Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680704281X/xu2320sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680704281X/xu2320Isup2.hkl |
CCDC reference: 622724
Key indicators
- Single-crystal X-ray study
- T = 200 K
- Mean (C-C) = 0.004 Å
- R factor = 0.027
- wR factor = 0.059
- Data-to-parameter ratio = 18.3
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X) Br1 - Cu1 .. 13.28 su PLAT430_ALERT_2_B Short Inter D...A Contact O3 .. O3 .. 2.79 Ang.
Alert level C PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.99 Ratio PLAT230_ALERT_2_C Hirshfeld Test Diff for O3 - N4 .. 6.81 su PLAT230_ALERT_2_C Hirshfeld Test Diff for C36 - C37 .. 5.27 su PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for N3 PLAT432_ALERT_2_C Short Inter X...Y Contact O3 .. C3 .. 2.99 Ang.
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1 (1) 1.08
0 ALERT level A = In general: serious problem 2 ALERT level B = Potentially serious problem 5 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 7 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 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
To a solution of 143 mg (1 mmol) CuBr 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 needle like red crystals suitable for X-ray studies. The crystals were collectedand dried in vacuo.
All H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H = 0.95 (aromatic) or 0.99 Å (methylene), Uiso(H) = 1.2 Ueq(C).
The coordination chemistry of copper(I) complexes has received increased attention over the last decades. This is mainly due to the potential application of these complexes in catalytic processes (Striejewske, 1998) photosensitization reactions (Bren et al., 1991) and light harvesting studies (Horvath, 1994). The steric, electronic, and conformational effects imparted by the coordinated ligands play an important role in modifying the properties of the prepared metal complex. A thorough understanding of these effects will serve as the basis for a rational design of complexes with specific and predictable properties. Here we report the synthesis and characterization of a new complex, (I), as well as molecular structure from single-crystal X-ray analysis. Here, we reported the results of the reaction of Cu(I) with N,N'-bis(2-nitrocinnamaldehyde)ethylenediamine and triphenylphosphine, which forms a copper Schiff base complex (Fig. 1).
The bond lengths and angles (Table 1) around the Cu in (I) are good agreement with the found in similar copper complexes. The Cu(1)—Br(1) bond lengths of 2.4411 (11) Å agree well with the same distance in other tetrahedral copper(I) complexes. The Cu(1)—P(1) distances are 2.2069 (13) Å which agree well with the same distances in other tetrahedral copper(I) phosphine complexes (Barron et al., 1988). 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 82.15 (7)°. The Br(1)—Cu(1)—P(1)angle is 114.54 (4)°, being somewhat larger than the values for a tetrahedron (Table 1). The single bond distance of C(3)—C(4), 1.446 (3) Å being slightly shorter than C(1)—C(2), 1.490 (3) Å indicates the existence of an extended electron delocalization in this complex.
For general background, see: Bren et al. (1991); Horvath (1994); Striejewske (1998). For related structures, see: Barron et al. (1988).
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); 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 (Sheldrick, 1997).
Fig. 1. The molecular structure of compound, with atom labels and 50% probability displacement ellipsoids. |
[CuBr(C18H15P)(C9H7NO2)2(C2H4N2)] | F(000) = 3200 |
Mr = 784.10 | Dx = 1.464 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71075 Å |
Hall symbol: -C 2yc | Cell parameters from 17438 reflections |
a = 31.288 (19) Å | θ = 3.0–27.4° |
b = 15.486 (9) Å | µ = 1.83 mm−1 |
c = 17.381 (10) Å | T = 200 K |
β = 122.34 (2)° | Block, red |
V = 7116 (7) Å3 | 0.26 × 0.20 × 0.18 mm |
Z = 8 |
Rigaku R-AXIS RAPID IP diffractometer | 8101 independent reflections |
Radiation source: fine-focus sealed tube | 5147 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
Detector resolution: 10.00 pixels mm-1 | θmax = 27.4°, θmin = 3.0° |
ω scans | h = −40→40 |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −20→19 |
Tmin = 0.635, Tmax = 0.720 | l = −22→18 |
24792 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)] = 0.027 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.059 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.022P)2] where P = (Fo2 + 2Fc2)/3 |
8101 reflections | (Δ/σ)max = 0.003 |
443 parameters | Δρmax = 0.45 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
[CuBr(C18H15P)(C9H7NO2)2(C2H4N2)] | V = 7116 (7) Å3 |
Mr = 784.10 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 31.288 (19) Å | µ = 1.83 mm−1 |
b = 15.486 (9) Å | T = 200 K |
c = 17.381 (10) Å | 0.26 × 0.20 × 0.18 mm |
β = 122.34 (2)° |
Rigaku R-AXIS RAPID IP diffractometer | 8101 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 5147 reflections with I > 2σ(I) |
Tmin = 0.635, Tmax = 0.720 | Rint = 0.027 |
24792 measured reflections |
R[F2 > 2σ(F2)] = 0.027 | 0 restraints |
wR(F2) = 0.059 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.45 e Å−3 |
8101 reflections | Δρmin = −0.36 e Å−3 |
443 parameters |
x | y | z | Uiso*/Ueq | ||
Br1 | 0.73895 (1) | 0.21194 (2) | 0.27023 (2) | 0.04174 (8) | |
Cu1 | 0.66984 (1) | 0.10741 (2) | 0.20239 (2) | 0.02458 (7) | |
P1 | 0.60586 (2) | 0.14022 (3) | 0.21692 (4) | 0.02312 (13) | |
O1 | 0.54777 (9) | 0.29990 (12) | −0.25066 (12) | 0.0780 (7) | |
O2 | 0.56141 (11) | 0.41867 (13) | −0.29544 (14) | 0.1012 (9) | |
O3 | 0.74427 (7) | −0.20459 (10) | 0.56309 (12) | 0.0417 (4) | |
O4 | 0.82159 (7) | −0.22703 (11) | 0.67454 (12) | 0.0562 (5) | |
N1 | 0.65620 (6) | 0.07940 (10) | 0.07370 (11) | 0.0241 (4) | |
N2 | 0.69483 (7) | −0.01979 (11) | 0.22714 (12) | 0.0292 (4) | |
N3 | 0.56248 (9) | 0.37427 (14) | −0.23709 (14) | 0.0498 (6) | |
N4 | 0.78663 (9) | −0.18000 (12) | 0.62149 (14) | 0.0357 (5) | |
C1 | 0.67318 (10) | −0.00878 (13) | 0.07142 (15) | 0.0370 (6) | |
H1A | 0.7082 | −0.0068 | 0.0849 | 0.044* | |
H1B | 0.6511 | −0.0334 | 0.0097 | 0.044* | |
C2 | 0.67151 (10) | −0.06515 (14) | 0.13921 (15) | 0.0428 (6) | |
H2A | 0.6360 | −0.0798 | 0.1174 | 0.051* | |
H2B | 0.6900 | −0.1196 | 0.1468 | 0.051* | |
C3 | 0.64364 (8) | 0.12863 (13) | 0.00597 (14) | 0.0276 (5) | |
H3 | 0.6436 | 0.1062 | −0.0449 | 0.033* | |
C4 | 0.62938 (8) | 0.21775 (13) | 0.00451 (14) | 0.0276 (5) | |
H4 | 0.6291 | 0.2396 | 0.0553 | 0.033* | |
C5 | 0.61667 (8) | 0.27048 (13) | −0.06515 (14) | 0.0283 (5) | |
H5 | 0.6157 | 0.2468 | −0.1165 | 0.034* | |
C6 | 0.60404 (8) | 0.36203 (14) | −0.06876 (15) | 0.0296 (5) | |
C7 | 0.58057 (9) | 0.41257 (13) | −0.14738 (15) | 0.0317 (5) | |
C8 | 0.57179 (10) | 0.49984 (15) | −0.14772 (18) | 0.0477 (7) | |
H8 | 0.5563 | 0.5317 | −0.2029 | 0.057* | |
C9 | 0.58561 (11) | 0.53990 (16) | −0.0676 (2) | 0.0589 (8) | |
H9 | 0.5794 | 0.5999 | −0.0668 | 0.071* | |
C10 | 0.60830 (13) | 0.49345 (17) | 0.0113 (2) | 0.0689 (9) | |
H10 | 0.6176 | 0.5212 | 0.0669 | 0.083* | |
C11 | 0.61791 (11) | 0.40660 (15) | 0.01102 (17) | 0.0487 (7) | |
H11 | 0.6345 | 0.3761 | 0.0671 | 0.058* | |
C12 | 0.72131 (9) | −0.06427 (14) | 0.29956 (15) | 0.0314 (5) | |
H12 | 0.7277 | −0.1234 | 0.2948 | 0.038* | |
C13 | 0.74164 (8) | −0.02660 (14) | 0.38822 (15) | 0.0302 (5) | |
H13 | 0.7385 | 0.0340 | 0.3920 | 0.036* | |
C14 | 0.76468 (8) | −0.07209 (14) | 0.46547 (14) | 0.0294 (5) | |
H14 | 0.7683 | −0.1325 | 0.4611 | 0.035* | |
C15 | 0.78476 (8) | −0.03598 (14) | 0.55608 (15) | 0.0288 (5) | |
C16 | 0.79624 (8) | −0.08569 (13) | 0.63139 (15) | 0.0290 (5) | |
C17 | 0.81345 (10) | −0.05208 (16) | 0.71668 (16) | 0.0470 (7) | |
H17 | 0.8209 | −0.0888 | 0.7661 | 0.056* | |
C18 | 0.81954 (11) | 0.03615 (17) | 0.72838 (17) | 0.0588 (8) | |
H18 | 0.8301 | 0.0611 | 0.7858 | 0.071* | |
C19 | 0.81029 (10) | 0.08818 (16) | 0.65625 (17) | 0.0476 (7) | |
H19 | 0.8152 | 0.1488 | 0.6647 | 0.057* | |
C20 | 0.79407 (9) | 0.05265 (15) | 0.57269 (16) | 0.0371 (6) | |
H20 | 0.7890 | 0.0893 | 0.5246 | 0.044* | |
C21 | 0.56473 (8) | 0.22662 (13) | 0.14153 (14) | 0.0259 (5) | |
C22 | 0.56463 (9) | 0.30877 (14) | 0.17307 (16) | 0.0374 (6) | |
H22 | 0.5843 | 0.3204 | 0.2366 | 0.045* | |
C23 | 0.53600 (10) | 0.37431 (15) | 0.11253 (17) | 0.0527 (8) | |
H23 | 0.5367 | 0.4306 | 0.1348 | 0.063* | |
C24 | 0.50679 (10) | 0.35815 (16) | 0.02082 (17) | 0.0441 (7) | |
H24 | 0.4869 | 0.4030 | −0.0203 | 0.053* | |
C25 | 0.50631 (9) | 0.27697 (15) | −0.01143 (16) | 0.0419 (6) | |
H25 | 0.4862 | 0.2656 | −0.0749 | 0.050* | |
C26 | 0.53508 (9) | 0.21187 (15) | 0.04829 (15) | 0.0347 (6) | |
H26 | 0.5346 | 0.1560 | 0.0253 | 0.042* | |
C27 | 0.56290 (8) | 0.04926 (13) | 0.19192 (14) | 0.0243 (5) | |
C28 | 0.51085 (9) | 0.05384 (16) | 0.14222 (16) | 0.0401 (6) | |
H28 | 0.4947 | 0.1079 | 0.1187 | 0.048* | |
C29 | 0.48189 (10) | −0.01954 (17) | 0.12612 (18) | 0.0493 (7) | |
H29 | 0.4460 | −0.0154 | 0.0914 | 0.059* | |
C30 | 0.50445 (10) | −0.09786 (16) | 0.15978 (17) | 0.0436 (7) | |
H30 | 0.4844 | −0.1480 | 0.1484 | 0.052* | |
C31 | 0.55592 (11) | −0.10335 (16) | 0.20979 (18) | 0.0493 (7) | |
H31 | 0.5718 | −0.1575 | 0.2336 | 0.059* | |
C32 | 0.58499 (9) | −0.03061 (14) | 0.22597 (16) | 0.0385 (6) | |
H32 | 0.6208 | −0.0353 | 0.2611 | 0.046* | |
C33 | 0.62006 (8) | 0.17584 (12) | 0.32871 (13) | 0.0232 (5) | |
C34 | 0.58210 (8) | 0.18790 (14) | 0.34743 (15) | 0.0322 (5) | |
H34 | 0.5480 | 0.1745 | 0.3022 | 0.039* | |
C35 | 0.59388 (9) | 0.21907 (14) | 0.43110 (15) | 0.0337 (6) | |
H35 | 0.5678 | 0.2280 | 0.4428 | 0.040* | |
C36 | 0.64343 (9) | 0.23719 (13) | 0.49750 (15) | 0.0318 (6) | |
H36 | 0.6514 | 0.2592 | 0.5547 | 0.038* | |
C37 | 0.68139 (9) | 0.22356 (13) | 0.48133 (14) | 0.0303 (5) | |
H37 | 0.7155 | 0.2351 | 0.5277 | 0.036* | |
C38 | 0.66975 (8) | 0.19283 (13) | 0.39707 (14) | 0.0264 (5) | |
H38 | 0.6961 | 0.1834 | 0.3862 | 0.032* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0467 (2) | 0.0473 (2) | 0.0391 (1) | −0.0234 (1) | 0.0282 (1) | −0.0204 (1) |
Cu1 | 0.0291 (2) | 0.0222 (1) | 0.0232 (1) | 0.0003 (1) | 0.0145 (1) | −0.0010 (1) |
P1 | 0.0246 (3) | 0.0226 (3) | 0.0205 (3) | −0.0019 (2) | 0.0110 (3) | −0.0027 (2) |
O1 | 0.1120 (19) | 0.0389 (12) | 0.0386 (12) | 0.0062 (12) | 0.0105 (13) | −0.0057 (9) |
O2 | 0.185 (3) | 0.0627 (15) | 0.0401 (14) | 0.0130 (16) | 0.0493 (16) | 0.0177 (11) |
O3 | 0.0517 (12) | 0.0331 (10) | 0.0443 (11) | −0.0100 (9) | 0.0284 (10) | −0.0077 (8) |
O4 | 0.0698 (14) | 0.0464 (11) | 0.0583 (13) | 0.0251 (10) | 0.0382 (12) | 0.0217 (10) |
N1 | 0.0282 (11) | 0.0232 (9) | 0.0216 (10) | −0.0019 (8) | 0.0138 (9) | −0.0008 (8) |
N2 | 0.0399 (12) | 0.0248 (10) | 0.0227 (11) | 0.0037 (9) | 0.0167 (10) | −0.0008 (8) |
N3 | 0.0670 (17) | 0.0371 (13) | 0.0280 (13) | 0.0115 (12) | 0.0139 (12) | 0.0051 (11) |
N4 | 0.0510 (15) | 0.0319 (11) | 0.0374 (13) | 0.0073 (11) | 0.0324 (13) | 0.0071 (10) |
C1 | 0.0563 (18) | 0.0240 (12) | 0.0286 (14) | 0.0024 (12) | 0.0212 (14) | −0.0029 (10) |
C2 | 0.0640 (19) | 0.0249 (13) | 0.0306 (14) | 0.0034 (13) | 0.0193 (14) | −0.0036 (11) |
C3 | 0.0304 (14) | 0.0277 (13) | 0.0220 (12) | −0.0025 (10) | 0.0122 (11) | −0.0032 (10) |
C4 | 0.0298 (13) | 0.0295 (12) | 0.0240 (12) | −0.0022 (10) | 0.0147 (11) | −0.0022 (10) |
C5 | 0.0329 (14) | 0.0301 (13) | 0.0233 (12) | −0.0002 (10) | 0.0159 (12) | −0.0008 (10) |
C6 | 0.0323 (14) | 0.0255 (12) | 0.0290 (13) | −0.0023 (10) | 0.0150 (12) | −0.0014 (10) |
C7 | 0.0327 (14) | 0.0278 (13) | 0.0298 (14) | 0.0004 (11) | 0.0135 (12) | −0.0013 (10) |
C8 | 0.0587 (19) | 0.0295 (14) | 0.0453 (17) | 0.0062 (13) | 0.0214 (16) | 0.0077 (12) |
C9 | 0.078 (2) | 0.0256 (14) | 0.065 (2) | 0.0047 (15) | 0.0322 (19) | −0.0057 (14) |
C10 | 0.113 (3) | 0.0371 (17) | 0.0447 (19) | 0.0046 (17) | 0.034 (2) | −0.0119 (14) |
C11 | 0.077 (2) | 0.0341 (15) | 0.0359 (16) | 0.0030 (14) | 0.0309 (16) | −0.0019 (12) |
C12 | 0.0428 (15) | 0.0213 (12) | 0.0295 (14) | 0.0063 (11) | 0.0190 (13) | 0.0019 (10) |
C13 | 0.0361 (15) | 0.0245 (12) | 0.0310 (14) | 0.0040 (11) | 0.0186 (13) | 0.0008 (10) |
C14 | 0.0345 (14) | 0.0243 (12) | 0.0290 (13) | 0.0017 (10) | 0.0166 (12) | 0.0018 (10) |
C15 | 0.0238 (13) | 0.0300 (13) | 0.0269 (13) | 0.0004 (10) | 0.0099 (12) | 0.0017 (10) |
C16 | 0.0323 (14) | 0.0296 (13) | 0.0281 (13) | −0.0008 (10) | 0.0181 (12) | 0.0010 (10) |
C17 | 0.0655 (19) | 0.0460 (16) | 0.0254 (14) | −0.0055 (14) | 0.0215 (15) | 0.0030 (12) |
C18 | 0.088 (2) | 0.0463 (17) | 0.0291 (16) | −0.0205 (16) | 0.0231 (17) | −0.0127 (13) |
C19 | 0.0615 (19) | 0.0357 (15) | 0.0388 (16) | −0.0153 (13) | 0.0224 (15) | −0.0070 (12) |
C20 | 0.0401 (16) | 0.0324 (14) | 0.0310 (14) | −0.0070 (12) | 0.0139 (13) | 0.0017 (11) |
C21 | 0.0239 (13) | 0.0281 (12) | 0.0233 (12) | 0.0004 (10) | 0.0110 (11) | 0.0012 (10) |
C22 | 0.0506 (17) | 0.0265 (13) | 0.0244 (13) | 0.0009 (12) | 0.0129 (13) | −0.0024 (11) |
C23 | 0.079 (2) | 0.0283 (15) | 0.0369 (17) | 0.0120 (14) | 0.0212 (16) | 0.0005 (12) |
C24 | 0.0541 (18) | 0.0396 (15) | 0.0339 (16) | 0.0157 (13) | 0.0204 (15) | 0.0114 (12) |
C25 | 0.0453 (16) | 0.0479 (16) | 0.0220 (13) | 0.0089 (13) | 0.0110 (13) | 0.0013 (12) |
C26 | 0.0417 (15) | 0.0331 (13) | 0.0259 (13) | 0.0055 (12) | 0.0159 (12) | −0.0039 (11) |
C27 | 0.0282 (13) | 0.0251 (12) | 0.0251 (13) | −0.0057 (10) | 0.0180 (12) | −0.0079 (10) |
C28 | 0.0323 (16) | 0.0351 (14) | 0.0455 (16) | −0.0053 (12) | 0.0159 (14) | −0.0054 (12) |
C29 | 0.0287 (16) | 0.0554 (18) | 0.0514 (18) | −0.0173 (14) | 0.0131 (14) | −0.0148 (15) |
C30 | 0.0582 (19) | 0.0388 (16) | 0.0444 (16) | −0.0257 (14) | 0.0346 (16) | −0.0168 (13) |
C31 | 0.060 (2) | 0.0283 (14) | 0.0591 (19) | −0.0071 (14) | 0.0311 (17) | 0.0033 (13) |
C32 | 0.0345 (15) | 0.0352 (14) | 0.0471 (16) | −0.0045 (12) | 0.0226 (14) | 0.0050 (12) |
C33 | 0.0276 (13) | 0.0177 (11) | 0.0198 (12) | −0.0008 (9) | 0.0098 (11) | 0.0004 (9) |
C34 | 0.0270 (14) | 0.0361 (13) | 0.0320 (14) | −0.0058 (11) | 0.0147 (12) | −0.0063 (11) |
C35 | 0.0426 (16) | 0.0303 (13) | 0.0345 (14) | −0.0008 (12) | 0.0248 (13) | −0.0035 (11) |
C36 | 0.0526 (17) | 0.0210 (12) | 0.0229 (13) | −0.0025 (11) | 0.0210 (13) | −0.0015 (10) |
C37 | 0.0320 (14) | 0.0316 (13) | 0.0231 (12) | −0.0043 (11) | 0.0120 (12) | −0.0017 (10) |
C38 | 0.0311 (14) | 0.0250 (12) | 0.0269 (13) | −0.0010 (10) | 0.0181 (12) | 0.0013 (10) |
Cu1—Br1 | 2.4411 (11) | C15—C16 | 1.390 (3) |
Cu1—N1 | 2.086 (2) | C15—C20 | 1.401 (3) |
Cu1—N2 | 2.078 (2) | C16—C17 | 1.380 (3) |
Cu1—P1 | 2.2069 (13) | C17—C18 | 1.380 (3) |
P1—C33 | 1.831 (2) | C17—H17 | 0.9500 |
P1—C27 | 1.832 (2) | C18—C19 | 1.384 (3) |
P1—C21 | 1.833 (2) | C18—H18 | 0.9500 |
O1—N3 | 1.216 (3) | C19—C20 | 1.371 (3) |
O2—N3 | 1.211 (3) | C19—H19 | 0.9500 |
O3—N4 | 1.222 (2) | C20—H20 | 0.9500 |
O4—N4 | 1.224 (2) | C21—C22 | 1.386 (3) |
N1—C3 | 1.275 (2) | C21—C26 | 1.390 (3) |
N1—C1 | 1.473 (3) | C22—C23 | 1.390 (3) |
N2—C12 | 1.277 (3) | C22—H22 | 0.9500 |
N2—C2 | 1.473 (3) | C23—C24 | 1.371 (3) |
N3—C7 | 1.470 (3) | C23—H23 | 0.9500 |
N4—C16 | 1.482 (3) | C24—C25 | 1.373 (3) |
C1—C2 | 1.490 (3) | C24—H24 | 0.9500 |
C1—H1A | 0.9900 | C25—C26 | 1.380 (3) |
C1—H1B | 0.9900 | C25—H25 | 0.9500 |
C2—H2A | 0.9900 | C26—H26 | 0.9500 |
C2—H2B | 0.9900 | C27—C28 | 1.378 (3) |
C3—C4 | 1.446 (3) | C27—C32 | 1.386 (3) |
C3—H3 | 0.9500 | C28—C29 | 1.385 (3) |
C4—C5 | 1.333 (3) | C28—H28 | 0.9500 |
C4—H4 | 0.9500 | C29—C30 | 1.367 (3) |
C5—C6 | 1.464 (3) | C29—H29 | 0.9500 |
C5—H5 | 0.9500 | C30—C31 | 1.363 (4) |
C6—C11 | 1.394 (3) | C30—H30 | 0.9500 |
C6—C7 | 1.395 (3) | C31—C32 | 1.379 (3) |
C7—C8 | 1.379 (3) | C31—H31 | 0.9500 |
C8—C9 | 1.367 (3) | C32—H32 | 0.9500 |
C8—H8 | 0.9500 | C33—C38 | 1.386 (3) |
C9—C10 | 1.363 (4) | C33—C34 | 1.402 (3) |
C9—H9 | 0.9500 | C34—C35 | 1.382 (3) |
C10—C11 | 1.379 (3) | C34—H34 | 0.9500 |
C10—H10 | 0.9500 | C35—C36 | 1.378 (3) |
C11—H11 | 0.9500 | C35—H35 | 0.9500 |
C12—C13 | 1.439 (3) | C36—C37 | 1.375 (3) |
C12—H12 | 0.9500 | C36—H36 | 0.9500 |
C13—C14 | 1.335 (3) | C37—C38 | 1.390 (3) |
C13—H13 | 0.9500 | C37—H37 | 0.9500 |
C14—C15 | 1.459 (3) | C38—H38 | 0.9500 |
C14—H14 | 0.9500 | ||
N2—Cu1—N1 | 82.15 (7) | C16—C15—C20 | 115.3 (2) |
N2—Cu1—P1 | 117.29 (5) | C16—C15—C14 | 123.3 (2) |
N1—Cu1—P1 | 119.52 (6) | C20—C15—C14 | 121.33 (19) |
N2—Cu1—Br1 | 113.00 (7) | C17—C16—C15 | 124.0 (2) |
N1—Cu1—Br1 | 106.03 (5) | C17—C16—N4 | 115.76 (19) |
P1—Cu1—Br1 | 114.54 (4) | C15—C16—N4 | 120.14 (19) |
C33—P1—C27 | 102.37 (9) | C18—C17—C16 | 118.4 (2) |
C33—P1—C21 | 102.58 (10) | C18—C17—H17 | 120.8 |
C27—P1—C21 | 104.26 (11) | C16—C17—H17 | 120.8 |
C33—P1—Cu1 | 118.08 (8) | C17—C18—C19 | 119.8 (2) |
C27—P1—Cu1 | 113.04 (7) | C17—C18—H18 | 120.1 |
C21—P1—Cu1 | 114.78 (7) | C19—C18—H18 | 120.1 |
C3—N1—C1 | 117.83 (17) | C20—C19—C18 | 120.3 (2) |
C3—N1—Cu1 | 130.59 (15) | C20—C19—H19 | 119.8 |
C1—N1—Cu1 | 110.58 (12) | C18—C19—H19 | 119.8 |
C12—N2—C2 | 117.77 (18) | C19—C20—C15 | 122.0 (2) |
C12—N2—Cu1 | 133.60 (15) | C19—C20—H20 | 119.0 |
C2—N2—Cu1 | 108.34 (13) | C15—C20—H20 | 119.0 |
O2—N3—O1 | 122.5 (2) | C22—C21—C26 | 118.1 (2) |
O2—N3—C7 | 118.8 (2) | C22—C21—P1 | 122.45 (17) |
O1—N3—C7 | 118.6 (2) | C26—C21—P1 | 119.29 (17) |
O3—N4—O4 | 125.1 (2) | C21—C22—C23 | 120.5 (2) |
O3—N4—C16 | 117.8 (2) | C21—C22—H22 | 119.7 |
O4—N4—C16 | 117.0 (2) | C23—C22—H22 | 119.7 |
N1—C1—C2 | 110.86 (17) | C24—C23—C22 | 120.4 (2) |
N1—C1—H1A | 109.5 | C24—C23—H23 | 119.8 |
C2—C1—H1A | 109.5 | C22—C23—H23 | 119.8 |
N1—C1—H1B | 109.5 | C23—C24—C25 | 119.8 (2) |
C2—C1—H1B | 109.5 | C23—C24—H24 | 120.1 |
H1A—C1—H1B | 108.1 | C25—C24—H24 | 120.1 |
N2—C2—C1 | 109.49 (19) | C24—C25—C26 | 120.1 (2) |
N2—C2—H2A | 109.8 | C24—C25—H25 | 120.0 |
C1—C2—H2A | 109.8 | C26—C25—H25 | 120.0 |
N2—C2—H2B | 109.8 | C25—C26—C21 | 121.1 (2) |
C1—C2—H2B | 109.8 | C25—C26—H26 | 119.4 |
H2A—C2—H2B | 108.2 | C21—C26—H26 | 119.4 |
N1—C3—C4 | 121.76 (19) | C28—C27—C32 | 117.8 (2) |
N1—C3—H3 | 119.1 | C28—C27—P1 | 125.49 (18) |
C4—C3—H3 | 119.1 | C32—C27—P1 | 116.74 (17) |
C5—C4—C3 | 122.67 (19) | C27—C28—C29 | 120.7 (2) |
C5—C4—H4 | 118.7 | C27—C28—H28 | 119.6 |
C3—C4—H4 | 118.7 | C29—C28—H28 | 119.6 |
C4—C5—C6 | 125.1 (2) | C30—C29—C28 | 120.6 (2) |
C4—C5—H5 | 117.5 | C30—C29—H29 | 119.7 |
C6—C5—H5 | 117.5 | C28—C29—H29 | 119.7 |
C11—C6—C7 | 114.7 (2) | C31—C30—C29 | 119.4 (2) |
C11—C6—C5 | 120.2 (2) | C31—C30—H30 | 120.3 |
C7—C6—C5 | 125.0 (2) | C29—C30—H30 | 120.3 |
C8—C7—C6 | 123.6 (2) | C30—C31—C32 | 120.3 (2) |
C8—C7—N3 | 115.4 (2) | C30—C31—H31 | 119.9 |
C6—C7—N3 | 121.02 (19) | C32—C31—H31 | 119.9 |
C9—C8—C7 | 119.1 (2) | C31—C32—C27 | 121.2 (2) |
C9—C8—H8 | 120.4 | C31—C32—H32 | 119.4 |
C7—C8—H8 | 120.4 | C27—C32—H32 | 119.4 |
C10—C9—C8 | 119.7 (2) | C38—C33—C34 | 118.48 (19) |
C10—C9—H9 | 120.1 | C38—C33—P1 | 119.40 (15) |
C8—C9—H9 | 120.1 | C34—C33—P1 | 122.11 (17) |
C9—C10—C11 | 120.6 (3) | C35—C34—C33 | 120.6 (2) |
C9—C10—H10 | 119.7 | C35—C34—H34 | 119.7 |
C11—C10—H10 | 119.7 | C33—C34—H34 | 119.7 |
C10—C11—C6 | 122.2 (2) | C36—C35—C34 | 120.0 (2) |
C10—C11—H11 | 118.9 | C36—C35—H35 | 120.0 |
C6—C11—H11 | 118.9 | C34—C35—H35 | 120.0 |
N2—C12—C13 | 121.3 (2) | C37—C36—C35 | 120.3 (2) |
N2—C12—H12 | 119.4 | C37—C36—H36 | 119.8 |
C13—C12—H12 | 119.4 | C35—C36—H36 | 119.8 |
C14—C13—C12 | 123.7 (2) | C36—C37—C38 | 120.0 (2) |
C14—C13—H13 | 118.2 | C36—C37—H37 | 120.0 |
C12—C13—H13 | 118.2 | C38—C37—H37 | 120.0 |
C13—C14—C15 | 124.9 (2) | C33—C38—C37 | 120.62 (19) |
C13—C14—H14 | 117.5 | C33—C38—H38 | 119.7 |
C15—C14—H14 | 117.5 | C37—C38—H38 | 119.7 |
N2—Cu1—P1—C33 | 89.94 (10) | C20—C15—C16—N4 | 178.3 (2) |
N1—Cu1—P1—C33 | −173.43 (9) | C14—C15—C16—N4 | −2.1 (3) |
Br1—Cu1—P1—C33 | −46.02 (8) | O3—N4—C16—C17 | 123.0 (2) |
N2—Cu1—P1—C27 | −29.44 (10) | O4—N4—C16—C17 | −55.0 (3) |
N1—Cu1—P1—C27 | 67.19 (9) | O3—N4—C16—C15 | −52.8 (3) |
Br1—Cu1—P1—C27 | −165.40 (7) | O4—N4—C16—C15 | 129.3 (2) |
N2—Cu1—P1—C21 | −148.85 (9) | C15—C16—C17—C18 | 0.2 (4) |
N1—Cu1—P1—C21 | −52.22 (10) | N4—C16—C17—C18 | −175.3 (2) |
Br1—Cu1—P1—C21 | 75.19 (9) | C16—C17—C18—C19 | −2.5 (4) |
N2—Cu1—N1—C3 | −170.9 (2) | C17—C18—C19—C20 | 1.4 (4) |
P1—Cu1—N1—C3 | 72.10 (19) | C18—C19—C20—C15 | 2.0 (4) |
Br1—Cu1—N1—C3 | −59.15 (19) | C16—C15—C20—C19 | −4.0 (3) |
N2—Cu1—N1—C1 | −2.85 (14) | C14—C15—C20—C19 | 176.3 (2) |
P1—Cu1—N1—C1 | −119.84 (14) | C33—P1—C21—C22 | 22.2 (2) |
Br1—Cu1—N1—C1 | 108.90 (14) | C27—P1—C21—C22 | 128.66 (18) |
N1—Cu1—N2—C12 | 164.7 (2) | Cu1—P1—C21—C22 | −107.14 (18) |
P1—Cu1—N2—C12 | −76.1 (2) | C33—P1—C21—C26 | −162.58 (17) |
Br1—Cu1—N2—C12 | 60.5 (2) | C27—P1—C21—C26 | −56.14 (19) |
N1—Cu1—N2—C2 | −21.89 (14) | Cu1—P1—C21—C26 | 68.06 (19) |
P1—Cu1—N2—C2 | 97.35 (14) | C26—C21—C22—C23 | −0.7 (3) |
Br1—Cu1—N2—C2 | −126.03 (13) | P1—C21—C22—C23 | 174.56 (19) |
C3—N1—C1—C2 | −163.0 (2) | C21—C22—C23—C24 | 1.1 (4) |
Cu1—N1—C1—C2 | 27.2 (2) | C22—C23—C24—C25 | −0.8 (4) |
C12—N2—C2—C1 | −142.5 (2) | C23—C24—C25—C26 | 0.1 (4) |
Cu1—N2—C2—C1 | 42.9 (2) | C24—C25—C26—C21 | 0.3 (4) |
N1—C1—C2—N2 | −46.8 (3) | C22—C21—C26—C25 | 0.0 (3) |
C1—N1—C3—C4 | −176.3 (2) | P1—C21—C26—C25 | −175.39 (18) |
Cu1—N1—C3—C4 | −8.9 (3) | C33—P1—C27—C28 | 94.3 (2) |
N1—C3—C4—C5 | 179.2 (2) | C21—P1—C27—C28 | −12.3 (2) |
C3—C4—C5—C6 | −177.2 (2) | Cu1—P1—C27—C28 | −137.58 (18) |
C4—C5—C6—C11 | 18.0 (3) | C33—P1—C27—C32 | −85.85 (17) |
C4—C5—C6—C7 | −165.5 (2) | C21—P1—C27—C32 | 167.55 (16) |
C11—C6—C7—C8 | 0.5 (4) | Cu1—P1—C27—C32 | 42.24 (18) |
C5—C6—C7—C8 | −176.1 (2) | C32—C27—C28—C29 | −0.9 (3) |
C11—C6—C7—N3 | −178.3 (2) | P1—C27—C28—C29 | 178.95 (17) |
C5—C6—C7—N3 | 5.1 (3) | C27—C28—C29—C30 | 0.4 (4) |
O2—N3—C7—C8 | 30.4 (4) | C28—C29—C30—C31 | 0.2 (4) |
O1—N3—C7—C8 | −147.5 (3) | C29—C30—C31—C32 | −0.3 (4) |
O2—N3—C7—C6 | −150.7 (3) | C30—C31—C32—C27 | −0.2 (4) |
O1—N3—C7—C6 | 31.4 (3) | C28—C27—C32—C31 | 0.8 (3) |
C6—C7—C8—C9 | −1.4 (4) | P1—C27—C32—C31 | −179.06 (18) |
N3—C7—C8—C9 | 177.4 (2) | C27—P1—C33—C38 | 133.75 (17) |
C7—C8—C9—C10 | 0.8 (4) | C21—P1—C33—C38 | −118.36 (17) |
C8—C9—C10—C11 | 0.7 (5) | Cu1—P1—C33—C38 | 8.93 (19) |
C9—C10—C11—C6 | −1.6 (5) | C27—P1—C33—C34 | −47.24 (19) |
C7—C6—C11—C10 | 1.0 (4) | C21—P1—C33—C34 | 60.65 (19) |
C5—C6—C11—C10 | 177.8 (3) | Cu1—P1—C33—C34 | −172.06 (14) |
C2—N2—C12—C13 | −174.4 (2) | C38—C33—C34—C35 | 2.4 (3) |
Cu1—N2—C12—C13 | −1.4 (3) | P1—C33—C34—C35 | −176.67 (16) |
N2—C12—C13—C14 | 172.3 (2) | C33—C34—C35—C36 | −1.1 (3) |
C12—C13—C14—C15 | −178.7 (2) | C34—C35—C36—C37 | −0.7 (3) |
C13—C14—C15—C16 | 162.4 (2) | C35—C36—C37—C38 | 1.2 (3) |
C13—C14—C15—C20 | −18.0 (3) | C34—C33—C38—C37 | −1.9 (3) |
C20—C15—C16—C17 | 2.9 (3) | P1—C33—C38—C37 | 177.19 (15) |
C14—C15—C16—C17 | −177.5 (2) | C36—C37—C38—C33 | 0.1 (3) |
Experimental details
Crystal data | |
Chemical formula | [CuBr(C18H15P)(C9H7NO2)2(C2H4N2)] |
Mr | 784.10 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 200 |
a, b, c (Å) | 31.288 (19), 15.486 (9), 17.381 (10) |
β (°) | 122.34 (2) |
V (Å3) | 7116 (7) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.83 |
Crystal size (mm) | 0.26 × 0.20 × 0.18 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID IP |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.635, 0.720 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24792, 8101, 5147 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.648 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.059, 1.03 |
No. of reflections | 8101 |
No. of parameters | 443 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.45, −0.36 |
Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2004), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 2007).
Cu1—Br1 | 2.4411 (11) | N2—C2 | 1.473 (3) |
Cu1—N1 | 2.086 (2) | N3—C7 | 1.470 (3) |
Cu1—N2 | 2.078 (2) | N4—C16 | 1.482 (3) |
Cu1—P1 | 2.2069 (13) | C1—C2 | 1.490 (3) |
P1—C33 | 1.831 (2) | C3—C4 | 1.446 (3) |
P1—C27 | 1.832 (2) | C4—C5 | 1.333 (3) |
P1—C21 | 1.833 (2) | C5—C6 | 1.464 (3) |
N1—C3 | 1.275 (2) | C12—C13 | 1.439 (3) |
N1—C1 | 1.473 (3) | C13—C14 | 1.335 (3) |
N2—C12 | 1.277 (3) | C14—C15 | 1.459 (3) |
N2—Cu1—N1 | 82.15 (7) | N2—Cu1—Br1 | 113.00 (7) |
N2—Cu1—P1 | 117.29 (5) | N1—Cu1—Br1 | 106.03 (5) |
N1—Cu1—P1 | 119.52 (6) | P1—Cu1—Br1 | 114.54 (4) |
The coordination chemistry of copper(I) complexes has received increased attention over the last decades. This is mainly due to the potential application of these complexes in catalytic processes (Striejewske, 1998) photosensitization reactions (Bren et al., 1991) and light harvesting studies (Horvath, 1994). The steric, electronic, and conformational effects imparted by the coordinated ligands play an important role in modifying the properties of the prepared metal complex. A thorough understanding of these effects will serve as the basis for a rational design of complexes with specific and predictable properties. Here we report the synthesis and characterization of a new complex, (I), as well as molecular structure from single-crystal X-ray analysis. Here, we reported the results of the reaction of Cu(I) with N,N'-bis(2-nitrocinnamaldehyde)ethylenediamine and triphenylphosphine, which forms a copper Schiff base complex (Fig. 1).
The bond lengths and angles (Table 1) around the Cu in (I) are good agreement with the found in similar copper complexes. The Cu(1)—Br(1) bond lengths of 2.4411 (11) Å agree well with the same distance in other tetrahedral copper(I) complexes. The Cu(1)—P(1) distances are 2.2069 (13) Å which agree well with the same distances in other tetrahedral copper(I) phosphine complexes (Barron et al., 1988). 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 82.15 (7)°. The Br(1)—Cu(1)—P(1)angle is 114.54 (4)°, being somewhat larger than the values for a tetrahedron (Table 1). The single bond distance of C(3)—C(4), 1.446 (3) Å being slightly shorter than C(1)—C(2), 1.490 (3) Å indicates the existence of an extended electron delocalization in this complex.