The title compound, [Cu(C3H9P4)4][CuCl2], previously reported by Chi et al. [J. Chem. Soc. Dalton Trans. (1992), pp. 3111-3117] has been rerefined with new intensity data. Geometric parameters agree quite well. However, our results are of significantly higher precision. Furthermore, our data indicate a different absolute structure than the one reported by Chi et al. The Cu, Cl atoms and one of the P atoms are located on a threefold rotation axis. As a result, there is just one third of both ions in the asymmetric unit.
Supporting information
CCDC reference: 199145
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (Cu-Cl) = 0.001 Å
- R factor = 0.031
- wR factor = 0.080
- Data-to-parameter ratio = 35.6
checkCIF/PLATON results
No syntax errors found
Alert level A
PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low ....... 0.91
| Author Response: The data are 96.2 % complete to 2theta = 50 deg.
|
Alert level C
PLAT242_ALERT_2_C Check Low U(eq) as Compared to Neighbors .... P1
PLAT242_ALERT_2_C Check Low U(eq) as Compared to Neighbors .... P2
PLAT244_ALERT_4_C Low Solvent U(eq) as Compared to Neighbors .... Cu2
Alert level G
REFLT03_ALERT_4_G WARNING: Large fraction of Friedel related reflns may
be needed to determine absolute structure
From the CIF: _diffrn_reflns_theta_max 31.32
From the CIF: _reflns_number_total 2172
Count of symmetry unique reflns 1486
Completeness (_total/calc) 146.16%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 686
Fraction of Friedel pairs measured 0.462
Are heavy atom types Z>Si present yes
1 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
3 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
2 ALERT type 2 Indicator that the structure model may be wrong or deficient
1 ALERT type 3 Indicator that the structure quality may be low
2 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 1990).
Crystal data top
[Cu(C3H9P4)4][CuCl2] | Dx = 1.361 Mg m−3 |
Mr = 502.27 | Mo Kα radiation, λ = 0.71073 Å |
Cubic, P213 | Cell parameters from 5949 reflections |
Hall symbol: P 2ac 2ab 3 | θ = 3.8–31.3° |
a = 13.4832 (11) Å | µ = 2.21 mm−1 |
V = 2451.2 (3) Å3 | T = 173 K |
Z = 4 | Block, colourless |
F(000) = 1040 | 0.50 × 0.40 × 0.30 mm |
Data collection top
Stoe IPDS-II two-circle diffractometer | 2172 independent reflections |
Radiation source: fine-focus sealed tube | 2035 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
ω scans | θmax = 31.3°, θmin = 3.7° |
Absorption correction: empirical (MULABS; Spek, 1990; Blessing, 1995) | h = −18→18 |
Tmin = 0.380, Tmax = 0.521 | k = −11→19 |
4186 measured reflections | l = −18→4 |
Refinement top
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)] = 0.031 | H-atom parameters constrained |
wR(F2) = 0.080 | w = 1/[σ2(Fo2) + (0.0565P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
2172 reflections | Δρmax = 0.28 e Å−3 |
61 parameters | Δρmin = −0.37 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 686 Friedels |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.012 (14) |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu1 | 0.543243 (16) | 0.543243 (16) | 0.543243 (16) | 0.03172 (9) | |
P1 | 0.44661 (4) | 0.44661 (4) | 0.44661 (4) | 0.0444 (2) | |
P2 | 0.56283 (4) | 0.69364 (4) | 0.47078 (5) | 0.04043 (13) | |
C1 | 0.4214 (5) | 0.3225 (3) | 0.4927 (5) | 0.0959 (16) | |
H1A | 0.3789 | 0.2872 | 0.4454 | 0.144* | |
H1B | 0.3876 | 0.3269 | 0.5569 | 0.144* | |
H1C | 0.4839 | 0.2864 | 0.5007 | 0.144* | |
C2 | 0.6560 (2) | 0.7748 (2) | 0.5257 (3) | 0.0580 (7) | |
H2A | 0.7195 | 0.7396 | 0.5295 | 0.087* | |
H2B | 0.6349 | 0.7940 | 0.5925 | 0.087* | |
H2C | 0.6636 | 0.8342 | 0.4846 | 0.087* | |
C3 | 0.4546 (2) | 0.7750 (2) | 0.4689 (5) | 0.0833 (14) | |
H3A | 0.3978 | 0.7392 | 0.4409 | 0.125* | |
H3B | 0.4688 | 0.8334 | 0.4281 | 0.125* | |
H3C | 0.4389 | 0.7960 | 0.5367 | 0.125* | |
C4 | 0.6003 (5) | 0.6932 (4) | 0.3404 (3) | 0.0843 (13) | |
H4A | 0.5550 | 0.6510 | 0.3023 | 0.127* | |
H4B | 0.6680 | 0.6674 | 0.3347 | 0.127* | |
H4C | 0.5979 | 0.7610 | 0.3143 | 0.127* | |
Cu2 | 0.86620 (2) | 0.86620 (2) | 0.86620 (2) | 0.04708 (13) | |
Cl1 | 0.95586 (7) | 0.95586 (7) | 0.95586 (7) | 0.0914 (6) | |
Cl2 | 0.77738 (7) | 0.77738 (7) | 0.77738 (7) | 0.1003 (7) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.03172 (9) | 0.03172 (9) | 0.03172 (9) | −0.00126 (8) | −0.00126 (8) | −0.00126 (8) |
P1 | 0.0444 (2) | 0.0444 (2) | 0.0444 (2) | −0.0078 (2) | −0.0078 (2) | −0.0078 (2) |
P2 | 0.0357 (3) | 0.0370 (2) | 0.0487 (3) | −0.00312 (18) | −0.0048 (2) | 0.0080 (2) |
C1 | 0.121 (4) | 0.0518 (17) | 0.115 (4) | −0.037 (2) | −0.030 (3) | 0.005 (2) |
C2 | 0.0480 (13) | 0.0481 (12) | 0.078 (2) | −0.0162 (10) | −0.0082 (13) | 0.0053 (13) |
C3 | 0.0450 (14) | 0.0497 (13) | 0.155 (4) | 0.0053 (11) | −0.015 (2) | 0.024 (2) |
C4 | 0.125 (4) | 0.077 (2) | 0.0507 (16) | −0.012 (2) | 0.006 (2) | 0.0215 (15) |
Cu2 | 0.04708 (13) | 0.04708 (13) | 0.04708 (13) | −0.00266 (12) | −0.00266 (12) | −0.00266 (12) |
Cl1 | 0.0914 (6) | 0.0914 (6) | 0.0914 (6) | −0.0242 (5) | −0.0242 (5) | −0.0242 (5) |
Cl2 | 0.1003 (7) | 0.1003 (7) | 0.1003 (7) | −0.0301 (6) | −0.0301 (6) | −0.0301 (6) |
Geometric parameters (Å, º) top
Cu1—P1 | 2.2567 (11) | C1—H1C | 0.9800 |
Cu1—P2i | 2.2663 (6) | C2—H2A | 0.9800 |
Cu1—P2 | 2.2664 (6) | C2—H2B | 0.9800 |
Cu1—P2ii | 2.2664 (6) | C2—H2C | 0.9800 |
P1—C1i | 1.818 (4) | C3—H3A | 0.9800 |
P1—C1 | 1.818 (4) | C3—H3B | 0.9800 |
P1—C1ii | 1.818 (4) | C3—H3C | 0.9800 |
P2—C2 | 1.823 (3) | C4—H4A | 0.9800 |
P2—C3 | 1.826 (3) | C4—H4B | 0.9800 |
P2—C4 | 1.829 (4) | C4—H4C | 0.9800 |
C1—H1A | 0.9800 | Cu2—Cl2 | 2.0743 (17) |
C1—H1B | 0.9800 | Cu2—Cl1 | 2.0938 (16) |
| | | |
P1—Cu1—P2i | 109.570 (18) | H1A—C1—H1C | 109.5 |
P1—Cu1—P2 | 109.569 (17) | H1B—C1—H1C | 109.5 |
P2i—Cu1—P2 | 109.372 (17) | P2—C2—H2A | 109.5 |
P1—Cu1—P2ii | 109.569 (17) | P2—C2—H2B | 109.5 |
P2i—Cu1—P2ii | 109.373 (18) | H2A—C2—H2B | 109.5 |
P2—Cu1—P2ii | 109.373 (18) | P2—C2—H2C | 109.5 |
C1i—P1—C1 | 101.9 (2) | H2A—C2—H2C | 109.5 |
C1i—P1—C1ii | 101.9 (2) | H2B—C2—H2C | 109.5 |
C1—P1—C1ii | 101.9 (2) | P2—C3—H3A | 109.5 |
C1i—P1—Cu1 | 116.26 (18) | P2—C3—H3B | 109.5 |
C1—P1—Cu1 | 116.26 (18) | H3A—C3—H3B | 109.5 |
C1ii—P1—Cu1 | 116.26 (18) | P2—C3—H3C | 109.5 |
C2—P2—C3 | 101.31 (18) | H3A—C3—H3C | 109.5 |
C2—P2—C4 | 101.7 (2) | H3B—C3—H3C | 109.5 |
C3—P2—C4 | 102.1 (3) | P2—C4—H4A | 109.5 |
C2—P2—Cu1 | 116.23 (11) | P2—C4—H4B | 109.5 |
C3—P2—Cu1 | 116.76 (13) | H4A—C4—H4B | 109.5 |
C4—P2—Cu1 | 116.35 (15) | P2—C4—H4C | 109.5 |
P1—C1—H1A | 109.5 | H4A—C4—H4C | 109.5 |
P1—C1—H1B | 109.5 | H4B—C4—H4C | 109.5 |
H1A—C1—H1B | 109.5 | Cl2—Cu2—Cl1 | 180.00 (3) |
P1—C1—H1C | 109.5 | | |
| | | |
P2i—Cu1—P1—C1i | −179.6 (3) | P1—Cu1—P2—C2 | −169.42 (13) |
P2—Cu1—P1—C1i | 60.4 (3) | P2i—Cu1—P2—C2 | 70.46 (13) |
P2ii—Cu1—P1—C1i | −59.6 (3) | P2ii—Cu1—P2—C2 | −49.30 (14) |
P2i—Cu1—P1—C1 | −59.6 (3) | P1—Cu1—P2—C3 | 71.0 (2) |
P2—Cu1—P1—C1 | −179.6 (3) | P2i—Cu1—P2—C3 | −49.1 (2) |
P2ii—Cu1—P1—C1 | 60.4 (3) | P2ii—Cu1—P2—C3 | −168.9 (2) |
P2i—Cu1—P1—C1ii | 60.4 (3) | P1—Cu1—P2—C4 | −49.7 (2) |
P2—Cu1—P1—C1ii | −59.6 (3) | P2i—Cu1—P2—C4 | −169.8 (2) |
P2ii—Cu1—P1—C1ii | −179.6 (3) | P2ii—Cu1—P2—C4 | 70.4 (2) |
Symmetry codes: (i) z, x, y; (ii) y, z, x. |