metal-organic compounds
Poly[[μ3-N,N′-bis(3-pyridylmethyl)thiourea-κ3N:N′:S]iodidocopper(I)]
aDepartment of Applied Chemistry, Zhejiang Sci-Tech University, Hang Zhou, 310018, People's Republic of China
*Correspondence e-mail: zhangshishen@126.com
In the title coordination polymer, [CuI(C13H14N4S)]n, the CuI 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).
Experimental
Crystal data
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Data collection: SMART (Bruker, 1998); cell 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
10.1107/S1600536808031188/ng2496sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808031188/ng2496Isup2.hkl
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.
H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 Å(aromatic) or 0.97 Å(aliphatic) and N—H = 0.86 Å, and with Uiso(H) = 1.2Ueq(C,N)
Data collection: SMART (Bruker, 1998); cell
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).Fig. 1. The asymmetric unit of the title compound showing 30° probability ellipsoids. | |
Fig. 2. The crystal packing of the title compound. |
[CuI(C13H14N4S)] | F(000) = 872 |
Mr = 448.78 | Dx = 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 |
Bruker SMART CCD diffractometer | 2750 independent reflections |
Radiation source: fine-focus sealed tube | 2418 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→15 |
Tmin = 0.541, Tmax = 0.678 | k = −9→9 |
8191 measured reflections | l = −15→16 |
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(Fo2) + (0.0275P)2 + 0.8144P] where P = (Fo2 + 2Fc2)/3 |
2750 reflections | (Δ/σ)max = 0.001 |
181 parameters | Δρmax = 0.73 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
[CuI(C13H14N4S)] | V = 1560.3 (2) Å3 |
Mr = 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)° |
Bruker SMART CCD diffractometer | 2750 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2418 reflections with I > 2σ(I) |
Tmin = 0.541, Tmax = 0.678 | Rint = 0.020 |
8191 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.062 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.73 e Å−3 |
2750 reflections | Δρmin = −0.28 e Å−3 |
181 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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) |
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) |
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)] |
Mr | 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) |
Tmin, Tmax | 0.541, 0.678 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8191, 2750, 2418 |
Rint | 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 |
Δρmax, Δρmin (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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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).