(2,2′-Bipyridine-κ²N,N′)iodido(piperidine-1-carbodithio­ato-κ²S,S′)copper(II)

In the title compound, [Cu(C₆H₁₀NS₂)I(C₁₀H₈N₂)], the Cu^II ion is coordinated by one iodide ion, two N atoms of the bipyridine ligand and two S atoms from the piperidine­carbodithio­ate ligand in a distorted square-pyramidal environment. π–π stacking inter­actions, with centroid–centroid distances of 3.643 (4) Å, between pyridyl rings of the bipyridyl ligands of neighbouring mol­ecules lead to chains propagating parallel to the a axis.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.008 Å
• R factor = 0.047
• wR factor = 0.108
• Data-to-parameter ratio = 19.0

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low .......       0.95
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  I1     --  Cu1     ..      23.72 su

Alert level C
            Value of measurement temperature given =   293.000
            Value of melting point given =     0.000
PLAT022_ALERT_3_C Ratio Unique / Expected Reflections too Low ....       0.93
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         S2
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.86
PLAT234_ALERT_4_C Large Hirshfeld Difference C8     --  C9      ..       0.10  Ang.
PLAT234_ALERT_4_C Large Hirshfeld Difference C14    --  C15     ..       0.10  Ang.

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      0.857
            Tmax scaled      0.857 Tmin scaled      0.643
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

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

   2 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
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Research into transition metal complexes has been rapidly expanding because of their fascinating structural diversity, as well as their potential applications as functional materials and enzymes (Noro et al., 2000; Yaghi et al., 1998). Dialkyldithiocarbamate anions, which are typical sulfur ligands, acting as monodentate, bidentate or bridging ligands, are often chosen for the preparation of complexes with a considerable structural variety (Engelhardt et al., 1988; Fernández et al., 2000; Koh et al., 2003). I report here the crystal structure of the title copper(II) complex, (I), containing a piperidyldithiocarbamate ligand.

The crystal structure of (I) is built of discrete molecules of the Cu^II complex (Fig. 1). The Cu^II ion is five-coordinated in a distorted square-pyramidal environment by one I atom in the apical position, two N atoms from the bipyridine ligand and two S atoms from the piperidyldithiocarbamate ligand in the basal plane (Table 1).

There is a π-π stacking interaction between the pyridyl rings R1 [N(2)/C(7)–C(11)] and R2 [N3/C(12)–C(16)] with a centroid-to-centroid distance of 3.643 (4) Å. These face-to-face interactions result in the complexes assembling into chains.

Related literature

For background to transition metal complexes, see: Engelhardt et al. (1988); Fernández et al. (2000); Koh et al. (2003); Noro et al. (2000); Yaghi et al. (1998).

S2. Experimental

A mixture of Cu(Ac)₂.H₂O (0.08 g, 0.4 mmol), NaS₂CNC₅H₁₀.2H₂O (0.09 g, 0.4 mmol), 2,2'-bipyridine (0.06 g 0.4 mmol) and NaI.2H₂O (0.07 g, 0.4 mmol) was stirred in DMF (15 ml). 2-PrOH was diffused into the resulting solution, yielding single crystals of (I).

S3. Refinement

H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 (aromatic) or 0.97 Å (piperidyl); U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear (Rigaku, 2000); data reduction: CrystalClear (Rigaku, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

Fig. 1. The molecular structure of (I), showing the atom-labelling scheme, with 30% probability displacement ellipsoids.

(2,2'-Bipyridine-κ²N,N')iodido(piperidine-1- carbodithioato-κ²S,S')copper(II)

Crystal data

[Cu(C6H10NS2)I(C10H8N2)]	F(000) = 996
Mr = 506.89	Dx = 1.829 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3988 reflections
a = 6.532 (3) Å	θ = 3.3–27.5°
b = 16.859 (7) Å	µ = 3.09 mm^−1
c = 17.578 (7) Å	T = 293 K
β = 108.047 (14)°	Prism, black
V = 1840.5 (14) Å^3	0.45 × 0.08 × 0.05 mm
Z = 4

Data collection

Rigaku Mercury CCD diffractometer	3946 independent reflections
Radiation source: Sealed Tube	3389 reflections with I > 2σ(I)
Graphite Monochromator monochromator	Rint = 0.036
ω scans	θmax = 27.5°, θmin = 2.4°
Absorption correction: multi-scan (CrystalClear; Rigaku,2000)	h = −8→6
Tmin = 0.751, Tmax = 1.000	k = −21→21
13746 measured reflections	l = −22→22

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.108	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.043P)^2 + 2.8277P] where P = (Fo^2 + 2Fc^2)/3
3946 reflections	(Δ/σ)max = 0.001
208 parameters	Δρmax = 0.52 e Å^−3
0 restraints	Δρmin = −0.63 e Å^−3

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.

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 (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.43714 (10)	0.66212 (3)	0.42086 (3)	0.04099 (17)
I1	0.19321 (6)	0.80141 (2)	0.36188 (2)	0.05420 (14)
S1	0.6396 (2)	0.64039 (8)	0.33518 (8)	0.0502 (3)
S2	0.2619 (3)	0.55763 (9)	0.34096 (8)	0.0586 (4)
N1	0.4731 (7)	0.5184 (2)	0.2378 (2)	0.0423 (9)
N2	0.6611 (7)	0.7232 (2)	0.5076 (2)	0.0401 (9)
N3	0.3271 (7)	0.6421 (2)	0.5154 (2)	0.0420 (9)
C1	0.4607 (8)	0.5651 (3)	0.2965 (3)	0.0386 (10)
C2	0.6306 (8)	0.5319 (3)	0.1943 (3)	0.0496 (12)
H2A	0.7044	0.4828	0.1907	0.059*
H2B	0.7370	0.5706	0.2225	0.059*
C3	0.5104 (9)	0.5620 (3)	0.1113 (3)	0.0556 (14)
H3A	0.6106	0.5693	0.0811	0.067*
H3B	0.4459	0.6130	0.1154	0.067*
C4	0.3347 (10)	0.5035 (4)	0.0674 (3)	0.0620 (15)
H4A	0.2530	0.5255	0.0160	0.074*
H4B	0.4004	0.4544	0.0578	0.074*
C5	0.1852 (9)	0.4865 (3)	0.1159 (3)	0.0533 (13)
H5A	0.1057	0.5342	0.1194	0.064*
H5B	0.0822	0.4461	0.0891	0.064*
C6	0.3075 (9)	0.4585 (3)	0.1993 (3)	0.0499 (13)
H6A	0.2094	0.4515	0.2304	0.060*
H6B	0.3757	0.4079	0.1966	0.060*
C7	0.8254 (8)	0.7641 (3)	0.4972 (3)	0.0464 (12)
H7A	0.8406	0.7663	0.4464	0.056*
C8	0.9733 (9)	0.8031 (3)	0.5591 (3)	0.0537 (13)
H8A	1.0845	0.8323	0.5503	0.064*
C9	0.9520 (10)	0.7979 (3)	0.6347 (4)	0.0615 (16)
H9A	1.0515	0.8226	0.6777	0.074*
C10	0.7829 (9)	0.7558 (3)	0.6462 (3)	0.0553 (14)
H10A	0.7675	0.7519	0.6969	0.066*
C11	0.6367 (8)	0.7197 (3)	0.5814 (3)	0.0430 (11)
C12	0.4453 (9)	0.6746 (3)	0.5851 (3)	0.0417 (11)
C13	0.3853 (10)	0.6676 (3)	0.6542 (3)	0.0528 (13)
H13A	0.4662	0.6917	0.7016	0.063*
C14	0.2037 (10)	0.6243 (3)	0.6510 (3)	0.0587 (15)
H14A	0.1636	0.6173	0.6970	0.070*
C15	0.0828 (10)	0.5918 (3)	0.5800 (4)	0.0614 (16)
H15A	−0.0417	0.5634	0.5769	0.074*
C16	0.1483 (9)	0.6016 (3)	0.5129 (3)	0.0515 (13)
H16A	0.0661	0.5794	0.4646	0.062*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0480 (4)	0.0472 (3)	0.0298 (3)	−0.0078 (3)	0.0150 (3)	−0.0058 (2)
I1	0.0605 (3)	0.0538 (2)	0.0489 (2)	0.00754 (16)	0.01783 (18)	0.01277 (15)
S1	0.0491 (8)	0.0629 (8)	0.0430 (6)	−0.0169 (6)	0.0207 (6)	−0.0195 (6)
S2	0.0670 (10)	0.0688 (8)	0.0495 (7)	−0.0287 (7)	0.0322 (7)	−0.0201 (6)
N1	0.043 (3)	0.048 (2)	0.0346 (19)	−0.0025 (18)	0.0103 (18)	−0.0079 (16)
N2	0.043 (3)	0.0428 (19)	0.0308 (18)	0.0023 (17)	0.0068 (17)	−0.0013 (15)
N3	0.057 (3)	0.0387 (19)	0.0343 (19)	0.0032 (18)	0.0195 (18)	0.0019 (15)
C1	0.044 (3)	0.040 (2)	0.031 (2)	−0.002 (2)	0.011 (2)	−0.0012 (17)
C2	0.043 (3)	0.062 (3)	0.042 (3)	−0.001 (2)	0.011 (2)	−0.017 (2)
C3	0.060 (4)	0.066 (3)	0.042 (3)	−0.010 (3)	0.019 (3)	−0.003 (2)
C4	0.069 (4)	0.070 (4)	0.038 (3)	−0.011 (3)	0.003 (3)	−0.004 (3)
C5	0.056 (4)	0.045 (3)	0.047 (3)	−0.010 (2)	−0.001 (3)	−0.001 (2)
C6	0.065 (4)	0.040 (2)	0.042 (3)	−0.012 (2)	0.013 (2)	−0.007 (2)
C7	0.047 (3)	0.048 (3)	0.044 (3)	−0.005 (2)	0.013 (2)	−0.002 (2)
C8	0.048 (3)	0.048 (3)	0.058 (3)	−0.002 (2)	0.005 (3)	−0.008 (2)
C9	0.060 (4)	0.053 (3)	0.054 (3)	0.001 (3)	−0.008 (3)	−0.019 (3)
C10	0.067 (4)	0.052 (3)	0.037 (3)	0.012 (3)	0.003 (3)	−0.007 (2)
C11	0.050 (3)	0.044 (2)	0.030 (2)	0.014 (2)	0.006 (2)	−0.0001 (18)
C12	0.058 (3)	0.042 (2)	0.027 (2)	0.012 (2)	0.016 (2)	0.0019 (17)
C13	0.071 (4)	0.054 (3)	0.037 (3)	0.017 (3)	0.022 (3)	0.010 (2)
C14	0.085 (5)	0.058 (3)	0.046 (3)	0.021 (3)	0.038 (3)	0.013 (2)
C15	0.082 (4)	0.046 (3)	0.073 (4)	0.007 (3)	0.048 (3)	0.006 (3)
C16	0.067 (4)	0.045 (3)	0.052 (3)	−0.004 (2)	0.033 (3)	−0.004 (2)

Geometric parameters (Å, º)

Cu1—N3	2.033 (4)	C5—C6	1.510 (7)
Cu1—N2	2.035 (4)	C5—H5A	0.9700
Cu1—S1	2.3205 (15)	C5—H5B	0.9700
Cu1—S2	2.3218 (15)	C6—H6A	0.9700
Cu1—I1	2.8470 (11)	C6—H6B	0.9700
S1—C1	1.717 (5)	C7—C8	1.379 (7)
S2—C1	1.716 (5)	C7—H7A	0.9300
N1—C1	1.320 (6)	C8—C9	1.380 (8)
N1—C2	1.476 (6)	C8—H8A	0.9300
N1—C6	1.482 (6)	C9—C10	1.379 (9)
N2—C7	1.335 (6)	C9—H9A	0.9300
N2—C11	1.357 (6)	C10—C11	1.380 (7)
N3—C16	1.342 (6)	C10—H10A	0.9300
N3—C12	1.345 (6)	C11—C12	1.481 (7)
C2—C3	1.514 (7)	C12—C13	1.392 (6)
C2—H2A	0.9700	C13—C14	1.380 (8)
C2—H2B	0.9700	C13—H13A	0.9300
C3—C4	1.529 (7)	C14—C15	1.369 (8)
C3—H3A	0.9700	C14—H14A	0.9300
C3—H3B	0.9700	C15—C16	1.384 (7)
C4—C5	1.511 (8)	C15—H15A	0.9300
C4—H4A	0.9700	C16—H16A	0.9300
C4—H4B	0.9700
N3—Cu1—N2	79.95 (16)	C6—C5—C4	111.5 (5)
N3—Cu1—S1	157.11 (12)	C6—C5—H5A	109.3
N2—Cu1—S1	98.30 (12)	C4—C5—H5A	109.3
N3—Cu1—S2	97.80 (12)	C6—C5—H5B	109.3
N2—Cu1—S2	160.43 (12)	C4—C5—H5B	109.3
S1—Cu1—S2	76.17 (5)	H5A—C5—H5B	108.0
N3—Cu1—I1	97.76 (11)	N1—C6—C5	108.8 (4)
N2—Cu1—I1	92.69 (11)	N1—C6—H6A	109.9
S1—Cu1—I1	105.13 (5)	C5—C6—H6A	109.9
S2—Cu1—I1	106.86 (6)	N1—C6—H6B	109.9
C1—S1—Cu1	85.37 (16)	C5—C6—H6B	109.9
C1—S2—Cu1	85.37 (16)	H6A—C6—H6B	108.3
C1—N1—C2	122.3 (4)	N2—C7—C8	122.3 (5)
C1—N1—C6	123.4 (4)	N2—C7—H7A	118.8
C2—N1—C6	113.3 (4)	C8—C7—H7A	118.8
C7—N2—C11	119.4 (4)	C7—C8—C9	118.3 (6)
C7—N2—Cu1	125.5 (3)	C7—C8—H8A	120.8
C11—N2—Cu1	115.1 (3)	C9—C8—H8A	120.8
C16—N3—C12	119.0 (4)	C10—C9—C8	119.9 (5)
C16—N3—Cu1	125.6 (3)	C10—C9—H9A	120.1
C12—N3—Cu1	115.4 (3)	C8—C9—H9A	120.1
N1—C1—S2	123.5 (4)	C9—C10—C11	119.2 (5)
N1—C1—S1	123.5 (4)	C9—C10—H10A	120.4
S2—C1—S1	113.1 (2)	C11—C10—H10A	120.4
N1—C2—C3	108.3 (4)	N2—C11—C10	120.9 (5)
N1—C2—H2A	110.0	N2—C11—C12	114.5 (4)
C3—C2—H2A	110.0	C10—C11—C12	124.7 (5)
N1—C2—H2B	110.0	N3—C12—C13	121.5 (5)
C3—C2—H2B	110.0	N3—C12—C11	115.1 (4)
H2A—C2—H2B	108.4	C13—C12—C11	123.4 (5)
C2—C3—C4	110.8 (4)	C14—C13—C12	118.7 (5)
C2—C3—H3A	109.5	C14—C13—H13A	120.6
C4—C3—H3A	109.5	C12—C13—H13A	120.6
C2—C3—H3B	109.5	C15—C14—C13	119.6 (5)
C4—C3—H3B	109.5	C15—C14—H14A	120.2
H3A—C3—H3B	108.1	C13—C14—H14A	120.2
C5—C4—C3	110.6 (4)	C14—C15—C16	119.1 (6)
C5—C4—H4A	109.5	C14—C15—H15A	120.4
C3—C4—H4A	109.5	C16—C15—H15A	120.4
C5—C4—H4B	109.5	N3—C16—C15	121.9 (5)
C3—C4—H4B	109.5	N3—C16—H16A	119.1
H4A—C4—H4B	108.1	C15—C16—H16A	119.1