Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803011929/om6144sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803011929/om6144Isup2.hkl
Contains datablock I

CCDC reference: 217366

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](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


Amber Alert 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

Comment top

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.

Experimental top

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.

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. A view of the molecular structure of (I) with the atom-numbering scheme and 30% displacement ellipsoids.
[Figure 2] Fig. 2. The two-dimensional network structure by hydrogen bonds of complex (I).
Bis(N,N-dimethylethylenediamine)copper(II) oxalate dihydrate top
Crystal data top
[Cu(C4H12N2)2]C2O4.2H2ODx = 1.591 Mg m3
Mr = 363.90Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PbcaCell parameters from 5693 reflections
a = 10.482 (3) Åθ = 3.1–25.0°
b = 11.026 (3) ŵ = 1.47 mm1
c = 13.146 (4) ÅT = 293 K
V = 1519.3 (8) Å3Prism, blue
Z = 40.30 × 0.20 × 0.05 mm
F(000) = 772
Data collection top
CCD area detector
diffractometer
1341 independent reflections
Radiation source: fine-focus sealed tube1021 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
ϕ and ω scansθmax = 25.0°, θmin = 3.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 512
Tmin = 0.779, Tmax = 0.929k = 1313
5693 measured reflectionsl = 1515
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.075H 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 parametersΔρmax = 0.37 e Å3
3 restraintsΔρmin = 0.42 e Å3
Crystal data top
[Cu(C4H12N2)2]C2O4.2H2OV = 1519.3 (8) Å3
Mr = 363.90Z = 4
Orthorhombic, PbcaMo Kα radiation
a = 10.482 (3) ŵ = 1.47 mm1
b = 11.026 (3) ÅT = 293 K
c = 13.146 (4) Å0.30 × 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 = 0.929Rint = 0.026
5693 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0283 restraints
wR(F2) = 0.075H atoms treated by a mixture of independent and constrained refinement
S = 1.09Δρmax = 0.37 e Å3
1341 reflectionsΔρmin = 0.42 e Å3
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
xyzUiso*/Ueq
Cu10.00001.00000.00000.02086 (15)
N10.13730 (19)1.11282 (18)0.04390 (15)0.0226 (5)
H1C0.20611.10260.00390.027*
H1D0.11031.18980.03670.027*
N20.01299 (18)0.93106 (17)0.14877 (15)0.0212 (4)
O10.60791 (17)0.89242 (16)0.04649 (15)0.0351 (5)
O20.40196 (19)0.87338 (18)0.01474 (17)0.0491 (6)
O30.6655 (2)0.64533 (18)0.07955 (17)0.0432 (5)
H3D0.644 (2)0.7222 (13)0.071 (3)0.061 (11)*
H3E0.7436 (15)0.633 (2)0.057 (2)0.053 (10)*
C10.1734 (3)1.0913 (2)0.15115 (19)0.0299 (6)
H1A0.19711.16740.18300.036*
H1B0.24641.03730.15410.036*
C20.0631 (3)1.0358 (2)0.20711 (19)0.0273 (6)
H2A0.09071.00910.27390.033*
H2B0.00371.09570.21600.033*
C30.1106 (3)0.8935 (3)0.1927 (2)0.0336 (6)
H3A0.09750.86310.26030.050*
H3B0.14760.83100.15120.050*
H3C0.16720.96190.19500.050*
C50.5030 (2)0.9317 (2)0.01752 (18)0.0241 (6)
C40.1016 (3)0.8275 (2)0.1568 (2)0.0342 (6)
H4A0.10420.79960.22600.051*
H4B0.18550.85260.13630.051*
H4C0.07290.76300.11350.051*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0214 (2)0.0215 (2)0.0197 (2)0.00504 (18)0.00071 (19)0.00352 (16)
N10.0227 (11)0.0204 (10)0.0247 (10)0.0010 (9)0.0006 (9)0.0027 (9)
N20.0219 (11)0.0197 (10)0.0220 (10)0.0012 (9)0.0030 (9)0.0021 (8)
O10.0265 (10)0.0293 (10)0.0494 (11)0.0052 (9)0.0009 (9)0.0041 (9)
O20.0290 (11)0.0317 (11)0.0864 (17)0.0100 (9)0.0111 (11)0.0153 (11)
O30.0379 (12)0.0340 (12)0.0577 (14)0.0022 (10)0.0121 (11)0.0096 (10)
C10.0315 (15)0.0289 (14)0.0293 (14)0.0068 (12)0.0063 (12)0.0013 (11)
C20.0343 (15)0.0253 (13)0.0223 (12)0.0011 (12)0.0028 (12)0.0022 (11)
C30.0285 (14)0.0436 (16)0.0287 (14)0.0083 (13)0.0062 (12)0.0083 (13)
C50.0269 (13)0.0196 (13)0.0258 (13)0.0002 (11)0.0036 (12)0.0009 (10)
C40.0410 (16)0.0264 (14)0.0351 (15)0.0082 (13)0.0022 (14)0.0036 (12)
Geometric parameters (Å, º) top
Cu1—N1i1.988 (2)O3—H3D0.884 (10)
Cu1—N11.988 (2)O3—H3E0.882 (10)
Cu1—N22.103 (2)C1—C21.501 (4)
Cu1—N2i2.103 (2)C1—H1A0.9700
Cu1—O3ii2.583 (2)C1—H1B0.9700
Cu1—O3iii2.583 (2)C2—H2A0.9700
N1—C11.479 (3)C2—H2B0.9700
N1—H1C0.9000C3—H3A0.9600
N1—H1D0.9000C3—H3B0.9600
N2—C41.476 (3)C3—H3C0.9600
N2—C31.478 (3)C5—C5iv1.576 (5)
N2—C21.482 (3)C4—H4A0.9600
O1—C51.242 (3)C4—H4B0.9600
O2—C51.240 (3)C4—H4C0.9600
N1i—Cu1—N1180.0N1—C1—C2109.6 (2)
N1i—Cu1—N295.20 (8)N1—C1—H1A109.8
N1—Cu1—N284.80 (8)C2—C1—H1A109.8
N1i—Cu1—N2i84.80 (8)N1—C1—H1B109.8
N1—Cu1—N2i95.20 (8)C2—C1—H1B109.8
N2—Cu1—N2i180.00 (10)H1A—C1—H1B108.2
N1i—Cu1—O3ii91.11 (8)N2—C2—C1109.7 (2)
N1—Cu1—O3ii88.89 (8)N2—C2—H2A109.7
N2—Cu1—O3ii83.75 (7)C1—C2—H2A109.7
N2i—Cu1—O3ii96.25 (7)N2—C2—H2B109.7
N1i—Cu1—O3iii88.89 (8)C1—C2—H2B109.7
N1—Cu1—O3iii91.11 (8)H2A—C2—H2B108.2
N2—Cu1—O3iii96.25 (7)N2—C3—H3A109.5
N2i—Cu1—O3iii83.75 (7)N2—C3—H3B109.5
O3ii—Cu1—O3iii180.0H3A—C3—H3B109.5
C1—N1—Cu1111.20 (15)N2—C3—H3C109.5
C1—N1—H1C109.4H3A—C3—H3C109.5
Cu1—N1—H1C109.4H3B—C3—H3C109.5
C1—N1—H1D109.4O2—C5—O1125.8 (2)
Cu1—N1—H1D109.4O2—C5—C5iv116.9 (3)
H1C—N1—H1D108.0O1—C5—C5iv117.3 (3)
C4—N2—C3107.9 (2)N2—C4—H4A109.5
C4—N2—C2110.0 (2)N2—C4—H4B109.5
C3—N2—C2109.11 (19)H4A—C4—H4B109.5
C4—N2—Cu1112.78 (16)N2—C4—H4C109.5
C3—N2—Cu1114.06 (15)H4A—C4—H4C109.5
C2—N2—Cu1102.86 (14)H4B—C4—H4C109.5
H3D—O3—H3E110.0 (15)
N2—Cu1—N1—C10.44 (17)O3iii—Cu1—N2—C3125.63 (17)
N2i—Cu1—N1—C1179.56 (17)N1i—Cu1—N2—C2154.19 (15)
O3ii—Cu1—N1—C183.39 (17)N1—Cu1—N2—C225.81 (15)
O3iii—Cu1—N1—C196.61 (17)O3ii—Cu1—N2—C263.65 (15)
N1i—Cu1—N2—C487.34 (17)O3iii—Cu1—N2—C2116.35 (15)
N1—Cu1—N2—C492.66 (17)Cu1—N1—C1—C225.6 (3)
O3ii—Cu1—N2—C4177.89 (17)C4—N2—C2—C173.6 (3)
O3iii—Cu1—N2—C42.11 (17)C3—N2—C2—C1168.2 (2)
N1i—Cu1—N2—C336.18 (18)Cu1—N2—C2—C146.8 (2)
N1—Cu1—N2—C3143.82 (18)N1—C1—C2—N249.8 (3)
O3ii—Cu1—N2—C354.37 (17)
Symmetry codes: (i) x, y+2, z; (ii) x+1/2, y+1/2, z; (iii) x1/2, y+3/2, z; (iv) x+1, y+2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1C···O1iv0.902.062.924 (3)161
N1—H1D···O2ii0.902.052.927 (3)165
O3—H3D···O10.88 (2)1.94 (2)2.824 (3)176 (3)
O3—H3E···O2v0.88 (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
Mr363.90
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)293
a, b, c (Å)10.482 (3), 11.026 (3), 13.146 (4)
V3)1519.3 (8)
Z4
Radiation typeMo Kα
µ (mm1)1.47
Crystal size (mm)0.30 × 0.20 × 0.05
Data collection
DiffractometerCCD area detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.779, 0.929
No. of measured, independent and
observed [I > 2σ(I)] reflections
5693, 1341, 1021
Rint0.026
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.028, 0.075, 1.09
No. of reflections1341
No. of parameters105
No. of restraints3
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.37, 0.42

Computer programs: Bruker SMART (Bruker, 1998), Bruker SMART, Bruker SHELXTL (Bruker, 1997), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), Bruker SHELXTL.

Selected geometric parameters (Å, º) top
Cu1—N1i1.988 (2)Cu1—N2i2.103 (2)
Cu1—N11.988 (2)Cu1—O3ii2.583 (2)
Cu1—N22.103 (2)Cu1—O3iii2.583 (2)
N1i—Cu1—N1180.0N2—Cu1—O3ii83.75 (7)
N1i—Cu1—N295.20 (8)N2i—Cu1—O3ii96.25 (7)
N1—Cu1—N284.80 (8)N1i—Cu1—O3iii88.89 (8)
N1i—Cu1—N2i84.80 (8)N1—Cu1—O3iii91.11 (8)
N1—Cu1—N2i95.20 (8)N2—Cu1—O3iii96.25 (7)
N2—Cu1—N2i180.00 (10)N2i—Cu1—O3iii83.75 (7)
N1i—Cu1—O3ii91.11 (8)O3ii—Cu1—O3iii180.0
N1—Cu1—O3ii88.89 (8)
Symmetry codes: (i) x, y+2, z; (ii) x+1/2, y+1/2, z; (iii) x1/2, y+3/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1C···O1iv0.9002.0602.924 (3)160.60
N1—H1D···O2ii0.9002.0482.927 (3)165.15
O3—H3D···O10.884 (15)1.942 (16)2.824 (3)176 (3)
O3—H3E···O2v0.881 (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.
 

Subscribe to Acta Crystallographica Section E: Crystallographic Communications

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds