(1,3-Propane­diamine-κ²N,N′)bis­(thio­cyanato-κN)copper(II)

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 Cu^II 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.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](N-C) = 0.005 Å
• Disorder in main residue
• R factor = 0.023
• wR factor = 0.066
• Data-to-parameter ratio = 13.3

checkCIF/PLATON results

No syntax errors found



Alert level C
STRVA01_ALERT_4_C           Flack test results are ambiguous.
           From the CIF: _refine_ls_abs_structure_Flack    0.500
           From the CIF: _refine_ls_abs_structure_Flack_su    0.020
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.92
PLAT076_ALERT_1_C Occupancy       0.50 less than 1.0 for Sp.pos  .        H3B
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C5
PLAT301_ALERT_3_C Main Residue  Disorder .........................      14.00 Perc.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          6

Alert level G
ABSTM02_ALERT_3_G  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      0.924
            Tmax scaled      0.513 Tmin scaled      0.467
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.48
           From the CIF: _reflns_number_total               1287
           Count of symmetry unique reflns          692
           Completeness (_total/calc)            185.98%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       595
           Fraction of Friedel pairs measured     0.860
           Are heavy atom types Z>Si present        yes
PLAT033_ALERT_2_G Flack Parameter Value Deviates 2 * su from zero.       0.50
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         63

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   4 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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 Cu^II 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

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).

S2. Experimental

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.

S3. Refinement

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

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

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)χopper(II)

Crystal data

[Cu(NCS)2(C3H10N2)]	F(000) = 516
Mr = 253.83	Dx = 1.633 Mg m^−3
Orthorhombic, Cmc21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2c -2	Cell parameters from 4527 reflections
a = 5.9505 (17) Å	θ = 2.7–27.5°
b = 20.478 (6) Å	µ = 2.47 mm^−1
c = 8.475 (2) Å	T = 295 K
V = 1032.7 (5) Å^3	Block, blue
Z = 4	0.32 × 0.30 × 0.27 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer	1287 independent reflections
Radiation source: fine-focus sealed tube	1264 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
ω scans	θmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
Tmin = 0.505, Tmax = 0.555	k = −26→26
4393 measured reflections	l = −11→11

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.023	w = 1/[σ^2(Fo^2) + (0.0479P)^2 + 0.1407P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.066	(Δ/σ)max < 0.001
S = 1.04	Δρmax = 0.34 e Å^−3
1287 reflections	Δρmin = −0.36 e Å^−3
97 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
63 restraints	Extinction coefficient: 0.010 (1)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 593 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.50 (2)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.5000	0.701275 (15)	0.5000	0.04011 (15)
S1	0.5000	0.80305 (4)	0.0035 (2)	0.0479 (2)
S2	0.5000	0.92135 (5)	0.6725 (2)	0.0766 (4)
N3	0.5000	0.72640 (19)	0.2739 (4)	0.0501 (7)
N4	0.5000	0.79405 (14)	0.5584 (5)	0.0516 (8)
C4	0.5000	0.75676 (17)	0.1619 (4)	0.0404 (7)
C5	0.5000	0.84648 (18)	0.6040 (5)	0.0481 (8)
N1	0.5000	0.67852 (16)	0.7296 (4)	0.0495 (7)
H11	0.6242	0.6940	0.7656	0.059*	0.25
H12	0.3953	0.7021	0.7703	0.059*	0.25
H13	0.5656	0.7100	0.7786	0.059*	0.25
H14	0.3623	0.6783	0.7603	0.059*	0.25
N2	0.5000	0.60769 (14)	0.4330 (4)	0.0529 (9)
H21	0.3721	0.6005	0.3890	0.064*	0.25
H22	0.5999	0.6040	0.3603	0.064*	0.25
H23	0.3616	0.5964	0.4224	0.064*	0.25
H24	0.5587	0.6065	0.3403	0.064*	0.25
C1	0.477 (2)	0.6158 (3)	0.8026 (9)	0.052 (2)	0.25
H1A	0.3715	0.6191	0.8896	0.063*	0.25
H1B	0.6209	0.6025	0.8453	0.063*	0.25
C2	0.396 (2)	0.5649 (4)	0.6890 (11)	0.072 (3)	0.25
H2A	0.2458	0.5770	0.6544	0.086*	0.25
H2B	0.3826	0.5239	0.7453	0.086*	0.25
C3	0.539 (3)	0.5537 (6)	0.5448 (12)	0.064 (3)	0.25
H3A	0.6960	0.5521	0.5743	0.077*	0.25
H3B	0.5000	0.5125	0.4959	0.077*	0.50
C1'	0.6032 (17)	0.6171 (4)	0.7849 (11)	0.052 (2)	0.25
H1'1	0.5751	0.6111	0.8967	0.063*	0.25
H1'2	0.7644	0.6181	0.7680	0.063*	0.25
C2'	0.497 (4)	0.5609 (4)	0.6903 (10)	0.072 (3)	0.25
H2'1	0.3377	0.5690	0.6767	0.086*	0.25
H2'2	0.5147	0.5202	0.7476	0.086*	0.25
C3'	0.611 (3)	0.5552 (6)	0.5270 (12)	0.064 (3)	0.25
H3'1	0.7717	0.5626	0.5348	0.077*	0.25
H3'2	0.5848	0.5126	0.4807	0.077*	0.25

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0494 (2)	0.0383 (2)	0.0327 (2)	0.000	0.000	0.00364 (17)
S1	0.0423 (4)	0.0641 (5)	0.0374 (4)	0.000	0.000	0.0121 (5)
S2	0.0979 (8)	0.0411 (5)	0.0909 (9)	0.000	0.000	−0.0032 (5)
N3	0.0439 (15)	0.065 (2)	0.0419 (17)	0.000	0.000	0.0092 (15)
N4	0.0581 (19)	0.0427 (15)	0.0541 (17)	0.000	0.000	0.0009 (12)
C4	0.0317 (13)	0.0519 (19)	0.0375 (16)	0.000	0.000	0.0009 (14)
C5	0.0492 (16)	0.0446 (17)	0.0506 (19)	0.000	0.000	0.0086 (16)
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)
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, º)

Cu1—N4	1.963 (3)	C1—H1A	0.97
Cu1—N3	1.984 (3)	C1—H1B	0.97
Cu1—N2	1.999 (3)	C2—C3	1.507 (9)
Cu1—N1	2.001 (3)	C2—H2A	0.97
S1—C4	1.644 (4)	C2—H2B	0.97
S2—C5	1.639 (4)	C3—H3A	0.97
N3—C4	1.134 (5)	C3—H3B	0.97
N4—C5	1.141 (5)	C1'—C2'	1.537 (10)
N1—C1	1.432 (7)	C1'—H1'1	0.97
N1—H11	0.86	C1'—H1'2	0.97
N1—H12	0.86	C2'—C3'	1.545 (10)
N2—C3	1.473 (9)	C2'—H2'1	0.97
N2—H21	0.86	C2'—H2'2	0.97
N2—H22	0.86	C3'—H3'1	0.97
C1—C2	1.499 (9)	C3'—H3'2	0.97
N4—Cu1—N3	89.57 (16)	C2—C1—H1B	109.2
N4—Cu1—N2	178.10 (16)	H1A—C1—H1B	107.9
N3—Cu1—N2	88.53 (15)	C1—C2—C3	116.4 (8)
N4—Cu1—N1	88.87 (16)	C1—C2—H2A	108.2
N3—Cu1—N1	178.44 (16)	C3—C2—H2A	108.2
N2—Cu1—N1	93.03 (14)	C1—C2—H2B	108.2
C4—N3—Cu1	161.8 (4)	C3—C2—H2B	108.2
C5—N4—Cu1	174.8 (4)	H2A—C2—H2B	107.3
N3—C4—S1	178.0 (4)	N2—C3—C2	108.6 (7)
N4—C5—S2	179.1 (4)	N2—C3—H3A	110.0
C1—N1—Cu1	129.0 (4)	C2—C3—H3A	110.0
C1—N1—H11	105.0	N2—C3—H3B	110.0
Cu1—N1—H11	105.0	C2—C3—H3B	110.0
C1—N1—H12	105.0	H3A—C3—H3B	108.3
Cu1—N1—H12	105.0	C2'—C1'—H1'1	110.2
H11—N1—H12	105.9	C2'—C1'—H1'2	110.2
C3—N2—Cu1	122.4 (5)	H1'1—C1'—H1'2	108.5
C3—N2—H21	106.7	C1'—C2'—C3'	110.1 (10)
Cu1—N2—H21	106.7	C1'—C2'—H2'1	109.6
C3—N2—H22	106.7	C3'—C2'—H2'1	109.6
Cu1—N2—H22	106.7	C1'—C2'—H2'2	109.6
H21—N2—H22	106.6	C3'—C2'—H2'2	109.6
N1—C1—C2	112.1 (6)	H2'1—C2'—H2'2	108.2
N1—C1—H1A	109.2	C2'—C3'—H3'1	111.1
C2—C1—H1A	109.2	C2'—C3'—H3'2	111.1
N1—C1—H1B	109.2	H3'1—C3'—H3'2	109.1
N4—Cu1—N3—C4	0	N1—Cu1—N2—C3	−10.6 (7)
N2—Cu1—N3—C4	180	Cu1—N1—C1—C2	−13.6 (13)
N4—Cu1—N1—C1	172.9 (7)	N1—C1—C2—C3	58.3 (14)
N2—Cu1—N1—C1	−7.1 (7)	Cu1—N2—C3—C2	46.8 (12)
N3—Cu1—N2—C3	169.4 (7)	C1—C2—C3—N2	−76.4 (13)