Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807023756/lh2374sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807023756/lh2374Isup2.hkl |
CCDC reference: 650679
Key indicators
- Single-crystal X-ray study
- T = 95 K
- Mean (C-C) = 0.007 Å
- R factor = 0.060
- wR factor = 0.168
- Data-to-parameter ratio = 16.1
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.96 PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Cu - N40 .. 5.90 su PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 7
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu (1) 1.19
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
The title compound was prepared by the reaction of CuClO4 with ca3-tren and KSCN (molar ratio 1:1:1) in a methanolic solution at 298 K. The blue precipitate was filtered and dried in vacuo. Turquoise crystals of (I) were obtained by slow diffusion of Et2O vapour into a nitromethan solution of the complex at 298 K. The measured crystal was bounded by the {010}, {001}, {101}, {101} and {111} pinacoids, the last two being of the bevel persuasion.
H atoms were made to ride on their associated carrier atoms, their displacement parameters being coupled to those of the carrier atoms (Uiso(H)/Ueq(C) were 1.5 for methyl groups and 1.2 for all other H atoms; C—H were 0.99 Å for methylene and 0.95Å for aromatic H atoms).
A comparison between room and low temperature data shows the lattice constants at 293 K are: a=10.263 (2), b=12.415 (3), c=15.536 (3) Å, α=107.70 (3), β=105.38 (3) γ=91.67 (3)°, V=1805.4 (6) Å3. Noteworthy the value of ε≈ 0.03. Unsurprisingly, the intramolecular distances and angles remain pratically the same, but there exist considerable variations in the intermolecular hydrogen bonds. Except for the C12—H12B···O1 bond they all shorten by between ~0.1 for the C18—H18···O3 bond and ~0.2Å for the C21—H21a···O3 bond.
Tripodal ligands generally coordinate to transition metal ions using all of their nitrogen atoms as donors (Scarpellini et al., 2004; Abdus Salam & Aoki, 2001; Raab et al., 2001; Chen et al., 2000; Su et al., 1999; Massoud et al., 1999). Six coordinate octahedral complexes containing such ligands invariably display cis geometries (Kwak et al., 1999; Saha et al., 2003). The steric constraints imposed by such ligands often result in trigonal bipyramidal geometries for five coordinate systems (Chen et al., 2000; Su et al., 1999), while rare examples of four coordinate complexes containing tripodal ligands display distored tetrahedral geometries (Patra & Goldberg, 2003; Wei et al., 1994; Alyea et al., 1990). The pseudohalide, NCS, is known to coordinate to metals (Laskowski et al., 1975; Kickelbick et al., 2003) and act as terminal ligand in these complexes. In this context, we decided to examine the nature of the copper(II) complex formed with the tripodal Schiff base ligand ca3-tren. Therefore, (I) has been synthesized and structurally investigated. Compound (I) is a monomeric complex (Fig. 1) in which the ca3-tren ligand is tetradentate and the thiocyanate anion is monodentate. The Cu—N bond lengths in (I) are in good agreement with the corresponding distances in related complexes (Abdus Salam et al., 2001; Chen et al., 2000). The coordination geometry around the CuII ion in (I) can be described as grossly distorted trigonal bipyramid with approximate molecular Cs symmetry with respect to the N4—N1—Cu—N40—C40—S plane. The N2—Cu—N3 angle across this plane is much larger than the analoguous N2—Cu—N1 and N3—Cu—N1 angles. The Cu—N1 bond is, naturally, the longest equatorial bond, since it has to accommodate the thiocyanate. In the three legs all atoms except the α carbons are essentially co-planar, with atoms N4 and N40 being in one of the planes. The angles between the planes of the legs are 81.8 (1)° between 1 and 2, 79.5 (1)° between 1 and 3 and 9.7 (1)° between 2 and 3 (the plane number is realted to the N atom label contained within each plane i.e. N1 = plane 1). It is noteworthy, that at 95 K the perchlorate anion, a notorious troublemaker, is perfectly ordered,[Cu(ca3-tren)(NCS)]ClO4 whereas at room temperature it is distributed between the position shown in Fig.1 and one staggered about the O1—Cl bond.
The crystal packing of (I), shown in Fig. 2., demonstrates that the main cohesion of this structure is due to hydrogen bonding. Two planes may be preceived in the structure accross which a minimum of bonding (other than van der Waals) seem to exist: (023) and (010). Otherwise there exist C—H···O bonds along [100], [032] and [011]. This bonding seems to be weaker along the latter two directions than along the a axis. One might even say that (I) has some pseudo layer-character with respect to (023) and (010), especially at room temperature. From the observation of some arching in the (b*,c*) layer, we may conclude the strongest cohesion exists along [100] and that the real structure consists of slightly disoriented (~5°) blocks bounded by (100), (023) and (010). This conjecture is further confirmed by the observation that crystal of (I) crumble into many tiny pieces at room temperature upon even a very gentle attempt at cutting them with the blade of a scalpel.EDITORS: Please check name
[Cu(ca3-tren)(NCS)]ClO4 At 95 K, most atoms are fairly isotropic, but there exists a remnant of some more pronounced disorder in the phenyl ring C36 → C311, i.e. two slightly rotated positions of the ring. Another occurrence of dynamic disorder has all but disappeared at 95 K; indeed at room temperature atoms C11, C21 and C31 were strongly elongated perpendicularly to the planes of the legs.
For related literature, see: Abdus & Aoki (2001); Alyea et al. (1990); Chen et al. (2000); Kickelbick et al. (2003); Kwak et al. (1999); Laskowski et al. (1975); Massoud et al. (1999); Patra & Goldberg (2003); Raab et al. (2001); Saha et al. (2003); Scarpellini et al. (2004); Su et al. (1999); Wei et al. (1994).
For related literature, see: Lu et al. (1996).
Data collection: X-AREA (Stoe & Cie, 2006); cell refinement: X-RED32 (Stoe & Cie, 2005); data reduction: X-RED32; program(s) used to solve structure: DIRDIF96 (Beurskens et al., 1996); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL, (Sheldrick, 1996); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003).
[Cu(NCS)(C33H36N4)]ClO4 | Z = 2 |
Mr = 709.73 | F(000) = 738 |
Triclinic, P1 | Dx = 1.382 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.1328 (13) Å | Cell parameters from 65844 reflections |
b = 12.3212 (17) Å | θ = 2.2–29.4° |
c = 15.0666 (18) Å | µ = 0.82 mm−1 |
α = 108.147 (10)° | T = 95 K |
β = 105.921 (10)° | Parallelepiped, blue |
γ = 91.638 (11)° | 0.31 × 0.23 × 0.22 mm |
V = 1705.5 (4) Å3 |
STOE IPDS II diffractometer | 6704 independent reflections |
Radiation source: fine-focus sealed tube | 5751 reflections with I > 2σ(I) |
Plane graphite monochromator | Rint = 0.068 |
Detector resolution: 6.67 pixels mm-1 | θmax = 26.0°, θmin = 2.2° |
rotation scans | h = −12→12 |
Absorption correction: integration (X-RED32; Stoe & Cie, 2005) | k = −15→15 |
Tmin = 0.773, Tmax = 0.859 | l = −18→18 |
20318 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)] = 0.060 | H-atom parameters constrained |
wR(F2) = 0.168 | w = 1/[σ2(Fo2) + (0.0566P)2 + 5.0438P] where P = (Fo2 + 2Fc2)/3 |
S = 1.18 | (Δ/σ)max = 0.001 |
6704 reflections | Δρmax = 0.67 e Å−3 |
416 parameters | Δρmin = −0.75 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0171 (16) |
[Cu(NCS)(C33H36N4)]ClO4 | γ = 91.638 (11)° |
Mr = 709.73 | V = 1705.5 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.1328 (13) Å | Mo Kα radiation |
b = 12.3212 (17) Å | µ = 0.82 mm−1 |
c = 15.0666 (18) Å | T = 95 K |
α = 108.147 (10)° | 0.31 × 0.23 × 0.22 mm |
β = 105.921 (10)° |
STOE IPDS II diffractometer | 6704 independent reflections |
Absorption correction: integration (X-RED32; Stoe & Cie, 2005) | 5751 reflections with I > 2σ(I) |
Tmin = 0.773, Tmax = 0.859 | Rint = 0.068 |
20318 measured reflections |
R[F2 > 2σ(F2)] = 0.060 | 0 restraints |
wR(F2) = 0.168 | H-atom parameters constrained |
S = 1.18 | Δρmax = 0.67 e Å−3 |
6704 reflections | Δρmin = −0.75 e Å−3 |
416 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 | ||
Cu | 0.28977 (5) | 0.83858 (4) | 0.11201 (3) | 0.02368 (18) | |
S | 0.35163 (11) | 1.24129 (10) | 0.16514 (8) | 0.0314 (3) | |
N40 | 0.3133 (4) | 1.0030 (3) | 0.1311 (3) | 0.0306 (8) | |
C40 | 0.3308 (4) | 1.1026 (4) | 0.1440 (3) | 0.0246 (8) | |
N4 | 0.2736 (3) | 0.6623 (3) | 0.0685 (2) | 0.0249 (7) | |
C11 | 0.3412 (4) | 0.6276 (4) | 0.1561 (3) | 0.0286 (9) | |
H11B | 0.4409 | 0.6437 | 0.1730 | 0.034* | |
H11A | 0.3178 | 0.5455 | 0.1405 | 0.034* | |
C12 | 0.2927 (4) | 0.6933 (4) | 0.2422 (3) | 0.0281 (9) | |
H12B | 0.1967 | 0.6657 | 0.2304 | 0.034* | |
H12A | 0.3473 | 0.6802 | 0.3009 | 0.034* | |
N1 | 0.3067 (3) | 0.8177 (3) | 0.2564 (2) | 0.0255 (7) | |
C13 | 0.3157 (4) | 0.8858 (4) | 0.3418 (3) | 0.0287 (9) | |
H13 | 0.3167 | 0.8542 | 0.3905 | 0.034* | |
C14 | 0.3247 (4) | 1.0100 (4) | 0.3672 (3) | 0.0265 (9) | |
H14 | 0.3239 | 1.0426 | 0.3190 | 0.032* | |
C15 | 0.3340 (4) | 1.0790 (4) | 0.4569 (3) | 0.0285 (9) | |
H15 | 0.3335 | 1.0433 | 0.5029 | 0.034* | |
C16 | 0.3450 (4) | 1.2056 (4) | 0.4915 (3) | 0.0249 (8) | |
C17 | 0.3537 (4) | 1.2651 (4) | 0.5892 (3) | 0.0285 (9) | |
H17 | 0.3522 | 1.2241 | 0.6314 | 0.034* | |
C18 | 0.3644 (5) | 1.3846 (4) | 0.6240 (3) | 0.0305 (9) | |
H18 | 0.3700 | 1.4226 | 0.6891 | 0.037* | |
C19 | 0.3667 (4) | 1.4473 (4) | 0.5623 (3) | 0.0298 (9) | |
H19 | 0.3739 | 1.5272 | 0.5857 | 0.036* | |
C110 | 0.3581 (4) | 1.3896 (4) | 0.4651 (3) | 0.0292 (9) | |
H110 | 0.3591 | 1.4313 | 0.4234 | 0.035* | |
C111 | 0.3480 (4) | 1.2707 (4) | 0.4300 (3) | 0.0278 (9) | |
H111 | 0.3432 | 1.2334 | 0.3650 | 0.033* | |
C21 | 0.1245 (4) | 0.6132 (4) | 0.0255 (3) | 0.0274 (9) | |
H21B | 0.0858 | 0.6094 | 0.0767 | 0.033* | |
H21A | 0.1152 | 0.5360 | −0.0203 | 0.033* | |
C22 | 0.0480 (4) | 0.6916 (4) | −0.0273 (3) | 0.0284 (9) | |
H22B | 0.0778 | 0.6877 | −0.0840 | 0.034* | |
H22A | −0.0510 | 0.6685 | −0.0487 | 0.034* | |
N2 | 0.0826 (3) | 0.8097 (3) | 0.0442 (2) | 0.0246 (7) | |
C23 | −0.0189 (4) | 0.8687 (4) | 0.0544 (3) | 0.0269 (9) | |
H23 | −0.1072 | 0.8346 | 0.0144 | 0.032* | |
C24 | −0.0063 (4) | 0.9828 (4) | 0.1227 (3) | 0.0267 (9) | |
H24 | 0.0794 | 1.0168 | 0.1673 | 0.032* | |
C25 | −0.1167 (4) | 1.0415 (4) | 0.1232 (3) | 0.0287 (9) | |
H25 | −0.2004 | 1.0036 | 0.0778 | 0.034* | |
C26 | −0.1197 (4) | 1.1572 (4) | 0.1865 (3) | 0.0277 (9) | |
C27 | −0.2479 (4) | 1.2014 (4) | 0.1804 (3) | 0.0293 (9) | |
H27 | −0.3285 | 1.1562 | 0.1362 | 0.035* | |
C28 | −0.2550 (5) | 1.3118 (4) | 0.2399 (3) | 0.0347 (10) | |
H28 | −0.3399 | 1.3400 | 0.2354 | 0.042* | |
C29 | −0.1353 (5) | 1.3798 (4) | 0.3059 (4) | 0.0381 (11) | |
H29 | −0.1395 | 1.4538 | 0.3453 | 0.046* | |
C210 | −0.0096 (5) | 1.3372 (4) | 0.3128 (4) | 0.0381 (11) | |
H210 | 0.0704 | 1.3828 | 0.3573 | 0.046* | |
C211 | −0.0013 (5) | 1.2273 (4) | 0.2543 (4) | 0.0358 (10) | |
H211 | 0.0842 | 1.2000 | 0.2602 | 0.043* | |
C31 | 0.3490 (4) | 0.6274 (4) | −0.0061 (3) | 0.0303 (9) | |
H31B | 0.2927 | 0.6333 | −0.0674 | 0.036* | |
H31A | 0.3656 | 0.5478 | −0.0171 | 0.036* | |
C32 | 0.4879 (4) | 0.7047 (4) | 0.0283 (3) | 0.0313 (9) | |
H32B | 0.5623 | 0.6649 | 0.0543 | 0.038* | |
H32A | 0.5050 | 0.7210 | −0.0268 | 0.038* | |
N3 | 0.4849 (4) | 0.8142 (3) | 0.1050 (2) | 0.0261 (7) | |
C33 | 0.6033 (4) | 0.8667 (4) | 0.1633 (3) | 0.0278 (9) | |
H33 | 0.6821 | 0.8366 | 0.1509 | 0.033* | |
C34 | 0.6215 (4) | 0.9695 (4) | 0.2467 (3) | 0.0280 (9) | |
H34 | 0.5454 | 1.0056 | 0.2578 | 0.034* | |
C35 | 0.7497 (4) | 1.0130 (4) | 0.3085 (3) | 0.0300 (9) | |
H35 | 0.8220 | 0.9726 | 0.2950 | 0.036* | |
C36 | 0.7862 (4) | 1.1176 (4) | 0.3947 (3) | 0.0298 (9) | |
C37 | 0.6895 (4) | 1.1914 (4) | 0.4190 (3) | 0.0303 (9) | |
H37 | 0.5981 | 1.1747 | 0.3794 | 0.036* | |
C38 | 0.7286 (5) | 1.2892 (4) | 0.5017 (3) | 0.0330 (10) | |
H38 | 0.6632 | 1.3369 | 0.5177 | 0.040* | |
C39 | 0.8650 (5) | 1.3156 (5) | 0.5604 (3) | 0.0389 (11) | |
H39 | 0.8910 | 1.3817 | 0.6153 | 0.047* | |
C310 | 0.9622 (5) | 1.2448 (5) | 0.5380 (4) | 0.0446 (13) | |
H310 | 1.0533 | 1.2624 | 0.5781 | 0.054* | |
C311 | 0.9238 (5) | 1.1464 (5) | 0.4550 (3) | 0.0376 (11) | |
H311 | 0.9900 | 1.0994 | 0.4395 | 0.045* | |
Cl | 0.13292 (10) | 0.33145 (9) | 0.81496 (7) | 0.0286 (3) | |
O1 | 0.0504 (3) | 0.4218 (3) | 0.8021 (2) | 0.0361 (7) | |
O2 | 0.1788 (3) | 0.3425 (3) | 0.9181 (2) | 0.0307 (7) | |
O3 | 0.2530 (4) | 0.3409 (3) | 0.7830 (3) | 0.0443 (9) | |
O4 | 0.0522 (4) | 0.2202 (3) | 0.7606 (3) | 0.0453 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu | 0.0197 (3) | 0.0303 (3) | 0.0191 (3) | 0.00149 (19) | 0.00357 (18) | 0.0075 (2) |
S | 0.0298 (6) | 0.0329 (6) | 0.0313 (6) | 0.0005 (4) | 0.0061 (4) | 0.0134 (5) |
N40 | 0.0212 (17) | 0.041 (2) | 0.0261 (19) | 0.0015 (15) | 0.0035 (14) | 0.0094 (16) |
C40 | 0.0189 (18) | 0.037 (2) | 0.0179 (19) | 0.0012 (16) | 0.0034 (15) | 0.0104 (17) |
N4 | 0.0188 (16) | 0.0334 (19) | 0.0223 (17) | 0.0022 (14) | 0.0061 (13) | 0.0091 (15) |
C11 | 0.027 (2) | 0.034 (2) | 0.025 (2) | 0.0038 (17) | 0.0051 (17) | 0.0114 (18) |
C12 | 0.029 (2) | 0.031 (2) | 0.024 (2) | 0.0003 (17) | 0.0037 (17) | 0.0118 (18) |
N1 | 0.0237 (17) | 0.0317 (19) | 0.0202 (17) | 0.0024 (14) | 0.0048 (13) | 0.0090 (15) |
C13 | 0.027 (2) | 0.039 (2) | 0.021 (2) | 0.0046 (18) | 0.0039 (16) | 0.0137 (18) |
C14 | 0.026 (2) | 0.032 (2) | 0.0201 (19) | 0.0019 (17) | 0.0049 (16) | 0.0093 (17) |
C15 | 0.029 (2) | 0.037 (2) | 0.022 (2) | 0.0033 (18) | 0.0069 (16) | 0.0144 (18) |
C16 | 0.0211 (19) | 0.035 (2) | 0.0188 (19) | 0.0038 (16) | 0.0048 (15) | 0.0092 (17) |
C17 | 0.030 (2) | 0.038 (2) | 0.020 (2) | 0.0041 (18) | 0.0079 (17) | 0.0124 (18) |
C18 | 0.032 (2) | 0.038 (2) | 0.022 (2) | 0.0068 (18) | 0.0073 (17) | 0.0092 (18) |
C19 | 0.029 (2) | 0.031 (2) | 0.031 (2) | 0.0063 (17) | 0.0094 (18) | 0.0135 (19) |
C110 | 0.029 (2) | 0.037 (2) | 0.024 (2) | 0.0033 (18) | 0.0060 (17) | 0.0157 (19) |
C111 | 0.025 (2) | 0.041 (2) | 0.0174 (19) | 0.0045 (17) | 0.0035 (16) | 0.0122 (18) |
C21 | 0.022 (2) | 0.032 (2) | 0.024 (2) | −0.0010 (16) | 0.0062 (16) | 0.0051 (18) |
C22 | 0.024 (2) | 0.035 (2) | 0.022 (2) | −0.0006 (17) | 0.0049 (16) | 0.0050 (18) |
N2 | 0.0240 (17) | 0.0324 (19) | 0.0187 (16) | 0.0034 (14) | 0.0071 (13) | 0.0097 (14) |
C23 | 0.024 (2) | 0.038 (2) | 0.0198 (19) | 0.0023 (17) | 0.0031 (16) | 0.0142 (18) |
C24 | 0.0219 (19) | 0.036 (2) | 0.024 (2) | 0.0036 (17) | 0.0061 (16) | 0.0138 (18) |
C25 | 0.024 (2) | 0.036 (2) | 0.025 (2) | 0.0040 (17) | 0.0043 (16) | 0.0126 (18) |
C26 | 0.023 (2) | 0.037 (2) | 0.028 (2) | 0.0056 (17) | 0.0081 (16) | 0.0157 (19) |
C27 | 0.026 (2) | 0.037 (2) | 0.027 (2) | 0.0059 (17) | 0.0062 (17) | 0.0139 (19) |
C28 | 0.025 (2) | 0.044 (3) | 0.040 (3) | 0.0107 (19) | 0.0123 (19) | 0.017 (2) |
C29 | 0.039 (3) | 0.037 (3) | 0.038 (3) | 0.008 (2) | 0.013 (2) | 0.009 (2) |
C210 | 0.028 (2) | 0.041 (3) | 0.041 (3) | 0.0022 (19) | 0.007 (2) | 0.010 (2) |
C211 | 0.022 (2) | 0.044 (3) | 0.039 (3) | 0.0071 (19) | 0.0052 (18) | 0.012 (2) |
C31 | 0.026 (2) | 0.039 (2) | 0.025 (2) | 0.0031 (18) | 0.0115 (17) | 0.0070 (19) |
C32 | 0.025 (2) | 0.036 (2) | 0.028 (2) | 0.0042 (18) | 0.0104 (17) | 0.0026 (19) |
N3 | 0.0254 (17) | 0.0298 (19) | 0.0214 (17) | 0.0013 (14) | 0.0067 (14) | 0.0065 (14) |
C33 | 0.022 (2) | 0.033 (2) | 0.029 (2) | 0.0030 (17) | 0.0093 (17) | 0.0116 (18) |
C34 | 0.025 (2) | 0.032 (2) | 0.026 (2) | 0.0015 (17) | 0.0056 (16) | 0.0095 (18) |
C35 | 0.022 (2) | 0.041 (2) | 0.029 (2) | 0.0030 (17) | 0.0051 (17) | 0.0157 (19) |
C36 | 0.027 (2) | 0.037 (2) | 0.025 (2) | −0.0007 (18) | 0.0017 (17) | 0.0153 (19) |
C37 | 0.027 (2) | 0.037 (2) | 0.022 (2) | −0.0024 (18) | −0.0019 (17) | 0.0120 (18) |
C38 | 0.035 (2) | 0.037 (2) | 0.024 (2) | 0.0014 (19) | 0.0028 (18) | 0.0113 (19) |
C39 | 0.039 (3) | 0.049 (3) | 0.022 (2) | −0.010 (2) | 0.0006 (19) | 0.012 (2) |
C310 | 0.025 (2) | 0.070 (4) | 0.026 (2) | −0.009 (2) | −0.0039 (18) | 0.010 (2) |
C311 | 0.025 (2) | 0.054 (3) | 0.029 (2) | 0.000 (2) | 0.0036 (18) | 0.010 (2) |
Cl | 0.0292 (5) | 0.0357 (6) | 0.0209 (5) | 0.0048 (4) | 0.0082 (4) | 0.0088 (4) |
O1 | 0.0363 (17) | 0.0405 (18) | 0.0314 (17) | 0.0103 (14) | 0.0055 (14) | 0.0155 (14) |
O2 | 0.0293 (15) | 0.0453 (18) | 0.0212 (15) | 0.0084 (13) | 0.0086 (12) | 0.0147 (14) |
O3 | 0.044 (2) | 0.063 (2) | 0.042 (2) | 0.0138 (17) | 0.0288 (16) | 0.0254 (18) |
O4 | 0.054 (2) | 0.0327 (18) | 0.0364 (19) | −0.0031 (16) | 0.0013 (16) | 0.0043 (15) |
Cu—N1 | 2.231 (3) | C24—C25 | 1.350 (6) |
Cu—N2 | 2.033 (3) | C24—H24 | 0.9300 |
Cu—N3 | 2.035 (3) | C25—C26 | 1.454 (6) |
Cu—N4 | 2.052 (4) | C25—H25 | 0.9300 |
Cu—N40 | 1.954 (4) | C26—C211 | 1.396 (6) |
S—C40 | 1.634 (4) | C26—C27 | 1.413 (6) |
N40—C40 | 1.180 (6) | C27—C28 | 1.394 (7) |
N4—C31 | 1.489 (5) | C27—H27 | 0.9300 |
N4—C21 | 1.495 (5) | C28—C29 | 1.386 (7) |
N4—C11 | 1.505 (5) | C28—H28 | 0.9300 |
C11—C12 | 1.517 (6) | C29—C210 | 1.381 (7) |
C11—H11B | 0.9700 | C29—H29 | 0.9300 |
C11—H11A | 0.9700 | C210—C211 | 1.386 (7) |
C12—N1 | 1.477 (5) | C210—H210 | 0.9300 |
C12—H12B | 0.9700 | C211—H211 | 0.9300 |
C12—H12A | 0.9700 | C31—C32 | 1.540 (6) |
N1—C13 | 1.276 (6) | C31—H31B | 0.9700 |
C13—C14 | 1.451 (6) | C31—H31A | 0.9700 |
C13—H13 | 0.9300 | C32—N3 | 1.486 (5) |
C14—C15 | 1.330 (6) | C32—H32B | 0.9700 |
C14—H14 | 0.9300 | C32—H32A | 0.9700 |
C15—C16 | 1.473 (6) | N3—C33 | 1.285 (5) |
C15—H15 | 0.9300 | C33—C34 | 1.444 (6) |
C16—C17 | 1.403 (6) | C33—H33 | 0.9300 |
C16—C111 | 1.407 (6) | C34—C35 | 1.352 (6) |
C17—C18 | 1.389 (6) | C34—H34 | 0.9300 |
C17—H17 | 0.9300 | C35—C36 | 1.466 (6) |
C18—C19 | 1.385 (6) | C35—H35 | 0.9300 |
C18—H18 | 0.9300 | C36—C37 | 1.401 (7) |
C19—C110 | 1.391 (6) | C36—C311 | 1.404 (6) |
C19—H19 | 0.9300 | C37—C38 | 1.388 (6) |
C110—C111 | 1.384 (6) | C37—H37 | 0.9300 |
C110—H110 | 0.9300 | C38—C39 | 1.387 (6) |
C111—H111 | 0.9300 | C38—H38 | 0.9300 |
C21—C22 | 1.533 (6) | C39—C310 | 1.377 (8) |
C21—H21B | 0.9700 | C39—H39 | 0.9300 |
C21—H21A | 0.9700 | C310—C311 | 1.395 (7) |
C22—N2 | 1.478 (6) | C310—H310 | 0.9300 |
C22—H22B | 0.9700 | C311—H311 | 0.9300 |
C22—H22A | 0.9700 | Cl—O3 | 1.440 (3) |
N2—C23 | 1.293 (6) | Cl—O1 | 1.441 (3) |
C23—C24 | 1.438 (6) | Cl—O4 | 1.445 (4) |
C23—H23 | 0.9300 | Cl—O2 | 1.456 (3) |
N1—Cu—N2 | 103.32 (13) | N2—C23—C24 | 125.2 (4) |
N1—Cu—N3 | 99.85 (13) | N2—C23—H23 | 117.4 |
N1—Cu—N4 | 81.66 (13) | C24—C23—H23 | 117.4 |
N1—Cu—N40 | 108.32 (14) | C25—C24—C23 | 121.1 (4) |
N2—Cu—N3 | 149.09 (14) | C25—C24—H24 | 119.4 |
N2—Cu—N4 | 83.58 (14) | C23—C24—H24 | 119.4 |
N2—Cu—N40 | 96.97 (14) | C24—C25—C26 | 127.4 (4) |
N3—Cu—N4 | 79.82 (14) | C24—C25—H25 | 116.3 |
N3—Cu—N40 | 94.85 (15) | C26—C25—H25 | 116.3 |
N4—Cu—N40 | 169.47 (15) | C211—C26—C27 | 117.9 (4) |
C40—N40—Cu | 178.4 (3) | C211—C26—C25 | 123.0 (4) |
N40—C40—S | 177.7 (4) | C27—C26—C25 | 119.1 (4) |
C31—N4—C21 | 111.0 (3) | C28—C27—C26 | 120.8 (4) |
C31—N4—C11 | 110.8 (3) | C28—C27—H27 | 119.6 |
C21—N4—C11 | 111.1 (3) | C26—C27—H27 | 119.6 |
C31—N4—Cu | 105.8 (3) | C29—C28—C27 | 119.9 (4) |
C21—N4—Cu | 109.5 (3) | C29—C28—H28 | 120.0 |
C11—N4—Cu | 108.5 (3) | C27—C28—H28 | 120.0 |
N4—C11—C12 | 110.0 (3) | C210—C29—C28 | 119.7 (5) |
N4—C11—H11B | 109.7 | C210—C29—H29 | 120.1 |
C12—C11—H11B | 109.7 | C28—C29—H29 | 120.1 |
N4—C11—H11A | 109.7 | C29—C210—C211 | 120.9 (4) |
C12—C11—H11A | 109.7 | C29—C210—H210 | 119.6 |
H11B—C11—H11A | 108.2 | C211—C210—H210 | 119.6 |
N1—C12—C11 | 110.2 (3) | C210—C211—C26 | 120.8 (4) |
N1—C12—H12B | 109.6 | C210—C211—H211 | 119.6 |
C11—C12—H12B | 109.6 | C26—C211—H211 | 119.6 |
N1—C12—H12A | 109.6 | N4—C31—C32 | 110.6 (3) |
C11—C12—H12A | 109.6 | N4—C31—H31B | 109.5 |
H12B—C12—H12A | 108.1 | C32—C31—H31B | 109.5 |
C13—N1—C12 | 116.6 (4) | N4—C31—H31A | 109.5 |
C13—N1—Cu | 135.1 (3) | C32—C31—H31A | 109.5 |
C12—N1—Cu | 108.2 (2) | H31B—C31—H31A | 108.1 |
N1—C13—C14 | 123.6 (4) | N3—C32—C31 | 110.1 (3) |
N1—C13—H13 | 118.2 | N3—C32—H32B | 109.6 |
C14—C13—H13 | 118.2 | C31—C32—H32B | 109.6 |
C15—C14—C13 | 122.2 (4) | N3—C32—H32A | 109.6 |
C15—C14—H14 | 118.9 | C31—C32—H32A | 109.6 |
C13—C14—H14 | 118.9 | H32B—C32—H32A | 108.2 |
C14—C15—C16 | 127.2 (4) | C33—N3—C32 | 115.8 (4) |
C14—C15—H15 | 116.4 | C33—N3—Cu | 131.2 (3) |
C16—C15—H15 | 116.4 | C32—N3—Cu | 112.1 (2) |
C17—C16—C111 | 117.9 (4) | N3—C33—C34 | 124.1 (4) |
C17—C16—C15 | 119.7 (4) | N3—C33—H33 | 118.0 |
C111—C16—C15 | 122.5 (4) | C34—C33—H33 | 118.0 |
C18—C17—C16 | 121.0 (4) | C35—C34—C33 | 119.7 (4) |
C18—C17—H17 | 119.5 | C35—C34—H34 | 120.1 |
C16—C17—H17 | 119.5 | C33—C34—H34 | 120.1 |
C19—C18—C17 | 120.4 (4) | C34—C35—C36 | 126.5 (4) |
C19—C18—H18 | 119.8 | C34—C35—H35 | 116.8 |
C17—C18—H18 | 119.8 | C36—C35—H35 | 116.8 |
C18—C19—C110 | 119.4 (4) | C37—C36—C311 | 118.2 (4) |
C18—C19—H19 | 120.3 | C37—C36—C35 | 122.7 (4) |
C110—C19—H19 | 120.3 | C311—C36—C35 | 119.1 (4) |
C111—C110—C19 | 120.6 (4) | C38—C37—C36 | 120.7 (4) |
C111—C110—H110 | 119.7 | C38—C37—H37 | 119.6 |
C19—C110—H110 | 119.7 | C36—C37—H37 | 119.6 |
C110—C111—C16 | 120.7 (4) | C39—C38—C37 | 120.0 (5) |
C110—C111—H111 | 119.6 | C39—C38—H38 | 120.0 |
C16—C111—H111 | 119.6 | C37—C38—H38 | 120.0 |
N4—C21—C22 | 108.0 (3) | C310—C39—C38 | 120.5 (5) |
N4—C21—H21B | 110.1 | C310—C39—H39 | 119.8 |
C22—C21—H21B | 110.1 | C38—C39—H39 | 119.8 |
N4—C21—H21A | 110.1 | C39—C310—C311 | 119.8 (4) |
C22—C21—H21A | 110.1 | C39—C310—H310 | 120.1 |
H21B—C21—H21A | 108.4 | C311—C310—H310 | 120.1 |
N2—C22—C21 | 106.5 (3) | C310—C311—C36 | 120.8 (5) |
N2—C22—H22B | 110.4 | C310—C311—H311 | 119.6 |
C21—C22—H22B | 110.4 | C36—C311—H311 | 119.6 |
N2—C22—H22A | 110.4 | O3—Cl—O1 | 109.8 (2) |
C21—C22—H22A | 110.4 | O3—Cl—O4 | 110.2 (2) |
H22B—C22—H22A | 108.6 | O1—Cl—O4 | 110.2 (2) |
C23—N2—C22 | 117.2 (3) | O3—Cl—O2 | 108.5 (2) |
C23—N2—Cu | 134.0 (3) | O1—Cl—O2 | 109.51 (19) |
C22—N2—Cu | 108.7 (2) | O4—Cl—O2 | 108.5 (2) |
N40—Cu—N4—C31 | 18.8 (9) | N4—Cu—N2—C23 | 154.0 (4) |
N2—Cu—N4—C31 | 112.4 (3) | N1—Cu—N2—C23 | 74.2 (4) |
N3—Cu—N4—C31 | −41.4 (2) | N40—Cu—N2—C22 | 147.5 (3) |
N1—Cu—N4—C31 | −143.0 (3) | N3—Cu—N2—C22 | 35.8 (4) |
N40—Cu—N4—C21 | −100.8 (8) | N4—Cu—N2—C22 | −21.9 (3) |
N2—Cu—N4—C21 | −7.2 (3) | N1—Cu—N2—C22 | −101.8 (3) |
N3—Cu—N4—C21 | −161.1 (3) | C22—N2—C23—C24 | 177.5 (4) |
N1—Cu—N4—C21 | 97.3 (3) | Cu—N2—C23—C24 | 1.8 (6) |
N40—Cu—N4—C11 | 137.8 (7) | N2—C23—C24—C25 | 174.8 (4) |
N2—Cu—N4—C11 | −128.6 (3) | C23—C24—C25—C26 | −179.2 (4) |
N3—Cu—N4—C11 | 77.5 (3) | C24—C25—C26—C211 | 3.8 (7) |
N1—Cu—N4—C11 | −24.1 (2) | C24—C25—C26—C27 | −175.7 (4) |
C31—N4—C11—C12 | 163.0 (3) | C211—C26—C27—C28 | 0.5 (6) |
C21—N4—C11—C12 | −73.2 (4) | C25—C26—C27—C28 | 180.0 (4) |
Cu—N4—C11—C12 | 47.3 (4) | C26—C27—C28—C29 | 0.1 (7) |
N4—C11—C12—N1 | −50.0 (4) | C27—C28—C29—C210 | −0.6 (7) |
C11—C12—N1—C13 | −156.8 (4) | C28—C29—C210—C211 | 0.3 (8) |
C11—C12—N1—Cu | 27.6 (4) | C29—C210—C211—C26 | 0.3 (8) |
N40—Cu—N1—C13 | 7.1 (4) | C27—C26—C211—C210 | −0.7 (7) |
N2—Cu—N1—C13 | −95.0 (4) | C25—C26—C211—C210 | 179.8 (4) |
N3—Cu—N1—C13 | 105.6 (4) | C21—N4—C31—C32 | 163.3 (4) |
N4—Cu—N1—C13 | −176.3 (4) | C11—N4—C31—C32 | −72.8 (4) |
N40—Cu—N1—C12 | −178.5 (2) | Cu—N4—C31—C32 | 44.6 (4) |
N2—Cu—N1—C12 | 79.4 (3) | N4—C31—C32—N3 | −20.4 (5) |
N3—Cu—N1—C12 | −80.0 (3) | C31—C32—N3—C33 | 156.1 (4) |
N4—Cu—N1—C12 | −1.9 (2) | C31—C32—N3—Cu | −14.0 (4) |
C12—N1—C13—C14 | −177.6 (4) | N40—Cu—N3—C33 | 52.3 (4) |
Cu—N1—C13—C14 | −3.5 (7) | N2—Cu—N3—C33 | 164.6 (3) |
N1—C13—C14—C15 | 180.0 (4) | N4—Cu—N3—C33 | −136.8 (4) |
C13—C14—C15—C16 | 179.3 (4) | N1—Cu—N3—C33 | −57.2 (4) |
C14—C15—C16—C17 | 179.8 (4) | N40—Cu—N3—C32 | −139.5 (3) |
C14—C15—C16—C111 | −0.5 (7) | N2—Cu—N3—C32 | −27.2 (4) |
C111—C16—C17—C18 | 0.2 (6) | N4—Cu—N3—C32 | 31.4 (3) |
C15—C16—C17—C18 | 179.9 (4) | N1—Cu—N3—C32 | 111.0 (3) |
C16—C17—C18—C19 | 0.0 (6) | C32—N3—C33—C34 | −175.2 (4) |
C17—C18—C19—C110 | 0.0 (7) | Cu—N3—C33—C34 | −7.4 (6) |
C18—C19—C110—C111 | −0.4 (6) | N3—C33—C34—C35 | 174.4 (4) |
C19—C110—C111—C16 | 0.6 (6) | C33—C34—C35—C36 | 178.4 (4) |
C17—C16—C111—C110 | −0.5 (6) | C34—C35—C36—C37 | −5.1 (7) |
C15—C16—C111—C110 | 179.8 (4) | C34—C35—C36—C311 | 175.7 (4) |
C31—N4—C21—C22 | −82.4 (4) | C311—C36—C37—C38 | −1.1 (7) |
C11—N4—C21—C22 | 153.9 (3) | C35—C36—C37—C38 | 179.7 (4) |
Cu—N4—C21—C22 | 34.0 (4) | C36—C37—C38—C39 | 0.9 (7) |
N4—C21—C22—N2 | −52.5 (4) | C37—C38—C39—C310 | −0.8 (7) |
C21—C22—N2—C23 | −130.9 (4) | C38—C39—C310—C311 | 0.9 (8) |
C21—C22—N2—Cu | 45.8 (3) | C39—C310—C311—C36 | −1.1 (8) |
N40—Cu—N2—C23 | −36.6 (4) | C37—C36—C311—C310 | 1.2 (7) |
N3—Cu—N2—C23 | −148.3 (4) | C35—C36—C311—C310 | −179.6 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12B···O1i | 0.97 | 2.55 | 3.521 (5) | 176 |
C21—H21A···O1ii | 0.97 | 2.49 | 3.320 (5) | 143 |
C21—H21A···O2ii | 0.97 | 2.45 | 3.359 (5) | 156 |
C32—H32B···O2iii | 0.97 | 2.55 | 3.362 (5) | 141 |
C18—H18···O3iv | 0.93 | 2.48 | 3.091 (5) | 123 |
C24—H24···N40 | 0.93 | 2.57 | 3.205 (5) | 126 |
C34—H34···N40 | 0.93 | 2.58 | 3.240 (5) | 128 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, y, z−1; (iii) −x+1, −y+1, −z+1; (iv) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | [Cu(NCS)(C33H36N4)]ClO4 |
Mr | 709.73 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 95 |
a, b, c (Å) | 10.1328 (13), 12.3212 (17), 15.0666 (18) |
α, β, γ (°) | 108.147 (10), 105.921 (10), 91.638 (11) |
V (Å3) | 1705.5 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.82 |
Crystal size (mm) | 0.31 × 0.23 × 0.22 |
Data collection | |
Diffractometer | STOE IPDS II |
Absorption correction | Integration (X-RED32; Stoe & Cie, 2005) |
Tmin, Tmax | 0.773, 0.859 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 20318, 6704, 5751 |
Rint | 0.068 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.060, 0.168, 1.18 |
No. of reflections | 6704 |
No. of parameters | 416 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.67, −0.75 |
Computer programs: X-AREA (Stoe & Cie, 2006), X-RED32 (Stoe & Cie, 2005), X-RED32, DIRDIF96 (Beurskens et al., 1996), SHELXL97 (Sheldrick, 1997), SHELXTL, (Sheldrick, 1996), SHELXTL and PLATON (Spek, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12B···O1i | 0.97 | 2.55 | 3.521 (5) | 175.7 |
C21—H21A···O1ii | 0.97 | 2.49 | 3.320 (5) | 143.3 |
C21—H21A···O2ii | 0.97 | 2.45 | 3.359 (5) | 155.9 |
C32—H32B···O2iii | 0.97 | 2.55 | 3.362 (5) | 141.3 |
C18—H18···O3iv | 0.93 | 2.48 | 3.091 (5) | 123.1 |
C24—H24···N40 | 0.93 | 2.57 | 3.205 (5) | 125.7 |
C34—H34···N40 | 0.93 | 2.58 | 3.240 (5) | 128.0 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, y, z−1; (iii) −x+1, −y+1, −z+1; (iv) x, y+1, z. |
Tripodal ligands generally coordinate to transition metal ions using all of their nitrogen atoms as donors (Scarpellini et al., 2004; Abdus Salam & Aoki, 2001; Raab et al., 2001; Chen et al., 2000; Su et al., 1999; Massoud et al., 1999). Six coordinate octahedral complexes containing such ligands invariably display cis geometries (Kwak et al., 1999; Saha et al., 2003). The steric constraints imposed by such ligands often result in trigonal bipyramidal geometries for five coordinate systems (Chen et al., 2000; Su et al., 1999), while rare examples of four coordinate complexes containing tripodal ligands display distored tetrahedral geometries (Patra & Goldberg, 2003; Wei et al., 1994; Alyea et al., 1990). The pseudohalide, NCS, is known to coordinate to metals (Laskowski et al., 1975; Kickelbick et al., 2003) and act as terminal ligand in these complexes. In this context, we decided to examine the nature of the copper(II) complex formed with the tripodal Schiff base ligand ca3-tren. Therefore, (I) has been synthesized and structurally investigated. Compound (I) is a monomeric complex (Fig. 1) in which the ca3-tren ligand is tetradentate and the thiocyanate anion is monodentate. The Cu—N bond lengths in (I) are in good agreement with the corresponding distances in related complexes (Abdus Salam et al., 2001; Chen et al., 2000). The coordination geometry around the CuII ion in (I) can be described as grossly distorted trigonal bipyramid with approximate molecular Cs symmetry with respect to the N4—N1—Cu—N40—C40—S plane. The N2—Cu—N3 angle across this plane is much larger than the analoguous N2—Cu—N1 and N3—Cu—N1 angles. The Cu—N1 bond is, naturally, the longest equatorial bond, since it has to accommodate the thiocyanate. In the three legs all atoms except the α carbons are essentially co-planar, with atoms N4 and N40 being in one of the planes. The angles between the planes of the legs are 81.8 (1)° between 1 and 2, 79.5 (1)° between 1 and 3 and 9.7 (1)° between 2 and 3 (the plane number is realted to the N atom label contained within each plane i.e. N1 = plane 1). It is noteworthy, that at 95 K the perchlorate anion, a notorious troublemaker, is perfectly ordered,[Cu(ca3-tren)(NCS)]ClO4 whereas at room temperature it is distributed between the position shown in Fig.1 and one staggered about the O1—Cl bond.
The crystal packing of (I), shown in Fig. 2., demonstrates that the main cohesion of this structure is due to hydrogen bonding. Two planes may be preceived in the structure accross which a minimum of bonding (other than van der Waals) seem to exist: (023) and (010). Otherwise there exist C—H···O bonds along [100], [032] and [011]. This bonding seems to be weaker along the latter two directions than along the a axis. One might even say that (I) has some pseudo layer-character with respect to (023) and (010), especially at room temperature. From the observation of some arching in the (b*,c*) layer, we may conclude the strongest cohesion exists along [100] and that the real structure consists of slightly disoriented (~5°) blocks bounded by (100), (023) and (010). This conjecture is further confirmed by the observation that crystal of (I) crumble into many tiny pieces at room temperature upon even a very gentle attempt at cutting them with the blade of a scalpel.EDITORS: Please check name
[Cu(ca3-tren)(NCS)]ClO4 At 95 K, most atoms are fairly isotropic, but there exists a remnant of some more pronounced disorder in the phenyl ring C36 → C311, i.e. two slightly rotated positions of the ring. Another occurrence of dynamic disorder has all but disappeared at 95 K; indeed at room temperature atoms C11, C21 and C31 were strongly elongated perpendicularly to the planes of the legs.