | 119.9 (3) |
N1—C3—C4 | 111.2 (3) | C16—C17—C18 | 119.5 (3) |
N3—C4—C3 | 109.5 (3) | N6—C18—C17 | 122.9 (3) |
N1—C5—C6 | 111.8 (3) | C7—N5—C15 | 118.2 (3) |
N4—C6—C5 | 110.3 (3) | C7—N5—Cd1 | 124.4 (2) |
C1—N1—C5 | 112.0 (3) | C15—N5—Cd1 | 117.18 (17) |
C1—N1—C3 | 111.5 (3) | C18—N6—C14 | 117.5 (3) |
C5—N1—C3 | 111.8 (3) | C18—N6—Cd1 | 124.9 (2) |
C1—N1—Cd1 | 106.7 (2) | C14—N6—Cd1 | 117.40 (17) |
C5—N1—Cd1 | 106.44 (19) | O1—N7—O3 | 119.3 (3) |
C3—N1—Cd1 | 108.12 (19) | O1—N7—O2 | 120.9 (3) |
C2—N2—Cd1 | 113.4 (2) | O3—N7—O2 | 119.7 (3) |
C4—N3—Cd1 | 108.68 (18) | O5—N8—O6 | 128.3 (6) |
C6—N4—Cd1 | 111.8 (2) | O5—N8—O4 | 122.3 (5) |
N5—C7—C8 | 122.6 (3) | O6—N8—O4 | 109.4 (5) |
N1—C1—C2—N2 | 57.4 (4) | C10—C11—C12—C13 | 2.0 (5) |
N1—C3—C4—N3 | 59.7 (4) | C11—C12—C13—C16 | 179.0 (3) |
N1—C5—C6—N4 | 59.2 (4) | C11—C12—C13—C14 | −0.1 (4) |
C2—C1—N1—C5 | 75.0 (4) | C16—C13—C14—N6 | 0.2 (4) |
C2—C1—N1—C3 | −158.9 (3) | C12—C13—C14—N6 | 179.4 (3) |
C2—C1—N1—Cd1 | −41.0 (3) | C16—C13—C14—C15 | 179.7 (2) |
C6—C5—N1—C1 | −156.1 (3) | C12—C13—C14—C15 | −1.1 (4) |
C6—C5—N1—C3 | 78.0 (4) | C9—C10—C15—N5 | 0.8 (4) |
C6—C5—N1—Cd1 | −39.9 (3) | C11—C10—C15—N5 | −179.5 (3) |
C4—C3—N1—C1 | 85.4 (4) | C9—C10—C15—C14 | −178.4 (3) |
C4—C3—N1—C5 | −148.4 (3) | C11—C10—C15—C14 | 1.2 (4) |
C4—C3—N1—Cd1 | −31.6 (3) | N6—C14—C15—N5 | 0.7 (4) |
N2—Cd1—N1—C1 | 13.8 (2) | C13—C14—C15—N5 | −178.8 (2) |
N4—Cd1—N1—C1 | 131.5 (2) | N6—C14—C15—C10 | −180.0 (2) |
N3—Cd1—N1—C1 | −117.7 (2) | C13—C14—C15—C10 | 0.6 (4) |
N6—Cd1—N1—C1 | 84.2 (3) | C14—C13—C16—C17 | 0.1 (4) |
N5—Cd1—N1—C1 | −51.7 (2) | C12—C13—C16—C17 | −179.1 (3) |
N2—Cd1—N1—C5 | −105.9 (2) | C13—C16—C17—C18 | −0.5 (5) |
N4—Cd1—N1—C5 | 11.8 (2) | C16—C17—C18—N6 | 0.5 (5) |
N3—Cd1—N1—C5 | 122.6 (2) | C8—C7—N5—C15 | −0.4 (5) |
N6—Cd1—N1—C5 | −35.5 (3) | C8—C7—N5—Cd1 | 173.9 (2) |
N5—Cd1—N1—C5 | −171.37 (19) | C10—C15—N5—C7 | −0.7 (4) |
N2—Cd1—N1—C3 | 133.8 (2) | C14—C15—N5—C7 | 178.5 (3) |
N4—Cd1—N1—C3 | −108.4 (2) | C10—C15—N5—Cd1 | −175.5 (2) |
N3—Cd1—N1—C3 | 2.3 (2) | C14—C15—N5—Cd1 | 3.8 (3) |
N6—Cd1—N1—C3 | −155.8 (2) | N2—Cd1—N5—C7 | −80.0 (2) |
N5—Cd1—N1—C3 | 68.4 (2) | N4—Cd1—N5—C7 | 154.3 (3) |
C1—C2—N2—Cd1 | −42.4 (3) | N3—Cd1—N5—C7 | 42.5 (2) |
N4—Cd1—N2—C2 | −49.7 (2) | N6—Cd1—N5—C7 | −178.8 (3) |
N3—Cd1—N2—C2 | 72.5 (2) | N1—Cd1—N5—C7 | −18.9 (3) |
N6—Cd1—N2—C2 | −139.0 (2) | N2—Cd1—N5—C15 | 94.4 (2) |
N5—Cd1—N2—C2 | 153.5 (2) | N4—Cd1—N5—C15 | −31.4 (3) |
N1—Cd1—N2—C2 | 15.2 (2) | N3—Cd1—N5—C15 | −143.19 (19) |
C3—C4—N3—Cd1 | −55.6 (3) | N6—Cd1—N5—C15 | −4.47 (18) |
N2—Cd1—N3—C4 | −29.9 (2) | N1—Cd1—N5—C15 | 155.42 (17) |
N4—Cd1—N3—C4 | 95.3 (2) | C17—C18—N6—C14 | −0.2 (5) |
N6—Cd1—N3—C4 | −165.74 (19) | C17—C18—N6—Cd1 | −174.4 (2) |
N5—Cd1—N3—C4 | −110.5 (2) | C13—C14—N6—C18 | −0.2 (4) |
N1—Cd1—N3—C4 | 27.6 (2) | C15—C14—N6—C18 | −179.6 (3) |
C5—C6—N4—Cd1 | −45.7 (4) | C13—C14—N6—Cd1 | 174.51 (19) |
N2—Cd1—N4—C6 | 82.4 (3) | C15—C14—N6—Cd1 | −4.9 (3) |
N3—Cd1—N4—C6 | −49.7 (3) | N2—Cd1—N6—C18 | 97.4 (2) |
N6—Cd1—N4—C6 | 177.9 (2) | N4—Cd1—N6—C18 | −12.8 (2) |
N5—Cd1—N4—C6 | −157.2 (2) | N3—Cd1—N6—C18 | −119.2 (2) |
N1—Cd1—N4—C6 | 17.7 (2) | N5—Cd1—N6—C18 | 179.1 (3) |
N5—C7—C8—C9 | 1.5 (5) | N1—Cd1—N6—C18 | 32.1 (3) |
C7—C8—C9—C10 | −1.3 (5) | N2—Cd1—N6—C14 | −76.8 (2) |
C8—C9—C10—C15 | 0.2 (5) | N4—Cd1—N6—C14 | 173.0 (2) |
C8—C9—C10—C11 | −179.4 (3) | N3—Cd1—N6—C14 | 66.6 (2) |
C15—C10—C11—C12 | −2.5 (4) | N5—Cd1—N6—C14 | 4.86 (18) |
C9—C10—C11—C12 | 177.1 (3) | N1—Cd1—N6—C14 | −142.1 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2C···O5 | 0.90 | 2.28 | 3.142 (7) | 162 |
N2—H2D···O5i | 0.90 | 2.08 | 2.977 (6) | 171 |
N3—H3C···O2ii | 0.90 | 2.20 | 3.060 (5) | 160 |
N3—H3D···O3iii | 0.90 | 2.66 | 3.282 (4) | 127 |
N4—H4C···O1W | 0.90 | 2.28 | 3.088 (5) | 150 |
N4—H4D···O2 | 0.90 | 2.35 | 3.104 (4) | 142 |
O1W—H1W···O6iv | 0.92 | 2.43 | 3.134 (7) | 134 |
O1W—H2W···O4iv | 0.88 | 2.38 | 3.188 (7) | 154 |
Symmetry codes: (i) −x, −y, −z; (ii) −x+1, y−1/2, −z+1/2; (iii) x, y−1, z; (iv) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | [Cd(C6H18N4)(C12H8N2)](NO3)2·H2O |
Mr | 580.88 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 11.385 (2), 9.951 (2), 20.745 (4) |
β (°) | 92.72 (3) |
V (Å3) | 2347.6 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.99 |
Crystal size (mm) | 0.21 × 0.13 × 0.07 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (Blessing, 1995) |
Tmin, Tmax | 0.820, 0.934 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12068, 4451, 3857 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.610 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.087, 1.10 |
No. of reflections | 4451 |
No. of parameters | 309 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.77, −0.61 |
Computer programs: SMART (Bruker, 1998), SAINT+ (Bruker, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2C···O5 | 0.90 | 2.28 | 3.142 (7) | 161.5 |
N2—H2D···O5i | 0.90 | 2.08 | 2.977 (6) | 171.4 |
N3—H3C···O2ii | 0.90 | 2.20 | 3.060 (5) | 159.5 |
N3—H3D···O3iii | 0.90 | 2.66 | 3.282 (4) | 127.3 |
N4—H4C···O1W | 0.90 | 2.28 | 3.088 (5) | 149.7 |
N4—H4D···O2 | 0.90 | 2.35 | 3.104 (4) | 141.5 |
O1W—H1W···O6iv | 0.92 | 2.43 | 3.134 (7) | 133.6 |
O1W—H2W···O4iv | 0.88 | 2.38 | 3.188 (7) | 153.7 |
Symmetry codes: (i) −x, −y, −z; (ii) −x+1, y−1/2, −z+1/2; (iii) x, y−1, z; (iv) x, y+1, z. |
Crystal engineering and the design of solid-state architectures are of considerable contemporary interest by virtue of the potential application of functional materials (Braga et al., 1998; Hagrman et al., 1999). Four main types of interactions have been exploited in the construction of supramolecular materials: (i) coordinate covalent bonds connecting metal centres and appropriate bi- or polydentate ligands (Wang et al., 1999); (ii) intermolecular hydrogen bonds (Aakeröy & Beatty, 1998); (iii) π–π interactions of aromatic rings (Ning et al., 1999); and (iv) charge-transfer interactions (Bailey et al., 1998). Among these interactions, hydrogen bonds and π–π stacking play vital roles in molecular recognition and supramolecular chemistry. Herein, we describe a three-dimensional supramolecular cadmium(II) complex, (I), directed by alternating hydrogen-bonding and π–π interactions. \scheme
The Cd atom of (I) adopts a distorted octahedral coordination with six N atoms from tren and phen. The Cd—N distances range from 2.314 to 2.508 Å, in accordance with those values previously reported (Klüfers & Mayer, 1998).
The crystal packing of the complex reveals offset π-stacking between the phen rings with the interplane distances of about 3.50 Å, which is comparable to the phen–phen distance of 3.24–3.42 Å in the stacking of [M(phen)2](X2) (Geremia et al., 1992; Ye et al., 1998). Two neighboring [Cd(phen)(tren)]2+ cations form a dimeric motif. Furthermore, nitates bridge the adjacent motifs by hydrogen bonds formed between nitrate and amine. Infinite one-dimensional polymeric zigzag motifs constructed via alternating hydrogen-bonding and π–π interactions are thus assembled (Munakata et al., 1996; Tse et al., 1998). These exotic supermotifs are further linked by another nitrate–amine hydrogen bond to extend into three-dimensional networks.