Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807042493/bt2493sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807042493/bt2493Isup2.hkl |
CCDC reference: 663559
To a solution of 190 mg (1 mmol) CuI in 5 ml acetonitril a solution of 261 mg (1 mmol) of PPh3 in 5 ml aetonitril was added. The mixture was stirred for 5 min and then 378 mg (1 mmol) of N,N'-bis(2-nitrocinnamaldehyde)ethylenediamine in 5 ml acetonitril were added and stirred for an additional 60 min. The volume of the solvent was reduced under vacuum to about 5 ml. The diffusion of diethyl ether vapor into the concentrated solution gave red crystals suitable for X-ray studies. The crystals were collected and dried in vacuo.
All H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H distances in the range 0.95–0.99 Å, with Uiso(H) = 1.2 Ueq(C).
Cinnamaldehyde and its derivatives condense with ethylenediamine to furnish a range of Schiff base compounds; a small number of such bis(cinnamaldehyde)ethylenediimine ligands have been used to furnish adducts with transition metals (Amirnasr et al., 2005; Amirnasr et al., 2006). The study of the variety of products in self-assembly processes between labile metal ions and flexible multidentate ligands is an interesting topic in supramolecular chemistry. Among such complexes whose structures have been described are, for example, the copper(I) iodide (Kickelbick et al., 2002), (triphenylphosphine)(halogen/pseudohalogeno)copper(I) (Kickelbick et al., 2003), copper(I) perchlorate (Meghdadi et al., 2002), and the cobalt(II) chloride, cobalt(II) bromide and nickel bromide (Amirnasr et al., 2003) adducts. Here, we report the result of the reaction of CuI with N,N'-bis(2-nitrocinnamaldehyde)ethylenediamine and triphenylphosphane, which forms a copper Schiff base complex (Fig. 1). However, the Cu(1)—I(1) bond length of 2.6145 (12) Å is slightly longer than reported (Barron, et al.,1988). The Cu(1)—P(1) distance [2.2119 (13) Å] is slightly longer than in other tetrahedral copper(I) phosphine complexes (Balogh-Heregovich, et al., 1999). While a tetrahedral geometry might be expected for a four coordinated copper(I) center the coordination sphere around copper(I) in this complex is distorted by the restricting bite angle of the chelating ligand. The N(1)—Cu(1)—N(2) angle is only 82.40 (5)°. The I(1)—Cu(1)—P(1) angle is 115.08 (4)°, being somewhat larger than the values for a tetrahedron (Table 1). The longer Cu(1)—I(1) and Cu(1)—P(1) distances and the larger deviations of angles from the ideal tetrahedral angle in this complex may be attributed to the mutual steric effects between the bulky I atom and the PPh3 ligand. The single bond distance of C(3)—C(4), 1.448 (2) Å being slightly shorter than C(1)—C(2), 1.509 (2) Å indicates the existence of an extended electron delocalization in this complex.
For related literature, see: Amirnasr et al. (2003, 2005, 2006); Balogh-Heregovich et al. (1999); Barron et al. (1988); Kickelbick et al. (2002, 2003); Meghdadi et al. (2002).
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2007); software used to prepare material for publication: SHELXL97.
Fig. 1. The molecular structure of compound, with atom labels and 50% probability displacement ellipsoids. |
[CuI(C20H18N4O4)(C18H15P)] | F(000) = 3344 |
Mr = 831.09 | Dx = 1.506 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71075 Å |
Hall symbol: -C 2yc | Cell parameters from 25590 reflections |
a = 31.64 (2) Å | θ = 3.0–27.4° |
b = 15.586 (10) Å | µ = 1.53 mm−1 |
c = 17.638 (11) Å | T = 200 K |
β = 122.54 (2)° | Plate, red |
V = 7333 (8) Å3 | 0.35 × 0.35 × 0.12 mm |
Z = 8 |
Rigaku R-AXIS RAPID diffractometer | 8296 independent reflections |
Radiation source: fine-focus sealed tube | 6482 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
Detector resolution: 10.00 pixels mm-1 | θmax = 27.4°, θmin = 3.0° |
ω scans | h = −39→40 |
Absorption correction: numerical (ABSCOR; Higashi, 1999) | k = −20→20 |
Tmin = 0.617, Tmax = 0.838 | l = −22→22 |
31361 measured reflections |
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)] = 0.022 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.051 | H-atom parameters constrained |
S = 0.94 | w = 1/[σ2(Fo2) + (0.028P)2] where P = (Fo2 + 2Fc2)/3 |
8296 reflections | (Δ/σ)max = 0.003 |
442 parameters | Δρmax = 0.51 e Å−3 |
0 restraints | Δρmin = −0.50 e Å−3 |
[CuI(C20H18N4O4)(C18H15P)] | V = 7333 (8) Å3 |
Mr = 831.09 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 31.64 (2) Å | µ = 1.53 mm−1 |
b = 15.586 (10) Å | T = 200 K |
c = 17.638 (11) Å | 0.35 × 0.35 × 0.12 mm |
β = 122.54 (2)° |
Rigaku R-AXIS RAPID diffractometer | 8296 independent reflections |
Absorption correction: numerical (ABSCOR; Higashi, 1999) | 6482 reflections with I > 2σ(I) |
Tmin = 0.617, Tmax = 0.838 | Rint = 0.021 |
31361 measured reflections |
R[F2 > 2σ(F2)] = 0.022 | 0 restraints |
wR(F2) = 0.051 | H-atom parameters constrained |
S = 0.94 | Δρmax = 0.51 e Å−3 |
8296 reflections | Δρmin = −0.50 e Å−3 |
442 parameters |
x | y | z | Uiso*/Ueq | ||
I1 | 0.741268 (5) | 0.210954 (8) | 0.272139 (8) | 0.04254 (5) | |
Cu1 | 0.665571 (7) | 0.104414 (12) | 0.197272 (12) | 0.02385 (5) | |
P1 | 0.602273 (16) | 0.13979 (3) | 0.21093 (3) | 0.02384 (9) | |
O1 | 0.54983 (8) | 0.29902 (10) | −0.24211 (10) | 0.0804 (6) | |
O2 | 0.55500 (10) | 0.42014 (12) | −0.29098 (11) | 0.1098 (9) | |
O3 | 0.74378 (5) | −0.20177 (8) | 0.56025 (9) | 0.0411 (3) | |
O4 | 0.82068 (6) | −0.22481 (9) | 0.66928 (10) | 0.0545 (4) | |
N1 | 0.65513 (5) | 0.07761 (8) | 0.07246 (8) | 0.0251 (3) | |
N2 | 0.68869 (5) | −0.02248 (8) | 0.22191 (9) | 0.0290 (3) | |
N3 | 0.56134 (7) | 0.37400 (12) | −0.23069 (11) | 0.0527 (5) | |
N4 | 0.78614 (6) | −0.17751 (10) | 0.61675 (10) | 0.0353 (4) | |
C1 | 0.67300 (7) | −0.00953 (11) | 0.07208 (11) | 0.0333 (4) | |
H1A | 0.7087 | −0.0074 | 0.0916 | 0.040* | |
H1B | 0.6536 | −0.0333 | 0.0104 | 0.040* | |
C2 | 0.66692 (7) | −0.06655 (11) | 0.13471 (11) | 0.0351 (4) | |
H2A | 0.6309 | −0.0784 | 0.1090 | 0.042* | |
H2B | 0.6843 | −0.1219 | 0.1429 | 0.042* | |
C3 | 0.64407 (6) | 0.12722 (11) | 0.00678 (10) | 0.0285 (4) | |
H3 | 0.6455 | 0.1056 | −0.0421 | 0.034* | |
C4 | 0.62934 (6) | 0.21555 (10) | 0.00470 (11) | 0.0295 (4) | |
H4 | 0.6265 | 0.2360 | 0.0526 | 0.035* | |
C5 | 0.61952 (6) | 0.26939 (11) | −0.06169 (11) | 0.0299 (4) | |
H5 | 0.6202 | 0.2472 | −0.1112 | 0.036* | |
C6 | 0.60769 (7) | 0.36057 (11) | −0.06315 (11) | 0.0328 (4) | |
C7 | 0.58224 (7) | 0.41167 (11) | −0.14084 (12) | 0.0389 (4) | |
C8 | 0.57386 (9) | 0.49842 (13) | −0.13877 (16) | 0.0573 (6) | |
H8 | 0.5567 | 0.5306 | −0.1930 | 0.069* | |
C9 | 0.59048 (11) | 0.53764 (14) | −0.05806 (17) | 0.0706 (7) | |
H9 | 0.5841 | 0.5969 | −0.0559 | 0.085* | |
C10 | 0.61655 (12) | 0.49031 (14) | 0.02022 (17) | 0.0735 (8) | |
H10 | 0.6287 | 0.5176 | 0.0765 | 0.088* | |
C11 | 0.62508 (9) | 0.40430 (13) | 0.01776 (14) | 0.0524 (6) | |
H11 | 0.6434 | 0.3735 | 0.0727 | 0.063* | |
C12 | 0.71458 (7) | −0.06699 (11) | 0.29366 (11) | 0.0327 (4) | |
H12 | 0.7203 | −0.1261 | 0.2892 | 0.039* | |
C13 | 0.73532 (7) | −0.02857 (11) | 0.38146 (11) | 0.0333 (4) | |
H13 | 0.7314 | 0.0314 | 0.3849 | 0.040* | |
C14 | 0.75971 (6) | −0.07328 (11) | 0.45771 (10) | 0.0305 (4) | |
H14 | 0.7628 | −0.1335 | 0.4536 | 0.037* | |
C15 | 0.78219 (6) | −0.03567 (11) | 0.54816 (11) | 0.0303 (4) | |
C16 | 0.79631 (7) | −0.08451 (11) | 0.62468 (11) | 0.0316 (4) | |
C17 | 0.81817 (8) | −0.04998 (13) | 0.70979 (12) | 0.0492 (5) | |
H17 | 0.8283 | −0.0858 | 0.7603 | 0.059* | |
C18 | 0.82500 (10) | 0.03758 (14) | 0.71991 (13) | 0.0626 (7) | |
H18 | 0.8387 | 0.0629 | 0.7775 | 0.075* | |
C19 | 0.81202 (9) | 0.08860 (13) | 0.64653 (13) | 0.0533 (6) | |
H19 | 0.8168 | 0.1489 | 0.6537 | 0.064* | |
C20 | 0.79210 (7) | 0.05210 (12) | 0.56304 (12) | 0.0404 (5) | |
H20 | 0.7848 | 0.0878 | 0.5138 | 0.049* | |
C21 | 0.56236 (6) | 0.22665 (11) | 0.13685 (10) | 0.0278 (4) | |
C22 | 0.53365 (7) | 0.21306 (12) | 0.04435 (11) | 0.0406 (5) | |
H22 | 0.5331 | 0.1577 | 0.0212 | 0.049* | |
C23 | 0.50589 (8) | 0.27885 (13) | −0.01449 (12) | 0.0479 (5) | |
H23 | 0.4863 | 0.2682 | −0.0774 | 0.057* | |
C24 | 0.50664 (8) | 0.35903 (14) | 0.01767 (13) | 0.0509 (6) | |
H24 | 0.4875 | 0.4040 | −0.0228 | 0.061* | |
C25 | 0.53513 (9) | 0.37449 (13) | 0.10860 (14) | 0.0548 (6) | |
H25 | 0.5360 | 0.4304 | 0.1309 | 0.066* | |
C26 | 0.56272 (8) | 0.30846 (12) | 0.16804 (12) | 0.0415 (5) | |
H26 | 0.5821 | 0.3196 | 0.2309 | 0.050* | |
C27 | 0.55921 (6) | 0.05006 (11) | 0.18611 (10) | 0.0276 (4) | |
C28 | 0.50778 (7) | 0.05445 (13) | 0.13479 (14) | 0.0481 (5) | |
H28 | 0.4918 | 0.1077 | 0.1091 | 0.058* | |
C29 | 0.47879 (8) | −0.01857 (16) | 0.11998 (15) | 0.0613 (7) | |
H29 | 0.4433 | −0.0146 | 0.0840 | 0.074* | |
C30 | 0.50081 (9) | −0.09547 (14) | 0.15654 (14) | 0.0508 (6) | |
H30 | 0.4809 | −0.1450 | 0.1462 | 0.061* | |
C31 | 0.55200 (9) | −0.10058 (13) | 0.20832 (16) | 0.0554 (6) | |
H31 | 0.5677 | −0.1539 | 0.2344 | 0.067* | |
C32 | 0.58105 (8) | −0.02865 (12) | 0.22291 (14) | 0.0452 (5) | |
H32 | 0.6165 | −0.0333 | 0.2587 | 0.054* | |
C33 | 0.61629 (6) | 0.17460 (10) | 0.32143 (10) | 0.0246 (3) | |
C34 | 0.57868 (7) | 0.18986 (12) | 0.33787 (12) | 0.0366 (4) | |
H34 | 0.5448 | 0.1789 | 0.2919 | 0.044* | |
C35 | 0.58985 (7) | 0.22083 (12) | 0.42039 (12) | 0.0380 (4) | |
H35 | 0.5637 | 0.2320 | 0.4303 | 0.046* | |
C36 | 0.63915 (7) | 0.23546 (11) | 0.48822 (11) | 0.0332 (4) | |
H36 | 0.6469 | 0.2569 | 0.5447 | 0.040* | |
C37 | 0.67701 (7) | 0.21905 (11) | 0.47403 (11) | 0.0335 (4) | |
H37 | 0.7109 | 0.2285 | 0.5210 | 0.040* | |
C38 | 0.66594 (6) | 0.18855 (11) | 0.39087 (11) | 0.0287 (4) | |
H38 | 0.6923 | 0.1772 | 0.3815 | 0.034* |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.04742 (8) | 0.05158 (9) | 0.03810 (7) | −0.02797 (6) | 0.02926 (6) | −0.02206 (6) |
Cu1 | 0.0270 (1) | 0.0217 (1) | 0.0231 (1) | −0.00045 (8) | 0.01369 (8) | −0.00149 (8) |
P1 | 0.0238 (2) | 0.0245 (2) | 0.02155 (19) | −0.00206 (17) | 0.01104 (17) | −0.00331 (17) |
O1 | 0.1126 (15) | 0.0405 (10) | 0.0416 (9) | 0.0017 (9) | 0.0107 (9) | −0.0032 (7) |
O2 | 0.185 (2) | 0.0629 (12) | 0.0351 (9) | −0.0072 (13) | 0.0281 (12) | 0.0173 (9) |
O3 | 0.0509 (9) | 0.0362 (8) | 0.0422 (7) | −0.0087 (6) | 0.0291 (7) | −0.0072 (6) |
O4 | 0.0648 (10) | 0.0503 (9) | 0.0553 (9) | 0.0256 (8) | 0.0369 (8) | 0.0212 (7) |
N1 | 0.0266 (7) | 0.0241 (7) | 0.0231 (7) | −0.0026 (6) | 0.0124 (6) | −0.0016 (6) |
N2 | 0.0380 (8) | 0.0218 (7) | 0.0240 (7) | 0.0012 (6) | 0.0146 (6) | −0.0004 (6) |
N3 | 0.0571 (11) | 0.0413 (10) | 0.0346 (9) | 0.0051 (9) | 0.0081 (8) | 0.0060 (9) |
N4 | 0.0489 (10) | 0.0345 (8) | 0.0353 (8) | 0.0080 (8) | 0.0310 (8) | 0.0060 (7) |
C1 | 0.0441 (11) | 0.0275 (9) | 0.0293 (9) | 0.0042 (8) | 0.0204 (8) | −0.0030 (8) |
C2 | 0.0479 (11) | 0.0240 (9) | 0.0281 (9) | 0.0011 (8) | 0.0170 (8) | −0.0027 (8) |
C3 | 0.0313 (9) | 0.0318 (9) | 0.0230 (8) | −0.0037 (7) | 0.0150 (7) | −0.0037 (7) |
C4 | 0.0335 (9) | 0.0302 (9) | 0.0252 (8) | −0.0023 (8) | 0.0161 (7) | −0.0019 (7) |
C5 | 0.0310 (9) | 0.0323 (10) | 0.0264 (8) | −0.0017 (8) | 0.0154 (7) | −0.0007 (8) |
C6 | 0.0388 (10) | 0.0288 (9) | 0.0341 (9) | −0.0037 (8) | 0.0218 (8) | 0.0008 (8) |
C7 | 0.0406 (11) | 0.0304 (10) | 0.0380 (10) | −0.0011 (8) | 0.0160 (9) | 0.0009 (9) |
C8 | 0.0653 (15) | 0.0331 (12) | 0.0591 (14) | 0.0033 (10) | 0.0239 (12) | 0.0098 (11) |
C9 | 0.105 (2) | 0.0278 (12) | 0.0800 (18) | 0.0040 (13) | 0.0506 (17) | −0.0032 (12) |
C10 | 0.128 (2) | 0.0386 (13) | 0.0591 (15) | −0.0027 (15) | 0.0533 (16) | −0.0112 (12) |
C11 | 0.0841 (17) | 0.0353 (11) | 0.0418 (11) | −0.0010 (11) | 0.0365 (12) | 0.0014 (9) |
C12 | 0.0420 (10) | 0.0241 (9) | 0.0301 (9) | 0.0058 (8) | 0.0181 (8) | 0.0013 (8) |
C13 | 0.0414 (10) | 0.0254 (9) | 0.0301 (9) | 0.0058 (8) | 0.0171 (8) | 0.0002 (8) |
C14 | 0.0370 (10) | 0.0258 (9) | 0.0279 (9) | 0.0044 (8) | 0.0169 (8) | 0.0019 (7) |
C15 | 0.0293 (9) | 0.0319 (10) | 0.0271 (8) | 0.0005 (7) | 0.0134 (7) | 0.0013 (7) |
C16 | 0.0338 (10) | 0.0314 (10) | 0.0294 (9) | −0.0027 (8) | 0.0170 (8) | 0.0002 (8) |
C17 | 0.0647 (14) | 0.0488 (13) | 0.0277 (9) | −0.0079 (11) | 0.0207 (10) | 0.0031 (9) |
C18 | 0.0921 (18) | 0.0526 (14) | 0.0318 (11) | −0.0282 (13) | 0.0260 (12) | −0.0148 (10) |
C19 | 0.0733 (16) | 0.0362 (12) | 0.0413 (11) | −0.0206 (11) | 0.0248 (11) | −0.0078 (10) |
C20 | 0.0494 (12) | 0.0338 (10) | 0.0336 (10) | −0.0071 (9) | 0.0193 (9) | 0.0012 (8) |
C21 | 0.0245 (9) | 0.0306 (9) | 0.0261 (8) | 0.0001 (7) | 0.0122 (7) | −0.0012 (7) |
C22 | 0.0468 (12) | 0.0417 (11) | 0.0276 (9) | 0.0086 (9) | 0.0163 (8) | −0.0040 (8) |
C23 | 0.0513 (13) | 0.0538 (13) | 0.0253 (9) | 0.0135 (10) | 0.0118 (9) | 0.0040 (9) |
C24 | 0.0585 (14) | 0.0451 (13) | 0.0387 (11) | 0.0187 (11) | 0.0193 (10) | 0.0137 (10) |
C25 | 0.0743 (16) | 0.0311 (11) | 0.0460 (12) | 0.0093 (11) | 0.0237 (12) | 0.0000 (10) |
C26 | 0.0506 (12) | 0.0318 (10) | 0.0297 (9) | 0.0006 (9) | 0.0133 (9) | −0.0026 (8) |
C27 | 0.0304 (9) | 0.0287 (9) | 0.0260 (8) | −0.0065 (7) | 0.0167 (7) | −0.0082 (7) |
C28 | 0.0324 (11) | 0.0413 (12) | 0.0564 (13) | −0.0063 (9) | 0.0146 (10) | −0.0064 (10) |
C29 | 0.0358 (12) | 0.0669 (16) | 0.0631 (15) | −0.0264 (11) | 0.0147 (11) | −0.0160 (13) |
C30 | 0.0626 (15) | 0.0465 (13) | 0.0512 (12) | −0.0306 (11) | 0.0359 (12) | −0.0217 (11) |
C31 | 0.0691 (16) | 0.0365 (12) | 0.0708 (15) | −0.0124 (11) | 0.0443 (13) | 0.0026 (11) |
C32 | 0.0375 (11) | 0.0393 (11) | 0.0579 (12) | −0.0066 (9) | 0.0251 (10) | 0.0061 (10) |
C33 | 0.0295 (9) | 0.0208 (8) | 0.0234 (8) | −0.0032 (7) | 0.0143 (7) | −0.0025 (7) |
C34 | 0.0318 (10) | 0.0437 (11) | 0.0352 (9) | −0.0068 (8) | 0.0185 (8) | −0.0109 (8) |
C35 | 0.0446 (11) | 0.0396 (11) | 0.0409 (10) | −0.0035 (9) | 0.0302 (9) | −0.0078 (9) |
C36 | 0.0531 (12) | 0.0235 (9) | 0.0255 (8) | −0.0022 (8) | 0.0227 (8) | −0.0013 (7) |
C37 | 0.0372 (10) | 0.0331 (10) | 0.0224 (8) | −0.0042 (8) | 0.0110 (7) | −0.0013 (8) |
C38 | 0.0289 (9) | 0.0300 (9) | 0.0273 (8) | −0.0010 (7) | 0.0151 (7) | 0.0007 (7) |
I1—Cu1 | 2.6145 (12) | C15—C20 | 1.396 (3) |
Cu1—N2 | 2.0721 (18) | C15—C16 | 1.397 (2) |
Cu1—N1 | 2.0851 (19) | C16—C17 | 1.380 (3) |
Cu1—P1 | 2.2119 (13) | C17—C18 | 1.378 (3) |
P1—C33 | 1.8329 (19) | C17—H17 | 0.9500 |
P1—C21 | 1.8329 (18) | C18—C19 | 1.380 (3) |
P1—C27 | 1.8337 (19) | C18—H18 | 0.9500 |
O1—N3 | 1.208 (2) | C19—C20 | 1.375 (3) |
O2—N3 | 1.208 (2) | C19—H19 | 0.9500 |
O3—N4 | 1.223 (2) | C20—H20 | 0.9500 |
O4—N4 | 1.228 (2) | C21—C26 | 1.386 (2) |
N1—C3 | 1.275 (2) | C21—C22 | 1.392 (2) |
N1—C1 | 1.472 (2) | C22—C23 | 1.386 (3) |
N2—C12 | 1.280 (2) | C22—H22 | 0.9500 |
N2—C2 | 1.474 (2) | C23—C24 | 1.367 (3) |
N3—C7 | 1.472 (3) | C23—H23 | 0.9500 |
N4—C16 | 1.475 (2) | C24—C25 | 1.374 (3) |
C1—C2 | 1.509 (2) | C24—H24 | 0.9500 |
C1—H1A | 0.9900 | C25—C26 | 1.391 (3) |
C1—H1B | 0.9900 | C25—H25 | 0.9500 |
C2—H2A | 0.9900 | C26—H26 | 0.9500 |
C2—H2B | 0.9900 | C27—C28 | 1.374 (3) |
C3—C4 | 1.448 (2) | C27—C32 | 1.386 (3) |
C3—H3 | 0.9500 | C28—C29 | 1.395 (3) |
C4—C5 | 1.334 (2) | C28—H28 | 0.9500 |
C4—H4 | 0.9500 | C29—C30 | 1.362 (3) |
C5—C6 | 1.466 (3) | C29—H29 | 0.9500 |
C5—H5 | 0.9500 | C30—C31 | 1.368 (3) |
C6—C11 | 1.400 (3) | C30—H30 | 0.9500 |
C6—C7 | 1.405 (3) | C31—C32 | 1.383 (3) |
C7—C8 | 1.382 (3) | C31—H31 | 0.9500 |
C8—C9 | 1.368 (3) | C32—H32 | 0.9500 |
C8—H8 | 0.9500 | C33—C34 | 1.389 (3) |
C9—C10 | 1.381 (3) | C33—C38 | 1.395 (2) |
C9—H9 | 0.9500 | C34—C35 | 1.387 (3) |
C10—C11 | 1.373 (3) | C34—H34 | 0.9500 |
C10—H10 | 0.9500 | C35—C36 | 1.382 (3) |
C11—H11 | 0.9500 | C35—H35 | 0.9500 |
C12—C13 | 1.447 (2) | C36—C37 | 1.373 (3) |
C12—H12 | 0.9500 | C36—H36 | 0.9500 |
C13—C14 | 1.332 (2) | C37—C38 | 1.395 (2) |
C13—H13 | 0.9500 | C37—H37 | 0.9500 |
C14—C15 | 1.474 (2) | C38—H38 | 0.9500 |
C14—H14 | 0.9500 | ||
N2—Cu1—N1 | 82.40 (5) | C20—C15—C16 | 115.43 (16) |
N2—Cu1—P1 | 116.96 (4) | C20—C15—C14 | 121.45 (15) |
N1—Cu1—P1 | 121.76 (5) | C16—C15—C14 | 123.10 (16) |
N2—Cu1—I1 | 112.09 (6) | C17—C16—C15 | 123.44 (18) |
N1—Cu1—I1 | 104.03 (4) | C17—C16—N4 | 116.27 (16) |
P1—Cu1—I1 | 115.08 (4) | C15—C16—N4 | 120.25 (15) |
C33—P1—C21 | 102.67 (8) | C18—C17—C16 | 118.62 (18) |
C33—P1—C27 | 101.74 (7) | C18—C17—H17 | 120.7 |
C21—P1—C27 | 104.74 (9) | C16—C17—H17 | 120.7 |
C33—P1—Cu1 | 118.30 (6) | C17—C18—C19 | 120.15 (18) |
C21—P1—Cu1 | 115.06 (7) | C17—C18—H18 | 119.9 |
C27—P1—Cu1 | 112.58 (7) | C19—C18—H18 | 119.9 |
C3—N1—C1 | 118.26 (14) | C20—C19—C18 | 120.0 (2) |
C3—N1—Cu1 | 130.38 (12) | C20—C19—H19 | 120.0 |
C1—N1—Cu1 | 110.27 (10) | C18—C19—H19 | 120.0 |
C12—N2—C2 | 118.06 (15) | C19—C20—C15 | 122.27 (17) |
C12—N2—Cu1 | 133.68 (12) | C19—C20—H20 | 118.9 |
C2—N2—Cu1 | 108.17 (10) | C15—C20—H20 | 118.9 |
O2—N3—O1 | 122.45 (19) | C26—C21—C22 | 117.78 (15) |
O2—N3—C7 | 118.44 (19) | C26—C21—P1 | 122.75 (13) |
O1—N3—C7 | 119.07 (17) | C22—C21—P1 | 119.22 (13) |
O3—N4—O4 | 124.75 (17) | C23—C22—C21 | 121.09 (17) |
O3—N4—C16 | 117.94 (15) | C23—C22—H22 | 119.5 |
O4—N4—C16 | 117.27 (16) | C21—C22—H22 | 119.5 |
N1—C1—C2 | 109.84 (14) | C24—C23—C22 | 120.21 (18) |
N1—C1—H1A | 109.7 | C24—C23—H23 | 119.9 |
C2—C1—H1A | 109.7 | C22—C23—H23 | 119.9 |
N1—C1—H1B | 109.7 | C23—C24—C25 | 119.91 (18) |
C2—C1—H1B | 109.7 | C23—C24—H24 | 120.0 |
H1A—C1—H1B | 108.2 | C25—C24—H24 | 120.0 |
N2—C2—C1 | 108.51 (15) | C24—C25—C26 | 120.12 (19) |
N2—C2—H2A | 110.0 | C24—C25—H25 | 119.9 |
C1—C2—H2A | 110.0 | C26—C25—H25 | 119.9 |
N2—C2—H2B | 110.0 | C21—C26—C25 | 120.89 (17) |
C1—C2—H2B | 110.0 | C21—C26—H26 | 119.6 |
H2A—C2—H2B | 108.4 | C25—C26—H26 | 119.6 |
N1—C3—C4 | 121.80 (15) | C28—C27—C32 | 117.91 (17) |
N1—C3—H3 | 119.1 | C28—C27—P1 | 125.74 (15) |
C4—C3—H3 | 119.1 | C32—C27—P1 | 116.35 (14) |
C5—C4—C3 | 122.70 (16) | C27—C28—C29 | 120.6 (2) |
C5—C4—H4 | 118.7 | C27—C28—H28 | 119.7 |
C3—C4—H4 | 118.7 | C29—C28—H28 | 119.7 |
C4—C5—C6 | 124.17 (16) | C30—C29—C28 | 120.8 (2) |
C4—C5—H5 | 117.9 | C30—C29—H29 | 119.6 |
C6—C5—H5 | 117.9 | C28—C29—H29 | 119.6 |
C11—C6—C7 | 115.05 (18) | C29—C30—C31 | 119.20 (19) |
C11—C6—C5 | 119.83 (16) | C29—C30—H30 | 120.4 |
C7—C6—C5 | 124.99 (16) | C31—C30—H30 | 120.4 |
C8—C7—C6 | 123.11 (18) | C30—C31—C32 | 120.4 (2) |
C8—C7—N3 | 115.92 (17) | C30—C31—H31 | 119.8 |
C6—C7—N3 | 120.94 (17) | C32—C31—H31 | 119.8 |
C9—C8—C7 | 119.5 (2) | C31—C32—C27 | 121.1 (2) |
C9—C8—H8 | 120.2 | C31—C32—H32 | 119.5 |
C7—C8—H8 | 120.2 | C27—C32—H32 | 119.5 |
C8—C9—C10 | 119.4 (2) | C34—C33—C38 | 118.49 (15) |
C8—C9—H9 | 120.3 | C34—C33—P1 | 121.89 (13) |
C10—C9—H9 | 120.3 | C38—C33—P1 | 119.60 (13) |
C11—C10—C9 | 120.8 (2) | C35—C34—C33 | 121.02 (17) |
C11—C10—H10 | 119.6 | C35—C34—H34 | 119.5 |
C9—C10—H10 | 119.6 | C33—C34—H34 | 119.5 |
C10—C11—C6 | 122.1 (2) | C36—C35—C34 | 119.88 (18) |
C10—C11—H11 | 118.9 | C36—C35—H35 | 120.1 |
C6—C11—H11 | 118.9 | C34—C35—H35 | 120.1 |
N2—C12—C13 | 120.96 (16) | C37—C36—C35 | 120.04 (16) |
N2—C12—H12 | 119.5 | C37—C36—H36 | 120.0 |
C13—C12—H12 | 119.5 | C35—C36—H36 | 120.0 |
C14—C13—C12 | 123.18 (17) | C36—C37—C38 | 120.31 (16) |
C14—C13—H13 | 118.4 | C36—C37—H37 | 119.8 |
C12—C13—H13 | 118.4 | C38—C37—H37 | 119.8 |
C13—C14—C15 | 124.41 (17) | C33—C38—C37 | 120.23 (17) |
C13—C14—H14 | 117.8 | C33—C38—H38 | 119.9 |
C15—C14—H14 | 117.8 | C37—C38—H38 | 119.9 |
N2—Cu1—P1—C33 | 89.15 (8) | C20—C15—C16—N4 | 177.93 (17) |
N1—Cu1—P1—C33 | −172.78 (7) | C14—C15—C16—N4 | −3.8 (3) |
I1—Cu1—P1—C33 | −45.59 (6) | O3—N4—C16—C17 | 128.03 (19) |
N2—Cu1—P1—C21 | −149.07 (7) | O4—N4—C16—C17 | −50.1 (2) |
N1—Cu1—P1—C21 | −51.00 (8) | O3—N4—C16—C15 | −49.5 (2) |
I1—Cu1—P1—C21 | 76.20 (8) | O4—N4—C16—C15 | 132.40 (18) |
N2—Cu1—P1—C27 | −29.16 (7) | C15—C16—C17—C18 | 2.3 (3) |
N1—Cu1—P1—C27 | 68.91 (7) | N4—C16—C17—C18 | −175.2 (2) |
I1—Cu1—P1—C27 | −163.90 (6) | C16—C17—C18—C19 | −2.7 (4) |
N2—Cu1—N1—C3 | −172.34 (16) | C17—C18—C19—C20 | 0.2 (4) |
P1—Cu1—N1—C3 | 70.57 (15) | C18—C19—C20—C15 | 2.9 (4) |
I1—Cu1—N1—C3 | −61.38 (15) | C16—C15—C20—C19 | −3.2 (3) |
N2—Cu1—N1—C1 | −4.73 (11) | C14—C15—C20—C19 | 178.53 (19) |
P1—Cu1—N1—C1 | −121.81 (10) | C33—P1—C21—C26 | 22.44 (18) |
I1—Cu1—N1—C1 | 106.23 (11) | C27—P1—C21—C26 | 128.39 (16) |
N1—Cu1—N2—C12 | 161.61 (18) | Cu1—P1—C21—C26 | −107.47 (16) |
P1—Cu1—N2—C12 | −76.52 (19) | C33—P1—C21—C22 | −163.50 (15) |
I1—Cu1—N2—C12 | 59.50 (18) | C27—P1—C21—C22 | −57.56 (16) |
N1—Cu1—N2—C2 | −21.93 (11) | Cu1—P1—C21—C22 | 66.59 (16) |
P1—Cu1—N2—C2 | 99.94 (12) | C26—C21—C22—C23 | −0.8 (3) |
I1—Cu1—N2—C2 | −124.04 (11) | P1—C21—C22—C23 | −175.12 (16) |
C3—N1—C1—C2 | −160.48 (15) | C21—C22—C23—C24 | 0.6 (3) |
Cu1—N1—C1—C2 | 30.21 (17) | C22—C23—C24—C25 | 0.2 (4) |
C12—N2—C2—C1 | −138.64 (17) | C23—C24—C25—C26 | −0.8 (4) |
Cu1—N2—C2—C1 | 44.27 (17) | C22—C21—C26—C25 | 0.2 (3) |
N1—C1—C2—N2 | −49.66 (19) | P1—C21—C26—C25 | 174.32 (18) |
C1—N1—C3—C4 | −175.95 (16) | C24—C25—C26—C21 | 0.6 (4) |
Cu1—N1—C3—C4 | −9.2 (2) | C33—P1—C27—C28 | 96.54 (17) |
N1—C3—C4—C5 | 177.32 (17) | C21—P1—C27—C28 | −10.09 (18) |
C3—C4—C5—C6 | −175.87 (16) | Cu1—P1—C27—C28 | −135.81 (16) |
C4—C5—C6—C11 | 25.8 (3) | C33—P1—C27—C32 | −83.40 (15) |
C4—C5—C6—C7 | −158.64 (19) | C21—P1—C27—C32 | 169.97 (14) |
C11—C6—C7—C8 | −1.2 (3) | Cu1—P1—C27—C32 | 44.25 (15) |
C5—C6—C7—C8 | −176.9 (2) | C32—C27—C28—C29 | −0.5 (3) |
C11—C6—C7—N3 | −179.21 (19) | P1—C27—C28—C29 | 179.55 (16) |
C5—C6—C7—N3 | 5.1 (3) | C27—C28—C29—C30 | 0.5 (3) |
O2—N3—C7—C8 | 26.0 (3) | C28—C29—C30—C31 | 0.0 (4) |
O1—N3—C7—C8 | −151.9 (2) | C29—C30—C31—C32 | −0.4 (3) |
O2—N3—C7—C6 | −155.9 (2) | C30—C31—C32—C27 | 0.4 (3) |
O1—N3—C7—C6 | 26.3 (3) | C28—C27—C32—C31 | 0.1 (3) |
C6—C7—C8—C9 | −0.5 (4) | P1—C27—C32—C31 | −179.95 (16) |
N3—C7—C8—C9 | 177.6 (2) | C21—P1—C33—C34 | 58.50 (16) |
C7—C8—C9—C10 | 1.7 (4) | C27—P1—C33—C34 | −49.74 (16) |
C8—C9—C10—C11 | −1.3 (4) | Cu1—P1—C33—C34 | −173.61 (12) |
C9—C10—C11—C6 | −0.5 (4) | C21—P1—C33—C38 | −119.77 (14) |
C7—C6—C11—C10 | 1.7 (3) | C27—P1—C33—C38 | 131.98 (14) |
C5—C6—C11—C10 | 177.7 (2) | Cu1—P1—C33—C38 | 8.11 (15) |
C2—N2—C12—C13 | −177.47 (16) | C38—C33—C34—C35 | 2.0 (3) |
Cu1—N2—C12—C13 | −1.3 (3) | P1—C33—C34—C35 | −176.30 (14) |
N2—C12—C13—C14 | 175.53 (18) | C33—C34—C35—C36 | −1.2 (3) |
C12—C13—C14—C15 | 178.60 (17) | C34—C35—C36—C37 | −0.2 (3) |
C13—C14—C15—C20 | −18.4 (3) | C35—C36—C37—C38 | 0.8 (3) |
C13—C14—C15—C16 | 163.49 (19) | C34—C33—C38—C37 | −1.5 (2) |
C20—C15—C16—C17 | 0.6 (3) | P1—C33—C38—C37 | 176.88 (13) |
C14—C15—C16—C17 | 178.83 (19) | C36—C37—C38—C33 | 0.1 (3) |
Experimental details
Crystal data | |
Chemical formula | [CuI(C20H18N4O4)(C18H15P)] |
Mr | 831.09 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 200 |
a, b, c (Å) | 31.64 (2), 15.586 (10), 17.638 (11) |
β (°) | 122.54 (2) |
V (Å3) | 7333 (8) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.53 |
Crystal size (mm) | 0.35 × 0.35 × 0.12 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID |
Absorption correction | Numerical (ABSCOR; Higashi, 1999) |
Tmin, Tmax | 0.617, 0.838 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 31361, 8296, 6482 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.648 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.022, 0.051, 0.94 |
No. of reflections | 8296 |
No. of parameters | 442 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.51, −0.50 |
Computer programs: PROCESS-AUTO (Rigaku, 1998), PROCESS-AUTO, CrystalStructure (Rigaku/MSC, 2004), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 2007), SHELXL97.
Cinnamaldehyde and its derivatives condense with ethylenediamine to furnish a range of Schiff base compounds; a small number of such bis(cinnamaldehyde)ethylenediimine ligands have been used to furnish adducts with transition metals (Amirnasr et al., 2005; Amirnasr et al., 2006). The study of the variety of products in self-assembly processes between labile metal ions and flexible multidentate ligands is an interesting topic in supramolecular chemistry. Among such complexes whose structures have been described are, for example, the copper(I) iodide (Kickelbick et al., 2002), (triphenylphosphine)(halogen/pseudohalogeno)copper(I) (Kickelbick et al., 2003), copper(I) perchlorate (Meghdadi et al., 2002), and the cobalt(II) chloride, cobalt(II) bromide and nickel bromide (Amirnasr et al., 2003) adducts. Here, we report the result of the reaction of CuI with N,N'-bis(2-nitrocinnamaldehyde)ethylenediamine and triphenylphosphane, which forms a copper Schiff base complex (Fig. 1). However, the Cu(1)—I(1) bond length of 2.6145 (12) Å is slightly longer than reported (Barron, et al.,1988). The Cu(1)—P(1) distance [2.2119 (13) Å] is slightly longer than in other tetrahedral copper(I) phosphine complexes (Balogh-Heregovich, et al., 1999). While a tetrahedral geometry might be expected for a four coordinated copper(I) center the coordination sphere around copper(I) in this complex is distorted by the restricting bite angle of the chelating ligand. The N(1)—Cu(1)—N(2) angle is only 82.40 (5)°. The I(1)—Cu(1)—P(1) angle is 115.08 (4)°, being somewhat larger than the values for a tetrahedron (Table 1). The longer Cu(1)—I(1) and Cu(1)—P(1) distances and the larger deviations of angles from the ideal tetrahedral angle in this complex may be attributed to the mutual steric effects between the bulky I atom and the PPh3 ligand. The single bond distance of C(3)—C(4), 1.448 (2) Å being slightly shorter than C(1)—C(2), 1.509 (2) Å indicates the existence of an extended electron delocalization in this complex.