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Reaction of CuCl2(H2O)2 with diethylenetriamine (henceforth dien) in a 1:1 ratio has led to the formation of a non-centrosymmetric di-μ-chloro bibridged binuclear CuII species in which a water molecule is coordinated axially to one of the CuII ions. [Cu2Cl2(C4H13N3)2(H2O)] contains dinuclear [(dien)2Cu2Cl2(H2O)]2+ cations and chloride ions. Both CuII ions in the dimer have a primary coordination sphere that is approximately planar, consisting of one dien molecule and one chloride ion. These monomeric units are linked via semicoordinate Cu—Cl bonds to form dinuclear units. One CuII ion has a 4+1 coordination geometry while the second expands to a 4+2 geometry by the incorporation of a water molecule. The dinuclear cation has crystallographic reflection symmetry, the mirror plane containing the central Cu2Cl2 unit and the central N atom of each dien ligand.
Supporting information
CCDC reference: 177191
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.015 Å
- R factor = 0.041
- wR factor = 0.116
- Data-to-parameter ratio = 22.0
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
REFLT_03
From the CIF: _diffrn_reflns_theta_max 27.50
From the CIF: _reflns_number_total 2243
TEST2: Reflns within _diffrn_reflns_theta_max
Count of symmetry unique reflns 2405
Completeness (_total/calc) 93.26%
Alert C: < 95% complete
PLAT_030 Alert C Refined Extinction parameter within range .... 3.00 Sigma
PLAT_162 Alert C Missing or Zero su (esd) on y-coordinate for . CL1
General Notes
ABSTM_02 When printed, the submitted absorption T values will be replaced
by the scaled T values. Since the ratio of scaled T's is
identical to the ratio of reported T values, the scaling does
not imply a change to the absorption corrections used in the
study.
Ratio of Tmax expected/reported 0.891
Tmax scaled 0.767 Tmin scaled 0.431
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
3 Alert Level C = Please check
Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: XS in SHELXTL (Bruker, 1998); program(s) used to refine structure: XL in SHELXTL; molecular graphics: XP in SHELXTL; software used to prepare material for publication: XCIF in SHELXTL.
Crystal data top
[Cu2Cl2(C4H13N3)2(H2O)] | F(000) = 502 |
Mr = 493.24 | Dx = 1.624 Mg m−3 |
Monoclinic, P21/m | Mo Kα radiation, λ = 0.71073 Å |
a = 6.7155 (8) Å | Cell parameters from 34 reflections |
b = 14.6106 (11) Å | θ = 5.9–15.0° |
c = 10.3011 (8) Å | µ = 2.65 mm−1 |
β = 95.333 (10)° | T = 293 K |
V = 1006.34 (16) Å3 | Parallelepiped, blue |
Z = 2 | 0.3 × 0.25 × 0.1 mm |
Data collection top
Four-circle diffractometer | 1948 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.051 |
Graphite monochromator | θmax = 27.5°, θmin = 2.0° |
ω scans | h = −1→8 |
Absorption correction: empirical (using intensity measurements) (XEMP; Siemens, 1990) | k = −1→18 |
Tmin = 0.484, Tmax = 0.861 | l = −13→13 |
3012 measured reflections | 3 standard reflections every 100 reflections |
2243 independent reflections | intensity decay: <3% |
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)] = 0.041 | H-atom parameters constrained |
wR(F2) = 0.116 | w = 1/[σ2(Fo2) + (0.0743P)2 + 0.9546P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
2243 reflections | Δρmax = 0.75 e Å−3 |
102 parameters | Δρmin = −0.57 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.009 (3) |
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 | 0.39424 (14) | 0.7500 | 1.06341 (9) | 0.0318 (4) | |
Cu2 | 0.57159 (14) | 0.7500 | 1.40987 (10) | 0.0328 (4) | |
Cl2 | 0.7211 (3) | 0.7500 | 1.1425 (2) | 0.0587 (8) | |
Cl3 | 0.2609 (3) | 0.7500 | 1.3003 (2) | 0.0453 (6) | |
N1 | 0.3840 (12) | 0.6159 (5) | 1.0301 (6) | 0.0605 (19) | |
H1A | 0.4657 | 0.6014 | 0.9686 | 0.073* | |
H1B | 0.4258 | 0.5854 | 1.1036 | 0.073* | |
C2 | 0.1794 (19) | 0.5893 (10) | 0.9864 (10) | 0.105 (5) | |
H2A | 0.1040 | 0.5796 | 1.0611 | 0.127* | |
H2B | 0.1797 | 0.5326 | 0.9375 | 0.127* | |
C3 | 0.0844 (14) | 0.6634 (11) | 0.9024 (9) | 0.103 (5) | |
H3A | 0.1453 | 0.6666 | 0.8207 | 0.124* | |
H3B | −0.0574 | 0.6515 | 0.8833 | 0.124* | |
N4 | 0.1159 (12) | 0.7500 | 0.9754 (8) | 0.072 (4) | |
H4 | 0.0306 | 0.7500 | 1.0391 | 0.086* | |
N11 | 0.5938 (8) | 0.6144 (4) | 1.4370 (5) | 0.0414 (12) | |
H11A | 0.5306 | 0.5980 | 1.5067 | 0.050* | |
H11B | 0.5357 | 0.5849 | 1.3666 | 0.050* | |
C12 | 0.8066 (12) | 0.5891 (6) | 1.4578 (8) | 0.058 (2) | |
H12A | 0.8610 | 0.5807 | 1.3746 | 0.070* | |
H12B | 0.8215 | 0.5321 | 1.5060 | 0.070* | |
C13 | 0.9168 (10) | 0.6647 (7) | 1.5336 (7) | 0.054 (2) | |
H13A | 0.8761 | 0.6676 | 1.6214 | 0.065* | |
H13B | 1.0599 | 0.6541 | 1.5389 | 0.065* | |
N14 | 0.8664 (4) | 0.7500 | 1.46409 (17) | 0.0383 (17) | |
H14 | 0.9310 | 0.7500 | 1.3903 | 0.046* | |
O | 0.4490 (4) | 0.7500 | 1.64280 (17) | 0.070 (2) | |
H0A | 0.4831 | 0.7099 | 1.6939 | 0.084* | |
Cl1 | 0.5645 (4) | 0.5562 | 1.75621 (17) | 0.0761 (8) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0276 (6) | 0.0407 (6) | 0.0269 (5) | 0.000 | 0.0020 (4) | 0.000 |
Cu2 | 0.0281 (6) | 0.0332 (6) | 0.0359 (6) | 0.000 | −0.0029 (4) | 0.000 |
Cl2 | 0.0262 (10) | 0.112 (3) | 0.0381 (12) | 0.000 | 0.0046 (8) | 0.000 |
Cl3 | 0.0243 (9) | 0.0834 (18) | 0.0285 (9) | 0.000 | 0.0041 (7) | 0.000 |
N1 | 0.097 (5) | 0.049 (4) | 0.038 (3) | −0.022 (4) | 0.019 (3) | −0.005 (3) |
C2 | 0.121 (10) | 0.134 (11) | 0.065 (6) | −0.093 (9) | 0.031 (7) | −0.031 (7) |
C3 | 0.055 (5) | 0.209 (15) | 0.046 (4) | −0.064 (7) | 0.003 (4) | −0.026 (7) |
N4 | 0.026 (4) | 0.161 (13) | 0.028 (4) | 0.000 | 0.003 (3) | 0.000 |
N11 | 0.050 (3) | 0.037 (3) | 0.036 (3) | 0.003 (2) | 0.003 (2) | −0.001 (2) |
C12 | 0.059 (4) | 0.054 (5) | 0.062 (5) | 0.026 (4) | 0.012 (4) | 0.007 (4) |
C13 | 0.035 (3) | 0.079 (6) | 0.047 (4) | 0.015 (4) | −0.001 (3) | 0.014 (4) |
N14 | 0.028 (3) | 0.059 (5) | 0.028 (3) | 0.000 | 0.007 (3) | 0.000 |
O | 0.094 (7) | 0.061 (5) | 0.055 (5) | 0.000 | 0.008 (5) | 0.000 |
Cl1 | 0.150 (2) | 0.0428 (11) | 0.0393 (9) | −0.0209 (13) | 0.0271 (12) | −0.0037 (8) |
Geometric parameters (Å, º) top
Cu1—N1 | 1.989 (7) | C3—N4 | 1.477 (14) |
Cu1—N1i | 1.990 (7) | C3—H3A | 0.9700 |
Cu1—N4 | 2.000 (8) | C3—H3B | 0.9700 |
Cu1—Cl2 | 2.269 (2) | N4—C3i | 1.477 (14) |
Cu1—Cl3 | 2.676 (2) | N4—H4 | 0.9100 |
Cu2—N11i | 2.005 (6) | N11—C12 | 1.472 (9) |
Cu2—N11 | 2.005 (6) | N11—H11A | 0.9000 |
Cu2—N14 | 2.006 (3) | N11—H11B | 0.9000 |
Cu2—Cl3 | 2.278 (2) | C12—C13 | 1.507 (13) |
Cu2—O | 2.608 (2) | C12—H12A | 0.9700 |
Cu2—Cl2 | 3.018 (2) | C12—H12B | 0.9700 |
N1—C2 | 1.459 (13) | C13—N14 | 1.461 (8) |
N1—H1A | 0.9000 | C13—H13A | 0.9700 |
N1—H1B | 0.9000 | C13—H13B | 0.9700 |
C2—C3 | 1.49 (2) | N14—C13i | 1.461 (8) |
C2—H2A | 0.9700 | N14—H14 | 0.9100 |
C2—H2B | 0.9700 | O—H0A | 0.8064 |
| | | |
N1—Cu1—N1i | 160.1 (4) | N4—C3—H3B | 110.3 |
N1—Cu1—N4 | 84.6 (2) | C2—C3—H3B | 110.3 |
N1i—Cu1—N4 | 84.6 (2) | H3A—C3—H3B | 108.6 |
N1—Cu1—Cl2 | 94.5 (2) | C3—N4—C3i | 117.9 (12) |
N1i—Cu1—Cl2 | 94.5 (2) | C3—N4—Cu1 | 108.3 (6) |
N4—Cu1—Cl2 | 174.1 (2) | C3i—N4—Cu1 | 108.3 (6) |
N1—Cu1—Cl3 | 98.53 (18) | C3—N4—H4 | 107.3 |
N1i—Cu1—Cl3 | 98.53 (18) | C3i—N4—H4 | 107.3 |
N4—Cu1—Cl3 | 92.0 (2) | Cu1—N4—H4 | 107.3 |
Cl2—Cu1—Cl3 | 93.84 (8) | C12—N11—Cu2 | 109.1 (5) |
N11i—Cu2—N11 | 162.6 (3) | C12—N11—H11A | 109.9 |
N11i—Cu2—N14 | 84.40 (17) | Cu2—N11—H11A | 109.9 |
N11—Cu2—N14 | 84.40 (17) | C12—N11—H11B | 109.9 |
N11i—Cu2—Cl3 | 97.00 (17) | Cu2—N11—H11B | 109.9 |
N11—Cu2—Cl3 | 97.00 (17) | H11A—N11—H11B | 108.3 |
N14—Cu2—Cl3 | 166.53 (9) | N11—C12—C13 | 108.3 (6) |
Cu2—Cl3—Cu1 | 94.77 (7) | N11—C12—H12A | 110.0 |
Cu2—Cl2—Cu1 | 86.27 (7) | C13—C12—H12A | 110.0 |
C2—N1—Cu1 | 109.4 (8) | N11—C12—H12B | 110.0 |
C2—N1—H1A | 109.8 | C13—C12—H12B | 110.0 |
Cu1—N1—H1A | 109.8 | H12A—C12—H12B | 108.4 |
C2—N1—H1B | 109.8 | N14—C13—C12 | 106.9 (5) |
Cu1—N1—H1B | 109.8 | N14—C13—H13A | 110.3 |
H1A—N1—H1B | 108.2 | C12—C13—H13A | 110.3 |
N1—C2—C3 | 109.0 (8) | N14—C13—H13B | 110.3 |
N1—C2—H2A | 109.9 | C12—C13—H13B | 110.3 |
C3—C2—H2A | 109.9 | H13A—C13—H13B | 108.6 |
N1—C2—H2B | 109.9 | C13i—N14—C13 | 117.0 (7) |
C3—C2—H2B | 109.9 | C13i—N14—Cu2 | 108.3 (3) |
H2A—C2—H2B | 108.3 | C13—N14—Cu2 | 108.3 (3) |
N4—C3—C2 | 107.1 (7) | C13i—N14—H14 | 107.6 |
N4—C3—H3A | 110.3 | C13—N14—H14 | 107.6 |
C2—C3—H3A | 110.3 | Cu2—N14—H14 | 107.6 |
Symmetry code: (i) x, −y+3/2, z. |
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