supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers buy article online

Acta Cryst. (2007). E63, m2347    [ doi:10.1107/S1600536807039645 ]

(1,3-Propanediamine-[kappa]2N,N')bis(thiocyanato-[kappa]N)copper(II)

Z.-L. You and S. W. Ng

Abstract top

The title compound, [Cu(NCS)2(C3H10N2)], synthesized from the reaction of propane-1,3-diamine, ammonium thiocyanate and copper acetate monohydrate in anhydrous methanol solution, is a mononuclear copper(II) complex which lies on a mirror plane. The CuII ion is four-coordinated by the two N atoms of the propane-1,3-diamine ligand and by two N atoms from two thiocyanate ligands, forming a square-planar geometry. The propane-1,3-diamine ligand is disordered over four orientations, two symmetry-independent and two related by mirror symmetry, each with an occupancy of 0.25. The refinement results indicate inversion twinning.

Comment top

Recently, we have reported the crystal structures of a few Schiff base metal complexes (You, Han et al., 2006; You, Wang & Han, 2006; You & Niu, 2006). As an extension of the work on the structural characterization of such complexes, the title copper(II) complex is reported here.

The complex is a mononuclear copper(II) complex, which lies on a mirror plane. The CuII ion is four-coordinated by two N atoms of the propane-1,3-diamine ligand and by two N atoms from two thiocyanate ligands, forming a square planar geometry (Table 1). The coordination bond lengths are within normal ranges and comparable to the values observed in other copper(II) complexes reported by us recently (You & Zhu, 2004; You et al., 2004; Ye & You, 2007).

Related literature top

For related structures, see: Ye & You (2007); You et al. (2004); You, Han et al. (2006); You, Wang & Han (2006); You & Niu (2006); You & Zhu (2004).

Experimental top

All the reagents used were of commercial grade and used without further purification. Propane-1,3-diamine (0.1 mmol, 7.4 mg), ammonium thiocyanate (0.2 mmol, 15.2 mg) and copper acetate monohydrate (0.1 mmol, 20.0 mg) were mixed in an anhydrous methanol solution (10 ml). The mixture was stirred at room temperature for 30 min to give a clear blue solution. After keeping the solution in air for a week, blue block-shaped crystals were formed.

Refinement top

All non-hydrogen atoms except the C atoms of the 1,3-propanediamine ligand lie on a mirror plane. The 1,3-propanediamine ligand is disordered over four orientations, two symmetry independent and two related by mirror symmetry, each with an occupancy of 0.25. The N—C bond distances were restrained to 1.45 (1) Å and the C–C distances to 1.54 (1) Å. The 1,3-related N···C distances were restrained to 2.35 (1) Å and the 1,3-related C···C distances to 2.51 (1) Å. Additionally, the displacement parameters of the primed atoms were set to those of the unprimed ones; the anisotropic displacement parameters of the entire ligand were restrained to be nearly isotropic. C– and N-bound H atoms were generated geometrically (C–H = 0.97 and N–H = 0.86 Å), and were included in the refinement in the riding model approximation. The refined Flack parameter of 0.50 (2) indicates that the crystal is an inversion twin.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures top
[Figure 1] Fig. 1. The structure of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme. Only one of the four disorder components is shown.
(1,3-Propanediamine-κ2N,N')bis(thiocyanato-κN)\ copper(II) top
Crystal data top
[Cu(NCS)2(C3H10N2)]F000 = 516
Mr = 253.83Dx = 1.633 Mg m−3
Orthorhombic, Cmc21Mo Kα radiation
λ = 0.71073 Å
Hall symbol: C 2c -2Cell parameters from 4527 reflections
a = 5.9505 (17) Åθ = 2.7–27.5º
b = 20.478 (6) ŵ = 2.47 mm−1
c = 8.475 (2) ÅT = 295 (2) K
V = 1032.7 (5) Å3Block, blue
Z = 40.32 × 0.30 × 0.27 mm
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer		1287 independent reflections
Radiation source: fine-focus sealed tube1264 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.020
T = 295(2) Kθmax = 27.5º
ω scansθmin = 2.0º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −7→7
Tmin = 0.505, Tmax = 0.555k = −26→26
4393 measured reflectionsl = −11→11
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.023  w = 1/[σ2(Fo2) + (0.0479P)2 + 0.1407P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.066(Δ/σ)max < 0.001
S = 1.04Δρmax = 0.34 e Å−3
1287 reflectionsΔρmin = −0.36 e Å−3
97 parametersExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
63 restraintsExtinction coefficient: 0.010 (1)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 593 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: 0.50 (2)
Crystal data top
[Cu(NCS)2(C3H10N2)]V = 1032.7 (5) Å3
Mr = 253.83Z = 4
Orthorhombic, Cmc21Mo Kα
a = 5.9505 (17) ŵ = 2.47 mm−1
b = 20.478 (6) ÅT = 295 (2) K
c = 8.475 (2) Å0.32 × 0.30 × 0.27 mm
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer		1287 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1264 reflections with I > 2σ(I)
Tmin = 0.505, Tmax = 0.555Rint = 0.020
4393 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.023H-atom parameters constrained
wR(F2) = 0.066Δρmax = 0.34 e Å−3
S = 1.04Δρmin = −0.36 e Å−3
1287 reflectionsAbsolute structure: Flack (1983), 593 Friedel pairs
97 parametersFlack parameter: 0.50 (2)
63 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cu10.50000.701275 (15)0.50000.04011 (15)
S10.50000.80305 (4)0.0035 (2)0.0479 (2)
S20.50000.92135 (5)0.6725 (2)0.0766 (4)
N30.50000.72640 (19)0.2739 (4)0.0501 (7)
N40.50000.79405 (14)0.5584 (5)0.0516 (8)
C40.50000.75676 (17)0.1619 (4)0.0404 (7)
C50.50000.84648 (18)0.6040 (5)0.0481 (8)
N10.50000.67852 (16)0.7296 (4)0.0495 (7)
H110.62420.69400.76560.059*0.25
H120.39530.70210.77030.059*0.25
H130.56560.71000.77860.059*0.25
H140.36230.67830.76030.059*0.25
N20.50000.60769 (14)0.4330 (4)0.0529 (9)
H210.37210.60050.38900.064*0.25
H220.59990.60400.36030.064*0.25
H230.36160.59640.42240.064*0.25
H240.55870.60650.34030.064*0.25
C10.477 (2)0.6158 (3)0.8026 (9)0.052 (2)0.25
H1A0.37150.61910.88960.063*0.25
H1B0.62090.60250.84530.063*0.25
C20.396 (2)0.5649 (4)0.6890 (11)0.072 (3)0.25
H2A0.24580.57700.65440.086*0.25
H2B0.38260.52390.74530.086*0.25
C30.539 (3)0.5537 (6)0.5448 (12)0.064 (3)0.25
H3A0.69600.55210.57430.077*0.25
H3B0.50000.51250.49590.077*0.50
C1'0.6032 (17)0.6171 (4)0.7849 (11)0.052 (2)0.25
H1'10.57510.61110.89670.063*0.25
H1'20.76440.61810.76800.063*0.25
C2'0.497 (4)0.5609 (4)0.6903 (10)0.072 (3)0.25
H2'10.33770.56900.67670.086*0.25
H2'20.51470.52020.74760.086*0.25
C3'0.611 (3)0.5552 (6)0.5270 (12)0.064 (3)0.25
H3'10.77170.56260.53480.077*0.25
H3'20.58480.51260.48070.077*0.25
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0494 (2)0.0383 (2)0.0327 (2)0.0000.0000.00364 (17)
S10.0423 (4)0.0641 (5)0.0374 (4)0.0000.0000.0121 (5)
S20.0979 (8)0.0411 (5)0.0909 (9)0.0000.000−0.0032 (5)
N30.0439 (15)0.065 (2)0.0419 (17)0.0000.0000.0092 (15)
N40.0581 (19)0.0427 (15)0.0541 (17)0.0000.0000.0009 (12)
C40.0317 (13)0.0519 (19)0.0375 (16)0.0000.0000.0009 (14)
C50.0492 (16)0.0446 (17)0.0506 (19)0.0000.0000.0086 (16)
N10.0533 (16)0.0577 (19)0.0374 (16)0.000 (11)0.000 (11)0.0062 (14)
N20.068 (2)0.0428 (16)0.0475 (17)−0.007 (7)−0.017 (6)−0.0033 (15)
C10.059 (7)0.055 (3)0.042 (3)−0.002 (4)0.000 (4)0.012 (2)
C20.077 (7)0.062 (3)0.077 (4)−0.025 (5)−0.010 (5)0.021 (3)
C30.078 (8)0.044 (2)0.072 (5)−0.001 (4)0.001 (4)0.000 (2)
N1'0.0533 (16)0.0577 (19)0.0374 (16)0.000 (11)0.000 (11)0.0062 (14)
N2'0.068 (2)0.0428 (16)0.0475 (17)−0.007 (7)−0.017 (6)−0.0033 (15)
C1'0.059 (7)0.055 (3)0.042 (3)−0.002 (4)0.000 (4)0.012 (2)
C2'0.077 (7)0.062 (3)0.077 (4)−0.025 (5)−0.010 (5)0.021 (3)
C3'0.078 (8)0.044 (2)0.072 (5)−0.001 (4)0.001 (4)0.000 (2)
Geometric parameters (Å, °) top
Cu1—N41.963 (3)C1—H1A0.97
Cu1—N31.984 (3)C1—H1B0.97
Cu1—N21.999 (3)C2—C31.507 (9)
Cu1—N12.001 (3)C2—H2A0.97
S1—C41.644 (4)C2—H2B0.97
S2—C51.639 (4)C3—H3A0.97
N3—C41.134 (5)C3—H3B0.97
N4—C51.141 (5)C1'—C2'1.537 (10)
N1—C11.432 (7)C1'—H1'10.97
N1—H110.86C1'—H1'20.97
N1—H120.86C2'—C3'1.545 (10)
N2—C31.473 (9)C2'—H2'10.97
N2—H210.86C2'—H2'20.97
N2—H220.86C3'—H3'10.97
C1—C21.499 (9)C3'—H3'20.97
N4—Cu1—N389.57 (16)C2—C1—H1B109.2
N4—Cu1—N2178.10 (16)H1A—C1—H1B107.9
N3—Cu1—N288.53 (15)C1—C2—C3116.4 (8)
N4—Cu1—N188.87 (16)C1—C2—H2A108.2
N3—Cu1—N1178.44 (16)C3—C2—H2A108.2
N2—Cu1—N193.03 (14)C1—C2—H2B108.2
C4—N3—Cu1161.8 (4)C3—C2—H2B108.2
C5—N4—Cu1174.8 (4)H2A—C2—H2B107.3
N3—C4—S1178.0 (4)N2—C3—C2108.6 (7)
N4—C5—S2179.1 (4)N2—C3—H3A110.0
C1—N1—Cu1129.0 (4)C2—C3—H3A110.0
C1—N1—H11105.0N2—C3—H3B110.0
Cu1—N1—H11105.0C2—C3—H3B110.0
C1—N1—H12105.0H3A—C3—H3B108.3
Cu1—N1—H12105.0C2'—C1'—H1'1110.2
H11—N1—H12105.9C2'—C1'—H1'2110.2
C3—N2—Cu1122.4 (5)H1'1—C1'—H1'2108.5
C3—N2—H21106.7C1'—C2'—C3'110.1 (10)
Cu1—N2—H21106.7C1'—C2'—H2'1109.6
C3—N2—H22106.7C3'—C2'—H2'1109.6
Cu1—N2—H22106.7C1'—C2'—H2'2109.6
H21—N2—H22106.6C3'—C2'—H2'2109.6
N1—C1—C2112.1 (6)H2'1—C2'—H2'2108.2
N1—C1—H1A109.2C2'—C3'—H3'1111.1
C2—C1—H1A109.2C2'—C3'—H3'2111.1
N1—C1—H1B109.2H3'1—C3'—H3'2109.1
N4—Cu1—N3—C40N1—Cu1—N2—C3−10.6 (7)
N2—Cu1—N3—C4180Cu1—N1—C1—C2−13.6 (13)
N4—Cu1—N1—C1172.9 (7)N1—C1—C2—C358.3 (14)
N2—Cu1—N1—C1−7.1 (7)Cu1—N2—C3—C246.8 (12)
N3—Cu1—N2—C3169.4 (7)C1—C2—C3—N2−76.4 (13)
Table 1
Selected geometric parameters (Å, °) top
Cu1—N41.963 (3)Cu1—N21.999 (3)
Cu1—N31.984 (3)Cu1—N12.001 (3)
N4—Cu1—N389.57 (16)N4—Cu1—N188.87 (16)
N4—Cu1—N2178.10 (16)N3—Cu1—N1178.44 (16)
N3—Cu1—N288.53 (15)N2—Cu1—N193.03 (14)
Acknowledgements top

This work was supported by the Scientific Research Foundation of the Education Office of Liaoning Province (project No. 20060495). We also thank the University of Malaya for support.

references
References top

Bruker (1998). SMART (Version 5.628) and SAINT (Version 6.02). Bruker AXS Inc., Madison, Wisconsin, USA.

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997a). SHELXL97 and SHELXS97. University of Göttingen, Germany.

Sheldrick, G. M. (1997b). SHELXTL. Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA.

Ye, L.-J. & You, Z. (2007). Acta Cryst. E63, m1837–?.

You, Z.-L., Chen, B., Zhu, H.-L. & Liu, W.-S. (2004). Acta Cryst. E60, m884–m886.

You, Z.-L., Han, X., Wang, J. & Niu, S.-Y. (2006). Acta Cryst. E62, m851–m853.

You, Z.-L. & Niu, S.-Y. (2006). Acta Cryst. E62, m922–m924.

You, Z.-L., Wang, J. & Han, X. (2006). Acta Cryst. E62, m860–m861.

You, Z.-L. & Zhu, H.-L. (2004). Acta Cryst. E60, m1079–m1080.