Poly[[μ3-N,N′-bis­(3-pyridylmeth­yl)­thio­urea-κ3N:N′:S]iodidocopper(I)]

Zhang, S.-S.

doi:10.1107/S1600536808031188

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page m1395

doi:10.1107/S1600536808031188

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Poly[[μ₃-N,N′-bis(3-pyridylmethyl)thiourea-κ³N:N′:S]iodidocopper(I)]

Shi-Shen Zhang ^a ^*

^aDepartment of Applied Chemistry, Zhejiang Sci-Tech University, Hang Zhou, 310018, People's Republic of China
^*Correspondence e-mail: zhangshishen@126.com

(Received 22 September 2008; accepted 26 September 2008; online 15 October 2008)

In the title coordination polymer, [CuI(C₁₃H₁₄N₄S)]_n, the Cu^I atom is coordinated by two N atoms from two N,N′-bis(3-pyridylmethyl)thiourea ligands, as well as by the S atom of a third ligand and an I atom to confer a distorted tetrahedral coordination at the metal centre. The coordination bonds give rise to a layer structure parallel to (010).

Related literature

For related literature, see: Li et al. (2002 ); Zhang et al. (2006 ).

Experimental

Crystal data

[CuI(C₁₃H₁₄N₄S)]
M_r = 448.78
Monoclinic, P 2₁ /c
a = 13.3610 (10) Å
b = 8.3673 (7) Å
c = 14.2686 (11) Å
β = 102.001 (2)°
V = 1560.3 (2) Å³
Z = 4
Mo Kα radiation
μ = 3.51 mm⁻¹
T = 294 (2) K
0.20 × 0.15 × 0.12 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.541, T_max = 0.678
8191 measured reflections
2750 independent reflections
2418 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.062
S = 1.06
2750 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.73 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808031188/ng2496sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808031188/ng2496Isup2.hkl

checkCIF report

Comment top

Flexible ligand has been considered as one of the most important type of organic ligand for their flexibility and conformational freedom allow for greater structural diversity. N,N'-bis(3-pyridylmethyl)thiurea, as one kind of those ligand, has usually been used to construct a great variety of structurally interesting entities. such as helix, macrocycle (Zhang et al., 2006; Li et al., 2002).

The asymmetric unit of the title compound (I) is illustrated in Fig. 1. Single-crystal X-ray diffraction shows that the asymmetric unit contains one Cu crystallographically nonequivalent atom. The Cu(I) atom coordinated by two N atoms from two N,N'-bis(3-pyridylmethyl)thiourea ligands as well as by the S atom of a third ligand to confer a tetrahedral geometry at the metal center. The Cu atom coordination by two N atoms to form a one-dimensional helix, and is then linked by the bond of Cu atom and S atom to extend to a two-dimensional structure. The crystal packing is stabilized by intermolecular π–π stacking interaction (Fig. 2).

Related literature top

For related literature, see: Li et al. (2002); Zhang et al. (2006).

Experimental top

a mixture of CuI (0.038 g, 0.2 nmol) and N,N'-bis(3-pyridylmethyl)thiurea (0.026 g, 0.1 nmol) in mole ratio of 2:1 in acetonitrile (6 cm³) was sealed in 15 cm³ Teflon-lined reactor and heated to 110°C for 10 h and then cooled to room temperature at a rate of 5°C/h. the yellow block crystal was obtianed in the yield of 35%.

The web of checkcif show one Alert level B (Hirshfeld Test Diff (M—X) I1 – Cu1.. 43.03 su), we think this is the result of the sightly distorted I atom for his unidentate coordination model.

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, 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 top

	Fig. 1. The asymmetric unit of the title compound showing 30° probability ellipsoids.
	Fig. 2. The crystal packing of the title compound.

Poly[[µ₃-N,N'-bis(3-pyridylmethyl)thiourea- κ³N:N':S]iodidocopper(I)] top

Crystal data top

[CuI(C₁₃H₁₄N₄S)]	F(000) = 872
M_r = 448.78	D_x = 1.910 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3234 reflections
a = 13.361 (1) Å	θ = 2.8–27.7°
b = 8.3673 (7) Å	µ = 3.51 mm⁻¹
c = 14.2686 (11) Å	T = 294 K
β = 102.001 (2)°	Block, yellow
V = 1560.3 (2) Å³	0.20 × 0.15 × 0.12 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	2750 independent reflections
Radiation source: fine-focus sealed tube	2418 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→15
T_min = 0.541, T_max = 0.678	k = −9→9
8191 measured reflections	l = −15→16

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.062	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0275P)² + 0.8144P] where P = (F_o² + 2F_c²)/3
2750 reflections	(Δ/σ)_max = 0.001
181 parameters	Δρ_max = 0.73 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

[CuI(C₁₃H₁₄N₄S)]	V = 1560.3 (2) Å³
M_r = 448.78	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.361 (1) Å	µ = 3.51 mm⁻¹
b = 8.3673 (7) Å	T = 294 K
c = 14.2686 (11) Å	0.20 × 0.15 × 0.12 mm
β = 102.001 (2)°

Data collection top

Bruker SMART CCD diffractometer	2750 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2418 reflections with I > 2σ(I)
T_min = 0.541, T_max = 0.678	R_int = 0.020
8191 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	0 restraints
wR(F²) = 0.062	H-atom parameters constrained
S = 1.06	Δρ_max = 0.73 e Å⁻³
2750 reflections	Δρ_min = −0.28 e Å⁻³
181 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. 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

	x	y	z	U_iso*/U_eq
C1	0.4137 (2)	0.8305 (4)	0.3317 (2)	0.0340 (7)
H1A	0.4469	0.7269	0.3368	0.041*
H1B	0.4581	0.9036	0.3739	0.041*
C2	0.4006 (2)	0.8893 (3)	0.2301 (2)	0.0290 (6)
C3	0.3491 (2)	1.0308 (3)	0.2012 (2)	0.0315 (7)
H3	0.3220	1.0879	0.2460	0.038*
C4	0.3768 (2)	1.0054 (4)	0.0489 (2)	0.0361 (7)
H4	0.3685	1.0441	−0.0134	0.043*
C5	0.4292 (2)	0.8663 (4)	0.0718 (2)	0.0402 (7)
H5	0.4565	0.8122	0.0260	0.048*
C6	0.4415 (2)	0.8065 (4)	0.1630 (2)	0.0376 (7)
H6	0.4770	0.7115	0.1795	0.045*
C7	−0.0360 (2)	0.7596 (4)	0.4500 (2)	0.0379 (7)
H7	−0.0490	0.7921	0.3863	0.045*
C8	0.0621 (2)	0.7151 (4)	0.4916 (2)	0.0372 (7)
C9	0.0813 (3)	0.6670 (5)	0.5858 (3)	0.0521 (9)
H9	0.1469	0.6365	0.6166	0.063*
C10	0.0020 (3)	0.6648 (5)	0.6337 (3)	0.0571 (10)
H10	0.0130	0.6307	0.6970	0.068*
C11	−0.0934 (3)	0.7134 (4)	0.5874 (2)	0.0445 (8)
H11	−0.1460	0.7147	0.6210	0.053*
C12	0.1456 (2)	0.7225 (4)	0.4347 (3)	0.0413 (8)
H12A	0.1909	0.6314	0.4502	0.050*
H12B	0.1157	0.7194	0.3667	0.050*
C13	0.2875 (2)	0.9112 (3)	0.4274 (2)	0.0309 (6)
Cu1	0.26574 (3)	1.19634 (5)	0.57370 (3)	0.04022 (12)
N1	0.20322 (18)	0.8710 (3)	0.45837 (19)	0.0397 (6)
H1	0.1810	0.9377	0.4952	0.048*
N2	0.31731 (18)	0.8164 (3)	0.36364 (17)	0.0317 (6)
H2	0.2765	0.7407	0.3393	0.038*
N3	0.33636 (18)	1.0893 (3)	0.11266 (18)	0.0328 (6)
N4	−0.11373 (19)	0.7591 (3)	0.4956 (2)	0.0396 (6)
S3	0.35264 (6)	1.07993 (10)	0.46956 (6)	0.0397 (2)
I1	0.24731 (2)	1.03780 (3)	0.728706 (18)	0.05208 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0309 (16)	0.0383 (16)	0.0344 (17)	0.0077 (12)	0.0101 (13)	−0.0001 (13)
C2	0.0242 (14)	0.0350 (16)	0.0285 (16)	−0.0015 (12)	0.0072 (12)	−0.0040 (13)
C3	0.0323 (16)	0.0333 (16)	0.0322 (17)	−0.0006 (12)	0.0140 (13)	−0.0037 (13)
C4	0.0379 (17)	0.0451 (17)	0.0268 (16)	−0.0068 (14)	0.0102 (14)	−0.0002 (14)
C5	0.0462 (19)	0.0439 (18)	0.0348 (18)	0.0034 (15)	0.0184 (15)	−0.0077 (15)
C6	0.0418 (18)	0.0334 (16)	0.0396 (19)	0.0072 (13)	0.0134 (14)	−0.0025 (14)
C7	0.0335 (17)	0.0461 (18)	0.0370 (18)	−0.0018 (14)	0.0139 (14)	−0.0007 (15)
C8	0.0338 (17)	0.0328 (16)	0.047 (2)	−0.0057 (13)	0.0128 (15)	−0.0044 (15)
C9	0.0371 (19)	0.065 (2)	0.052 (2)	0.0022 (16)	0.0035 (16)	0.0058 (19)
C10	0.055 (2)	0.076 (3)	0.040 (2)	−0.0008 (19)	0.0097 (17)	0.0101 (19)
C11	0.0411 (19)	0.056 (2)	0.040 (2)	−0.0058 (16)	0.0171 (15)	0.0028 (17)
C12	0.0329 (17)	0.0378 (17)	0.056 (2)	−0.0043 (14)	0.0151 (15)	−0.0110 (16)
C13	0.0311 (16)	0.0309 (15)	0.0312 (16)	0.0012 (12)	0.0079 (13)	−0.0013 (13)
Cu1	0.0403 (2)	0.0416 (2)	0.0416 (2)	−0.00434 (17)	0.01496 (18)	−0.00960 (18)
N1	0.0378 (14)	0.0374 (14)	0.0495 (17)	−0.0068 (12)	0.0223 (13)	−0.0140 (13)
N2	0.0346 (14)	0.0321 (13)	0.0297 (13)	−0.0022 (10)	0.0097 (11)	−0.0049 (11)
N3	0.0324 (13)	0.0361 (13)	0.0311 (14)	−0.0004 (11)	0.0099 (11)	0.0023 (11)
N4	0.0324 (14)	0.0475 (16)	0.0412 (16)	−0.0010 (12)	0.0129 (12)	0.0011 (13)
S3	0.0369 (4)	0.0383 (4)	0.0488 (5)	−0.0085 (3)	0.0203 (4)	−0.0128 (4)
I1	0.07354 (19)	0.04215 (15)	0.04564 (16)	0.00823 (11)	0.02411 (12)	0.01044 (10)

Geometric parameters (Å, º) top

C1—N2	1.457 (4)	C9—H9	0.9300
C1—C2	1.506 (4)	C10—C11	1.370 (5)
C1—H1A	0.9700	C10—H10	0.9300
C1—H1B	0.9700	C11—N4	1.337 (4)
C2—C6	1.384 (4)	C11—H11	0.9300
C2—C3	1.388 (4)	C12—N1	1.464 (4)
C3—N3	1.332 (4)	C12—H12A	0.9700
C3—H3	0.9300	C12—H12B	0.9700
C4—N3	1.348 (4)	C13—N2	1.330 (4)
C4—C5	1.363 (4)	C13—N1	1.335 (4)
C4—H4	0.9300	C13—S3	1.701 (3)
C5—C6	1.371 (5)	Cu1—N3ⁱ	2.049 (2)
C5—H5	0.9300	Cu1—N4ⁱⁱ	2.099 (3)
C6—H6	0.9300	Cu1—S3	2.2852 (8)
C7—N4	1.335 (4)	Cu1—I1	2.6341 (5)
C7—C8	1.372 (4)	N1—H1	0.8600
C7—H7	0.9300	N2—H2	0.8600
C8—C9	1.374 (5)	N3—Cu1ⁱⁱⁱ	2.049 (2)
C8—C12	1.512 (4)	N4—Cu1ⁱⁱ	2.099 (3)
C9—C10	1.376 (5)

N2—C1—C2	113.3 (2)	C9—C10—H10	120.3
N2—C1—H1A	108.9	N4—C11—C10	122.4 (3)
C2—C1—H1A	108.9	N4—C11—H11	118.8
N2—C1—H1B	108.9	C10—C11—H11	118.8
C2—C1—H1B	108.9	N1—C12—C8	108.8 (2)
H1A—C1—H1B	107.7	N1—C12—H12A	109.9
C6—C2—C3	117.6 (3)	C8—C12—H12A	109.9
C6—C2—C1	121.3 (3)	N1—C12—H12B	109.9
C3—C2—C1	121.1 (2)	C8—C12—H12B	109.9
N3—C3—C2	123.6 (3)	H12A—C12—H12B	108.3
N3—C3—H3	118.2	N2—C13—N1	118.0 (3)
C2—C3—H3	118.2	N2—C13—S3	122.2 (2)
N3—C4—C5	122.7 (3)	N1—C13—S3	119.8 (2)
N3—C4—H4	118.6	N3ⁱ—Cu1—N4ⁱⁱ	108.54 (10)
C5—C4—H4	118.6	N3ⁱ—Cu1—S3	106.38 (7)
C4—C5—C6	119.6 (3)	N4ⁱⁱ—Cu1—S3	110.01 (8)
C4—C5—H5	120.2	N3ⁱ—Cu1—I1	109.34 (7)
C6—C5—H5	120.2	N4ⁱⁱ—Cu1—I1	103.57 (7)
C5—C6—C2	119.1 (3)	S3—Cu1—I1	118.69 (3)
C5—C6—H6	120.4	C13—N1—C12	125.3 (2)
C2—C6—H6	120.4	C13—N1—H1	117.4
N4—C7—C8	123.9 (3)	C12—N1—H1	117.4
N4—C7—H7	118.0	C13—N2—C1	125.2 (3)
C8—C7—H7	118.0	C13—N2—H2	117.4
C7—C8—C9	118.0 (3)	C1—N2—H2	117.4
C7—C8—C12	120.1 (3)	C3—N3—C4	117.3 (3)
C9—C8—C12	121.9 (3)	C3—N3—Cu1ⁱⁱⁱ	122.7 (2)
C8—C9—C10	118.8 (3)	C4—N3—Cu1ⁱⁱⁱ	119.9 (2)
C8—C9—H9	120.6	C7—N4—C11	117.2 (3)
C10—C9—H9	120.6	C7—N4—Cu1ⁱⁱ	123.0 (2)
C11—C10—C9	119.5 (3)	C11—N4—Cu1ⁱⁱ	119.4 (2)
C11—C10—H10	120.3	C13—S3—Cu1	106.95 (10)

Symmetry codes: (i) x, −y+5/2, z+1/2; (ii) −x, −y+2, −z+1; (iii) x, −y+5/2, z−1/2.

Experimental details

Crystal data
Chemical formula	[CuI(C₁₃H₁₄N₄S)]
M_r	448.78
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	13.361 (1), 8.3673 (7), 14.2686 (11)
β (°)	102.001 (2)
V (Å³)	1560.3 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.51
Crystal size (mm)	0.20 × 0.15 × 0.12

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.541, 0.678
No. of measured, independent and observed [I > 2σ(I)] reflections	8191, 2750, 2418
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.062, 1.06
No. of reflections	2750
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.73, −0.28

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported by the Foundation for Young Researchers of the Key Laboratory of Advanced Textile Materials and Manufacturing Technology, Ministry of Education (grant No. 2007QN05).

References

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