Tris(N,N′-dibutyl­thio­urea-κS)iodidocopper(I) 0.6-hydrate

In the title complex, [CuI(C₉H₂₀N₂S)₃]·0.6H₂O, the Cu^I and I atoms lie on a threefold rotation axis. The partially occupied water mol­ecule is disordered across an inversion centre. Each Cu^I centre binds to the S atoms of three N,N′-dibutyl­thio­urea ligands and I⁻ in a distorted tetra­hedral environment. N—H...I and C—H...S inter­actions are observed in the complex mol­ecule. Inter­molecular N—H...S hydrogen bonds link the mol­ecules into a two-dimensional network parallel to the ab plane.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.009 Å
• H-atom completeness 99%
• Disorder in solvent or counterion
• R factor = 0.062
• wR factor = 0.173
• Data-to-parameter ratio = 30.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?
PLAT077_ALERT_4_C Unitcell contains non-integer number of atoms ..          ?
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.24
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.13 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.11 Ratio
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      60.00 Perc.
PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          9

Alert level G
FORMU01_ALERT_2_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and the formula from the _atom_site* data.
            Atom count from _chemical_formula_sum:C27 H61.2 Cu1 I1 N6 O0.6 S3
            Atom count from the _atom_site data:  C27 H60 Cu1 I1 N6 O0.6 S3
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional?
           From the CIF: _cell_formula_units_Z    2
           From the CIF: _chemical_formula_sum  C27 H61.20 Cu I N6 O0.60 S3
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C         54.00     54.00    0.00
           H        122.40    120.00    2.40
           Cu         2.00      2.00    0.00
           I          2.00      2.00    0.00
           N         12.00     12.00    0.00
           O          1.20      1.20    0.00
           S          6.00      6.00    0.00

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

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

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S1. Comment

Crystal structures of several copper(I) complexes of thiourea and its derivatives have been reported (Eller et al., 1977; Stocker et al., 1996; Girling & Amma, 1971; Atkinson et al., 1985; Dubler & Bensch, 1986). They show that a wide variety of stoichiometries and structural diversity exist for these complexes, with the copper to sulfur ratio ranging from 1:4 as in monomeric [Cu(tu)₄(SiF₆)_0.5] (Hunt et al., 1979) to 1:1.5 as in tetrameric [Cu₄(tu)₆(NO₃)₄].4H₂O (Griffith et al., 1976). We are interested in understanding the correlation of the geometries of such complexes with the nature of substituents on thiourea and the strength and size of the other coordinating ligands. Previously, we have reported the crystal structure of tetrakis(N-methylthiourea-κS)copper(I) iodide (Mufakkar et al., 2007). Now we report here the crystal structure of the title complex.

In the molecule of the title complex, atoms Cu1 and I1 lie on a threefold rotation axis and the asymmetric unit therefore contains one third of the complex molecule (Fig. 1). The asymmetric unit also contains a partially occupied water molecule, disordered across a inversion center. The coordination of Cu1 is a distorted tetrahedron, being coordinated by the S atoms of the three N,N'-dibutylthiourea ligands, with S—Cu—S angles of 99.32 (4)° (Table 1). These angles are smaller than those observed in related structures (Bombicz et al., 2004; Lobana et al., 2006; Mufakkar et al., 2007). However, the Cu—S bond distances [2.3543 (12) Å] of the title complex lie within the range of those found in the Cu^I complexes with tetrahedral geometry (Bombicz et al., 2004; Lobana et al., 2006; Mufakkar et al., 2007). The fourth coordination of Cu^I is occupied by the I1 atom with a Cu1—I1 distance of 2.6251 (10) Å and S—Cu—I angle of 118.34 (3)°. The dihedral angle between the mean planes of S1/N1/N2/C1/C2/C6/C7 and C2/C3/C4/C5 is 80.2 (6)°. All other bond lengths and angles are in normal ranges (Allen et al., 1987).

The I atom is involved in an intramolecular N—H···I hydrogen bond and the S atoms form weak C—H···S intramolecular interactions (Fig. 1). Intermolecular N—H···S hydrogen bonds stabilize the crystal structure (Table 2). In the crystal packing (Fig. 2), the molecules are arranged into a two-dimensional network parallel to the ab plane.

Related literature

For related literature on values of bond lengths, see: Allen et al. (1987). For related structures, see: Bombicz et al. (2004); Lobana et al. (2006); Mufakkar et al. (2007). For related literature on the coordination chemistry of copper, see: Atkinson et al. (1985); Bombicz et al. (2004); Dubler & Bensch (1986); Eller et al. (1977); Girling & Amma (1971); Griffith et al. (1976); Hunt et al. (1979); Kaim & Schwederski (1994); Lobana et al. (2006); Stocker et al. (1996).

S2. Experimental

To a solution of copper(I) iodide (0.19 g, 1.0 mmol) in acetonitrile (15 ml) was added 2 molar equivalents of N,N'-dibutylthiourea in acetonitrile (10 ml). The mixture was stirred for half an hour. A clear solution was obtained. The solution was concentrated by slow evaporation at room temperature to yield colourless single crystals of the title compound suitable for x-ray stucture determination after several days.

S3. Refinement

All H atoms were positioned geometrically and allowed to ride on their parent atoms, with N—H = 0.86 Å and C—H = 0.96 or 0.97 Å. The U_iso values were constrained to be 1.5U_eq of the carrier atom for methyl H atoms and 1.2U_eq for the remaining H atoms. A rotating group model was used for the methyl groups. The H atoms of the partially occupied disordered water molecule could not be located. The highest residual peak is located 1.03 Å from I1 and the deepest hole is located 0.80 Å from I1.

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure: SHELXTL (Sheldrick, 1998); molecular graphics: SHELXTL (Sheldrick, 1998); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003).

Figures

	Fig. 1. The structure of the title compound, showing 50% probability displacement ellipsoids and the atomic numbering. For clarity, only N-bound H atoms and those involving in weak C—H···S interactions (dashed lines) are shown. Symmetry codes: (i) -x + y+1, -x + 1, z; (ii) -y + 1, x-y, z.
	Fig. 2. The crystal packing of the title compound, viewed along the c axis. Hydrogen bonds are shown as dashed lines.

Iodidotris(N,N'-dibutylthiourea-κS)copper(I) 0.6-hydrate

Crystal data

[Cu(C9H20N2S)3I]·0.6(H2O)	Dx = 1.396 Mg m^−3
Mr = 766.24	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3	Cell parameters from 3632 reflections
Hall symbol: -P 3	θ = 1.7–30.4°
a = 13.5514 (3) Å	µ = 1.65 mm^−1
c = 11.4588 (6) Å	T = 100 K
V = 1822.38 (11) Å^3	Plate, colourless
Z = 2	0.48 × 0.27 × 0.10 mm
F(000) = 800

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	3632 independent reflections
Radiation source: fine-focus sealed tube	2454 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.090
Detector resolution: 8.33 pixels mm^-1	θmax = 30.4°, θmin = 1.7°
ω scans	h = −19→18
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −18→18
Tmin = 0.508, Tmax = 0.851	l = −15→15
21130 measured reflections

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.173	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0894P)^2 + 1.4942P] where P = (Fo^2 + 2Fc^2)/3
3632 reflections	(Δ/σ)max = 0.001
120 parameters	Δρmax = 2.54 e Å^−3
0 restraints	Δρmin = −1.13 e Å^−3

Special details

Experimental. The low-temparture data was collected with the Oxford Cyrosystem Cobra low-temperature attachment.

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	Occ. (<1)
I1	0.6667	0.3333	0.71844 (4)	0.02975 (18)
Cu1	0.6667	0.3333	0.94753 (8)	0.0274 (2)
S1	0.70138 (9)	0.50061 (9)	1.04506 (9)	0.0267 (3)
N1	0.6251 (4)	0.6474 (3)	1.0253 (3)	0.0312 (9)
H1	0.6035	0.6851	0.9824	0.037*
N2	0.6362 (4)	0.5666 (3)	0.8559 (3)	0.0317 (9)
H2	0.6547	0.5227	0.8197	0.038*
C1	0.6508 (4)	0.5764 (4)	0.9706 (4)	0.0247 (9)
C2	0.6302 (5)	0.6675 (5)	1.1508 (4)	0.0433 (13)
H2A	0.6334	0.6061	1.1909	0.052*
H2B	0.5608	0.6659	1.1751	0.052*
C3	0.7295 (5)	0.7776 (5)	1.1870 (5)	0.0484 (14)
H3A	0.7337	0.8383	1.1386	0.058*
H3B	0.7990	0.7748	1.1755	0.058*
C4	0.7200 (6)	0.8035 (6)	1.3162 (5)	0.0582 (17)
H4A	0.6477	0.8005	1.3286	0.070*
H4B	0.7211	0.7454	1.3647	0.070*
C5	0.8158 (7)	0.9192 (7)	1.3530 (6)	0.077 (2)
H5A	0.8021	0.9356	1.4309	0.115*
H5B	0.8196	0.9763	1.3006	0.115*
H5C	0.8866	0.9192	1.3509	0.115*
C6	0.5907 (5)	0.6256 (4)	0.7868 (4)	0.0337 (11)
H6A	0.6413	0.7072	0.7937	0.040*
H6B	0.5170	0.6078	0.8179	0.040*
C7	0.5777 (6)	0.5925 (5)	0.6594 (5)	0.0478 (14)
H7A	0.5342	0.5101	0.6527	0.057*
H7B	0.6524	0.6182	0.6258	0.057*
C8	0.5178 (7)	0.6442 (5)	0.5911 (5)	0.0553 (16)
H8A	0.5101	0.6196	0.5105	0.066*
H8B	0.4417	0.6148	0.6226	0.066*
C9	0.5787 (7)	0.7727 (6)	0.5941 (6)	0.071 (2)
H9A	0.5432	0.7995	0.5401	0.106*
H9B	0.6571	0.8026	0.5728	0.106*
H9C	0.5746	0.7977	0.6714	0.106*
O1W	0.0000	0.0000	0.042 (7)	0.31 (4)	0.60

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.0312 (2)	0.0312 (2)	0.0267 (3)	0.01562 (11)	0.000	0.000
Cu1	0.0270 (3)	0.0270 (3)	0.0283 (5)	0.01350 (17)	0.000	0.000
S1	0.0267 (6)	0.0264 (6)	0.0275 (5)	0.0137 (5)	−0.0003 (4)	−0.0003 (4)
N1	0.041 (2)	0.033 (2)	0.0266 (19)	0.0237 (19)	−0.0042 (16)	−0.0031 (16)
N2	0.044 (2)	0.034 (2)	0.0259 (19)	0.026 (2)	0.0012 (17)	−0.0026 (16)
C1	0.020 (2)	0.024 (2)	0.028 (2)	0.0097 (17)	0.0004 (16)	0.0002 (17)
C2	0.060 (4)	0.044 (3)	0.035 (3)	0.032 (3)	−0.011 (2)	−0.010 (2)
C3	0.053 (4)	0.043 (3)	0.050 (3)	0.025 (3)	−0.004 (3)	0.003 (3)
C4	0.066 (4)	0.057 (4)	0.042 (3)	0.024 (3)	−0.006 (3)	−0.009 (3)
C5	0.085 (6)	0.075 (5)	0.049 (4)	0.024 (4)	−0.020 (4)	−0.022 (4)
C6	0.047 (3)	0.034 (3)	0.027 (2)	0.026 (2)	−0.001 (2)	0.0024 (19)
C7	0.073 (4)	0.051 (3)	0.035 (3)	0.042 (3)	−0.004 (3)	−0.004 (2)
C8	0.084 (5)	0.057 (4)	0.034 (3)	0.042 (4)	−0.016 (3)	−0.005 (3)
C9	0.095 (6)	0.067 (5)	0.058 (4)	0.047 (5)	−0.003 (4)	0.006 (3)
O1W	0.30 (3)	0.30 (3)	0.32 (13)	0.149 (15)	0.000	0.000

Geometric parameters (Å, º)

I1—Cu1	2.6251 (10)	C4—H4A	0.97
Cu1—S1	2.3543 (12)	C4—H4B	0.97
Cu1—S1^i	2.3543 (12)	C5—H5A	0.96
Cu1—S1^ii	2.3543 (12)	C5—H5B	0.96
S1—C1	1.720 (4)	C5—H5C	0.96
N1—C1	1.331 (5)	C6—C7	1.513 (7)
N1—C2	1.460 (6)	C6—H6A	0.97
N1—H1	0.86	C6—H6B	0.97
N2—C1	1.326 (6)	C7—C8	1.527 (8)
N2—C6	1.462 (6)	C7—H7A	0.97
N2—H2	0.86	C7—H7B	0.97
C2—C3	1.484 (8)	C8—C9	1.509 (9)
C2—H2A	0.97	C8—H8A	0.97
C2—H2B	0.97	C8—H8B	0.97
C3—C4	1.543 (8)	C9—H9A	0.96
C3—H3A	0.97	C9—H9B	0.96
C3—H3B	0.97	C9—H9C	0.96
C4—C5	1.512 (9)
S1—Cu1—S1^i	99.32 (4)	C3—C4—H4B	109.2
S1—Cu1—S1^ii	99.32 (4)	H4A—C4—H4B	107.9
S1^i—Cu1—S1^ii	99.32 (4)	C4—C5—H5A	109.5
S1—Cu1—I1	118.34 (3)	C4—C5—H5B	109.5
S1^i—Cu1—I1	118.34 (3)	H5A—C5—H5B	109.5
S1^ii—Cu1—I1	118.34 (3)	C4—C5—H5C	109.5
C1—S1—Cu1	113.09 (15)	H5A—C5—H5C	109.5
C1—N1—C2	126.5 (4)	H5B—C5—H5C	109.5
C1—N1—H1	116.8	N2—C6—C7	112.2 (4)
C2—N1—H1	116.8	N2—C6—H6A	109.2
C1—N2—C6	124.4 (4)	C7—C6—H6A	109.2
C1—N2—H2	117.8	N2—C6—H6B	109.2
C6—N2—H2	117.8	C7—C6—H6B	109.2
N2—C1—N1	117.3 (4)	H6A—C6—H6B	107.9
N2—C1—S1	121.1 (3)	C6—C7—C8	111.6 (5)
N1—C1—S1	121.6 (3)	C6—C7—H7A	109.3
N1—C2—C3	113.4 (5)	C8—C7—H7A	109.3
N1—C2—H2A	108.9	C6—C7—H7B	109.3
C3—C2—H2A	108.9	C8—C7—H7B	109.3
N1—C2—H2B	108.9	H7A—C7—H7B	108.0
C3—C2—H2B	108.9	C9—C8—C7	114.1 (6)
H2A—C2—H2B	107.7	C9—C8—H8A	108.7
C2—C3—C4	111.1 (5)	C7—C8—H8A	108.7
C2—C3—H3A	109.4	C9—C8—H8B	108.7
C4—C3—H3A	109.4	C7—C8—H8B	108.7
C2—C3—H3B	109.4	H8A—C8—H8B	107.6
C4—C3—H3B	109.4	C8—C9—H9A	109.5
H3A—C3—H3B	108.0	C8—C9—H9B	109.5
C5—C4—C3	112.2 (6)	H9A—C9—H9B	109.5
C5—C4—H4A	109.2	C8—C9—H9C	109.5
C3—C4—H4A	109.2	H9A—C9—H9C	109.5
C5—C4—H4B	109.2	H9B—C9—H9C	109.5
S1^i—Cu1—S1—C1	162.01 (17)	Cu1—S1—C1—N1	155.8 (3)
S1^ii—Cu1—S1—C1	−96.85 (17)	C1—N1—C2—C3	104.8 (6)
I1—Cu1—S1—C1	32.58 (17)	N1—C2—C3—C4	170.6 (5)
C6—N2—C1—N1	−2.0 (7)	C2—C3—C4—C5	−175.9 (6)
C6—N2—C1—S1	178.3 (4)	C1—N2—C6—C7	−176.8 (5)
C2—N1—C1—N2	177.3 (5)	N2—C6—C7—C8	173.5 (5)
C2—N1—C1—S1	−3.0 (7)	C6—C7—C8—C9	59.6 (8)
Cu1—S1—C1—N2	−24.4 (4)

Symmetry codes: (i) −x+y+1, −x+1, z; (ii) −y+1, x−y, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1^iii	0.86	2.57	3.347 (5)	151
N2—H2···I1	0.86	2.89	3.735 (4)	167
C2—H2A···S1	0.97	2.65	3.114 (7)	110

Symmetry code: (iii) y, −x+y+1, −z+2.