The title complex, [Cd
2(C
11H
14N
3O
3)
2(NCS)
2(CH
4O)
2], is an interesting thiocyanate-bridged dinuclear cadmium(II) compound. It is located on a crystallographic inversion center. The Cd
II atom is six-coordinated in an octahedral configuration by one O and two N atoms of one Schiff base ligand and by the terminal N atom of a bridging thiocyanate ligand, defining the basal plane, and by the terminal S atom of another bridging thiocyanate ligand and by the O atom of a coordinated methanol molecule, occupying the axial positions. The molecules are linked through intermolecular O-H
O hydrogen bonds, forming chains running along the
b axis.
Supporting information
CCDC reference: 282182
5-Nitrosalicylaldehyde (0.1 mmol, 16.7 mg) and N,N-dimethylethane-1,2-diamine (0.1 mmol, 8.8 mg) were dissolved in MeOH (10 ml). The mixture was stirred at room temperature for 10 min to give a yellow solution. To the solution was added an MeOH solution (5 ml) of Cd(CH3COO)2·4H2O (0.1 mmol, 30.3 mg), with stirring. The mixture was stirred for another 10 min at room temperature. After keeping the filtrate in air for 3 d, colorless block-shaped crystals were formed.
Atom H4 was located in a difference Fourier map and refined isotropically, with the O—H distance restrained to 0.88 (1) Å. The other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances in the range 0.93–0.97 Å, and with Uiso(H) = 1.2 or 1.5Ueq(C). The C9/N3/C10/C11 moieties are disordered over two distinct sites, with occupancies of 0.535 (5) and 0.465 (5).
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.
di-µ-thiocyanato-bis((methanol){4-nitro-2-[2- (dimethylamino)ethyliminomethyl]phenolato}cadmium(II)]
top
Crystal data top
[Cd2(C11H14N3O2)2(NCS)2(CH4O)2] | Z = 1 |
Mr = 877.55 | F(000) = 440 |
Triclinic, P1 | Dx = 1.751 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.286 (1) Å | Cell parameters from 5707 reflections |
b = 8.946 (1) Å | θ = 2.4–28.3° |
c = 11.971 (2) Å | µ = 1.46 mm−1 |
α = 110.019 (2)° | T = 298 K |
β = 92.705 (2)° | Block, colorless |
γ = 91.482 (2)° | 0.32 × 0.21 × 0.11 mm |
V = 832.0 (2) Å3 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3686 independent reflections |
Radiation source: fine-focus sealed tube | 3559 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.016 |
ω scans | θmax = 27.5°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→10 |
Tmin = 0.652, Tmax = 0.856 | k = −11→11 |
7155 measured reflections | l = −15→15 |
Refinement top
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)] = 0.025 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.062 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | w = 1/[σ2(Fo2) + (0.034P)2 + 0.1681P] where P = (Fo2 + 2Fc2)/3 |
3686 reflections | (Δ/σ)max < 0.001 |
253 parameters | Δρmax = 0.34 e Å−3 |
21 restraints | Δρmin = −0.55 e Å−3 |
Crystal data top
[Cd2(C11H14N3O2)2(NCS)2(CH4O)2] | γ = 91.482 (2)° |
Mr = 877.55 | V = 832.0 (2) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.286 (1) Å | Mo Kα radiation |
b = 8.946 (1) Å | µ = 1.46 mm−1 |
c = 11.971 (2) Å | T = 298 K |
α = 110.019 (2)° | 0.32 × 0.21 × 0.11 mm |
β = 92.705 (2)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3686 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3559 reflections with I > 2σ(I) |
Tmin = 0.652, Tmax = 0.856 | Rint = 0.016 |
7155 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.025 | 21 restraints |
wR(F2) = 0.062 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | Δρmax = 0.34 e Å−3 |
3686 reflections | Δρmin = −0.55 e Å−3 |
253 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) |
Cd1 | 0.404413 (17) | 0.167141 (16) | 0.357952 (12) | 0.03278 (7) | |
S1 | 0.40874 (8) | 0.64051 (7) | 0.72641 (6) | 0.04685 (15) | |
O1 | 0.7429 (3) | −0.5691 (2) | −0.11703 (18) | 0.0644 (5) | |
O2 | 0.8870 (2) | −0.6258 (2) | 0.01713 (19) | 0.0596 (5) | |
O3 | 0.61049 (18) | 0.00293 (17) | 0.33886 (13) | 0.0372 (3) | |
O4 | 0.2822 (2) | −0.00646 (18) | 0.44507 (13) | 0.0406 (4) | |
N1 | 0.7969 (3) | −0.5386 (2) | −0.01447 (19) | 0.0458 (5) | |
N2 | 0.3463 (2) | 0.0052 (2) | 0.16408 (16) | 0.0378 (4) | |
N3 | 0.1300 (15) | 0.2208 (12) | 0.3100 (12) | 0.0328 (15) | 0.535 (6) |
N4 | 0.4184 (3) | 0.3495 (2) | 0.54200 (18) | 0.0498 (5) | |
C1 | 0.6517 (2) | −0.1192 (2) | 0.25131 (17) | 0.0302 (4) | |
C2 | 0.5694 (2) | −0.1759 (2) | 0.13573 (17) | 0.0319 (4) | |
C3 | 0.6226 (3) | −0.3127 (2) | 0.04980 (18) | 0.0348 (4) | |
H3 | 0.5702 | −0.3500 | −0.0257 | 0.042* | |
C4 | 0.7505 (3) | −0.3927 (2) | 0.0748 (2) | 0.0370 (5) | |
C5 | 0.8340 (3) | −0.3390 (3) | 0.1858 (2) | 0.0395 (5) | |
H5 | 0.9210 | −0.3937 | 0.2019 | 0.047* | |
C6 | 0.7861 (3) | −0.2049 (3) | 0.27064 (19) | 0.0374 (5) | |
H6 | 0.8437 | −0.1678 | 0.3442 | 0.045* | |
C7 | 0.4265 (3) | −0.1102 (3) | 0.09989 (18) | 0.0363 (4) | |
H7 | 0.3884 | −0.1573 | 0.0208 | 0.044* | |
C8 | 0.1994 (3) | 0.0455 (4) | 0.1107 (2) | 0.0578 (7) | 0.535 (6) |
H8A | 0.1555 | −0.0475 | 0.0461 | 0.069* | 0.535 (6) |
H8B | 0.2249 | 0.1281 | 0.0781 | 0.069* | 0.535 (6) |
C9 | 0.0783 (5) | 0.1013 (6) | 0.1999 (4) | 0.0489 (14) | 0.535 (6) |
H9A | −0.0104 | 0.1417 | 0.1644 | 0.059* | 0.535 (6) |
H9B | 0.0356 | 0.0100 | 0.2170 | 0.059* | 0.535 (6) |
C10 | 0.0231 (10) | 0.2286 (12) | 0.4068 (7) | 0.0613 (19) | 0.535 (6) |
H10A | −0.0832 | 0.2551 | 0.3865 | 0.092* | 0.535 (6) |
H10B | 0.0655 | 0.3087 | 0.4793 | 0.092* | 0.535 (6) |
H10C | 0.0176 | 0.1272 | 0.4177 | 0.092* | 0.535 (6) |
C11 | 0.1338 (12) | 0.3849 (11) | 0.2984 (8) | 0.064 (2) | 0.535 (6) |
H11A | 0.2093 | 0.3881 | 0.2407 | 0.096* | 0.535 (6) |
H11B | 0.1665 | 0.4638 | 0.3741 | 0.096* | 0.535 (6) |
H11C | 0.0280 | 0.4064 | 0.2730 | 0.096* | 0.535 (6) |
C12 | 0.2508 (3) | −0.1696 (3) | 0.3773 (2) | 0.0488 (6) | |
H12A | 0.1748 | −0.1794 | 0.3118 | 0.073* | |
H12B | 0.2065 | −0.2232 | 0.4268 | 0.073* | |
H12C | 0.3497 | −0.2169 | 0.3472 | 0.073* | |
C13 | 0.4147 (3) | 0.4694 (3) | 0.61719 (19) | 0.0350 (4) | |
N3' | 0.1515 (18) | 0.2586 (12) | 0.3043 (13) | 0.0303 (16) | 0.465 (6) |
C8' | 0.1994 (3) | 0.0455 (4) | 0.1107 (2) | 0.0578 (7) | 0.465 (6) |
H8'1 | 0.2172 | 0.0339 | 0.0288 | 0.069* | 0.465 (6) |
H8'2 | 0.1131 | −0.0304 | 0.1096 | 0.069* | 0.465 (6) |
C9' | 0.1470 (7) | 0.2038 (6) | 0.1707 (5) | 0.0492 (16) | 0.465 (6) |
H9'1 | 0.0370 | 0.2099 | 0.1416 | 0.059* | 0.465 (6) |
H9'2 | 0.2141 | 0.2780 | 0.1481 | 0.059* | 0.465 (6) |
C10' | 0.0161 (12) | 0.1761 (15) | 0.3407 (10) | 0.078 (3) | 0.465 (6) |
H10D | 0.0131 | 0.2161 | 0.4259 | 0.117* | 0.465 (6) |
H10E | 0.0322 | 0.0637 | 0.3140 | 0.117* | 0.465 (6) |
H10F | −0.0844 | 0.1952 | 0.3056 | 0.117* | 0.465 (6) |
C11' | 0.1396 (15) | 0.4252 (12) | 0.3517 (8) | 0.060 (2) | 0.465 (6) |
H11D | 0.0406 | 0.4544 | 0.3214 | 0.090* | 0.465 (6) |
H11E | 0.2296 | 0.4760 | 0.3291 | 0.090* | 0.465 (6) |
H11F | 0.1406 | 0.4587 | 0.4370 | 0.090* | 0.465 (6) |
H4 | 0.319 (4) | 0.002 (4) | 0.5179 (15) | 0.080* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cd1 | 0.03754 (10) | 0.02599 (9) | 0.03024 (10) | 0.00490 (6) | −0.00079 (6) | 0.00391 (6) |
S1 | 0.0591 (4) | 0.0338 (3) | 0.0398 (3) | −0.0032 (3) | 0.0132 (3) | 0.0016 (2) |
O1 | 0.0731 (14) | 0.0526 (11) | 0.0471 (11) | 0.0072 (10) | 0.0118 (10) | −0.0105 (9) |
O2 | 0.0618 (12) | 0.0351 (9) | 0.0772 (13) | 0.0146 (8) | 0.0211 (10) | 0.0103 (9) |
O3 | 0.0443 (8) | 0.0329 (8) | 0.0263 (7) | 0.0097 (6) | −0.0024 (6) | −0.0002 (6) |
O4 | 0.0586 (10) | 0.0318 (8) | 0.0289 (7) | 0.0019 (7) | 0.0001 (7) | 0.0076 (6) |
N1 | 0.0452 (11) | 0.0335 (10) | 0.0490 (12) | −0.0013 (9) | 0.0183 (9) | 0.0000 (9) |
N2 | 0.0389 (10) | 0.0368 (10) | 0.0336 (9) | 0.0052 (8) | −0.0058 (7) | 0.0076 (8) |
N4 | 0.0737 (15) | 0.0333 (10) | 0.0365 (11) | −0.0067 (10) | 0.0074 (10) | 0.0046 (9) |
C1 | 0.0346 (10) | 0.0269 (9) | 0.0276 (9) | 0.0022 (8) | 0.0046 (7) | 0.0072 (8) |
C2 | 0.0353 (10) | 0.0305 (10) | 0.0271 (10) | 0.0005 (8) | 0.0039 (8) | 0.0061 (8) |
C3 | 0.0405 (11) | 0.0323 (10) | 0.0265 (10) | −0.0025 (8) | 0.0051 (8) | 0.0032 (8) |
C4 | 0.0405 (12) | 0.0279 (10) | 0.0377 (11) | 0.0018 (9) | 0.0141 (9) | 0.0035 (9) |
C5 | 0.0409 (12) | 0.0380 (11) | 0.0410 (12) | 0.0113 (9) | 0.0085 (9) | 0.0137 (10) |
C6 | 0.0401 (11) | 0.0393 (11) | 0.0306 (10) | 0.0073 (9) | 0.0007 (8) | 0.0087 (9) |
C7 | 0.0436 (12) | 0.0351 (11) | 0.0256 (10) | −0.0003 (9) | −0.0021 (8) | 0.0050 (8) |
C12 | 0.0606 (16) | 0.0351 (12) | 0.0447 (13) | −0.0042 (11) | −0.0018 (11) | 0.0072 (10) |
C13 | 0.0385 (11) | 0.0343 (11) | 0.0321 (10) | −0.0029 (9) | 0.0025 (8) | 0.0117 (9) |
N3 | 0.035 (4) | 0.018 (4) | 0.050 (3) | −0.002 (3) | 0.001 (2) | 0.019 (3) |
C8 | 0.0540 (15) | 0.0682 (18) | 0.0445 (14) | 0.0200 (13) | −0.0129 (11) | 0.0115 (13) |
C9 | 0.043 (3) | 0.050 (3) | 0.053 (3) | 0.003 (2) | −0.008 (2) | 0.017 (2) |
C10 | 0.042 (3) | 0.082 (5) | 0.072 (4) | 0.021 (3) | 0.021 (4) | 0.038 (4) |
C11 | 0.065 (4) | 0.050 (5) | 0.082 (6) | 0.014 (4) | −0.003 (5) | 0.028 (5) |
N3' | 0.032 (4) | 0.013 (4) | 0.050 (3) | −0.003 (3) | 0.005 (2) | 0.016 (3) |
C8' | 0.0540 (15) | 0.0682 (18) | 0.0445 (14) | 0.0200 (13) | −0.0129 (11) | 0.0115 (13) |
C9' | 0.055 (3) | 0.042 (3) | 0.049 (3) | 0.014 (2) | −0.011 (2) | 0.015 (2) |
C10' | 0.044 (4) | 0.106 (9) | 0.113 (9) | 0.021 (5) | 0.018 (6) | 0.070 (8) |
C11' | 0.074 (5) | 0.038 (5) | 0.062 (5) | 0.028 (4) | −0.002 (5) | 0.010 (4) |
Geometric parameters (Å, º) top
Cd1—N4 | 2.244 (2) | C12—H12A | 0.96 |
Cd1—O3 | 2.250 (2) | C12—H12B | 0.96 |
Cd1—N2 | 2.296 (2) | C12—H12C | 0.96 |
Cd1—O4 | 2.378 (2) | N3—C9 | 1.421 (13) |
Cd1—N3' | 2.408 (15) | N3—C10 | 1.476 (13) |
Cd1—N3 | 2.419 (13) | N3—C11 | 1.521 (12) |
Cd1—S1i | 2.7527 (8) | C8—C9 | 1.469 (5) |
S1—C13 | 1.642 (2) | C8—H8A | 0.97 |
O1—N1 | 1.222 (3) | C8—H8B | 0.9700 |
O2—N1 | 1.231 (3) | C9—H9A | 0.9700 |
O3—C1 | 1.295 (2) | C9—H9B | 0.9700 |
O4—C12 | 1.417 (3) | C10—H10A | 0.96 |
O4—H4 | 0.887 (10) | C10—H10B | 0.96 |
N1—C4 | 1.450 (3) | C10—H10C | 0.96 |
N2—C7 | 1.280 (3) | C11—H11A | 0.96 |
N2—C8 | 1.458 (3) | C11—H11B | 0.96 |
N4—C13 | 1.142 (3) | C11—H11C | 0.96 |
C1—C6 | 1.422 (3) | N3'—C11' | 1.410 (14) |
C1—C2 | 1.431 (3) | N3'—C10' | 1.489 (13) |
C2—C3 | 1.400 (3) | N3'—C9' | 1.502 (16) |
C2—C7 | 1.446 (3) | C9'—H9'1 | 0.9700 |
C3—C4 | 1.371 (3) | C9'—H9'2 | 0.9700 |
C3—H3 | 0.93 | C10'—H10D | 0.9600 |
C4—C5 | 1.392 (3) | C10'—H10E | 0.9600 |
C5—C6 | 1.363 (3) | C10'—H10F | 0.9600 |
C5—H5 | 0.93 | C11'—H11D | 0.9600 |
C6—H6 | 0.93 | C11'—H11E | 0.9600 |
C7—H7 | 0.93 | C11'—H11F | 0.9600 |
| | | |
N4—Cd1—O3 | 109.81 (7) | C1—C6—H6 | 118.6 |
N4—Cd1—N2 | 168.91 (7) | N2—C7—C2 | 127.71 (19) |
O3—Cd1—N2 | 81.28 (6) | N2—C7—H7 | 116.1 |
N4—Cd1—O4 | 85.89 (6) | C2—C7—H7 | 116.1 |
O3—Cd1—O4 | 83.00 (6) | O4—C12—H12A | 109.5 |
N2—Cd1—O4 | 95.72 (6) | O4—C12—H12B | 109.5 |
N4—Cd1—N3' | 92.9 (4) | H12A—C12—H12B | 109.5 |
O3—Cd1—N3' | 156.8 (3) | O4—C12—H12C | 109.5 |
N2—Cd1—N3' | 76.0 (4) | H12A—C12—H12C | 109.5 |
O4—Cd1—N3' | 94.4 (2) | H12B—C12—H12C | 109.5 |
N4—Cd1—N3 | 94.8 (3) | N4—C13—S1 | 179.3 (2) |
O3—Cd1—N3 | 151.7 (3) | C9—N3—C10 | 113.1 (7) |
N2—Cd1—N3 | 74.5 (3) | C9—N3—C11 | 110.9 (9) |
O4—Cd1—N3 | 85.14 (18) | C10—N3—C11 | 106.5 (10) |
N3'—Cd1—N3 | 9.6 (2) | C9—N3—Cd1 | 107.1 (7) |
N4—Cd1—S1i | 91.83 (6) | C10—N3—Cd1 | 111.7 (7) |
O3—Cd1—S1i | 89.50 (4) | C11—N3—Cd1 | 107.3 (6) |
N2—Cd1—S1i | 88.20 (5) | N2—C8—C9 | 110.6 (3) |
O4—Cd1—S1i | 170.90 (4) | N2—C8—H8A | 109.5 |
N3'—Cd1—S1i | 94.5 (2) | C9—C8—H8A | 109.5 |
N3—Cd1—S1i | 103.85 (17) | N2—C8—H8B | 109.5 |
C13—S1—Cd1i | 100.71 (8) | C9—C8—H8B | 109.5 |
C1—O3—Cd1 | 132.37 (13) | H8A—C8—H8B | 108.1 |
C12—O4—Cd1 | 120.30 (14) | N3—C9—C8 | 117.3 (6) |
C12—O4—H4 | 109 (2) | N3—C9—H9A | 108.0 |
Cd1—O4—H4 | 117 (2) | C8—C9—H9A | 108.0 |
O1—N1—O2 | 123.5 (2) | N3—C9—H9B | 108.0 |
O1—N1—C4 | 118.1 (2) | C8—C9—H9B | 108.0 |
O2—N1—C4 | 118.4 (2) | H9A—C9—H9B | 107.2 |
C7—N2—C8 | 118.3 (2) | C11'—N3'—C10' | 110.9 (12) |
C7—N2—Cd1 | 128.37 (15) | C11'—N3'—C9' | 110.2 (8) |
C8—N2—Cd1 | 113.35 (15) | C10'—N3'—C9' | 108.9 (10) |
C13—N4—Cd1 | 160.4 (2) | C11'—N3'—Cd1 | 113.7 (9) |
O3—C1—C6 | 118.39 (18) | C10'—N3'—Cd1 | 109.1 (7) |
O3—C1—C2 | 124.34 (18) | C9'—N3'—Cd1 | 103.7 (8) |
C6—C1—C2 | 117.26 (18) | N3'—C9'—H9'1 | 108.2 |
C3—C2—C1 | 118.78 (19) | N3'—C9'—H9'2 | 108.2 |
C3—C2—C7 | 115.31 (18) | H9'1—C9'—H9'2 | 107.3 |
C1—C2—C7 | 125.78 (18) | N3'—C10'—H10D | 109.5 |
C4—C3—C2 | 121.3 (2) | N3'—C10'—H10E | 109.5 |
C4—C3—H3 | 119.4 | H10D—C10'—H10E | 109.5 |
C2—C3—H3 | 119.4 | N3'—C10'—H10F | 109.5 |
C3—C4—C5 | 121.13 (19) | H10D—C10'—H10F | 109.5 |
C3—C4—N1 | 119.7 (2) | H10E—C10'—H10F | 109.5 |
C5—C4—N1 | 119.1 (2) | N3'—C11'—H11D | 109.5 |
C6—C5—C4 | 118.8 (2) | N3'—C11'—H11E | 109.5 |
C6—C5—H5 | 120.6 | H11D—C11'—H11E | 109.5 |
C4—C5—H5 | 120.6 | N3'—C11'—H11F | 109.5 |
C5—C6—C1 | 122.7 (2) | H11D—C11'—H11F | 109.5 |
C5—C6—H6 | 118.6 | H11E—C11'—H11F | 109.5 |
| | | |
N4—Cd1—O3—C1 | 179.25 (18) | C2—C1—C6—C5 | −2.3 (3) |
N2—Cd1—O3—C1 | −0.73 (18) | C8—N2—C7—C2 | −176.3 (2) |
O4—Cd1—O3—C1 | 96.19 (18) | Cd1—N2—C7—C2 | 4.7 (4) |
N3'—Cd1—O3—C1 | 11.3 (6) | C3—C2—C7—N2 | 173.8 (2) |
N3—Cd1—O3—C1 | 30.3 (6) | C1—C2—C7—N2 | −2.1 (4) |
S1i—Cd1—O3—C1 | −88.99 (18) | N4—Cd1—N3—C9 | −171.3 (4) |
N4—Cd1—O4—C12 | −172.50 (18) | O3—Cd1—N3—C9 | −20.5 (8) |
O3—Cd1—O4—C12 | −61.95 (17) | N2—Cd1—N3—C9 | 11.4 (4) |
N2—Cd1—O4—C12 | 18.51 (18) | O4—Cd1—N3—C9 | −85.9 (4) |
N3'—Cd1—O4—C12 | 94.9 (4) | N3'—Cd1—N3—C9 | 110 (4) |
N3—Cd1—O4—C12 | 92.3 (4) | S1i—Cd1—N3—C9 | 95.6 (4) |
N4—Cd1—N2—C7 | 177.1 (3) | N4—Cd1—N3—C10 | −47.0 (7) |
O3—Cd1—N2—C7 | −3.0 (2) | O3—Cd1—N3—C10 | 103.9 (9) |
O4—Cd1—N2—C7 | −85.0 (2) | N2—Cd1—N3—C10 | 135.8 (7) |
N3'—Cd1—N2—C7 | −178.2 (3) | O4—Cd1—N3—C10 | 38.5 (6) |
N3—Cd1—N2—C7 | −168.3 (3) | N3'—Cd1—N3—C10 | −126 (4) |
S1i—Cd1—N2—C7 | 86.8 (2) | S1i—Cd1—N3—C10 | −140.1 (6) |
N4—Cd1—N2—C8 | −1.9 (4) | N4—Cd1—N3—C11 | 69.4 (7) |
O3—Cd1—N2—C8 | 178.03 (19) | O3—Cd1—N3—C11 | −139.7 (4) |
O4—Cd1—N2—C8 | 96.03 (18) | N2—Cd1—N3—C11 | −107.8 (8) |
N3'—Cd1—N2—C8 | 2.9 (3) | O4—Cd1—N3—C11 | 154.9 (8) |
N3—Cd1—N2—C8 | 12.7 (2) | N3'—Cd1—N3—C11 | −10 (3) |
S1i—Cd1—N2—C8 | −92.20 (18) | S1i—Cd1—N3—C11 | −23.6 (8) |
O3—Cd1—N4—C13 | 137.5 (6) | C7—N2—C8—C9 | 146.1 (3) |
N2—Cd1—N4—C13 | −42.7 (8) | Cd1—N2—C8—C9 | −34.8 (3) |
O4—Cd1—N4—C13 | −141.5 (6) | C10—N3—C9—C8 | −159.6 (7) |
N3'—Cd1—N4—C13 | −47.3 (7) | C11—N3—C9—C8 | 80.8 (10) |
N3—Cd1—N4—C13 | −56.7 (6) | Cd1—N3—C9—C8 | −36.1 (6) |
S1i—Cd1—N4—C13 | 47.3 (6) | N2—C8—C9—N3 | 49.4 (6) |
Cd1—O3—C1—C6 | −176.20 (14) | N4—Cd1—N3'—C11' | 37.3 (9) |
Cd1—O3—C1—C2 | 3.0 (3) | O3—Cd1—N3'—C11' | −154.1 (6) |
O3—C1—C2—C3 | −177.82 (19) | N2—Cd1—N3'—C11' | −141.8 (10) |
C6—C1—C2—C3 | 1.4 (3) | O4—Cd1—N3'—C11' | 123.4 (9) |
O3—C1—C2—C7 | −2.1 (3) | N3—Cd1—N3'—C11' | 139 (5) |
C6—C1—C2—C7 | 177.11 (19) | S1i—Cd1—N3'—C11' | −54.8 (9) |
C1—C2—C3—C4 | 0.3 (3) | N4—Cd1—N3'—C10' | −87.1 (9) |
C7—C2—C3—C4 | −175.86 (19) | O3—Cd1—N3'—C10' | 81.5 (12) |
C2—C3—C4—C5 | −1.2 (3) | N2—Cd1—N3'—C10' | 93.8 (9) |
C2—C3—C4—N1 | 176.80 (19) | O4—Cd1—N3'—C10' | −1.0 (9) |
O1—N1—C4—C3 | 14.7 (3) | N3—Cd1—N3'—C10' | 14 (3) |
O2—N1—C4—C3 | −164.6 (2) | S1i—Cd1—N3'—C10' | −179.2 (9) |
O1—N1—C4—C5 | −167.2 (2) | N4—Cd1—N3'—C9' | 156.9 (4) |
O2—N1—C4—C5 | 13.5 (3) | O3—Cd1—N3'—C9' | −34.4 (8) |
C3—C4—C5—C6 | 0.3 (3) | N2—Cd1—N3'—C9' | −22.2 (4) |
N1—C4—C5—C6 | −177.7 (2) | O4—Cd1—N3'—C9' | −117.0 (4) |
C4—C5—C6—C1 | 1.5 (3) | N3—Cd1—N3'—C9' | −102 (4) |
O3—C1—C6—C5 | 176.9 (2) | S1i—Cd1—N3'—C9' | 64.9 (4) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···O3ii | 0.89 (1) | 1.80 (1) | 2.685 (2) | 174 (3) |
Symmetry code: (ii) −x+1, −y, −z+1. |
Experimental details
Crystal data |
Chemical formula | [Cd2(C11H14N3O2)2(NCS)2(CH4O)2] |
Mr | 877.55 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 8.286 (1), 8.946 (1), 11.971 (2) |
α, β, γ (°) | 110.019 (2), 92.705 (2), 91.482 (2) |
V (Å3) | 832.0 (2) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.46 |
Crystal size (mm) | 0.32 × 0.21 × 0.11 |
|
Data collection |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.652, 0.856 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7155, 3686, 3559 |
Rint | 0.016 |
(sin θ/λ)max (Å−1) | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.062, 1.10 |
No. of reflections | 3686 |
No. of parameters | 253 |
No. of restraints | 21 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.34, −0.55 |
Selected geometric parameters (Å, º) topCd1—N4 | 2.244 (2) | Cd1—N3 | 2.419 (13) |
Cd1—O3 | 2.250 (2) | Cd1—S1i | 2.7527 (8) |
Cd1—N2 | 2.296 (2) | N2—C7 | 1.280 (3) |
Cd1—O4 | 2.378 (2) | N2—C8 | 1.458 (3) |
| | | |
N4—Cd1—O3 | 109.81 (7) | N2—Cd1—N3 | 74.5 (3) |
N4—Cd1—N2 | 168.91 (7) | O4—Cd1—N3 | 85.14 (18) |
O3—Cd1—N2 | 81.28 (6) | N4—Cd1—S1i | 91.83 (6) |
N4—Cd1—O4 | 85.89 (6) | O3—Cd1—S1i | 89.50 (4) |
O3—Cd1—O4 | 83.00 (6) | N2—Cd1—S1i | 88.20 (5) |
N2—Cd1—O4 | 95.72 (6) | O4—Cd1—S1i | 170.90 (4) |
N4—Cd1—N3 | 94.8 (3) | N3—Cd1—S1i | 103.85 (17) |
O3—Cd1—N3 | 151.7 (3) | | |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···O3ii | 0.887 (10) | 1.801 (11) | 2.685 (2) | 174 (3) |
Symmetry code: (ii) −x+1, −y, −z+1. |
Metal-organic complexes containing bridging ligands are of current interest because of their interesting molecular topologies and crystal-packing motifs, as well as the fact that they may be designed with specific functionalities (Batten & Robson, 1998; Abourahma et al., 2002; Konar et al., 2002). In addition to being robust and thermally stable, some possess photoluminescent properties, a feature that has contributed to d10 metal polynuclear complexes being investigated in the search for new materials (Weidenbruch et al., 1989; Kunkely & Vogler, 1990; Bertoncello et al., 1992). Among the CdII coordination polymers featuring interesting supramolecular structures, such as one-dimensional helical ribbons or molecular zippers, two-dimensional molecular square or triangular grids, and interpenetrating/non-interpenetrating three-dimensional networks (Dai et al., 2002; Chen et al., 2003; Luo et al., 2003), most of them possess photoluminescent properties (Xiong et al., 2000; Wang et al., 2003).
Owing to the versatile coordination modes of the ambidentate thiocyanate ligand, this pseudohalide ligand has become one of the most extensively studied building blocks in the multi-dimensional complexes (Sailaja et al., 2003; Dey et al., 2004). Thiocyanate complexes of various dimensionalities have been obtained (Zurowska et al., 2002; Zhang et al., 2003; You, 2005a). A major obstacle to a more comprehensive study of such thiocyanate-based polymeric coordination complexes is the lack of rational synthetic procedures, since with the present state of knowledge it is hardly possible to determine which coordination mode will be adopted by the thiocyanate ligand and whether the sought-after alternating chain structure will finally be formed (Tercero et al., 2002; Ribas et al., 1999; Liu et al., 2003).
Our work is aimed at obtaining multi-dimensional polymetallic complexes. Based on the above considerations, we designed and synthesized a tridentate ligand, 4-nitro-2-(2-dimethylaminoethyliminomethyl)phenol (NDAP). The reason we use NDAP as ligand is that it could adopt an almost fixed coordination mode through the three donor atoms (You, 2005b; Yue et al., 2005). The second ligand, viz. thiocyanate, is a well known bridging group. It readily bridges different metal ions through the terminal donor atoms, forming polynuclear complexes (Kuang et al., 2001). CdII is a good candidate for octahedral coordination geometry. We report here the dinuclear structure of the title compound, (I), formed by the reaction of the NDAP ligand, ammonium thiocyanate and CdII acetate.
Complex (I) (Fig. 1) contains two Cd(NDAP) units connected to each other by two bridging thiocyanate anions. The CdII atom is in an octahedral coordination environment and is six-coordinated by one O and two N atoms of one Schiff base ligand and by one teminal N atom of a bridging thiocyanate ligand, defining the basal plane, and by one terminal S atom of another bridging thiocyanate ligand, together with one O atom of a coordinated MeOH molecule, occupying the axial positions. The Schiff base ligand acts as a tridentate ligand and ligates to the metal via three O– and N-donor atoms. The thiocyanate anion acts as a bridging ligand and ligates to two different but symmetry-related CdII atoms via the terminal N and S atoms.
The three trans angles at the CdII atom lie in the range 151.7 (3)–170.90 (4)° (Table 1). The other angles subtended at the CdII atom range from 74.5 (3) to 109.81 (7)°, indicating a somewhat distorted octahedral geometry. The bond lengths subtended at Cd1 are comparable to those observed in other Schiff base–cadmium(II) complexes (You et al., 2004) and, as expected, the bond involving amine atom N3 [2.419 (13) Å] is longer than that involving imine atom N2 [2.296 (2) Å] (Mondal et al., 2001). The Cd1—S1i bond [symmetry code: (i) 1 − x, 1 − y, 1 − z] is much longer than the other bonds, indicating that the Cd—S bond is not very strong. The bridging thiocyanate group is nearly linear and shows bent coordination modes with the metal atoms [N4—C13—S1 = 179.3 (2)°, Cd1—N4—C13 = 160.4 (2)° and Cd1i—S1—C13 = 100.71 (8)°]. The N2—Cd1—N3(or N3') bond angle [mean 75.3 (3)°] of the five-membered chelate ring is much smaller than 90°, as a result of the strain created by the five-membered chelate rings Cd1/N2/C8/C9/N3 and Cd1/N2/C8'/C9'/N3'.
The C7═N2 bond length [1.280 (3) Å] conforms to the normal value for a double bond, while the C8—N2 bond length [1.458 (3) Å] conforms to the normal value for a single bond. The O1/N1/O2 plane and the C1–C6 phenyl ring are not coplanar, having a dihedral angle of 14.7 (3)°.
In the crystal structure, the molecules are linked by the intermolecular O—H···O hydrogen bonds, forming chains running along the b axis (Table 2 and Fig. 2).