Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807037567/bi2209sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807037567/bi2209Isup2.hkl |
CCDC reference: 663545
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.009 Å
- Disorder in solvent or counterion
- R factor = 0.049
- wR factor = 0.194
- Data-to-parameter ratio = 13.3
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 3.26 PLAT243_ALERT_4_C High 'Solvent' Ueq as Compared to Neighbors for F2' PLAT243_ALERT_4_C High 'Solvent' Ueq as Compared to Neighbors for F3 PLAT243_ALERT_4_C High 'Solvent' Ueq as Compared to Neighbors for F4 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for F3' PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for B1 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for C38 PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 41.00 Perc. PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 9 PLAT431_ALERT_2_C Short Inter HL..A Contact F3 .. N1 .. 2.81 Ang. PLAT431_ALERT_2_C Short Inter HL..A Contact F3' .. N1 .. 2.98 Ang.
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 93
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 12 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 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 7 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For related literature concerning diphospinoamine complexes, see: Ahuja et al. (2007); İrişli & Şen (2005); Liu et al. (2002); Sekabunga et al. (2002).
[Cu(CH3CN)4](BF4) (0.372 g, 1.0 mmol) was dissolved in CH2Cl2 (15 ml) under nitrogen, and a solution of dppa (0.385 g, 1.0 mmol) and phen (0.18 g, 1.0 mmol) in CH2Cl2 (10 ml) was added at room temperature. The filtrate was kept under a diethyl ether atmosphere for three weeks, during which time yellow block-shaped crystals were formed.
H atoms were placed geometrically and allowed to ride during refinement with C—H = 0.93 Å or 0.97 Å for the CH2Cl2 molecule and with Uiso(H) = 1.2Ueq(C). The tetrafluoroborate anion is modelled as disordered over two orientations with equal site occupancies. All B—F distances were restrained to be 1.38 (1) Å, and the F···F distances within each component were restrained to be equal with an effective standard uncertainty of 0.02 Å (SADI instruction in SHELXL). The C—Cl distances in the CH2Cl2 molecule were restrained to be 1.74 (1) Å.
Diphosphinoamine ligands can bind to metals in monodentate, bidentate, chelating and bridging modes and their complexes find application in diverse areas such as supramolecular design, photophysics and catalysis (Liu et al., 2002; İrişli & Şen, 2005; Ahuja et al., 2007; Sekabunga et al., 2002). The title compound is a new CuI complex with bis(diphenylphosphino)amine (dppa).
The compound consists of [Cu2(phen)2(dppa)2]2+ cations (phen is 1,10-phenanthroline) located on 2-fold rotation axes. The two CuI atoms are bridged by two dppa ligands to form an eight-membered Cu2P4N2 ring. The distance between the two metal centres is 3.616 (4) Å, which is too long for any significant metal–metal bonding interaction. Each CuI atom adopts a distorted tetrahedral coordination geometry, with the angles around CuI ranging from 79.5 (2) ° for N2—Cu1—N3 to 135.28 (5) ° for P1—Cu1—P2A (where the suffix A denotes the symmetry operator -x, y, 1/2 - z).
For related literature concerning diphospinoamine complexes, see: Ahuja et al. (2007); İrişli & Şen (2005); Liu et al. (2002); Sekabunga et al. (2002).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.
[Cu2(C25H21NP2)2(C12H8N2)2](BF4)2·CH2Cl2 | F(000) = 3088 |
Mr = 1514.76 | Dx = 1.385 Mg m−3 |
Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2n 2ab | Cell parameters from 9095 reflections |
a = 19.8730 (15) Å | θ = 2.3–25.5° |
b = 17.4039 (13) Å | µ = 0.81 mm−1 |
c = 21.0008 (16) Å | T = 294 K |
V = 7263.5 (9) Å3 | Block, yellow |
Z = 4 | 0.26 × 0.18 × 0.10 mm |
Bruker SMART CCD area-detector diffractometer | 6356 independent reflections |
Radiation source: fine-focus sealed tube | 4243 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
φ and ω scans | θmax = 25.0°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −23→23 |
Tmin = 0.833, Tmax = 0.919 | k = −20→17 |
34870 measured reflections | l = −24→20 |
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.195 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.1181P)2 + 8.285P] where P = (Fo2 + 2Fc2)/3 |
6356 reflections | (Δ/σ)max = 0.001 |
478 parameters | Δρmax = 0.96 e Å−3 |
93 restraints | Δρmin = −0.30 e Å−3 |
[Cu2(C25H21NP2)2(C12H8N2)2](BF4)2·CH2Cl2 | V = 7263.5 (9) Å3 |
Mr = 1514.76 | Z = 4 |
Orthorhombic, Pbcn | Mo Kα radiation |
a = 19.8730 (15) Å | µ = 0.81 mm−1 |
b = 17.4039 (13) Å | T = 294 K |
c = 21.0008 (16) Å | 0.26 × 0.18 × 0.10 mm |
Bruker SMART CCD area-detector diffractometer | 6356 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 4243 reflections with I > 2σ(I) |
Tmin = 0.833, Tmax = 0.919 | Rint = 0.046 |
34870 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 93 restraints |
wR(F2) = 0.195 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.96 e Å−3 |
6356 reflections | Δρmin = −0.30 e Å−3 |
478 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 | Occ. (<1) | |
Cu1 | 0.02403 (3) | 0.72312 (3) | 0.33303 (2) | 0.0378 (2) | |
P1 | 0.10615 (5) | 0.64958 (6) | 0.28923 (5) | 0.0348 (3) | |
P2 | −0.08734 (6) | 0.71415 (6) | 0.34225 (5) | 0.0333 (3) | |
N2 | 0.0610 (2) | 0.7281 (2) | 0.42839 (17) | 0.0428 (9) | |
N3 | 0.07362 (19) | 0.8288 (2) | 0.33142 (17) | 0.0410 (9) | |
C1 | 0.1811 (2) | 0.6657 (3) | 0.3371 (2) | 0.0381 (10) | |
C2 | 0.1936 (3) | 0.6201 (3) | 0.3902 (2) | 0.0523 (12) | |
H2 | 0.1665 | 0.5775 | 0.3980 | 0.063* | |
C3 | 0.2450 (3) | 0.6370 (4) | 0.4311 (3) | 0.0688 (16) | |
H3 | 0.2527 | 0.6055 | 0.4662 | 0.083* | |
C4 | 0.2851 (4) | 0.6993 (4) | 0.4213 (3) | 0.084 (2) | |
H4 | 0.3196 | 0.7108 | 0.4495 | 0.101* | |
C5 | 0.2737 (3) | 0.7454 (4) | 0.3686 (3) | 0.0790 (19) | |
H5 | 0.3013 | 0.7876 | 0.3611 | 0.095* | |
C6 | 0.2215 (3) | 0.7291 (3) | 0.3270 (3) | 0.0553 (13) | |
H6 | 0.2137 | 0.7609 | 0.2922 | 0.066* | |
C7 | 0.1003 (2) | 0.5451 (3) | 0.2906 (2) | 0.0424 (11) | |
C8 | 0.1512 (3) | 0.4987 (3) | 0.2659 (3) | 0.0644 (15) | |
H8 | 0.1893 | 0.5210 | 0.2479 | 0.077* | |
C9 | 0.1450 (4) | 0.4195 (4) | 0.2682 (3) | 0.083 (2) | |
H9 | 0.1789 | 0.3886 | 0.2515 | 0.100* | |
C10 | 0.0898 (5) | 0.3868 (4) | 0.2948 (4) | 0.088 (2) | |
H10 | 0.0858 | 0.3336 | 0.2958 | 0.106* | |
C11 | 0.0402 (4) | 0.4314 (4) | 0.3200 (4) | 0.080 (2) | |
H11 | 0.0028 | 0.4084 | 0.3385 | 0.096* | |
C12 | 0.0453 (3) | 0.5111 (3) | 0.3183 (3) | 0.0554 (13) | |
H12 | 0.0115 | 0.5413 | 0.3359 | 0.067* | |
N1 | −0.13374 (19) | 0.6728 (2) | 0.28423 (17) | 0.0402 (9) | |
C13 | −0.1069 (2) | 0.6535 (3) | 0.4112 (2) | 0.0401 (10) | |
C14 | −0.1192 (3) | 0.5761 (3) | 0.4043 (3) | 0.0598 (14) | |
H14 | −0.1212 | 0.5540 | 0.3641 | 0.072* | |
C15 | −0.1285 (4) | 0.5311 (4) | 0.4590 (4) | 0.085 (2) | |
H15 | −0.1377 | 0.4789 | 0.4549 | 0.102* | |
C16 | −0.1244 (4) | 0.5631 (4) | 0.5182 (3) | 0.087 (2) | |
H16 | −0.1304 | 0.5327 | 0.5541 | 0.104* | |
C17 | −0.1116 (3) | 0.6393 (4) | 0.5247 (3) | 0.0733 (17) | |
H17 | −0.1082 | 0.6609 | 0.5651 | 0.088* | |
C18 | −0.1037 (3) | 0.6842 (3) | 0.4720 (2) | 0.0558 (13) | |
H18 | −0.0959 | 0.7365 | 0.4770 | 0.067* | |
C19 | −0.1318 (2) | 0.8025 (3) | 0.3631 (2) | 0.0379 (10) | |
C20 | −0.2006 (3) | 0.8095 (3) | 0.3566 (3) | 0.0542 (13) | |
H20 | −0.2255 | 0.7681 | 0.3415 | 0.065* | |
C21 | −0.2330 (3) | 0.8772 (3) | 0.3720 (3) | 0.0657 (15) | |
H21 | −0.2795 | 0.8812 | 0.3675 | 0.079* | |
C22 | −0.1963 (3) | 0.9387 (3) | 0.3940 (3) | 0.0690 (16) | |
H22 | −0.2178 | 0.9846 | 0.4037 | 0.083* | |
C23 | −0.1283 (3) | 0.9323 (3) | 0.4016 (3) | 0.0708 (17) | |
H23 | −0.1035 | 0.9738 | 0.4168 | 0.085* | |
C24 | −0.0962 (3) | 0.8639 (3) | 0.3866 (3) | 0.0537 (13) | |
H24 | −0.0499 | 0.8595 | 0.3924 | 0.064* | |
C25 | 0.0563 (3) | 0.6769 (3) | 0.4752 (2) | 0.0530 (12) | |
H25 | 0.0308 | 0.6328 | 0.4686 | 0.064* | |
C26 | 0.0880 (3) | 0.6868 (4) | 0.5337 (3) | 0.0669 (16) | |
H26 | 0.0825 | 0.6505 | 0.5658 | 0.080* | |
C27 | 0.1265 (4) | 0.7492 (4) | 0.5435 (3) | 0.0778 (19) | |
H27 | 0.1476 | 0.7559 | 0.5826 | 0.093* | |
C28 | 0.1353 (3) | 0.8041 (3) | 0.4956 (3) | 0.0648 (15) | |
C29 | 0.1773 (4) | 0.8697 (4) | 0.5002 (3) | 0.088 (2) | |
H29 | 0.2003 | 0.8787 | 0.5380 | 0.106* | |
C30 | 0.1850 (4) | 0.9189 (4) | 0.4521 (4) | 0.091 (2) | |
H30 | 0.2133 | 0.9609 | 0.4569 | 0.109* | |
C31 | 0.1503 (3) | 0.9080 (3) | 0.3931 (3) | 0.0663 (15) | |
C32 | 0.1572 (4) | 0.9563 (4) | 0.3403 (3) | 0.0786 (19) | |
H32 | 0.1848 | 0.9994 | 0.3428 | 0.094* | |
C33 | 0.1238 (3) | 0.9406 (3) | 0.2854 (3) | 0.0710 (17) | |
H33 | 0.1282 | 0.9725 | 0.2501 | 0.085* | |
C34 | 0.0835 (3) | 0.8769 (3) | 0.2829 (3) | 0.0526 (12) | |
H34 | 0.0615 | 0.8664 | 0.2448 | 0.063* | |
C35 | 0.1080 (2) | 0.8435 (3) | 0.3865 (2) | 0.0453 (11) | |
C36 | 0.1003 (3) | 0.7908 (3) | 0.4380 (2) | 0.0452 (11) | |
B1 | 0.1709 (3) | 0.1415 (3) | 0.2016 (3) | 0.0675 (19) | |
F1 | 0.1630 (2) | 0.2187 (2) | 0.2035 (2) | 0.0981 (13) | |
F2 | 0.1308 (7) | 0.1095 (8) | 0.1551 (7) | 0.106 (6) | 0.50 |
F3 | 0.2349 (5) | 0.1189 (8) | 0.1952 (6) | 0.124 (6) | 0.50 |
F4 | 0.1463 (7) | 0.1148 (7) | 0.2595 (5) | 0.132 (5) | 0.50 |
F4' | 0.1836 (6) | 0.1066 (6) | 0.2591 (4) | 0.106 (4) | 0.50 |
F3' | 0.2306 (4) | 0.1295 (6) | 0.1665 (5) | 0.079 (3) | 0.50 |
F2' | 0.1202 (7) | 0.1039 (9) | 0.1708 (8) | 0.116 (7) | 0.50 |
C38 | 0.9690 (8) | 0.1159 (5) | 0.1366 (5) | 0.101 (5) | 0.50 |
H38A | 0.9298 | 0.1019 | 0.1615 | 0.122* | 0.50 |
H38B | 1.0087 | 0.0972 | 0.1587 | 0.122* | 0.50 |
Cl1 | 0.9641 (3) | 0.0732 (5) | 0.0619 (3) | 0.163 (2) | 0.50 |
Cl2 | 0.9731 (2) | 0.2138 (2) | 0.1298 (4) | 0.139 (2) | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0379 (3) | 0.0375 (4) | 0.0380 (3) | −0.0015 (2) | 0.0012 (2) | −0.0012 (2) |
P1 | 0.0355 (6) | 0.0346 (6) | 0.0343 (6) | 0.0007 (5) | 0.0006 (5) | 0.0041 (5) |
P2 | 0.0365 (6) | 0.0327 (6) | 0.0308 (6) | −0.0001 (5) | 0.0019 (4) | −0.0031 (4) |
N2 | 0.042 (2) | 0.051 (2) | 0.0350 (19) | 0.0004 (19) | 0.0016 (17) | −0.0008 (17) |
N3 | 0.044 (2) | 0.037 (2) | 0.042 (2) | −0.0030 (17) | 0.0016 (16) | −0.0014 (17) |
C1 | 0.034 (2) | 0.039 (2) | 0.041 (2) | 0.0019 (19) | 0.0031 (18) | −0.0007 (19) |
C2 | 0.055 (3) | 0.049 (3) | 0.053 (3) | 0.000 (2) | −0.009 (2) | 0.009 (2) |
C3 | 0.075 (4) | 0.071 (4) | 0.060 (3) | 0.010 (3) | −0.027 (3) | 0.008 (3) |
C4 | 0.071 (4) | 0.104 (5) | 0.078 (4) | −0.011 (4) | −0.031 (3) | −0.003 (4) |
C5 | 0.067 (4) | 0.090 (5) | 0.080 (4) | −0.033 (4) | −0.016 (3) | 0.005 (4) |
C6 | 0.046 (3) | 0.064 (4) | 0.056 (3) | −0.007 (3) | −0.003 (2) | 0.005 (3) |
C7 | 0.055 (3) | 0.033 (2) | 0.038 (2) | 0.000 (2) | −0.009 (2) | 0.0076 (19) |
C8 | 0.077 (4) | 0.050 (3) | 0.066 (3) | 0.014 (3) | 0.008 (3) | 0.009 (3) |
C9 | 0.127 (6) | 0.052 (4) | 0.071 (4) | 0.023 (4) | −0.001 (4) | 0.004 (3) |
C10 | 0.141 (7) | 0.043 (4) | 0.080 (5) | −0.011 (4) | −0.035 (5) | 0.012 (3) |
C11 | 0.092 (5) | 0.062 (4) | 0.086 (5) | −0.031 (4) | −0.025 (4) | 0.027 (4) |
C12 | 0.058 (3) | 0.051 (3) | 0.057 (3) | −0.011 (3) | −0.008 (3) | 0.012 (3) |
N1 | 0.044 (2) | 0.041 (2) | 0.0348 (19) | −0.0029 (17) | 0.0031 (16) | −0.0101 (16) |
C13 | 0.034 (2) | 0.041 (3) | 0.045 (3) | 0.0016 (19) | 0.0036 (19) | 0.006 (2) |
C14 | 0.072 (4) | 0.043 (3) | 0.064 (3) | −0.007 (3) | −0.003 (3) | 0.005 (3) |
C15 | 0.100 (5) | 0.049 (4) | 0.105 (6) | −0.012 (3) | −0.005 (4) | 0.030 (4) |
C16 | 0.103 (5) | 0.091 (5) | 0.066 (4) | −0.003 (4) | 0.008 (4) | 0.041 (4) |
C17 | 0.090 (5) | 0.083 (5) | 0.047 (3) | 0.006 (4) | 0.016 (3) | 0.015 (3) |
C18 | 0.070 (3) | 0.056 (3) | 0.042 (3) | 0.007 (3) | 0.009 (2) | 0.006 (2) |
C19 | 0.046 (3) | 0.035 (2) | 0.032 (2) | 0.001 (2) | 0.0057 (19) | 0.0000 (18) |
C20 | 0.055 (3) | 0.046 (3) | 0.062 (3) | 0.003 (2) | 0.002 (3) | −0.011 (3) |
C21 | 0.056 (3) | 0.070 (4) | 0.071 (4) | 0.021 (3) | 0.006 (3) | −0.007 (3) |
C22 | 0.085 (5) | 0.045 (3) | 0.077 (4) | 0.019 (3) | 0.010 (3) | −0.008 (3) |
C23 | 0.079 (4) | 0.046 (3) | 0.088 (4) | −0.005 (3) | 0.009 (3) | −0.024 (3) |
C24 | 0.052 (3) | 0.046 (3) | 0.063 (3) | −0.003 (2) | 0.004 (2) | −0.014 (2) |
C25 | 0.053 (3) | 0.059 (3) | 0.047 (3) | 0.009 (3) | 0.004 (2) | 0.007 (2) |
C26 | 0.086 (4) | 0.071 (4) | 0.044 (3) | 0.011 (3) | −0.002 (3) | 0.002 (3) |
C27 | 0.103 (5) | 0.088 (5) | 0.042 (3) | 0.020 (4) | −0.016 (3) | −0.009 (3) |
C28 | 0.075 (4) | 0.064 (4) | 0.056 (3) | 0.007 (3) | −0.017 (3) | −0.019 (3) |
C29 | 0.112 (6) | 0.075 (4) | 0.077 (4) | −0.008 (4) | −0.044 (4) | −0.021 (4) |
C30 | 0.105 (6) | 0.066 (4) | 0.101 (5) | −0.030 (4) | −0.034 (4) | −0.016 (4) |
C31 | 0.073 (4) | 0.054 (3) | 0.072 (4) | −0.012 (3) | −0.009 (3) | −0.011 (3) |
C32 | 0.096 (5) | 0.051 (4) | 0.088 (5) | −0.026 (3) | 0.001 (4) | −0.003 (3) |
C33 | 0.083 (4) | 0.050 (3) | 0.079 (4) | −0.016 (3) | 0.002 (3) | 0.010 (3) |
C34 | 0.060 (3) | 0.045 (3) | 0.053 (3) | −0.002 (2) | 0.005 (2) | −0.001 (2) |
C35 | 0.045 (3) | 0.040 (3) | 0.051 (3) | −0.002 (2) | −0.001 (2) | −0.010 (2) |
C36 | 0.054 (3) | 0.044 (3) | 0.038 (2) | 0.004 (2) | −0.002 (2) | −0.008 (2) |
B1 | 0.068 (5) | 0.064 (5) | 0.071 (5) | −0.015 (4) | −0.010 (4) | 0.015 (4) |
F1 | 0.112 (3) | 0.073 (3) | 0.110 (3) | −0.003 (2) | −0.003 (2) | 0.004 (2) |
F2 | 0.090 (8) | 0.116 (9) | 0.113 (8) | −0.001 (6) | −0.029 (6) | −0.023 (6) |
F3 | 0.086 (7) | 0.134 (8) | 0.151 (10) | 0.002 (6) | −0.035 (6) | −0.025 (7) |
F4 | 0.156 (9) | 0.128 (8) | 0.113 (7) | −0.030 (7) | 0.039 (7) | 0.033 (6) |
F4' | 0.129 (7) | 0.097 (6) | 0.091 (6) | −0.035 (6) | −0.028 (5) | 0.033 (5) |
F3' | 0.046 (5) | 0.091 (6) | 0.100 (7) | −0.016 (4) | −0.012 (4) | −0.006 (5) |
F2' | 0.064 (7) | 0.144 (13) | 0.139 (12) | −0.038 (7) | −0.028 (7) | −0.034 (9) |
C38 | 0.090 (11) | 0.079 (10) | 0.135 (14) | −0.024 (8) | −0.022 (9) | 0.037 (10) |
Cl1 | 0.129 (4) | 0.217 (6) | 0.143 (4) | −0.018 (4) | −0.006 (3) | −0.062 (4) |
Cl2 | 0.101 (3) | 0.079 (3) | 0.238 (6) | 0.010 (2) | 0.051 (3) | 0.018 (3) |
Cu1—N2 | 2.135 (4) | C17—C18 | 1.364 (7) |
Cu1—N3 | 2.088 (4) | C17—H17 | 0.930 |
Cu1—P1 | 2.2687 (12) | C18—H18 | 0.930 |
Cu1—P2 | 2.2272 (13) | C19—C24 | 1.373 (7) |
P1—N1i | 1.686 (4) | C19—C20 | 1.380 (7) |
P1—C1 | 1.818 (4) | C20—C21 | 1.382 (7) |
P1—C7 | 1.822 (5) | C20—H20 | 0.930 |
P2—N1 | 1.689 (4) | C21—C22 | 1.374 (9) |
P2—C19 | 1.826 (4) | C21—H21 | 0.930 |
P2—C13 | 1.833 (4) | C22—C23 | 1.366 (9) |
N2—C25 | 1.329 (6) | C22—H22 | 0.930 |
N2—C36 | 1.358 (6) | C23—C24 | 1.388 (8) |
N3—C34 | 1.332 (6) | C23—H23 | 0.930 |
N3—C35 | 1.368 (6) | C24—H24 | 0.930 |
C1—C6 | 1.380 (7) | C25—C26 | 1.391 (7) |
C1—C2 | 1.392 (6) | C25—H25 | 0.930 |
C2—C3 | 1.367 (7) | C26—C27 | 1.345 (9) |
C2—H2 | 0.930 | C26—H26 | 0.930 |
C3—C4 | 1.362 (9) | C27—C28 | 1.399 (9) |
C3—H3 | 0.930 | C27—H27 | 0.930 |
C4—C5 | 1.384 (9) | C28—C36 | 1.415 (7) |
C4—H4 | 0.930 | C28—C29 | 1.417 (9) |
C5—C6 | 1.385 (8) | C29—C30 | 1.333 (10) |
C5—H5 | 0.930 | C29—H29 | 0.930 |
C6—H6 | 0.930 | C30—C31 | 1.431 (9) |
C7—C12 | 1.372 (7) | C30—H30 | 0.930 |
C7—C8 | 1.394 (7) | C31—C32 | 1.398 (9) |
C8—C9 | 1.385 (8) | C31—C35 | 1.408 (7) |
C8—H8 | 0.930 | C32—C33 | 1.360 (9) |
C9—C10 | 1.357 (11) | C32—H32 | 0.930 |
C9—H9 | 0.930 | C33—C34 | 1.369 (8) |
C10—C11 | 1.360 (11) | C33—H33 | 0.930 |
C10—H10 | 0.930 | C34—H34 | 0.930 |
C11—C12 | 1.392 (9) | C35—C36 | 1.426 (7) |
C11—H11 | 0.930 | B1—F1 | 1.353 (6) |
C12—H12 | 0.930 | B1—F2 | 1.379 (9) |
N1—P1i | 1.686 (4) | B1—F3 | 1.339 (9) |
C13—C14 | 1.377 (7) | B1—F4 | 1.389 (8) |
C13—C18 | 1.385 (7) | B1—F2' | 1.366 (8) |
C14—C15 | 1.402 (8) | B1—F4' | 1.374 (8) |
C14—H14 | 0.930 | B1—F3' | 1.414 (8) |
C15—C16 | 1.366 (10) | C38—Cl2 | 1.711 (9) |
C15—H15 | 0.930 | C38—Cl1 | 1.739 (10) |
C16—C17 | 1.357 (10) | C38—H38A | 0.970 |
C16—H16 | 0.930 | C38—H38B | 0.970 |
P1—Cu1—N2 | 98.96 (11) | C17—C18—C13 | 121.5 (5) |
P1—Cu1—N3 | 98.69 (11) | C17—C18—H18 | 119.2 |
P1—Cu1—P2 | 135.28 (5) | C13—C18—H18 | 119.2 |
P2—Cu1—N2 | 105.24 (11) | C24—C19—C20 | 118.5 (4) |
P2—Cu1—N3 | 122.16 (11) | C24—C19—P2 | 119.4 (4) |
N2—Cu1—N3 | 79.47 (15) | C20—C19—P2 | 122.0 (4) |
N1i—P1—C1 | 101.66 (19) | C19—C20—C21 | 121.0 (5) |
N1i—P1—C7 | 105.9 (2) | C19—C20—H20 | 119.5 |
C1—P1—C7 | 101.4 (2) | C21—C20—H20 | 119.5 |
N1i—P1—Cu1 | 117.99 (14) | C22—C21—C20 | 119.6 (5) |
C1—P1—Cu1 | 106.13 (14) | C22—C21—H21 | 120.2 |
C7—P1—Cu1 | 120.71 (17) | C20—C21—H21 | 120.2 |
N1—P2—C19 | 105.5 (2) | C23—C22—C21 | 120.2 (5) |
N1—P2—C13 | 102.1 (2) | C23—C22—H22 | 119.9 |
C19—P2—C13 | 101.1 (2) | C21—C22—H22 | 119.9 |
N1—P2—Cu1 | 120.64 (14) | C22—C23—C24 | 119.8 (5) |
C19—P2—Cu1 | 116.27 (15) | C22—C23—H23 | 120.1 |
C13—P2—Cu1 | 108.62 (15) | C24—C23—H23 | 120.1 |
C25—N2—C36 | 117.9 (4) | C19—C24—C23 | 120.9 (5) |
C25—N2—Cu1 | 130.0 (3) | C19—C24—H24 | 119.6 |
C36—N2—Cu1 | 111.7 (3) | C23—C24—H24 | 119.6 |
C34—N3—C35 | 117.1 (4) | N2—C25—C26 | 122.7 (5) |
C34—N3—Cu1 | 129.4 (3) | N2—C25—H25 | 118.7 |
C35—N3—Cu1 | 112.8 (3) | C26—C25—H25 | 118.7 |
C6—C1—C2 | 118.3 (4) | C27—C26—C25 | 119.5 (6) |
C6—C1—P1 | 121.1 (4) | C27—C26—H26 | 120.3 |
C2—C1—P1 | 120.0 (4) | C25—C26—H26 | 120.3 |
C3—C2—C1 | 121.0 (5) | C26—C27—C28 | 120.9 (5) |
C3—C2—H2 | 119.5 | C26—C27—H27 | 119.6 |
C1—C2—H2 | 119.5 | C28—C27—H27 | 119.6 |
C4—C3—C2 | 120.8 (6) | C27—C28—C36 | 116.2 (6) |
C4—C3—H3 | 119.6 | C27—C28—C29 | 125.1 (6) |
C2—C3—H3 | 119.6 | C36—C28—C29 | 118.6 (6) |
C3—C4—C5 | 119.2 (6) | C30—C29—C28 | 122.2 (6) |
C3—C4—H4 | 120.4 | C30—C29—H29 | 118.9 |
C5—C4—H4 | 120.4 | C28—C29—H29 | 118.9 |
C4—C5—C6 | 120.4 (6) | C29—C30—C31 | 121.1 (6) |
C4—C5—H5 | 119.8 | C29—C30—H30 | 119.5 |
C6—C5—H5 | 119.8 | C31—C30—H30 | 119.5 |
C1—C6—C5 | 120.3 (5) | C32—C31—C35 | 117.4 (5) |
C1—C6—H6 | 119.9 | C32—C31—C30 | 124.0 (6) |
C5—C6—H6 | 119.9 | C35—C31—C30 | 118.5 (6) |
C12—C7—C8 | 119.1 (5) | C33—C32—C31 | 120.2 (6) |
C12—C7—P1 | 119.2 (4) | C33—C32—H32 | 119.9 |
C8—C7—P1 | 121.7 (4) | C31—C32—H32 | 119.9 |
C9—C8—C7 | 119.9 (6) | C32—C33—C34 | 118.7 (6) |
C9—C8—H8 | 120.0 | C32—C33—H33 | 120.6 |
C7—C8—H8 | 120.0 | C34—C33—H33 | 120.6 |
C10—C9—C8 | 120.3 (7) | N3—C34—C33 | 124.5 (5) |
C10—C9—H9 | 119.9 | N3—C34—H34 | 117.7 |
C8—C9—H9 | 119.9 | C33—C34—H34 | 117.7 |
C9—C10—C11 | 120.4 (6) | N3—C35—C31 | 122.0 (5) |
C9—C10—H10 | 119.8 | N3—C35—C36 | 117.8 (4) |
C11—C10—H10 | 119.8 | C31—C35—C36 | 120.2 (5) |
C10—C11—C12 | 120.4 (7) | N2—C36—C28 | 122.8 (5) |
C10—C11—H11 | 119.8 | N2—C36—C35 | 117.8 (4) |
C12—C11—H11 | 119.8 | C28—C36—C35 | 119.3 (5) |
C7—C12—C11 | 120.0 (6) | F3—B1—F1 | 113.9 (8) |
C7—C12—H12 | 120.0 | F3—B1—F2 | 111.0 (8) |
C11—C12—H12 | 120.0 | F1—B1—F2 | 110.8 (8) |
P1i—N1—P2 | 125.8 (2) | F3—B1—F4 | 108.9 (8) |
C14—C13—C18 | 118.8 (5) | F1—B1—F4 | 105.4 (7) |
C14—C13—P2 | 121.2 (4) | F2—B1—F4 | 106.4 (9) |
C18—C13—P2 | 119.8 (4) | F1—B1—F2' | 113.8 (8) |
C13—C14—C15 | 119.0 (6) | F1—B1—F4' | 115.7 (7) |
C13—C14—H14 | 120.5 | F2'—B1—F4' | 109.9 (8) |
C15—C14—H14 | 120.5 | F1—B1—F3' | 105.1 (6) |
C16—C15—C14 | 120.6 (6) | F2'—B1—F3' | 107.5 (9) |
C16—C15—H15 | 119.7 | F4'—B1—F3' | 103.8 (7) |
C14—C15—H15 | 119.7 | Cl2—C38—Cl1 | 110.7 (7) |
C17—C16—C15 | 120.2 (6) | Cl2—C38—H38A | 109.5 |
C17—C16—H16 | 119.9 | Cl1—C38—H38A | 109.5 |
C15—C16—H16 | 119.9 | Cl2—C38—H38B | 109.5 |
C16—C17—C18 | 119.9 (6) | Cl1—C38—H38B | 109.5 |
C16—C17—H17 | 120.1 | H38A—C38—H38B | 108.1 |
C18—C17—H17 | 120.1 | ||
N3—Cu1—P1—N1i | −58.92 (19) | Cu1—P2—C13—C14 | −95.0 (4) |
N2—Cu1—P1—N1i | −139.54 (19) | N1—P2—C13—C18 | −152.1 (4) |
P2—Cu1—P1—N1i | 97.95 (17) | C19—P2—C13—C18 | −43.4 (4) |
N3—Cu1—P1—C1 | 54.15 (18) | Cu1—P2—C13—C18 | 79.4 (4) |
N2—Cu1—P1—C1 | −26.47 (19) | C18—C13—C14—C15 | 0.5 (8) |
P2—Cu1—P1—C1 | −148.98 (15) | P2—C13—C14—C15 | 174.9 (5) |
N3—Cu1—P1—C7 | 168.4 (2) | C13—C14—C15—C16 | −1.1 (10) |
N2—Cu1—P1—C7 | 87.8 (2) | C14—C15—C16—C17 | 0.4 (12) |
P2—Cu1—P1—C7 | −34.70 (19) | C15—C16—C17—C18 | 0.8 (11) |
N3—Cu1—P2—N1 | 118.7 (2) | C16—C17—C18—C13 | −1.5 (9) |
N2—Cu1—P2—N1 | −154.27 (19) | C14—C13—C18—C17 | 0.8 (8) |
P1—Cu1—P2—N1 | −33.96 (18) | P2—C13—C18—C17 | −173.7 (5) |
N3—Cu1—P2—C19 | −11.0 (2) | N1—P2—C19—C24 | −151.9 (4) |
N2—Cu1—P2—C19 | 76.01 (19) | C13—P2—C19—C24 | 102.1 (4) |
P1—Cu1—P2—C19 | −163.68 (16) | Cu1—P2—C19—C24 | −15.3 (4) |
N3—Cu1—P2—C13 | −124.1 (2) | N1—P2—C19—C20 | 28.6 (4) |
N2—Cu1—P2—C13 | −37.12 (19) | C13—P2—C19—C20 | −77.4 (4) |
P1—Cu1—P2—C13 | 83.19 (17) | Cu1—P2—C19—C20 | 165.3 (4) |
N3—Cu1—N2—C25 | −177.5 (4) | C24—C19—C20—C21 | 1.2 (8) |
P2—Cu1—N2—C25 | 61.8 (4) | P2—C19—C20—C21 | −179.3 (4) |
P1—Cu1—N2—C25 | −80.3 (4) | C19—C20—C21—C22 | 0.3 (9) |
N3—Cu1—N2—C36 | −4.7 (3) | C20—C21—C22—C23 | −1.2 (9) |
P2—Cu1—N2—C36 | −125.4 (3) | C21—C22—C23—C24 | 0.6 (10) |
P1—Cu1—N2—C36 | 92.6 (3) | C20—C19—C24—C23 | −1.9 (8) |
N2—Cu1—N3—C34 | 175.7 (4) | P2—C19—C24—C23 | 178.6 (4) |
P2—Cu1—N3—C34 | −82.9 (4) | C22—C23—C24—C19 | 1.0 (9) |
P1—Cu1—N3—C34 | 78.1 (4) | C36—N2—C25—C26 | 2.4 (7) |
N2—Cu1—N3—C35 | 5.7 (3) | Cu1—N2—C25—C26 | 174.9 (4) |
P2—Cu1—N3—C35 | 107.2 (3) | N2—C25—C26—C27 | −1.8 (9) |
P1—Cu1—N3—C35 | −91.9 (3) | C25—C26—C27—C28 | −0.2 (10) |
N1i—P1—C1—C6 | 41.9 (4) | C26—C27—C28—C36 | 1.4 (9) |
C7—P1—C1—C6 | 151.0 (4) | C26—C27—C28—C29 | −176.8 (7) |
Cu1—P1—C1—C6 | −82.1 (4) | C27—C28—C29—C30 | 178.1 (7) |
N1i—P1—C1—C2 | −147.0 (4) | C36—C28—C29—C30 | −0.1 (11) |
C7—P1—C1—C2 | −37.9 (4) | C28—C29—C30—C31 | 0.6 (12) |
Cu1—P1—C1—C2 | 89.0 (4) | C29—C30—C31—C32 | −178.5 (8) |
C6—C1—C2—C3 | −0.7 (8) | C29—C30—C31—C35 | −0.6 (11) |
P1—C1—C2—C3 | −172.0 (4) | C35—C31—C32—C33 | 0.2 (10) |
C1—C2—C3—C4 | 0.5 (9) | C30—C31—C32—C33 | 178.1 (7) |
C2—C3—C4—C5 | −0.7 (11) | C31—C32—C33—C34 | 0.1 (10) |
C3—C4—C5—C6 | 1.1 (11) | C35—N3—C34—C33 | −2.1 (8) |
C2—C1—C6—C5 | 1.0 (8) | Cu1—N3—C34—C33 | −171.7 (4) |
P1—C1—C6—C5 | 172.3 (5) | C32—C33—C34—N3 | 1.0 (10) |
C4—C5—C6—C1 | −1.2 (10) | C34—N3—C35—C31 | 2.3 (7) |
N1i—P1—C7—C12 | −137.2 (4) | Cu1—N3—C35—C31 | 173.6 (4) |
C1—P1—C7—C12 | 117.0 (4) | C34—N3—C35—C36 | −177.3 (4) |
Cu1—P1—C7—C12 | 0.3 (4) | Cu1—N3—C35—C36 | −6.0 (5) |
N1i—P1—C7—C8 | 44.6 (5) | C32—C31—C35—N3 | −1.4 (8) |
C1—P1—C7—C8 | −61.1 (4) | C30—C31—C35—N3 | −179.5 (6) |
Cu1—P1—C7—C8 | −177.8 (4) | C32—C31—C35—C36 | 178.2 (5) |
C12—C7—C8—C9 | 1.5 (8) | C30—C31—C35—C36 | 0.2 (9) |
P1—C7—C8—C9 | 179.6 (5) | C25—N2—C36—C28 | −1.1 (7) |
C7—C8—C9—C10 | −0.4 (10) | Cu1—N2—C36—C28 | −174.8 (4) |
C8—C9—C10—C11 | −0.7 (11) | C25—N2—C36—C35 | 176.8 (4) |
C9—C10—C11—C12 | 0.6 (10) | Cu1—N2—C36—C35 | 3.0 (5) |
C8—C7—C12—C11 | −1.5 (8) | C27—C28—C36—N2 | −0.8 (8) |
P1—C7—C12—C11 | −179.7 (4) | C29—C28—C36—N2 | 177.5 (5) |
C10—C11—C12—C7 | 0.5 (9) | C27—C28—C36—C35 | −178.7 (5) |
C19—P2—N1—P1i | 122.7 (3) | C29—C28—C36—C35 | −0.3 (8) |
C13—P2—N1—P1i | −132.0 (3) | N3—C35—C36—N2 | 2.0 (7) |
Cu1—P2—N1—P1i | −11.6 (3) | C31—C35—C36—N2 | −177.7 (5) |
N1—P2—C13—C14 | 33.5 (4) | N3—C35—C36—C28 | 179.9 (5) |
C19—P2—C13—C14 | 142.2 (4) | C31—C35—C36—C28 | 0.3 (7) |
Symmetry code: (i) −x, y, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cu2(C25H21NP2)2(C12H8N2)2](BF4)2·CH2Cl2 |
Mr | 1514.76 |
Crystal system, space group | Orthorhombic, Pbcn |
Temperature (K) | 294 |
a, b, c (Å) | 19.8730 (15), 17.4039 (13), 21.0008 (16) |
V (Å3) | 7263.5 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.81 |
Crystal size (mm) | 0.26 × 0.18 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.833, 0.919 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 34870, 6356, 4243 |
Rint | 0.046 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.195, 1.01 |
No. of reflections | 6356 |
No. of parameters | 478 |
No. of restraints | 93 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.96, −0.30 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.
Cu1—N2 | 2.135 (4) | Cu1—P1 | 2.2687 (12) |
Cu1—N3 | 2.088 (4) | Cu1—P2 | 2.2272 (13) |
P1—Cu1—N2 | 98.96 (11) | P2—Cu1—N2 | 105.24 (11) |
P1—Cu1—N3 | 98.69 (11) | P2—Cu1—N3 | 122.16 (11) |
P1—Cu1—P2 | 135.28 (5) | N2—Cu1—N3 | 79.47 (15) |
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Diphosphinoamine ligands can bind to metals in monodentate, bidentate, chelating and bridging modes and their complexes find application in diverse areas such as supramolecular design, photophysics and catalysis (Liu et al., 2002; İrişli & Şen, 2005; Ahuja et al., 2007; Sekabunga et al., 2002). The title compound is a new CuI complex with bis(diphenylphosphino)amine (dppa).
The compound consists of [Cu2(phen)2(dppa)2]2+ cations (phen is 1,10-phenanthroline) located on 2-fold rotation axes. The two CuI atoms are bridged by two dppa ligands to form an eight-membered Cu2P4N2 ring. The distance between the two metal centres is 3.616 (4) Å, which is too long for any significant metal–metal bonding interaction. Each CuI atom adopts a distorted tetrahedral coordination geometry, with the angles around CuI ranging from 79.5 (2) ° for N2—Cu1—N3 to 135.28 (5) ° for P1—Cu1—P2A (where the suffix A denotes the symmetry operator -x, y, 1/2 - z).