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Acta Cryst. (2003). C59, m392-m395
https://doi.org/10.1107/S0108270103017621
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Bis­(dicyan­amido)(diethyl­enetri­amine-[kappa]3N)copper(II) and (dicyan­amido)(tri­ethyl­enetetr­amine-[kappa]4N)copper(II) dicyan­amide

J. Luo, X-G. Zhou, L.-H. Weng and X.-F. Hou
Two new complexes, [Cu(C2N3)2(dien)] (dien is diethyl­ene­tri­amine, C4H13N3), (I), and [Cu(C2N3)(trien)](C2N3) (trien is triethyl­ene­tetr­amine, C6H18N4), (II), have been characterized by single-crystal X-ray diffraction. Both complexes display a distorted tetragonal-pyramidal geometry. In (I), the Cu atom is coordinated in the basal plane by three diethyl­ene­tri­amine N atoms [Cu-N = 2.000 (2), 2.004 (2) and 2.025 (2) Å] and one terminal N atom [Cu-N = 1.974 (2) Å] from one monodentate dicyan­amide group, and in the apical position by one terminal N atom [Cu-N = 2.280 (2) Å] from the other monodentate dicyan­amide group. In (II), the Cu atom is surrounded by four triethyl­ene­tetr­amine N atoms [Cu-N = 2.012 (2), 2.014 (2), 2.019 (2) and 2.031 (2) Å in the basal plane] and a terminal N atom [Cu-N = 2.130 (2) Å in the apical site] from one monodentate dicyan­amide group. The other dicyan­amide anion is not directly coordinated to the metal atom. In both (I) and (II), hydro­gen-bond interactions between the uncoordinated terminal N atoms of two dicyan­amide ions and the amine H atoms lead to the formation of three-dimensional networks.
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Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103017621/sq1027sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103017621/sq1027Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103017621/sq1027IIsup3.hkl
Contains datablock II

CCDC references: 224489; 224490

Comment top

Recently, dicyanamide complexes have attracted considerable interest because of their fascinating magnetic properties (Batten et al., 1998; Jensen et al., 1999; Manson et al., 1999) and diverse structural types (Manson et al., 1998; Batten et al., 1999; Vangdal et al., 2002). For example, the three-dimensional compound [Cr(C2N3)2] is found to be magnetically ordered at temperatures as high as 47 K. It is well known that the structures and the magnetic properties of complexes are related to the nature of the co-ligands (Dasna et al., 1999; Jensen et al., 2001; Jensen et al., 2002; Carranza et al., 2002). Although much effort has recently been focused on studies of dicyanamide complexes with amine co-ligands, including diaminopropane (Li et al., 2002; Wang et al., 2002; Chen et al., 2003) and macrocyclic polyamines (Cho et al., 2002; Gu et al., 2003; Paraschiv et al., 2003), very few dicyanamide complexes with diethylenetriamine or triethylenetetramine as co-ligands are reported (Brezina et al., 1999). In order to study further how the nature of co-ligands affects the structures and properties of dicyanamide complexes, we report here the syntheses and crystal structures of two new copper dicyanamide complexes, namely [Cu(dien)(C2N3)2], (I), and [Cu(trien)(C2N3)2], (II).

In (I), the copper ion is bonded to three diethylenetriamine N atoms and two terminal N atoms from two different dicyanamide anions, thus forming a distorted tetragonal-pyramidal geometry, in which the basal plane comprises the three diethylenetriamine N atoms (atoms N1, N2 and N3) and one nitrile N atom (N4) of a monodentate dicyanamide group, while the apical site is occupied by one nitrile N atom (N7) of the other monodentate dicyanamide group (Fig. 1). Two different hydrogen-bond interactions are observed in (I) (Table 2). The intramolecular hydrogen-bond interaction between one bonded dicyanamide N atom and the H atom on the nodal dien N atom (N7···H2C—N2) results in a relatively small N7—Cu1—N2 angle of 87.31 (9)°. The intermolecular hydrogen-bonding interactions between the uncoordinated terminal N atoms of the dicyanamides and the terminal amino dien H atoms [N···N = 3.008 (4)–3.156 (3) Å, H···N = 2.21 (4)–2.40 (3) Å and N—H···N = 145 (3)–175 (3)°] are dedicated to the construction of a three-dimensional network (Fig. 2).

In (II), the copper ion is bonded to four N atoms (atoms N4, N5, N6 and N7) from the triethylenetetramine molecule in the basal plane and one terminal N atom (N1) from a dicyanamide group in the apical site, thus forming the cation, while the other dicyanamide anion does not enter the inner coordination sphere (Fig. 3), but is linked to the cation via a hydrogen bond (Table 4). This phenomenon is also found in some other dicyanamide complexes (Claramunt et al., 2000; He et al., 2002; Marshall et al., 2002). The cations are cross-linked to form a two-dimensional network via intermolecular hydrogen bonds [N···N = 3.155 (3)–3.164 (3) Å, H···N = 2.33–2.53 Å and N—H···N = 127.5–153.8°), and the layers are linked to one another by uncoordinated dicyanamide bridges via hydrogen bonds [N···N = 3.010 (3)–3.213 (3) Å, H···N = 2.14 (3)–2.60 (2) Å, N—H···N = 129.8–160.1°], forming a three-dimensional structure (Fig. 4). The Cu—Ndien distances in (I) [2.000 (2)–2.025 (2) Å] are almost equal to the Cu—Ntrien distances in (II) [2.012 (2)–2.031 (2) Å], and are similar to the corresponding distances in aliphatic amine copper complexes (Suenaga et al., 1997; Baesjou et al., 2000). The Cu—Ndicyanamide distances of (I) are quite different; the axial Cu–Ndicyanamide distance [2.280 (2) Å] is obviously longer than the basal Cu—Ndicyanamide distance [1.974 (2) Å], while the Cu—Ndicyanamide distance [2.130 (2) Å] in (II) is intermediate between these two distances?. The Cu—Ndicyanamide distances in (I) are comparable to the corresponding distances in [Cu(phen)(C2N3)2] (phen is 1,10-phenanthroline; Wang et al., 2000), while the axial Cu—Ndicyanamide distance of (II) is slightly shorter than that of [Cu(dmbipy)(C2N3)2] [2.247 (2) Å; dmbipy is 5,5'-dimethyl-2,2'-bipyridine; Kooijman et al., 2002). The distortion of the tetragonal pyramid can be described by the parameter t (t shows the relative amount of trigonality; t=0 for a tetragonal pyramid and t=1 for a trigonal bipyramide; Addison et al., 1984), which is 0.18 and 0.16 for (I) and (II), respectively. In (I), the Nbasal—Cu—Nbasal (for two neighbouring basal N atoms) and Napical—Cu—Nbasal angles range from 84.02 (9) to 94.98 (10)° and 87.31 (9) to 101.00 (9)°, respectively. The corresponding values in (II) are 84.03 (8)–97.74 (8)° and 98.25 (9)–104.63 (9)°, respectively, indicating that the distortion of the tetragonal pyramid in (I) and (II) is not serious.

In (I) (Table 1) and (II) (Table 3), every dicyanamide group is almost planar, with C≡N triple-bond distances in the range 1.133 (3)–1.145 (3) Å, C—N single-bond distances in the range 1.288 (3)–1.306 (3) Å, and C—N—C and N—C—N angles of 120.5 (3)–123.4 (3)° and 172.0 (3)–176.4 (3)°, respectively. These values are in good agreement with other dicyanamide-containing compounds (Kurmoo et al., 1998; Batten et al., 1999; Carranza et al., 2002; Vangdal et al., 2002).

Experimental top

A solution of diethylenetriamine (0.60 mmol, 61.90 mg) in ethanol (4 ml) and a solution of copper acetate (0.60 mmol, 119.79 mg) in ethanol (4 ml) were mixed and stirred for 5 min. To the resulting deep-blue mixture was added an aqueous solution (2 ml) of sodium dicyanamide (0.60 mmol, 53.42 mg). After stirred for another 5 min, the solution was filtered and the filtrate was slowly evaporated in air. After one week, deep-blue block-shaped crystals of (I) were isolated in 35% yield. Analysis calculated for C8H13N9Cu: C 32.16, H 4.39, N 42.19%; found: C 31.84, H 4.43, N 42.30%. Complex (II) was prepared in a similar manner (yield 27%). Analysis calculated for C10H18N10Cu: C 35.13, H 5.31, N 40.97; found C 34.83, H 5.17, N 41.29%.

Refinement top

In (I), the position of the amine H atom was found in a difference Fourier map and refined freely, along with the isotropic displacement parameter. The other H atoms were then constrained to an ideal geometry, with C—H distances of 0.97 Å. In (II), atoms H5 and H6 were located in a difference Fourier map. All other H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.97 Å and N—H distances of 0.90 Å.

Structure description top

Recently, dicyanamide complexes have attracted considerable interest because of their fascinating magnetic properties (Batten et al., 1998; Jensen et al., 1999; Manson et al., 1999) and diverse structural types (Manson et al., 1998; Batten et al., 1999; Vangdal et al., 2002). For example, the three-dimensional compound [Cr(C2N3)2] is found to be magnetically ordered at temperatures as high as 47 K. It is well known that the structures and the magnetic properties of complexes are related to the nature of the co-ligands (Dasna et al., 1999; Jensen et al., 2001; Jensen et al., 2002; Carranza et al., 2002). Although much effort has recently been focused on studies of dicyanamide complexes with amine co-ligands, including diaminopropane (Li et al., 2002; Wang et al., 2002; Chen et al., 2003) and macrocyclic polyamines (Cho et al., 2002; Gu et al., 2003; Paraschiv et al., 2003), very few dicyanamide complexes with diethylenetriamine or triethylenetetramine as co-ligands are reported (Brezina et al., 1999). In order to study further how the nature of co-ligands affects the structures and properties of dicyanamide complexes, we report here the syntheses and crystal structures of two new copper dicyanamide complexes, namely [Cu(dien)(C2N3)2], (I), and [Cu(trien)(C2N3)2], (II).

In (I), the copper ion is bonded to three diethylenetriamine N atoms and two terminal N atoms from two different dicyanamide anions, thus forming a distorted tetragonal-pyramidal geometry, in which the basal plane comprises the three diethylenetriamine N atoms (atoms N1, N2 and N3) and one nitrile N atom (N4) of a monodentate dicyanamide group, while the apical site is occupied by one nitrile N atom (N7) of the other monodentate dicyanamide group (Fig. 1). Two different hydrogen-bond interactions are observed in (I) (Table 2). The intramolecular hydrogen-bond interaction between one bonded dicyanamide N atom and the H atom on the nodal dien N atom (N7···H2C—N2) results in a relatively small N7—Cu1—N2 angle of 87.31 (9)°. The intermolecular hydrogen-bonding interactions between the uncoordinated terminal N atoms of the dicyanamides and the terminal amino dien H atoms [N···N = 3.008 (4)–3.156 (3) Å, H···N = 2.21 (4)–2.40 (3) Å and N—H···N = 145 (3)–175 (3)°] are dedicated to the construction of a three-dimensional network (Fig. 2).

In (II), the copper ion is bonded to four N atoms (atoms N4, N5, N6 and N7) from the triethylenetetramine molecule in the basal plane and one terminal N atom (N1) from a dicyanamide group in the apical site, thus forming the cation, while the other dicyanamide anion does not enter the inner coordination sphere (Fig. 3), but is linked to the cation via a hydrogen bond (Table 4). This phenomenon is also found in some other dicyanamide complexes (Claramunt et al., 2000; He et al., 2002; Marshall et al., 2002). The cations are cross-linked to form a two-dimensional network via intermolecular hydrogen bonds [N···N = 3.155 (3)–3.164 (3) Å, H···N = 2.33–2.53 Å and N—H···N = 127.5–153.8°), and the layers are linked to one another by uncoordinated dicyanamide bridges via hydrogen bonds [N···N = 3.010 (3)–3.213 (3) Å, H···N = 2.14 (3)–2.60 (2) Å, N—H···N = 129.8–160.1°], forming a three-dimensional structure (Fig. 4). The Cu—Ndien distances in (I) [2.000 (2)–2.025 (2) Å] are almost equal to the Cu—Ntrien distances in (II) [2.012 (2)–2.031 (2) Å], and are similar to the corresponding distances in aliphatic amine copper complexes (Suenaga et al., 1997; Baesjou et al., 2000). The Cu—Ndicyanamide distances of (I) are quite different; the axial Cu–Ndicyanamide distance [2.280 (2) Å] is obviously longer than the basal Cu—Ndicyanamide distance [1.974 (2) Å], while the Cu—Ndicyanamide distance [2.130 (2) Å] in (II) is intermediate between these two distances?. The Cu—Ndicyanamide distances in (I) are comparable to the corresponding distances in [Cu(phen)(C2N3)2] (phen is 1,10-phenanthroline; Wang et al., 2000), while the axial Cu—Ndicyanamide distance of (II) is slightly shorter than that of [Cu(dmbipy)(C2N3)2] [2.247 (2) Å; dmbipy is 5,5'-dimethyl-2,2'-bipyridine; Kooijman et al., 2002). The distortion of the tetragonal pyramid can be described by the parameter t (t shows the relative amount of trigonality; t=0 for a tetragonal pyramid and t=1 for a trigonal bipyramide; Addison et al., 1984), which is 0.18 and 0.16 for (I) and (II), respectively. In (I), the Nbasal—Cu—Nbasal (for two neighbouring basal N atoms) and Napical—Cu—Nbasal angles range from 84.02 (9) to 94.98 (10)° and 87.31 (9) to 101.00 (9)°, respectively. The corresponding values in (II) are 84.03 (8)–97.74 (8)° and 98.25 (9)–104.63 (9)°, respectively, indicating that the distortion of the tetragonal pyramid in (I) and (II) is not serious.

In (I) (Table 1) and (II) (Table 3), every dicyanamide group is almost planar, with C≡N triple-bond distances in the range 1.133 (3)–1.145 (3) Å, C—N single-bond distances in the range 1.288 (3)–1.306 (3) Å, and C—N—C and N—C—N angles of 120.5 (3)–123.4 (3)° and 172.0 (3)–176.4 (3)°, respectively. These values are in good agreement with other dicyanamide-containing compounds (Kurmoo et al., 1998; Batten et al., 1999; Carranza et al., 2002; Vangdal et al., 2002).

Computing details top

For both compounds, data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2000); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. A view of the molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. The three-dimensional network of (I), formed by hydrogen-bonding interactions.
[Figure 3] Fig. 3. A view of the molecule of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 4] Fig. 4. Three-dimensional network of (II), formed by hydrogen-bonding interactions.
(I) Bis(dicyanamido)(diethylenetriamine-κ3N)copper(II) top
Crystal data top
[Cu(C2N3)2(C4H13N3)]Dx = 1.654 Mg m−3
Mr = 298.81Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121Cell parameters from 3569 reflections
a = 7.0284 (10) Åθ = 2.2–27.1°
b = 12.935 (2) ŵ = 1.82 mm−1
c = 13.197 (2) ÅT = 293 K
V = 1199.8 (3) Å3Block, blue
Z = 40.30 × 0.20 × 0.10 mm
F(000) = 612
Data collection top
Brucker SMART APEX CCD area-detector
diffractometer		2367 independent reflections
Radiation source: fine-focus sealed tube2249 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.027
ω scansθmax = 26.0°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −8→4
Tmin = 0.611, Tmax = 0.839k = −15→15
5547 measured reflectionsl = −16→16
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.025H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.059 w = 1/[σ2(Fo2) + (0.0287P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
2367 reflectionsΔρmax = 0.27 e Å−3
183 parametersΔρmin = −0.44 e Å−3
0 restraintsAbsolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.020 (14)
Crystal data top
[Cu(C2N3)2(C4H13N3)]V = 1199.8 (3) Å3
Mr = 298.81Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 7.0284 (10) ŵ = 1.82 mm−1
b = 12.935 (2) ÅT = 293 K
c = 13.197 (2) Å0.30 × 0.20 × 0.10 mm
Data collection top
Brucker SMART APEX CCD area-detector
diffractometer		2367 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2249 reflections with I > 2σ(I)
Tmin = 0.611, Tmax = 0.839Rint = 0.027
5547 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.025H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.059Δρmax = 0.27 e Å−3
S = 1.05Δρmin = −0.44 e Å−3
2367 reflectionsAbsolute structure: Flack (1983)
183 parametersAbsolute structure parameter: 0.020 (14)
0 restraints
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. The bond distances and angles of dien, 1.462 (3) Å-1.511 (3) Å and 106.3 (2)°-118.2 (2)°, are repectively comparable to those in polyamine complexes(Bu et al., 1996; Kimura et al., 1988). 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
Cu10.95883 (4)0.96084 (2)0.24282 (2)0.02998 (10)
N10.7580 (4)0.88265 (19)0.31811 (18)0.0332 (5)
H1C0.802 (4)0.825 (2)0.331 (2)0.042 (9)*
H1D0.654 (4)0.877 (2)0.281 (2)0.045 (9)*
N21.0033 (3)1.03132 (17)0.37778 (15)0.0275 (4)
H2C0.952 (4)1.086 (2)0.3722 (19)0.027 (7)*
N31.2115 (4)1.0223 (2)0.20637 (18)0.0361 (6)
H3C1.287 (5)0.968 (3)0.192 (2)0.066 (11)*
H3D1.195 (5)1.053 (2)0.162 (2)0.044 (11)*
N40.9385 (4)0.87574 (17)0.11913 (17)0.0439 (6)
N50.8205 (4)0.79770 (18)−0.03619 (18)0.0483 (7)
N60.9615 (4)0.66567 (17)−0.14489 (18)0.0436 (6)
N70.7733 (4)1.09871 (18)0.20021 (18)0.0444 (6)
N80.7240 (5)1.27143 (19)0.1303 (2)0.0685 (10)
N90.6794 (4)1.31208 (17)−0.0473 (2)0.0502 (7)
C10.7184 (4)0.93856 (19)0.41347 (19)0.0318 (6)
H1A0.65190.89380.46060.038*
H1B0.63950.99850.40020.038*
C20.9067 (3)0.97153 (19)0.45735 (17)0.0302 (5)
H2A0.88741.01380.51720.036*
H2B0.98190.91160.47600.036*
C31.2078 (4)1.0491 (2)0.38769 (19)0.0338 (6)
H3A1.27260.98490.40340.041*
H3B1.23271.09810.44170.041*
C41.2775 (4)1.09161 (19)0.2877 (2)0.0385 (7)
H4A1.22771.16070.27720.046*
H4B1.41541.09520.28760.046*
C50.8928 (4)0.83515 (18)0.0463 (2)0.0345 (6)
C60.9041 (4)0.72757 (19)−0.09089 (19)0.0311 (6)
C70.7502 (4)1.1780 (2)0.1649 (2)0.0405 (7)
C80.6995 (4)1.28723 (18)0.0343 (2)0.0386 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.03301 (16)0.03245 (15)0.02449 (15)−0.00364 (13)0.00039 (13)−0.00426 (14)
N10.0353 (14)0.0315 (12)0.0328 (12)−0.0046 (11)−0.0050 (11)−0.0003 (10)
N20.0303 (12)0.0245 (10)0.0277 (10)0.0007 (9)−0.0012 (8)−0.0015 (9)
N30.0384 (14)0.0374 (14)0.0324 (13)0.0010 (11)0.0051 (11)0.0017 (11)
N40.0441 (14)0.0506 (14)0.0370 (13)−0.0030 (13)0.0012 (12)−0.0159 (12)
N50.0515 (15)0.0548 (14)0.0385 (14)0.0125 (13)−0.0116 (12)−0.0225 (12)
N60.0452 (13)0.0452 (13)0.0405 (13)0.0031 (13)−0.0019 (13)−0.0133 (11)
N70.0471 (15)0.0470 (14)0.0393 (14)0.0101 (12)−0.0030 (11)0.0099 (11)
N80.131 (3)0.0413 (14)0.0326 (16)0.0252 (18)0.0109 (17)0.0070 (11)
N90.0657 (18)0.0412 (13)0.0437 (16)0.0049 (13)−0.0053 (14)0.0095 (12)
C10.0284 (13)0.0347 (14)0.0324 (13)0.0009 (11)0.0042 (11)0.0025 (11)
C20.0325 (14)0.0319 (12)0.0264 (12)−0.0011 (11)0.0001 (10)0.0025 (11)
C30.0306 (13)0.0375 (14)0.0334 (13)−0.0027 (12)−0.0047 (11)−0.0034 (12)
C40.0364 (15)0.0333 (14)0.0458 (17)−0.0057 (12)0.0001 (12)0.0043 (12)
C50.0363 (15)0.0322 (13)0.0350 (15)0.0009 (12)0.0063 (12)−0.0027 (12)
C60.0310 (14)0.0360 (14)0.0264 (13)−0.0030 (11)−0.0038 (11)0.0007 (11)
C70.0418 (17)0.0517 (17)0.0280 (15)0.0069 (15)0.0031 (12)0.0005 (14)
C80.0448 (16)0.0262 (13)0.0448 (18)0.0072 (12)0.0042 (14)0.0017 (12)
Geometric parameters (Å, º) top
Cu1—N41.974 (2)N5—C61.300 (3)
Cu1—N12.000 (2)N6—C61.145 (3)
Cu1—N32.004 (2)N7—C71.138 (3)
Cu1—N22.025 (2)N8—C81.294 (4)
Cu1—N72.280 (2)N8—C71.305 (4)
N1—C11.478 (3)N9—C81.133 (4)
N1—H1C0.83 (3)C1—C21.506 (3)
N1—H1D0.89 (3)C1—H1A0.9700
N2—C31.462 (3)C1—H1B0.9700
N2—C21.470 (3)C2—H2A0.9700
N2—H2C0.80 (3)C2—H2B0.9700
N3—C41.473 (4)C3—C41.511 (3)
N3—H3C0.90 (4)C3—H3A0.9700
N3—H3D0.71 (3)C3—H3B0.9700
N4—C51.142 (3)C4—H4A0.9700
N5—C51.295 (3)C4—H4B0.9700
N4—Cu1—N194.46 (10)C7—N7—Cu1152.6 (3)
N4—Cu1—N394.98 (10)C8—N8—C7120.5 (3)
N1—Cu1—N3160.88 (11)N1—C1—C2107.5 (2)
N4—Cu1—N2171.68 (10)N1—C1—H1A110.2
N1—Cu1—N284.24 (9)C2—C1—H1A110.2
N3—Cu1—N284.02 (9)N1—C1—H1B110.2
N4—Cu1—N7101.00 (9)C2—C1—H1B110.2
N1—Cu1—N796.57 (11)H1A—C1—H1B108.5
N3—Cu1—N797.89 (11)N2—C2—C1106.3 (2)
N2—Cu1—N787.31 (9)N2—C2—H2A110.5
C1—N1—Cu1108.0 (2)C1—C2—H2A110.5
C1—N1—H1C110 (2)N2—C2—H2B110.5
Cu1—N1—H1C107 (2)C1—C2—H2B110.5
C1—N1—H1D111 (2)H2A—C2—H2B108.7
Cu1—N1—H1D111 (2)N2—C3—C4107.3 (2)
H1C—N1—H1D110 (3)N2—C3—H3A110.2
C3—N2—C2118.2 (2)C4—C3—H3A110.2
C3—N2—Cu1107.54 (15)N2—C3—H3B110.2
C2—N2—Cu1108.66 (14)C4—C3—H3B110.2
C3—N2—H2C108 (2)H3A—C3—H3B108.5
C2—N2—H2C109 (2)N3—C4—C3108.2 (2)
Cu1—N2—H2C104 (2)N3—C4—H4A110.1
C4—N3—Cu1110.2 (2)C3—C4—H4A110.1
C4—N3—H3C116 (2)N3—C4—H4B110.1
Cu1—N3—H3C105 (2)C3—C4—H4B110.1
C4—N3—H3D108 (3)H4A—C4—H4B108.4
Cu1—N3—H3D106 (3)N4—C5—N5172.0 (3)
H3C—N3—H3D111 (3)N6—C6—N5173.1 (3)
C5—N4—Cu1166.7 (2)N7—C7—N8176.4 (3)
C5—N5—C6123.4 (3)N9—C8—N8172.6 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1C···N9i0.83 (3)2.40 (3)3.113 (4)145 (3)
N1—H1D···N6ii0.89 (3)2.31 (3)3.156 (3)159 (2)
N2—H2C···N70.80 (3)2.60 (3)2.977 (3)111 (2)
N3—H3C···N6iii0.90 (4)2.21 (4)3.108 (4)175 (3)
N3—H3D···N9iv0.71 (3)2.32 (3)3.008 (4)164 (3)
Symmetry codes: (i) −x+3/2, −y+2, z+1/2; (ii) x−1/2, −y+3/2, −z; (iii) x+1/2, −y+3/2, −z; (iv) x+1/2, −y+5/2, −z.
(II) Bis(dicyanamido)(triethylenetetramine-κ4N)copper(II) dicyanamide top
Crystal data top
[Cu(C2N3)(C6H18N4)](C2N3)F(000) = 708
Mr = 341.88Dx = 1.550 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 7.4132 (11) ÅCell parameters from 3137 reflections
b = 15.170 (2) Åθ = 2.7–26.3°
c = 13.312 (2) ŵ = 1.50 mm−1
β = 101.881 (2)°T = 298 K
V = 1465.0 (4) Å3Block, blue
Z = 40.30 × 0.20 × 0.10 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		3185 independent reflections
Radiation source: fine-focus sealed tube2668 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
ω scansθmax = 27.0°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −9→6
Tmin = 0.661, Tmax = 0.864k = −17→19
7199 measured reflectionsl = −17→15
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)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.087H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.0432P)2]
where P = (Fo2 + 2Fc2)/3
3185 reflections(Δ/σ)max = 0.001
198 parametersΔρmax = 0.54 e Å−3
0 restraintsΔρmin = −0.44 e Å−3
Crystal data top
[Cu(C2N3)(C6H18N4)](C2N3)V = 1465.0 (4) Å3
Mr = 341.88Z = 4
Monoclinic, P21/nMo Kα radiation
a = 7.4132 (11) ŵ = 1.50 mm−1
b = 15.170 (2) ÅT = 298 K
c = 13.312 (2) Å0.30 × 0.20 × 0.10 mm
β = 101.881 (2)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		3185 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2668 reflections with I > 2σ(I)
Tmin = 0.661, Tmax = 0.864Rint = 0.026
7199 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0350 restraints
wR(F2) = 0.087H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.54 e Å−3
3185 reflectionsΔρmin = −0.44 e Å−3
198 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. The bond distances and angles of trien, 1.463 (3) Å-1.510 (4) Å and 106.7 (2)°-116.0 (2)°). are in normal range observed in polyamine complexes (Bu et al., 1996; Kimura et al., 1988). 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
Cu10.04937 (4)0.527946 (16)0.74734 (2)0.03280 (11)
N10.2770 (3)0.46029 (14)0.83875 (18)0.0526 (6)
N20.5100 (4)0.38257 (15)0.9613 (2)0.0673 (7)
N30.5109 (4)0.22981 (16)1.0134 (2)0.0705 (8)
N40.1881 (3)0.60787 (12)0.66895 (15)0.0424 (5)
H4A0.28570.57940.65390.051*
H4B0.11430.62530.60990.051*
N50.0252 (3)0.63742 (13)0.83136 (16)0.0364 (5)
N6−0.1513 (3)0.47994 (12)0.81406 (15)0.0372 (5)
N7−0.0503 (3)0.44384 (13)0.63245 (15)0.0406 (5)
H7A−0.10030.47400.57530.049*
H7B0.04120.40990.61870.049*
N80.0595 (4)0.68929 (16)0.06855 (18)0.0637 (7)
N90.0669 (4)0.84954 (15)0.07253 (18)0.0652 (8)
N100.1956 (4)0.94976 (15)−0.03788 (19)0.0571 (6)
C10.3795 (4)0.41999 (16)0.89540 (19)0.0404 (6)
C20.5018 (4)0.30071 (17)0.98574 (18)0.0434 (6)
C30.2493 (4)0.68403 (17)0.7345 (2)0.0504 (7)
H3A0.28800.73110.69450.060*
H3B0.35290.66780.78860.060*
C40.0899 (4)0.71409 (16)0.7802 (2)0.0466 (6)
H4C0.12900.76090.82950.056*
H4D−0.00880.73630.72670.056*
C5−0.1705 (4)0.63871 (15)0.8387 (2)0.0425 (6)
H5A−0.24760.65100.77200.051*
H5B−0.19150.68410.88620.051*
C6−0.2165 (4)0.54928 (15)0.87618 (19)0.0453 (6)
H6A−0.15770.54220.94790.054*
H6B−0.34870.54420.87020.054*
C7−0.2922 (4)0.44363 (17)0.72977 (19)0.0458 (6)
H7C−0.35920.49090.68930.055*
H7D−0.37930.40770.75690.055*
C8−0.1915 (4)0.38838 (17)0.6646 (2)0.0491 (7)
H8A−0.13380.33820.70370.059*
H8B−0.27740.36650.60470.059*
C90.0689 (4)0.76398 (18)0.06679 (17)0.0436 (6)
C100.1396 (4)0.89899 (16)0.01102 (19)0.0434 (6)
H50.081 (4)0.6301 (15)0.8879 (18)0.038 (7)*
H6−0.097 (4)0.4363 (17)0.8570 (19)0.045 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.03316 (18)0.03215 (17)0.03512 (17)0.00101 (12)0.01177 (13)−0.00145 (11)
N10.0416 (14)0.0542 (13)0.0608 (14)0.0088 (11)0.0079 (12)0.0131 (11)
N20.0516 (17)0.0473 (13)0.0915 (18)0.0008 (12)−0.0120 (14)0.0113 (12)
N30.071 (2)0.0601 (14)0.0804 (18)0.0091 (15)0.0157 (15)0.0241 (14)
N40.0447 (13)0.0431 (11)0.0445 (11)0.0012 (10)0.0212 (10)−0.0007 (9)
N50.0386 (13)0.0381 (11)0.0337 (11)−0.0005 (9)0.0102 (10)−0.0020 (8)
N60.0413 (13)0.0335 (10)0.0390 (11)−0.0009 (9)0.0134 (10)−0.0006 (8)
N70.0392 (12)0.0441 (11)0.0401 (11)0.0028 (10)0.0121 (10)−0.0073 (9)
N80.080 (2)0.0470 (14)0.0682 (16)−0.0006 (13)0.0253 (15)0.0116 (11)
N90.098 (2)0.0433 (13)0.0668 (15)−0.0013 (13)0.0460 (16)0.0012 (11)
N100.0574 (17)0.0492 (13)0.0708 (16)−0.0009 (12)0.0276 (14)0.0052 (12)
C10.0332 (14)0.0405 (13)0.0508 (14)0.0005 (12)0.0162 (12)0.0014 (11)
C20.0412 (16)0.0495 (15)0.0395 (13)0.0074 (13)0.0086 (12)0.0024 (11)
C30.0504 (17)0.0470 (14)0.0577 (16)−0.0131 (13)0.0202 (14)−0.0024 (12)
C40.0556 (18)0.0347 (12)0.0540 (15)−0.0058 (12)0.0215 (13)−0.0054 (11)
C50.0418 (16)0.0415 (13)0.0478 (14)0.0064 (12)0.0175 (12)−0.0049 (11)
C60.0477 (16)0.0489 (14)0.0455 (14)−0.0001 (12)0.0241 (13)−0.0036 (11)
C70.0392 (15)0.0504 (14)0.0504 (15)−0.0090 (12)0.0152 (12)−0.0019 (12)
C80.0522 (18)0.0443 (14)0.0516 (15)−0.0111 (13)0.0124 (14)−0.0096 (11)
C90.0452 (16)0.0504 (16)0.0365 (13)0.0006 (13)0.0114 (12)0.0053 (11)
C100.0434 (16)0.0394 (13)0.0480 (14)0.0016 (12)0.0111 (12)−0.0048 (11)
Geometric parameters (Å, º) top
Cu1—N72.012 (2)N7—H7B0.9000
Cu1—N42.014 (2)N8—C91.136 (3)
Cu1—N62.019 (2)N9—C91.301 (3)
Cu1—N52.031 (2)N9—C101.306 (3)
Cu1—N12.130 (2)N10—C101.141 (3)
N1—C11.133 (3)C3—C41.506 (4)
N2—C21.288 (3)C3—H3A0.9700
N2—C11.295 (3)C3—H3B0.9700
N3—C21.134 (3)C4—H4C0.9700
N4—C31.463 (3)C4—H4D0.9700
N4—H4A0.9000C5—C61.509 (3)
N4—H4B0.9000C5—H5A0.9700
N5—C51.474 (3)C5—H5B0.9700
N5—C41.477 (3)C6—H6A0.9700
N5—H50.79 (2)C6—H6B0.9700
N6—C71.474 (3)C7—C81.510 (4)
N6—C61.479 (3)C7—H7C0.9700
N6—H60.91 (3)C7—H7D0.9700
N7—C81.473 (3)C8—H8A0.9700
N7—H7A0.9000C8—H8B0.9700
N7—Cu1—N497.74 (8)N4—C3—C4107.9 (2)
N7—Cu1—N685.24 (8)N4—C3—H3A110.1
N4—Cu1—N6161.06 (9)C4—C3—H3A110.1
N7—Cu1—N5151.29 (9)N4—C3—H3B110.1
N4—Cu1—N584.57 (8)C4—C3—H3B110.1
N6—Cu1—N584.03 (8)H3A—C3—H3B108.4
N7—Cu1—N1104.63 (9)N5—C4—C3107.7 (2)
N4—Cu1—N199.05 (9)N5—C4—H4C110.2
N6—Cu1—N198.25 (9)C3—C4—H4C110.2
N5—Cu1—N1103.23 (9)N5—C4—H4D110.2
C1—N1—Cu1169.8 (2)C3—C4—H4D110.2
C2—N2—C1121.7 (3)H4C—C4—H4D108.5
C3—N4—Cu1107.15 (15)N5—C5—C6107.6 (2)
C3—N4—H4A110.3N5—C5—H5A110.2
Cu1—N4—H4A110.3C6—C5—H5A110.2
C3—N4—H4B110.3N5—C5—H5B110.2
Cu1—N4—H4B110.3C6—C5—H5B110.2
H4A—N4—H4B108.5H5A—C5—H5B108.5
C5—N5—C4116.0 (2)N6—C6—C5109.4 (2)
C5—N5—Cu1104.29 (14)N6—C6—H6A109.8
C4—N5—Cu1108.42 (14)C5—C6—H6A109.8
C5—N5—H5106 (2)N6—C6—H6B109.8
C4—N5—H5113 (2)C5—C6—H6B109.8
Cu1—N5—H5109 (2)H6A—C6—H6B108.2
C7—N6—C6115.4 (2)N6—C7—C8106.7 (2)
C7—N6—Cu1105.72 (15)N6—C7—H7C110.4
C6—N6—Cu1110.16 (14)C8—C7—H7C110.4
C7—N6—H6111 (2)N6—C7—H7D110.4
C6—N6—H6109 (2)C8—C7—H7D110.4
Cu1—N6—H6106 (2)H7C—C7—H7D108.6
C8—N7—Cu1108.26 (14)N7—C8—C7108.3 (2)
C8—N7—H7A110.0N7—C8—H8A110.0
Cu1—N7—H7A110.0C7—C8—H8A110.0
C8—N7—H7B110.0N7—C8—H8B110.0
Cu1—N7—H7B110.0C7—C8—H8B110.0
H7A—N7—H7B108.4H8A—C8—H8B108.4
C9—N9—C10121.7 (2)N8—C9—N9173.2 (3)
N1—C1—N2172.8 (3)N10—C10—N9172.6 (3)
N3—C2—N2173.3 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N6—H6···N8i0.91 (3)2.14 (3)3.010 (3)159 (2)
N5—H5···N8ii0.79 (2)2.60 (2)3.213 (3)136 (2)
N7—H7B···N3iii0.902.533.155 (3)128
N7—H7B···N10iv0.902.493.142 (3)130
N7—H7A···N10v0.902.233.088 (3)160
N4—H4B···N3vi0.902.333.164 (3)154
N4—H4A···N10iv0.902.523.188 (3)131
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, y, z+1; (iii) x−1/2, −y+1/2, z−1/2; (iv) −x+1/2, y−1/2, −z+1/2; (v) x−1/2, −y+3/2, z+1/2; (vi) −x+1/2, y+1/2, −z+3/2.

Experimental details

(I)(II)
Crystal data
Chemical formula[Cu(C2N3)2(C4H13N3)][Cu(C2N3)(C6H18N4)](C2N3)
Mr298.81341.88
Crystal system, space groupOrthorhombic, P212121Monoclinic, P21/n
Temperature (K)293298
a, b, c (Å)7.0284 (10), 12.935 (2), 13.197 (2)7.4132 (11), 15.170 (2), 13.312 (2)
α, β, γ (°)90, 90, 9090, 101.881 (2), 90
V (Å3)1199.8 (3)1465.0 (4)
Z44
Radiation typeMo KαMo Kα
µ (mm−1)1.821.50
Crystal size (mm)0.30 × 0.20 × 0.100.30 × 0.20 × 0.10
Data collection
DiffractometerBrucker SMART APEX CCD area-detectorBruker SMART APEX CCD area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)		Multi-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.611, 0.8390.661, 0.864
No. of measured, independent and
observed [I > 2σ(I)] reflections		5547, 2367, 2249 7199, 3185, 2668
Rint0.0270.026
(sin θ/λ)max (Å−1)0.6170.639
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.025, 0.059, 1.05 0.035, 0.087, 1.03
No. of reflections23673185
No. of parameters183198
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)0.27, −0.440.54, −0.44
Absolute structureFlack (1983)?
Absolute structure parameter0.020 (14)?

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 2000), SHELXTL.

Selected geometric parameters (Å, º) for (I) top
Cu1—N41.974 (2)Cu1—N22.025 (2)
Cu1—N12.000 (2)Cu1—N72.280 (2)
Cu1—N32.004 (2)
N4—Cu1—N194.46 (10)N3—Cu1—N284.02 (9)
N4—Cu1—N394.98 (10)N4—Cu1—N7101.00 (9)
N1—Cu1—N3160.88 (11)N1—Cu1—N796.57 (11)
N4—Cu1—N2171.68 (10)N3—Cu1—N797.89 (11)
N1—Cu1—N284.24 (9)N2—Cu1—N787.31 (9)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1—H1C···N9i0.83 (3)2.40 (3)3.113 (4)145 (3)
N1—H1D···N6ii0.89 (3)2.31 (3)3.156 (3)159 (2)
N2—H2C···N70.80 (3)2.60 (3)2.977 (3)111 (2)
N3—H3C···N6iii0.90 (4)2.21 (4)3.108 (4)175 (3)
N3—H3D···N9iv0.71 (3)2.32 (3)3.008 (4)164 (3)
Symmetry codes: (i) −x+3/2, −y+2, z+1/2; (ii) x−1/2, −y+3/2, −z; (iii) x+1/2, −y+3/2, −z; (iv) x+1/2, −y+5/2, −z.
Selected geometric parameters (Å, º) for (II) top
Cu1—N72.012 (2)Cu1—N52.031 (2)
Cu1—N42.014 (2)Cu1—N12.130 (2)
Cu1—N62.019 (2)
N7—Cu1—N497.74 (8)N6—Cu1—N584.03 (8)
N7—Cu1—N685.24 (8)N7—Cu1—N1104.63 (9)
N4—Cu1—N6161.06 (9)N4—Cu1—N199.05 (9)
N7—Cu1—N5151.29 (9)N6—Cu1—N198.25 (9)
N4—Cu1—N584.57 (8)N5—Cu1—N1103.23 (9)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N6—H6···N8i0.91 (3)2.14 (3)3.010 (3)159 (2)
N5—H5···N8ii0.79 (2)2.60 (2)3.213 (3)136 (2)
N7—H7B···N3iii0.902.533.155 (3)127.5
N7—H7B···N10iv0.902.493.142 (3)129.8
N7—H7A···N10v0.902.233.088 (3)160.1
N4—H4B···N3vi0.902.333.164 (3)153.8
N4—H4A···N10iv0.902.523.188 (3)131.2
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, y, z+1; (iii) x−1/2, −y+1/2, z−1/2; (iv) −x+1/2, y−1/2, −z+1/2; (v) x−1/2, −y+3/2, z+1/2; (vi) −x+1/2, y+1/2, −z+3/2.
 

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