Bis(N,N-dimethylethylenediamine)copper(II) oxalate dihydrate, [Cu(C4H12N2)2](C2O4)·2H2O, has been synthesized. Both the cation and anion are centrosymmetric. The Cu atom is in a distorted square geometry, coordinated by the four N atoms of the bidentate ligands. There are long [2.583 (2) Å] axial contacts to water. The crystal structure of the complex has a two-dimensional structure through hydrogen bonding.
Supporting information
CCDC reference: 217366
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.004 Å
- R factor = 0.028
- wR factor = 0.075
- Data-to-parameter ratio = 12.8
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level B:
PLAT_369 Alert B Long C(sp2)-C(sp2) Bond C5 - C5_a = 1.58 Ang.
| Author response: In C~2~O~4~, the bond C(5) - C(5)a is a single bond.
|
0 Alert Level A = Potentially serious problem
1 Alert Level B = Potential problem
0 Alert Level C = Please check
0.5 mmol K2[Cu(C2O4)2]·2H2O was dissolved in 10 ml distilled water and 0.5 mmol N,N-dimethylethylenediamine in 5 ml H2O was added dropwise. The mixture was stirred for 0.5 h and then filtrated. The filtrate was allowed to stand in air at room temperature for several weeks, yielding blue single crystals suitable for X-ray analysis.
H atoms of the water molecules were located in a difference Fourier map and were refined isotropically with restrained bond lengths. H atoms of N,N-dimethylethylenediamine for (I) were generated geometrically and refined using a riding model with C—H = 0.97 Å for CH2, C—H = 0.96 Å for CH3 and N—H = 0.90 Å.
Data collection: Bruker SMART (Bruker, 1998); cell refinement: Bruker SMART; data reduction: Bruker SHELXTL (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Bruker SHELXTL; software used to prepare material for publication: Bruker SHELXTL.
Bis(
N,
N-dimethylethylenediamine)copper(II) oxalate dihydrate
top
Crystal data top
[Cu(C4H12N2)2]C2O4.2H2O | Dx = 1.591 Mg m−3 |
Mr = 363.90 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 5693 reflections |
a = 10.482 (3) Å | θ = 3.1–25.0° |
b = 11.026 (3) Å | µ = 1.47 mm−1 |
c = 13.146 (4) Å | T = 293 K |
V = 1519.3 (8) Å3 | Prism, blue |
Z = 4 | 0.30 × 0.20 × 0.05 mm |
F(000) = 772 | |
Data collection top
CCD area detector diffractometer | 1341 independent reflections |
Radiation source: fine-focus sealed tube | 1021 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
ϕ and ω scans | θmax = 25.0°, θmin = 3.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −5→12 |
Tmin = 0.779, Tmax = 0.929 | k = −13→13 |
5693 measured reflections | l = −15→15 |
Refinement top
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)] = 0.028 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.075 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0325P)2 + 1.2775P] where P = (Fo2 + 2Fc2)/3 |
1341 reflections | (Δ/σ)max < 0.001 |
105 parameters | Δρmax = 0.37 e Å−3 |
3 restraints | Δρmin = −0.42 e Å−3 |
Crystal data top
[Cu(C4H12N2)2]C2O4.2H2O | V = 1519.3 (8) Å3 |
Mr = 363.90 | Z = 4 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 10.482 (3) Å | µ = 1.47 mm−1 |
b = 11.026 (3) Å | T = 293 K |
c = 13.146 (4) Å | 0.30 × 0.20 × 0.05 mm |
Data collection top
CCD area detector diffractometer | 1341 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1021 reflections with I > 2σ(I) |
Tmin = 0.779, Tmax = 0.929 | Rint = 0.026 |
5693 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.028 | 3 restraints |
wR(F2) = 0.075 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | Δρmax = 0.37 e Å−3 |
1341 reflections | Δρmin = −0.42 e Å−3 |
105 parameters | |
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 | 0.0000 | 1.0000 | 0.0000 | 0.02086 (15) | |
N1 | 0.13730 (19) | 1.11282 (18) | 0.04390 (15) | 0.0226 (5) | |
H1C | 0.2061 | 1.1026 | 0.0039 | 0.027* | |
H1D | 0.1103 | 1.1898 | 0.0367 | 0.027* | |
N2 | 0.01299 (18) | 0.93106 (17) | 0.14877 (15) | 0.0212 (4) | |
O1 | 0.60791 (17) | 0.89242 (16) | 0.04649 (15) | 0.0351 (5) | |
O2 | 0.40196 (19) | 0.87338 (18) | 0.01474 (17) | 0.0491 (6) | |
O3 | 0.6655 (2) | 0.64533 (18) | 0.07955 (17) | 0.0432 (5) | |
H3D | 0.644 (2) | 0.7222 (13) | 0.071 (3) | 0.061 (11)* | |
H3E | 0.7436 (15) | 0.633 (2) | 0.057 (2) | 0.053 (10)* | |
C1 | 0.1734 (3) | 1.0913 (2) | 0.15115 (19) | 0.0299 (6) | |
H1A | 0.1971 | 1.1674 | 0.1830 | 0.036* | |
H1B | 0.2464 | 1.0373 | 0.1541 | 0.036* | |
C2 | 0.0631 (3) | 1.0358 (2) | 0.20711 (19) | 0.0273 (6) | |
H2A | 0.0907 | 1.0091 | 0.2739 | 0.033* | |
H2B | −0.0037 | 1.0957 | 0.2160 | 0.033* | |
C3 | −0.1106 (3) | 0.8935 (3) | 0.1927 (2) | 0.0336 (6) | |
H3A | −0.0975 | 0.8631 | 0.2603 | 0.050* | |
H3B | −0.1476 | 0.8310 | 0.1512 | 0.050* | |
H3C | −0.1672 | 0.9619 | 0.1950 | 0.050* | |
C5 | 0.5030 (2) | 0.9317 (2) | 0.01752 (18) | 0.0241 (6) | |
C4 | 0.1016 (3) | 0.8275 (2) | 0.1568 (2) | 0.0342 (6) | |
H4A | 0.1042 | 0.7996 | 0.2260 | 0.051* | |
H4B | 0.1855 | 0.8526 | 0.1363 | 0.051* | |
H4C | 0.0729 | 0.7630 | 0.1135 | 0.051* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0214 (2) | 0.0215 (2) | 0.0197 (2) | −0.00504 (18) | −0.00071 (19) | 0.00352 (16) |
N1 | 0.0227 (11) | 0.0204 (10) | 0.0247 (10) | −0.0010 (9) | 0.0006 (9) | 0.0027 (9) |
N2 | 0.0219 (11) | 0.0197 (10) | 0.0220 (10) | −0.0012 (9) | 0.0030 (9) | 0.0021 (8) |
O1 | 0.0265 (10) | 0.0293 (10) | 0.0494 (11) | 0.0052 (9) | −0.0009 (9) | 0.0041 (9) |
O2 | 0.0290 (11) | 0.0317 (11) | 0.0864 (17) | −0.0100 (9) | −0.0111 (11) | 0.0153 (11) |
O3 | 0.0379 (12) | 0.0340 (12) | 0.0577 (14) | −0.0022 (10) | 0.0121 (11) | 0.0096 (10) |
C1 | 0.0315 (15) | 0.0289 (14) | 0.0293 (14) | −0.0068 (12) | −0.0063 (12) | 0.0013 (11) |
C2 | 0.0343 (15) | 0.0253 (13) | 0.0223 (12) | −0.0011 (12) | −0.0028 (12) | −0.0022 (11) |
C3 | 0.0285 (14) | 0.0436 (16) | 0.0287 (14) | −0.0083 (13) | 0.0062 (12) | 0.0083 (13) |
C5 | 0.0269 (13) | 0.0196 (13) | 0.0258 (13) | 0.0002 (11) | 0.0036 (12) | −0.0009 (10) |
C4 | 0.0410 (16) | 0.0264 (14) | 0.0351 (15) | 0.0082 (13) | −0.0022 (14) | 0.0036 (12) |
Geometric parameters (Å, º) top
Cu1—N1i | 1.988 (2) | O3—H3D | 0.884 (10) |
Cu1—N1 | 1.988 (2) | O3—H3E | 0.882 (10) |
Cu1—N2 | 2.103 (2) | C1—C2 | 1.501 (4) |
Cu1—N2i | 2.103 (2) | C1—H1A | 0.9700 |
Cu1—O3ii | 2.583 (2) | C1—H1B | 0.9700 |
Cu1—O3iii | 2.583 (2) | C2—H2A | 0.9700 |
N1—C1 | 1.479 (3) | C2—H2B | 0.9700 |
N1—H1C | 0.9000 | C3—H3A | 0.9600 |
N1—H1D | 0.9000 | C3—H3B | 0.9600 |
N2—C4 | 1.476 (3) | C3—H3C | 0.9600 |
N2—C3 | 1.478 (3) | C5—C5iv | 1.576 (5) |
N2—C2 | 1.482 (3) | C4—H4A | 0.9600 |
O1—C5 | 1.242 (3) | C4—H4B | 0.9600 |
O2—C5 | 1.240 (3) | C4—H4C | 0.9600 |
| | | |
N1i—Cu1—N1 | 180.0 | N1—C1—C2 | 109.6 (2) |
N1i—Cu1—N2 | 95.20 (8) | N1—C1—H1A | 109.8 |
N1—Cu1—N2 | 84.80 (8) | C2—C1—H1A | 109.8 |
N1i—Cu1—N2i | 84.80 (8) | N1—C1—H1B | 109.8 |
N1—Cu1—N2i | 95.20 (8) | C2—C1—H1B | 109.8 |
N2—Cu1—N2i | 180.00 (10) | H1A—C1—H1B | 108.2 |
N1i—Cu1—O3ii | 91.11 (8) | N2—C2—C1 | 109.7 (2) |
N1—Cu1—O3ii | 88.89 (8) | N2—C2—H2A | 109.7 |
N2—Cu1—O3ii | 83.75 (7) | C1—C2—H2A | 109.7 |
N2i—Cu1—O3ii | 96.25 (7) | N2—C2—H2B | 109.7 |
N1i—Cu1—O3iii | 88.89 (8) | C1—C2—H2B | 109.7 |
N1—Cu1—O3iii | 91.11 (8) | H2A—C2—H2B | 108.2 |
N2—Cu1—O3iii | 96.25 (7) | N2—C3—H3A | 109.5 |
N2i—Cu1—O3iii | 83.75 (7) | N2—C3—H3B | 109.5 |
O3ii—Cu1—O3iii | 180.0 | H3A—C3—H3B | 109.5 |
C1—N1—Cu1 | 111.20 (15) | N2—C3—H3C | 109.5 |
C1—N1—H1C | 109.4 | H3A—C3—H3C | 109.5 |
Cu1—N1—H1C | 109.4 | H3B—C3—H3C | 109.5 |
C1—N1—H1D | 109.4 | O2—C5—O1 | 125.8 (2) |
Cu1—N1—H1D | 109.4 | O2—C5—C5iv | 116.9 (3) |
H1C—N1—H1D | 108.0 | O1—C5—C5iv | 117.3 (3) |
C4—N2—C3 | 107.9 (2) | N2—C4—H4A | 109.5 |
C4—N2—C2 | 110.0 (2) | N2—C4—H4B | 109.5 |
C3—N2—C2 | 109.11 (19) | H4A—C4—H4B | 109.5 |
C4—N2—Cu1 | 112.78 (16) | N2—C4—H4C | 109.5 |
C3—N2—Cu1 | 114.06 (15) | H4A—C4—H4C | 109.5 |
C2—N2—Cu1 | 102.86 (14) | H4B—C4—H4C | 109.5 |
H3D—O3—H3E | 110.0 (15) | | |
| | | |
N2—Cu1—N1—C1 | −0.44 (17) | O3iii—Cu1—N2—C3 | −125.63 (17) |
N2i—Cu1—N1—C1 | 179.56 (17) | N1i—Cu1—N2—C2 | −154.19 (15) |
O3ii—Cu1—N1—C1 | 83.39 (17) | N1—Cu1—N2—C2 | 25.81 (15) |
O3iii—Cu1—N1—C1 | −96.61 (17) | O3ii—Cu1—N2—C2 | −63.65 (15) |
N1i—Cu1—N2—C4 | 87.34 (17) | O3iii—Cu1—N2—C2 | 116.35 (15) |
N1—Cu1—N2—C4 | −92.66 (17) | Cu1—N1—C1—C2 | −25.6 (3) |
O3ii—Cu1—N2—C4 | 177.89 (17) | C4—N2—C2—C1 | 73.6 (3) |
O3iii—Cu1—N2—C4 | −2.11 (17) | C3—N2—C2—C1 | −168.2 (2) |
N1i—Cu1—N2—C3 | −36.18 (18) | Cu1—N2—C2—C1 | −46.8 (2) |
N1—Cu1—N2—C3 | 143.82 (18) | N1—C1—C2—N2 | 49.8 (3) |
O3ii—Cu1—N2—C3 | 54.37 (17) | | |
Symmetry codes: (i) −x, −y+2, −z; (ii) −x+1/2, y+1/2, z; (iii) x−1/2, −y+3/2, −z; (iv) −x+1, −y+2, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1C···O1iv | 0.90 | 2.06 | 2.924 (3) | 161 |
N1—H1D···O2ii | 0.90 | 2.05 | 2.927 (3) | 165 |
O3—H3D···O1 | 0.88 (2) | 1.94 (2) | 2.824 (3) | 176 (3) |
O3—H3E···O2v | 0.88 (2) | 1.91 (2) | 2.779 (3) | 169 |
Symmetry codes: (ii) −x+1/2, y+1/2, z; (iv) −x+1, −y+2, −z; (v) x+1/2, −y+3/2, −z. |
Experimental details
Crystal data |
Chemical formula | [Cu(C4H12N2)2]C2O4.2H2O |
Mr | 363.90 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 293 |
a, b, c (Å) | 10.482 (3), 11.026 (3), 13.146 (4) |
V (Å3) | 1519.3 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.47 |
Crystal size (mm) | 0.30 × 0.20 × 0.05 |
|
Data collection |
Diffractometer | CCD area detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.779, 0.929 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5693, 1341, 1021 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.075, 1.09 |
No. of reflections | 1341 |
No. of parameters | 105 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.37, −0.42 |
Selected geometric parameters (Å, º) topCu1—N1i | 1.988 (2) | Cu1—N2i | 2.103 (2) |
Cu1—N1 | 1.988 (2) | Cu1—O3ii | 2.583 (2) |
Cu1—N2 | 2.103 (2) | Cu1—O3iii | 2.583 (2) |
| | | |
N1i—Cu1—N1 | 180.0 | N2—Cu1—O3ii | 83.75 (7) |
N1i—Cu1—N2 | 95.20 (8) | N2i—Cu1—O3ii | 96.25 (7) |
N1—Cu1—N2 | 84.80 (8) | N1i—Cu1—O3iii | 88.89 (8) |
N1i—Cu1—N2i | 84.80 (8) | N1—Cu1—O3iii | 91.11 (8) |
N1—Cu1—N2i | 95.20 (8) | N2—Cu1—O3iii | 96.25 (7) |
N2—Cu1—N2i | 180.00 (10) | N2i—Cu1—O3iii | 83.75 (7) |
N1i—Cu1—O3ii | 91.11 (8) | O3ii—Cu1—O3iii | 180.0 |
N1—Cu1—O3ii | 88.89 (8) | | |
Symmetry codes: (i) −x, −y+2, −z; (ii) −x+1/2, y+1/2, z; (iii) x−1/2, −y+3/2, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1C···O1iv | 0.900 | 2.060 | 2.924 (3) | 160.60 |
N1—H1D···O2ii | 0.900 | 2.048 | 2.927 (3) | 165.15 |
O3—H3D···O1 | 0.884 (15) | 1.942 (16) | 2.824 (3) | 176 (3) |
O3—H3E···O2v | 0.881 (17) | 1.910 (19) | 2.779 (3) | 168.53 |
Symmetry codes: (ii) −x+1/2, y+1/2, z; (iv) −x+1, −y+2, −z; (v) x+1/2, −y+3/2, −z. |
Mononuclear complexes containing N,N-dimethylethylenediamine (dmen) have been studied extensively. These complexes have an important role in thermal and magnetic chemistry (Smékal et al., 2002; Senocq et al., 1999). Otherwise, dmen also can form supramolecular complexes with other bridging ligands, such as N3−, SCN− and Cl− (Mondal et al., 2000; Bian et al., 2003). In this paper, bis(N,N-dimethylethylenediamine)copper(II) oxalate dihydrate(I) has been synthesized and its structure described.
The structure of (I) is shown in Fig. 1. The geometrical parameters and hydrogen-bond data for (I) are listed in Table 1 and Table 2, respectively. The Cu atom in (I) is in a distorted square geometry with four N atoms of two bidentate ligands, with the distances ranging from 1.988 (2) to 2.103 (2) Å. The values are similar to other copper(II) complexes containing dmen (Narayanan et al., 1995; Senocq et al., 1999). However, the distances of the central atom and two hydrate O atoms show some weak interaction, which may be viewed as a weak coordination mode (Guilera et al., 1999; Sun et al., 2001). Thus the environment of the Cu atom can also be described as a tetragonally distorted octahedron. The basal plane contains the four N atoms, N1, N2, N1A and N2A, at an average distance of 2.051 (6) Å, while the axial positions are filled by two water-O atoms at a distance of 2.583 (2) Å.
The crystals exhibit a number of hydrogen bonds (Fig. 2). The H atoms of the water molecules and the N atoms of the ligands are involved in hydrogen bonding with the oxalate dianion. An infinite two-dimensional network of extensive hydrogen bonds stabilizes the crystal structure.