Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113011943/bg3157sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113011943/bg3157Isup2.hkl |
CCDC reference: 950430
All chemicals were commercial products of reagent grade and were used without further purification. N,N'-Dibenzyl-N''-(trichloroacetyl)phosphoramide (HL) was prepared according to the method of Ovchynnikov (2010). The sodium salt NaL was obtained from a methanol solution by treatment of the ligand with an equimolar ratio of sodium methoxide. The salt was a white fine-grained substance which was soluble in alcohols and acetone, and insoluble in non-polar aprotic organic solvents.
The title complex, [Cu(L)Cl(phen)], was obtained by an exchange reaction of a solution of NaL (2 mmol) in methanol (10 ml) with a solution of hydrated copper(II) chloride (1 mmol) in methanol (15 ml). A solution of 1,10-phenanthroline (1 mmol) in 2-propan-2-ol (30 ml) was then added and the resulting solution stirred under heating and finally cooled. After a while, green crystals precipitated from the bleached solution. They were filtered off, washed with cool propan-2-ol and dried over CaCl2 (yield 77%). Single crystals of [Cu(L)Cl(phen)] were obtained by slow crystallization from a propan-2-ol–methanol (5:1 v/v) mixture.
The trichloromethyl group in the phosphoramidate ligand is disordered over a major and a minor orientation, with refined occupancies of 0.749 (7) and 0.251 (7), respectively. Standard restraints on the C—Cl distances [1.77 (1) Å] were used for the refinement of the disordered group. H atoms were located theoretically and subsequently treated as riding atoms, with C—H = 0.97 (CH2) or 0.93 Å (aromatic), and N—H = 0.86 Å, and with Uiso(H) = 1.2Ueq(C,N). [Please check added text]
Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
[Cu(C16H16Cl3N3O2P)Cl(C12H8N2)] | F(000) = 1420 |
Mr = 698.83 | Dx = 1.545 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
a = 16.4404 (5) Å | Cell parameters from 8509 reflections |
b = 21.0317 (6) Å | θ = 2.8–34.6° |
c = 9.8219 (3) Å | µ = 1.17 mm−1 |
β = 117.814 (3)° | T = 293 K |
V = 3003.75 (16) Å3 | Plate, green |
Z = 4 | 0.40 × 0.20 × 0.20 mm |
Oxford Xcalibur3 diffractometer | 6579 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 4685 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
Detector resolution: 16.1827 pixels mm-1 | θmax = 30.0°, θmin = 3.0° |
ω scans | h = −23→22 |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | k = −29→29 |
Tmin = 0.651, Tmax = 0.799 | l = −11→13 |
12387 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)] = 0.039 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.101 | w = 1/[σ2(Fo2) + (0.0543P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.006 |
6579 reflections | Δρmax = 0.68 e Å−3 |
406 parameters | Δρmin = −0.43 e Å−3 |
8 restraints | Absolute structure: Flack (1983), 2267 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.006 (12) |
[Cu(C16H16Cl3N3O2P)Cl(C12H8N2)] | V = 3003.75 (16) Å3 |
Mr = 698.83 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 16.4404 (5) Å | µ = 1.17 mm−1 |
b = 21.0317 (6) Å | T = 293 K |
c = 9.8219 (3) Å | 0.40 × 0.20 × 0.20 mm |
β = 117.814 (3)° |
Oxford Xcalibur3 diffractometer | 6579 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | 4685 reflections with I > 2σ(I) |
Tmin = 0.651, Tmax = 0.799 | Rint = 0.024 |
12387 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.101 | Δρmax = 0.68 e Å−3 |
S = 1.04 | Δρmin = −0.43 e Å−3 |
6579 reflections | Absolute structure: Flack (1983), 2267 Friedel pairs |
406 parameters | Absolute structure parameter: −0.006 (12) |
8 restraints |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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 | Occ. (<1) | |
Cu1 | 0.20196 (3) | 0.175873 (19) | 0.05397 (4) | 0.03932 (12) | |
Cl4 | 0.31424 (7) | 0.16554 (5) | 0.33193 (12) | 0.0538 (3) | |
P1 | 0.09286 (6) | 0.26507 (4) | 0.14434 (10) | 0.0346 (2) | |
N1 | 0.0149 (2) | 0.20904 (14) | 0.1015 (4) | 0.0399 (6) | |
O1 | 0.15305 (18) | 0.25715 (11) | 0.0683 (3) | 0.0433 (6) | |
C1 | 0.0300 (2) | 0.15251 (17) | 0.0618 (4) | 0.0374 (7) | |
N2 | 0.1614 (2) | 0.27172 (15) | 0.3272 (4) | 0.0449 (7) | |
H2A | 0.213 (3) | 0.2442 (16) | 0.369 (4) | 0.030 (9)* | |
O2 | 0.09746 (17) | 0.12909 (11) | 0.0553 (3) | 0.0440 (6) | |
C2 | −0.0487 (2) | 0.10605 (15) | 0.0216 (3) | 0.0484 (9) | |
Cl1A | −0.0340 (3) | 0.0674 (2) | 0.1884 (3) | 0.156 (3) | 0.747 (7) |
Cl2A | −0.15787 (12) | 0.14336 (13) | −0.0580 (6) | 0.1069 (15) | 0.747 (7) |
Cl3A | −0.05584 (19) | 0.04899 (13) | −0.1101 (4) | 0.1008 (13) | 0.747 (7) |
Cl1B | −0.0041 (6) | 0.0324 (4) | 0.117 (2) | 0.157 (7) | 0.253 (7) |
Cl2B | −0.1351 (7) | 0.1206 (4) | 0.0673 (18) | 0.113 (5) | 0.253 (7) |
Cl3B | −0.0845 (12) | 0.0773 (11) | −0.1647 (11) | 0.247 (11) | 0.253 (7) |
N3 | 0.0297 (2) | 0.32885 (13) | 0.0949 (4) | 0.0387 (6) | |
H3A | −0.025 (3) | 0.3247 (15) | 0.036 (4) | 0.029 (9)* | |
C3 | 0.1360 (3) | 0.2888 (2) | 0.4447 (5) | 0.0544 (10) | |
H3B | 0.0854 | 0.3188 | 0.3999 | 0.065* | |
H3C | 0.1876 | 0.3111 | 0.5255 | 0.065* | |
N4 | 0.2365 (2) | 0.09668 (14) | −0.0210 (3) | 0.0417 (7) | |
C4 | 0.1079 (3) | 0.2360 (2) | 0.5194 (4) | 0.0532 (10) | |
N5 | 0.2735 (2) | 0.21737 (15) | −0.0419 (4) | 0.0452 (7) | |
C5 | 0.0728 (4) | 0.2506 (3) | 0.6184 (5) | 0.0740 (14) | |
H5A | 0.0679 | 0.2929 | 0.6408 | 0.089* | |
C6 | 0.0446 (4) | 0.2031 (5) | 0.6851 (6) | 0.095 (2) | |
H6A | 0.0205 | 0.2138 | 0.7510 | 0.114* | |
C7 | 0.0523 (4) | 0.1410 (4) | 0.6542 (7) | 0.095 (2) | |
H7A | 0.0331 | 0.1091 | 0.6984 | 0.114* | |
C8 | 0.0881 (4) | 0.1254 (3) | 0.5589 (7) | 0.0816 (17) | |
H8A | 0.0938 | 0.0828 | 0.5390 | 0.098* | |
C9 | 0.1163 (4) | 0.1726 (2) | 0.4907 (6) | 0.0630 (12) | |
H9A | 0.1408 | 0.1615 | 0.4257 | 0.076* | |
C10 | 0.0691 (3) | 0.39174 (18) | 0.1075 (5) | 0.0515 (10) | |
H10A | 0.1239 | 0.3946 | 0.2063 | 0.062* | |
H10B | 0.0255 | 0.4228 | 0.1076 | 0.062* | |
C11 | 0.0947 (3) | 0.41017 (17) | −0.0162 (5) | 0.0470 (9) | |
C12 | 0.0321 (4) | 0.4071 (2) | −0.1686 (6) | 0.0682 (13) | |
H12A | −0.0275 | 0.3934 | −0.1975 | 0.082* | |
C13 | 0.0567 (5) | 0.4240 (3) | −0.2797 (8) | 0.092 (2) | |
H13A | 0.0131 | 0.4209 | −0.3827 | 0.110* | |
C14 | 0.1405 (7) | 0.4447 (3) | −0.2449 (9) | 0.099 (2) | |
H14A | 0.1557 | 0.4558 | −0.3219 | 0.119* | |
C15 | 0.2049 (5) | 0.4493 (3) | −0.0904 (10) | 0.095 (2) | |
H15A | 0.2637 | 0.4642 | −0.0632 | 0.114* | |
C16 | 0.1818 (4) | 0.4318 (2) | 0.0242 (7) | 0.0694 (13) | |
H16A | 0.2252 | 0.4347 | 0.1273 | 0.083* | |
C17 | 0.2128 (3) | 0.03728 (19) | −0.0126 (5) | 0.0526 (10) | |
H17A | 0.1744 | 0.0289 | 0.0309 | 0.063* | |
C18 | 0.2444 (4) | −0.0132 (2) | −0.0680 (6) | 0.0623 (12) | |
H18A | 0.2266 | −0.0545 | −0.0610 | 0.075* | |
C19 | 0.3003 (4) | −0.0026 (2) | −0.1314 (6) | 0.0640 (12) | |
H19A | 0.3226 | −0.0365 | −0.1649 | 0.077* | |
C20 | 0.3246 (3) | 0.0600 (2) | −0.1464 (5) | 0.0568 (11) | |
C21 | 0.3783 (4) | 0.0787 (3) | −0.2207 (6) | 0.0727 (14) | |
H21A | 0.4045 | 0.0475 | −0.2549 | 0.087* | |
C22 | 0.3910 (3) | 0.1387 (3) | −0.2411 (6) | 0.0701 (14) | |
H22A | 0.4228 | 0.1488 | −0.2955 | 0.084* | |
C23 | 0.3575 (3) | 0.1900 (2) | −0.1821 (5) | 0.0565 (11) | |
C24 | 0.3678 (3) | 0.2549 (3) | −0.1998 (5) | 0.0684 (14) | |
H24A | 0.3992 | 0.2684 | −0.2525 | 0.082* | |
C25 | 0.3321 (3) | 0.2983 (3) | −0.1404 (6) | 0.0674 (13) | |
H25A | 0.3381 | 0.3415 | −0.1538 | 0.081* | |
C26 | 0.2865 (3) | 0.2778 (2) | −0.0590 (6) | 0.0568 (11) | |
H26A | 0.2645 | 0.3081 | −0.0153 | 0.068* | |
C27 | 0.2899 (2) | 0.1082 (2) | −0.0874 (4) | 0.0425 (8) | |
C28 | 0.3084 (3) | 0.1738 (2) | −0.1035 (4) | 0.0443 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0372 (2) | 0.0394 (2) | 0.0502 (3) | 0.0030 (2) | 0.02775 (19) | 0.0027 (2) |
Cl4 | 0.0379 (5) | 0.0595 (6) | 0.0512 (6) | 0.0066 (4) | 0.0100 (4) | 0.0012 (4) |
P1 | 0.0320 (4) | 0.0338 (5) | 0.0416 (5) | 0.0005 (4) | 0.0203 (4) | 0.0003 (4) |
N1 | 0.0352 (15) | 0.0394 (16) | 0.0507 (17) | −0.0046 (12) | 0.0247 (13) | −0.0038 (13) |
O1 | 0.0406 (13) | 0.0373 (13) | 0.0631 (16) | 0.0013 (10) | 0.0336 (12) | 0.0037 (11) |
C1 | 0.0351 (17) | 0.0376 (17) | 0.0386 (19) | −0.0029 (14) | 0.0165 (15) | −0.0001 (14) |
N2 | 0.0361 (16) | 0.0513 (18) | 0.0420 (18) | 0.0030 (14) | 0.0139 (14) | 0.0028 (13) |
O2 | 0.0395 (14) | 0.0347 (13) | 0.0647 (17) | −0.0001 (10) | 0.0300 (13) | −0.0046 (11) |
C2 | 0.048 (2) | 0.049 (2) | 0.059 (2) | −0.0107 (17) | 0.0336 (19) | −0.0101 (17) |
Cl1A | 0.172 (4) | 0.186 (4) | 0.0794 (16) | −0.114 (3) | 0.0338 (18) | 0.0351 (18) |
Cl2A | 0.0359 (8) | 0.0744 (15) | 0.185 (3) | −0.0092 (8) | 0.0306 (13) | −0.0522 (18) |
Cl3A | 0.0817 (16) | 0.0895 (17) | 0.161 (3) | −0.0395 (12) | 0.0813 (19) | −0.0851 (19) |
Cl1B | 0.114 (6) | 0.064 (5) | 0.306 (18) | 0.004 (4) | 0.107 (9) | 0.068 (7) |
Cl2B | 0.095 (6) | 0.085 (5) | 0.217 (13) | −0.047 (5) | 0.122 (8) | −0.069 (7) |
Cl3B | 0.207 (14) | 0.48 (3) | 0.053 (5) | −0.246 (17) | 0.059 (7) | −0.102 (9) |
N3 | 0.0336 (16) | 0.0385 (16) | 0.0445 (17) | 0.0056 (12) | 0.0185 (14) | 0.0052 (12) |
C3 | 0.052 (2) | 0.063 (3) | 0.043 (2) | 0.003 (2) | 0.0181 (19) | −0.0042 (18) |
N4 | 0.0426 (17) | 0.0454 (18) | 0.0421 (16) | 0.0045 (13) | 0.0241 (14) | 0.0032 (13) |
C4 | 0.045 (2) | 0.071 (3) | 0.036 (2) | −0.0007 (19) | 0.0122 (17) | 0.0034 (18) |
N5 | 0.0401 (16) | 0.055 (2) | 0.0456 (18) | 0.0027 (14) | 0.0246 (14) | 0.0066 (15) |
C5 | 0.072 (3) | 0.106 (4) | 0.042 (3) | −0.006 (3) | 0.024 (2) | −0.011 (2) |
C6 | 0.061 (3) | 0.189 (8) | 0.036 (3) | −0.001 (4) | 0.023 (2) | 0.016 (4) |
C7 | 0.073 (4) | 0.133 (6) | 0.060 (4) | −0.021 (4) | 0.016 (3) | 0.034 (4) |
C8 | 0.086 (4) | 0.093 (4) | 0.067 (3) | 0.003 (3) | 0.037 (3) | 0.033 (3) |
C9 | 0.065 (3) | 0.072 (3) | 0.055 (3) | 0.000 (2) | 0.030 (2) | 0.011 (2) |
C10 | 0.062 (3) | 0.0330 (19) | 0.069 (3) | 0.0018 (17) | 0.039 (2) | −0.0050 (17) |
C11 | 0.051 (2) | 0.0310 (18) | 0.061 (3) | 0.0030 (15) | 0.028 (2) | 0.0035 (15) |
C12 | 0.075 (4) | 0.070 (3) | 0.057 (3) | −0.005 (3) | 0.029 (3) | 0.006 (2) |
C13 | 0.118 (6) | 0.086 (4) | 0.080 (4) | 0.002 (4) | 0.053 (4) | 0.024 (3) |
C14 | 0.163 (7) | 0.068 (4) | 0.106 (5) | 0.004 (4) | 0.095 (5) | 0.028 (3) |
C15 | 0.098 (5) | 0.067 (4) | 0.154 (7) | −0.014 (3) | 0.087 (5) | 0.009 (4) |
C16 | 0.060 (3) | 0.062 (3) | 0.085 (4) | −0.009 (2) | 0.033 (3) | −0.003 (2) |
C17 | 0.055 (2) | 0.050 (2) | 0.054 (2) | 0.0077 (19) | 0.026 (2) | 0.0008 (18) |
C18 | 0.068 (3) | 0.050 (3) | 0.069 (3) | 0.010 (2) | 0.033 (3) | −0.002 (2) |
C19 | 0.066 (3) | 0.064 (3) | 0.062 (3) | 0.014 (2) | 0.030 (2) | −0.015 (2) |
C20 | 0.040 (2) | 0.083 (3) | 0.045 (2) | 0.007 (2) | 0.0180 (18) | −0.011 (2) |
C21 | 0.058 (3) | 0.104 (4) | 0.072 (3) | −0.003 (3) | 0.043 (3) | −0.022 (3) |
C22 | 0.048 (3) | 0.120 (5) | 0.056 (3) | −0.005 (3) | 0.035 (2) | −0.014 (3) |
C23 | 0.041 (2) | 0.092 (3) | 0.038 (2) | −0.009 (2) | 0.0199 (18) | 0.0124 (19) |
C24 | 0.040 (2) | 0.112 (4) | 0.058 (3) | −0.006 (2) | 0.027 (2) | 0.019 (3) |
C25 | 0.052 (3) | 0.072 (3) | 0.078 (3) | −0.003 (2) | 0.030 (2) | 0.026 (3) |
C26 | 0.052 (2) | 0.054 (3) | 0.076 (3) | −0.003 (2) | 0.040 (2) | 0.010 (2) |
C27 | 0.0316 (17) | 0.064 (2) | 0.0331 (19) | 0.0026 (16) | 0.0164 (15) | −0.0050 (16) |
C28 | 0.0333 (18) | 0.064 (2) | 0.0331 (18) | 0.0010 (16) | 0.0134 (15) | 0.0026 (16) |
Cu1—O1 | 1.922 (2) | C8—C9 | 1.394 (7) |
Cu1—O2 | 1.985 (3) | C8—H8A | 0.9300 |
Cu1—N4 | 2.007 (3) | C9—H9A | 0.9300 |
Cu1—N5 | 2.016 (3) | C10—C11 | 1.510 (6) |
Cu1—Cl4 | 2.4910 (10) | C10—H10A | 0.9700 |
P1—O1 | 1.501 (3) | C10—H10B | 0.9700 |
P1—N2 | 1.621 (3) | C11—C12 | 1.366 (6) |
P1—N3 | 1.625 (3) | C11—C16 | 1.373 (7) |
P1—N1 | 1.644 (3) | C12—C13 | 1.375 (8) |
N1—C1 | 1.310 (5) | C12—H12A | 0.9300 |
C1—O2 | 1.242 (4) | C13—C14 | 1.330 (10) |
C1—C2 | 1.519 (5) | C13—H13A | 0.9300 |
N2—C3 | 1.443 (5) | C14—C15 | 1.391 (11) |
N2—H2A | 0.95 (4) | C14—H14A | 0.9300 |
C2—Cl2B | 1.705 (4) | C15—C16 | 1.394 (9) |
C2—Cl3A | 1.728 (3) | C15—H15A | 0.9300 |
C2—Cl1A | 1.742 (3) | C16—H16A | 0.9300 |
C2—Cl3B | 1.748 (5) | C17—C18 | 1.397 (6) |
C2—Cl2A | 1.772 (3) | C17—H17A | 0.9300 |
C2—Cl1B | 1.783 (5) | C18—C19 | 1.348 (7) |
N3—C10 | 1.453 (5) | C18—H18A | 0.9300 |
N3—H3A | 0.82 (4) | C19—C20 | 1.402 (7) |
C3—C4 | 1.516 (6) | C19—H19A | 0.9300 |
C3—H3B | 0.9700 | C20—C27 | 1.413 (6) |
C3—H3C | 0.9700 | C20—C21 | 1.438 (7) |
N4—C17 | 1.322 (5) | C21—C22 | 1.311 (8) |
N4—C27 | 1.337 (5) | C21—H21A | 0.9300 |
C4—C5 | 1.377 (7) | C22—C23 | 1.450 (7) |
C4—C9 | 1.383 (6) | C22—H22A | 0.9300 |
N5—C26 | 1.314 (5) | C23—C24 | 1.396 (7) |
N5—C28 | 1.364 (5) | C23—C28 | 1.395 (5) |
C5—C6 | 1.387 (9) | C24—C25 | 1.355 (8) |
C5—H5A | 0.9300 | C24—H24A | 0.9300 |
C6—C7 | 1.362 (10) | C25—C26 | 1.395 (7) |
C6—H6A | 0.9300 | C25—H25A | 0.9300 |
C7—C8 | 1.357 (10) | C26—H26A | 0.9300 |
C7—H7A | 0.9300 | C27—C28 | 1.438 (6) |
O1—Cu1—O2 | 92.72 (10) | C8—C7—C6 | 120.1 (6) |
O1—Cu1—N4 | 164.68 (12) | C8—C7—H7A | 120.0 |
O2—Cu1—N4 | 89.13 (11) | C6—C7—H7A | 120.0 |
O1—Cu1—N5 | 90.24 (12) | C7—C8—C9 | 120.5 (6) |
O2—Cu1—N5 | 155.89 (12) | C7—C8—H8A | 119.7 |
N4—Cu1—N5 | 82.03 (13) | C9—C8—H8A | 119.7 |
O1—Cu1—Cl4 | 96.82 (9) | C4—C9—C8 | 120.2 (5) |
O2—Cu1—Cl4 | 98.67 (8) | C4—C9—H9A | 119.9 |
N4—Cu1—Cl4 | 97.93 (9) | C8—C9—H9A | 119.9 |
N5—Cu1—Cl4 | 104.72 (10) | N3—C10—C11 | 116.5 (3) |
O1—P1—N2 | 106.41 (17) | N3—C10—H10A | 108.2 |
O1—P1—N3 | 114.83 (16) | C11—C10—H10A | 108.2 |
N2—P1—N3 | 106.06 (17) | N3—C10—H10B | 108.2 |
O1—P1—N1 | 114.13 (15) | C11—C10—H10B | 108.2 |
N2—P1—N1 | 113.64 (17) | H10A—C10—H10B | 107.3 |
N3—P1—N1 | 101.66 (16) | C12—C11—C16 | 118.9 (5) |
C1—N1—P1 | 119.6 (2) | C12—C11—C10 | 121.3 (4) |
P1—O1—Cu1 | 122.03 (15) | C16—C11—C10 | 119.8 (4) |
O2—C1—N1 | 132.2 (3) | C11—C12—C13 | 120.4 (5) |
O2—C1—C2 | 113.8 (3) | C11—C12—H12A | 119.8 |
N1—C1—C2 | 113.9 (3) | C13—C12—H12A | 119.8 |
C3—N2—P1 | 126.6 (3) | C14—C13—C12 | 122.3 (6) |
C3—N2—H2A | 110 (2) | C14—C13—H13A | 118.8 |
P1—N2—H2A | 116 (2) | C12—C13—H13A | 118.8 |
C1—O2—Cu1 | 126.9 (2) | C13—C14—C15 | 118.2 (6) |
C1—C2—Cl2B | 121.9 (3) | C13—C14—H14A | 120.9 |
C1—C2—Cl3A | 113.2 (2) | C15—C14—H14A | 120.9 |
Cl2B—C2—Cl3A | 123.2 (4) | C14—C15—C16 | 120.5 (6) |
C1—C2—Cl1A | 109.1 (2) | C14—C15—H15A | 119.7 |
Cl2B—C2—Cl1A | 66.6 (5) | C16—C15—H15A | 119.7 |
Cl3A—C2—Cl1A | 108.1 (3) | C11—C16—C15 | 119.6 (5) |
C1—C2—Cl3B | 108.9 (5) | C11—C16—H16A | 120.2 |
Cl2B—C2—Cl3B | 115.0 (7) | C15—C16—H16A | 120.2 |
Cl3A—C2—Cl3B | 26.4 (8) | N4—C17—C18 | 121.3 (4) |
Cl1A—C2—Cl3B | 130.9 (7) | N4—C17—H17A | 119.4 |
C1—C2—Cl2A | 113.2 (2) | C18—C17—H17A | 119.4 |
Cl2B—C2—Cl2A | 40.5 (5) | C19—C18—C17 | 120.8 (5) |
Cl3A—C2—Cl2A | 106.0 (2) | C19—C18—H18A | 119.6 |
Cl1A—C2—Cl2A | 106.8 (3) | C17—C18—H18A | 119.6 |
Cl3B—C2—Cl2A | 85.1 (8) | C18—C19—C20 | 119.5 (4) |
C1—C2—Cl1B | 109.3 (4) | C18—C19—H19A | 120.3 |
Cl2B—C2—Cl1B | 101.8 (5) | C20—C19—H19A | 120.3 |
Cl3A—C2—Cl1B | 70.1 (6) | C19—C20—C27 | 116.2 (4) |
Cl1A—C2—Cl1B | 41.9 (5) | C19—C20—C21 | 125.6 (4) |
Cl3B—C2—Cl1B | 96.2 (9) | C27—C20—C21 | 118.2 (5) |
Cl2A—C2—Cl1B | 134.4 (4) | C22—C21—C20 | 121.4 (5) |
C10—N3—P1 | 121.9 (3) | C22—C21—H21A | 119.3 |
C10—N3—H3A | 117 (2) | C20—C21—H21A | 119.3 |
P1—N3—H3A | 118 (2) | C21—C22—C23 | 122.5 (5) |
N2—C3—C4 | 118.1 (4) | C21—C22—H22A | 118.7 |
N2—C3—H3B | 107.8 | C23—C22—H22A | 118.7 |
C4—C3—H3B | 107.8 | C24—C23—C28 | 116.3 (4) |
N2—C3—H3C | 107.8 | C24—C23—C22 | 125.9 (4) |
C4—C3—H3C | 107.8 | C28—C23—C22 | 117.7 (4) |
H3B—C3—H3C | 107.1 | C25—C24—C23 | 120.2 (4) |
C17—N4—C27 | 118.7 (3) | C25—C24—H24A | 119.9 |
C17—N4—Cu1 | 128.2 (3) | C23—C24—H24A | 119.9 |
C27—N4—Cu1 | 113.0 (3) | C24—C25—C26 | 119.8 (5) |
C5—C4—C9 | 118.2 (5) | C24—C25—H25A | 120.1 |
C5—C4—C3 | 120.1 (4) | C26—C25—H25A | 120.1 |
C9—C4—C3 | 121.7 (4) | N5—C26—C25 | 122.3 (5) |
C26—N5—C28 | 117.8 (4) | N5—C26—H26A | 118.8 |
C26—N5—Cu1 | 130.1 (3) | C25—C26—H26A | 118.8 |
C28—N5—Cu1 | 112.0 (3) | N4—C27—C20 | 123.5 (4) |
C4—C5—C6 | 121.1 (6) | N4—C27—C28 | 116.6 (3) |
C4—C5—H5A | 119.5 | C20—C27—C28 | 119.8 (4) |
C6—C5—H5A | 119.5 | N5—C28—C23 | 123.6 (4) |
C7—C6—C5 | 119.9 (6) | N5—C28—C27 | 116.2 (3) |
C7—C6—H6A | 120.0 | C23—C28—C27 | 120.2 (4) |
C5—C6—H6A | 120.0 | ||
O1—P1—N1—C1 | 26.5 (3) | C3—C4—C5—C6 | 178.5 (5) |
N2—P1—N1—C1 | −95.8 (3) | C4—C5—C6—C7 | 0.6 (8) |
N3—P1—N1—C1 | 150.7 (3) | C5—C6—C7—C8 | 0.4 (9) |
N2—P1—O1—Cu1 | 83.6 (2) | C6—C7—C8—C9 | −0.7 (9) |
N3—P1—O1—Cu1 | −159.34 (18) | C5—C4—C9—C8 | 1.1 (7) |
N1—P1—O1—Cu1 | −42.5 (2) | C3—C4—C9—C8 | −178.7 (5) |
O2—Cu1—O1—P1 | 28.1 (2) | C7—C8—C9—C4 | −0.1 (9) |
N4—Cu1—O1—P1 | 124.8 (4) | P1—N3—C10—C11 | 77.7 (4) |
N5—Cu1—O1—P1 | −175.8 (2) | N3—C10—C11—C12 | 54.3 (5) |
Cl4—Cu1—O1—P1 | −70.93 (18) | N3—C10—C11—C16 | −127.1 (4) |
P1—N1—C1—O2 | 4.0 (6) | C16—C11—C12—C13 | 1.4 (7) |
P1—N1—C1—C2 | −178.6 (2) | C10—C11—C12—C13 | −180.0 (5) |
O1—P1—N2—C3 | 170.9 (3) | C11—C12—C13—C14 | −0.9 (10) |
N3—P1—N2—C3 | 48.2 (4) | C12—C13—C14—C15 | −0.2 (10) |
N1—P1—N2—C3 | −62.7 (4) | C13—C14—C15—C16 | 0.9 (10) |
N1—C1—O2—Cu1 | −16.8 (6) | C12—C11—C16—C15 | −0.7 (7) |
C2—C1—O2—Cu1 | 165.8 (2) | C10—C11—C16—C15 | −179.4 (4) |
O1—Cu1—O2—C1 | 0.7 (3) | C14—C15—C16—C11 | −0.4 (8) |
N4—Cu1—O2—C1 | −164.1 (3) | C27—N4—C17—C18 | 1.7 (6) |
N5—Cu1—O2—C1 | −96.0 (4) | Cu1—N4—C17—C18 | −178.7 (3) |
Cl4—Cu1—O2—C1 | 98.0 (3) | N4—C17—C18—C19 | 0.2 (7) |
O2—C1—C2—Cl2B | 163.5 (7) | C17—C18—C19—C20 | −2.1 (7) |
N1—C1—C2—Cl2B | −14.4 (8) | C18—C19—C20—C27 | 2.1 (7) |
O2—C1—C2—Cl3A | −30.8 (4) | C18—C19—C20—C21 | −175.6 (5) |
N1—C1—C2—Cl3A | 151.3 (3) | C19—C20—C21—C22 | 174.0 (5) |
O2—C1—C2—Cl1A | 89.7 (4) | C27—C20—C21—C22 | −3.6 (7) |
N1—C1—C2—Cl1A | −88.2 (4) | C20—C21—C22—C23 | 4.1 (8) |
O2—C1—C2—Cl3B | −58.7 (10) | C21—C22—C23—C24 | −179.6 (5) |
N1—C1—C2—Cl3B | 123.4 (9) | C21—C22—C23—C28 | −1.2 (7) |
O2—C1—C2—Cl2A | −151.5 (3) | C28—C23—C24—C25 | 0.8 (7) |
N1—C1—C2—Cl2A | 30.6 (4) | C22—C23—C24—C25 | 179.2 (5) |
O2—C1—C2—Cl1B | 45.2 (7) | C23—C24—C25—C26 | 1.2 (7) |
N1—C1—C2—Cl1B | −132.7 (7) | C28—N5—C26—C25 | 1.7 (7) |
O1—P1—N3—C10 | −54.3 (3) | Cu1—N5—C26—C25 | −174.5 (3) |
N2—P1—N3—C10 | 62.9 (3) | C24—C25—C26—N5 | −2.5 (8) |
N1—P1—N3—C10 | −178.0 (3) | C17—N4—C27—C20 | −1.6 (5) |
P1—N2—C3—C4 | 88.4 (4) | Cu1—N4—C27—C20 | 178.7 (3) |
O1—Cu1—N4—C17 | −116.7 (5) | C17—N4—C27—C28 | 175.8 (3) |
O2—Cu1—N4—C17 | −19.5 (3) | Cu1—N4—C27—C28 | −4.0 (4) |
N5—Cu1—N4—C17 | −177.0 (3) | C19—C20—C27—N4 | −0.3 (6) |
Cl4—Cu1—N4—C17 | 79.1 (3) | C21—C20—C27—N4 | 177.6 (4) |
O1—Cu1—N4—C27 | 63.0 (6) | C19—C20—C27—C28 | −177.6 (4) |
O2—Cu1—N4—C27 | 160.2 (3) | C21—C20—C27—C28 | 0.3 (6) |
N5—Cu1—N4—C27 | 2.7 (2) | C26—N5—C28—C23 | 0.5 (6) |
Cl4—Cu1—N4—C27 | −101.2 (2) | Cu1—N5—C28—C23 | 177.3 (3) |
N2—C3—C4—C5 | −172.3 (4) | C26—N5—C28—C27 | −177.8 (4) |
N2—C3—C4—C9 | 7.5 (6) | Cu1—N5—C28—C27 | −0.9 (4) |
O1—Cu1—N5—C26 | 8.7 (4) | C24—C23—C28—N5 | −1.7 (6) |
O2—Cu1—N5—C26 | 105.9 (4) | C22—C23—C28—N5 | 179.7 (4) |
N4—Cu1—N5—C26 | 175.4 (4) | C24—C23—C28—C27 | 176.5 (4) |
Cl4—Cu1—N5—C26 | −88.4 (4) | C22—C23—C28—C27 | −2.1 (6) |
O1—Cu1—N5—C28 | −167.6 (3) | N4—C27—C28—N5 | 3.3 (5) |
O2—Cu1—N5—C28 | −70.4 (4) | C20—C27—C28—N5 | −179.2 (3) |
N4—Cu1—N5—C28 | −0.9 (3) | N4—C27—C28—C23 | −175.0 (3) |
Cl4—Cu1—N5—C28 | 95.3 (2) | C20—C27—C28—C23 | 2.4 (5) |
C9—C4—C5—C6 | −1.4 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3A···Cl4i | 0.82 (4) | 2.47 (4) | 3.270 (3) | 167 (3) |
N2—H2A···Cl4 | 0.95 (4) | 2.49 (4) | 3.346 (3) | 150 (3) |
Symmetry code: (i) x−1/2, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C16H16Cl3N3O2P)Cl(C12H8N2)] |
Mr | 698.83 |
Crystal system, space group | Monoclinic, Cc |
Temperature (K) | 293 |
a, b, c (Å) | 16.4404 (5), 21.0317 (6), 9.8219 (3) |
β (°) | 117.814 (3) |
V (Å3) | 3003.75 (16) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.17 |
Crystal size (mm) | 0.40 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Oxford Xcalibur3 diffractometer |
Absorption correction | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) |
Tmin, Tmax | 0.651, 0.799 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12387, 6579, 4685 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.703 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.101, 1.04 |
No. of reflections | 6579 |
No. of parameters | 406 |
No. of restraints | 8 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.68, −0.43 |
Absolute structure | Flack (1983), 2267 Friedel pairs |
Absolute structure parameter | −0.006 (12) |
Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012).
Cu1—O1 | 1.922 (2) | P1—O1 | 1.501 (3) |
Cu1—O2 | 1.985 (3) | P1—N2 | 1.621 (3) |
Cu1—N4 | 2.007 (3) | P1—N3 | 1.625 (3) |
Cu1—N5 | 2.016 (3) | P1—N1 | 1.644 (3) |
Cu1—Cl4 | 2.4910 (10) | C1—O2 | 1.242 (4) |
O1—P1—N1 | 114.13 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3A···Cl4i | 0.82 (4) | 2.47 (4) | 3.270 (3) | 167 (3) |
N2—H2A···Cl4 | 0.95 (4) | 2.49 (4) | 3.346 (3) | 150 (3) |
Symmetry code: (i) x−1/2, −y+1/2, z−1/2. |
Cg···Cg | IPD (Å) | DA (°) | CCD (Å) |
Cg1···Cg2ii | 3.549 (2) | 10.4 (2) | 3.40 (8) |
Cg2···Cg3ii | 3.774 (3) | 7.6 (2) | 3.55 (4) |
Symmetry code: (ii) x, y, z - 1. Notes: Cg1 Cg2 and Cg3 are the centroids of the Cu1/N4/C27/C28/N5, N5/C23–26/C28 and C4–C9 rings, respectively. CCD is the centroid-to-centroid distance (distance between group centroids), DA is the dihedral angle (angle subtended by both planes) and IPD is the interplanar distance (distance from one plane to the neighbouring centroid). For details, see Janiak (2000). |
The synthesis of coordination compounds of carbacylamidophosphates (CAPh) have been the subject of important developments in recent years (Gholivand et al., 2010; Sokolov et al., 2008; Trush et al., 2005; Gubina et al., 2000). On the other hand, CAPhs containing the [C(O)NHP(O)] structural unit have been known for a considerable time (Amirkhanov et al., 1997; Ovchynnikov et al., 1998; Ly & Woollins, 1998). This interest is due to their coordination chemistry as a consequence of the steric control that this ligand system may impart compared with, for example, β-diketonates (Kepert, 1987; Gorkum et al., 2005). The especially interesting feature of CAPh ligands is the bidentate chelating character of their coordination to the central metal atom (Bundya et al., 1999).
On the other hand, carbacylamidophosphate complexes formulated as ML2 {where M = CoII, MnII, CuII or NiII, and L = [Cl3C(O)NP(O)R2]-, with R = NHCH2Ph, NHCH2CH═CH2 or NEt2} are neutral species with an unsaturated coordination environment of the metal cations that readily coordinate additional bidentate chelating donor groups like 2,2'-dipyridyl or 1,10-phenanthroline (phen), hereinafter generically Lig (Dickman, 1999; Gubina et al., 2009). It is common knowledge that, in general, multidentate ligands with nitrogen heterocycles feature prominently as building blocks in the design of metal–ligand networks (Janiak, 2000). Moreover, such compounds can display biological activity (Gholivand et al., 2012; Ekstrom et al., 2006).
Unlike the case of previously known coordination compounds of common formula ML2(Lig) [see Gubina et al. (2009) and Bundya et al. (1999)], the same mixing procedure led in the present case to a totally different complex, the title compound, (I), formulated as [Cu(L)Cl(phen)], which we report herein. It is interesting to note that the composition of the complex obtained in the solid state indicates the presence of equilibrium in solution, viz.
phen + Cu2+ + 2Cl- + 2L- + 2Na+ CuCl(L)(phen) + Cl- + 2Na+ + L- [Sarah: see scheme 2 in trash for format, but include as text]
In (I) (Fig. 1), the copper(II) cation presents a square-pyramidal environment, with the basal plane defined by two O atoms from a carbonyl and a phosphoryl group (O1 and O2) and two N atoms from a phen molecule (N1 and N2). A coordinated Cl atom (Cl1) occupies the apex. The mean-square plane passing through the basal atoms N4/N5/O1/O2 [maximum deviation = 0.083 (2) Å for O3] is 0.324 (2) Å from the cation.
The organic N,N'-dibenzyl-N''-(trichloroacetyl)phosphoramidate (L) ligand is coordinated in a bidentate manner via the O atoms of the phosphoryl and carbonyl groups, forming a six-membered chelate (Fig. 1). The Cu—O1(═P1) bond is shorter than the Cu1—O2(═C1) bond (Table 1) and this can be explained by the stronger affinity to copper shown by the phosphoryl group compared with the carbonyl group. A similar difference in bond lengths is observed for complexes with deprotonated CAPh ligands (Gubina et al., 2000).
The six-membered metallocycle of (I) is far from planar, but presents a fairly planar subgroup [atoms Cu1/C1/O1/O2; maximum deviation from the least-squares plane = 0.003 (2) Å for O2], leaving the remaining two atoms on the same side of the plane [N1 at 0.259 (3) Å and P1 at 0.603 (3)Å], in an `envelope-like' shape.
Deprotonation of the amide N atom in (I) changes the bond lengths in the C1—(═O2)—N1—P1—(═O1) fragment with respect to that in the free ligand (Lfree). The P1—O1 and O2—C1 bonds in (I) (Table 1) are slightly longer than the corresponding bonds in Lfree [1.4787 (15) and 1.213 (2) Å, respectively; Ovchynnikov, 2010]. The P1—N1 and C1—N1 bonds are, in turn, notably shortened [1.7055 (17) and 1.354 (3) Å, respectively, in Lfree], which indicates resonance delocalization of the negative charge. Charge redistribution from the N atom to the O atoms also affects the bond angles in the slightly distorted tetrahedral geometry around the P atom; the maximum deviation from ideal values is for the N1—P1—O1 angle, which is involved in the formation of the six-membered chelate ring, whereas in Lfree this angle is 106.89 (8)°, less than the ideal tetrahedral value. The carbonyl atom has an sp2 character.
Regarding noncovalent interactions, the structure displays N—H···Cl hydrogen bonds (Table 2). One of these is intramolecular and a second links the molecules into [101] chains (Fig. 2). There are also intermolecular stacking interactions (Table 3) linking the chains along [001], forming two-dimensional structures parallel to (010) (Fig. 3).