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In the polymeric title compound, [CuI(C10H8N4)]n, the CuI atom is in a four-coordinated tetra­hedral geometry, formed by two I atoms and two pyridine N atoms from two different 4,4'-(diazenedi­yl)dipyridine (4,4'-azpy) ligands. Two [mu]2-I atoms link two CuI atoms to form a planar rhomboid [Cu2I2] cluster located on an inversion centre, where the distance between two CuI atoms is 2.7781 (15) Å and the Cu-I bond lengths are 2.6290 (13) and 2.7495 (15) Å. The bridging 4,4'-azpy ligands connect the [Cu2I2] clusters into a two-dimensional (2-D) double-layered grid-like network [parallel to the (10\overline{2}) plane], with a (4,4)-connected topology. Two 2-D grid-like networks inter­weave each other by long 4,4'-azpy bridging ligands to form a dense 2-D double-layered network. To the best of our knowledge, this inter­woven 2-D[rightwards arrow]2-D network is observed for the first time in [Cu2I2]-organic compounds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113000942/sk3470sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113000942/sk3470Isup2.hkl
Contains datablock I

CCDC reference: 925752

Comment top

In recent years, the construction of multidimensional cluster-based coordination polymers have been a major focus of research in the field of chemistry and materials science, due to not only their aesthetically intriguing structural features (Schubert, 2011; Zhang, Song et al., 2008) but also because of their potentially useful applications, such as magnetism (Imai et al., 2009), photoluminescence (Perruchas et al., 2011), ion exchange (Mrutu et al., 2011), catalysis (Tan et al., 2012), adsorption (Li et al., 2010) and nonlinear optical properties (Zhang, Cao et al., 2008; Zhang, Meng et al., 2010). The strategy popularly used is a building-block approach (Hu et al., 2005; Eddaoudi et al., 2001) and much effort has been devoted to the connection of suitable predetermined building blocks into frameworks in order to obtain desired structures and properties.

As an important kind of cluster, copper(I) halide clusters have been widely studied due to their diverse structures and applications (Peng et al., 2010; Zhang, Wu et al., 2010). Up to now, copper(I) halide cluster-based coordination polymers with various structural motifs have been constructed, such as rhomboid [Cu2I2] dimers (Niu et al., 2006; Araki et al., 2005), cubane-like [Cu4I4] tetramers (Blake et al., 2001; Chen et al., 2008), zigzag chains (Graham et al., 2000; Cheng et al., 2004), double-stranded ladders (Graham et al., 2000) and two-dimensional [CuI]n layers (Peng et al., 2005). Various bridging ligands, such as phosphines, anilines, pyridine-type ligands and thioethers, have been applied in constructing CuX-based coordination polymers (Peng et al., 2010). Herein, we have used 4,4'-(diazenediyl)dipyridine (4,4'-azpy) ligands as long bridges to construct the CuI-based coordination polymer poly[[µ-4,4'-(diazenediyl)dipyridine]-µ2-iodido-copper(I)], (I), which is formed by [Cu2I2] clusters and single 4,4'-azpy bridges, and exhibits a novel twofold interwoven two-dimensional two-dimensional (2-D 2-D) network.

X-ray crystallographic analysis revealed that (I) crystallizes in the monoclinic space group P2/c with each [Cu2I2] cluster linked to four other [Cu2I2] clusters through long single 4,4'-azpy bridges, furnishing a 2-D double-layered grid-like network with a (4,4)-connected topology (Figs. 2 and 3). As shown in Fig. 1, the CuI atom is bonded by two I atoms and two pyridine N atoms from two 4,4'-azpy ligands, forming a four-coordinated tetrahedral geometry. The Cu1—N1 and Cu1—N2 bond lengths are 2.037 (6) and 2.045 (6) Å, respectively, and the N1—Cu1—N2 angle is 123.7 (3)°. The planar rhomboid [Cu2I2] cluster is formed by two µ2-I atoms linking two CuI atoms. In the [Cu2I2] cluster, the distance between two CuI atoms is 2.7781 (15) Å, and the Cu—I bonds lengths are 2.6290 (13) and 2.7495 (15) Å. The I—Cu—I and Cu—I—Cu angles are 117.85 (4) and 62.15 (4)°, respectively.

The 4,4'-azpy ligands connect the [Cu2I2] clusters into a 2-D double-layered grid-like network with a (4,4)-connected topology. The NN bond length is 1.240 (9) Å and the average distances between C and N atoms in the pyridine rings is 1.331 (9) Å. In the (4,4) network, the [Cu2I2] clusters shows a unique ABAB arrangement (Fig. 2) and the 4,4'-azpy ligand is slightly distorted because the angle between the planes of the two pyridine is 8.9 (4)°. Interestingly, the 2-D net exhibits a rare double-layered structure (Fig. 3a), which should be due to the distances between the two CuI atoms in the [Cu2I2] clusters. The lengths of the two diagonals in the grid, constructed by four [Cu2I2] clusters and four 4,4'-azpy bridges, are 16.149 (2) and 22.883 (3) Å (Fig. 2). Therefore, each layer has enough empty space, which results in two layers interweaving each other by long 4,4'-azpy bridging ligands to form a new dense two-dimensional double-layered network (Fig. 3b).

In previous work, the phenomena of interpenetration and catenation have appeared in CuX-based coordination polymers. In [Cu2Br2{1,2-bis(pyridin-4-yl)ethane}2]n (Hu et al., 2006), two sets of (4,4) layers adopt the diagonal–diagonal fourfold interpenetration mode, giving high catenation and generating a 2-D 3-D (three-dimensional) interpenetrating framework. In [Cu2Br2{1,3-bis(pyridin-4-yl)propane}2]n (Hu et al., 2006), the 2-D polycatenane network is formed by interlocking of 1-D (one-dimensional) double-stranded tubular chains. However, interwoven 2-D 2-D networks are very scarce in coordination polymers and, to the best of our knowledge, the novel interwoven 2-D 2-D network in (I) is the first to be found in a [Cu2X2]–organic compound.

In fact, this experiment was designed to synthesize W/S/Cu cluster-based coordination polymers. In the first step of the preparation, the cubane-shaped {[(t-Bu)4N]3[WOS3(CuI)3I]} W/S/Cu cluster was synthesized. It was hoped that in the next step the W/S/Cu clusters would be bridged by long 4,4'-azpy ligands to form a cubane-shaped W/S/Cu cluster-based coordination polymer. However, in the second step, the W/S/Cu clusters were decomposed by water from the acetonitrile or dimethylformamide solvent in the solvothermal reaction. As a result, the unexpected [Cu2I2]-based coordination polymer (I) was obtained.

In summary, an unexpected [Cu2I2]-based coordination polymer, (I), with a two-dimensional double-layered grid-like (4,4) network is obtained from a solvothermal reaction which was originally designed to synthesize W/S/Cu cluster-based coordination polymers. This interwoven two-dimensional two-dimensional network in (I) is firstly found in [Cu2I2]-organic compounds.

Related literature top

For related literature, see: Araki et al. (2005); Blake et al. (2001); Chen et al. (2008); Cheng et al. (2004); Eddaoudi et al. (2001); Graham et al. (2000); Hu et al. (2005, 2006); Imai et al. (2009); Li et al. (2010); Mrutu et al. (2011); Niu et al. (2006); Peng et al. (2005, 2010); Perruchas et al. (2011); Schubert (2011); Tan et al. (2012); Zhang, Cao, Zhang, Meng, Matsumoto, Song, Ma, Chen, Tatsumi & Humphrey (2008); Zhang, Meng, Song, Zhao, Li, Qu, Sun, Humphrey & Zhang (2010); Zhang, Song, Yang, Humphrey & Zhang (2008); Zhang, Wu, Liu, Dou, Bu & Feng (2010).

Experimental top

(NH4)2WOS3 (0.335 g, 1 mmol), CuSCN (0.568 g, 3 mmol) and (t-Bu)4NI (1.119 g, 3 mmol) were added to dimethylformamide (DMF, 2 ml) and the resulting solution was stirred thoroughly for 5 min. After filtration, i-PrOH (5 ml) was carefully layered on the surface of the the red filtrate. Red block-shaped crystals were obtained after two weeks. These crystals (0.0734 g) and 4,4'-(diazenediyl)dipyridine (0.0183 g, 0.1 mmol) were added to acetonitrile (2 ml) and DMF (1 ml) and the resulting solution was stirred thoroughly for 10 min in a vacuum. The solution was then sealed and heated in an oven at 373 K for 48 h, and then cooled to room temperature at a rate of 3 K h-1, producing brown block-shaped crystals (yield 0.0287 g). Analysis calculated for C10H8CuIN4: C 32.06, H 2.15, N 14.95%; found: C 31.88, H 2.19, N 15.15%. IR (KBr, cm-1): 3053 (w), 2108 (s h), 1595 (s h), 1563 (w), 1413 (s h), 1224 (m), 1048 (w), 928 (s h), 841 (s h), 569 (m), 430 (m). [What does the "h" represent in the peak assignments?]

Refinement top

H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C).

Computing details top

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

Figures top
[Figure 1] Fig. 1. The structure of a portion of the title compound, showing the atom-labelling scheme and 50% probability displacement ellipsoids. All H atoms have been omitted. [Symmetry codes: (i) -x, -y+1, -z+1; (ii) x+1, -y+2, z+1/2.]
[Figure 2] Fig. 2. A fragment of the two-dimensional (4,4) network showing the [Cu2I2] clusters in a unique ABAB arrangement. The diagonal distances between the centers of the [Cu2I2] clusters are 16.149 (2) and 22.883 (3) Å.
[Figure 3] Fig. 3. (a) A packing diagram of the two-dimensional (4,4) networks showing the double-layer structures. (In the electronic version of the paper, CuI atoms are green, I atoms are purple, C atoms are grey and N atoms are blue.) (b) The novel two-dimensional twofold interwoven networks. (In the electronic version of the paper, the different layers layers are highlighted in red and blue.)
poly[[µ-4,4'-(diazenediyl)dipyridine]-µ2-iodido-copper(I)] top
Crystal data top
[CuI(C10H8N4)]F(000) = 712
Mr = 374.65Dx = 2.085 Mg m3
Monoclinic, P2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ycCell parameters from 3410 reflections
a = 9.7137 (19) Åθ = 2.5–28.9°
b = 8.0745 (16) ŵ = 4.39 mm1
c = 15.396 (3) ÅT = 150 K
β = 98.73 (3)°Block, brown
V = 1193.6 (4) Å30.2 × 0.18 × 0.15 mm
Z = 4
Data collection top
Rigaku Saturn724+ (2x2 bin mode)
diffractometer
2171 independent reflections
Radiation source: fine-focus sealed tube1674 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.053
ω scansθmax = 25.3°, θmin = 2.9°
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2008)
h = 119
Tmin = 0.795, Tmax = 1.000k = 98
6682 measured reflectionsl = 1718
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.060Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.093H-atom parameters constrained
S = 1.17 w = 1/[σ2(Fo2) + (0.0198P)2 + 2.6592P]
where P = (Fo2 + 2Fc2)/3
2171 reflections(Δ/σ)max < 0.001
145 parametersΔρmax = 0.80 e Å3
0 restraintsΔρmin = 0.63 e Å3
Crystal data top
[CuI(C10H8N4)]V = 1193.6 (4) Å3
Mr = 374.65Z = 4
Monoclinic, P2/cMo Kα radiation
a = 9.7137 (19) ŵ = 4.39 mm1
b = 8.0745 (16) ÅT = 150 K
c = 15.396 (3) Å0.2 × 0.18 × 0.15 mm
β = 98.73 (3)°
Data collection top
Rigaku Saturn724+ (2x2 bin mode)
diffractometer
2171 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2008)
1674 reflections with I > 2σ(I)
Tmin = 0.795, Tmax = 1.000Rint = 0.053
6682 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0600 restraints
wR(F2) = 0.093H-atom parameters constrained
S = 1.17Δρmax = 0.80 e Å3
2171 reflectionsΔρmin = 0.63 e Å3
145 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
xyzUiso*/Ueq
I10.10063 (6)0.31252 (6)0.41593 (4)0.0507 (2)
Cu10.05260 (10)0.62373 (12)0.45162 (7)0.0496 (3)
N10.0745 (6)0.7213 (8)0.3467 (4)0.0404 (16)
N20.2398 (6)0.7250 (8)0.5042 (4)0.0440 (17)
N30.5868 (7)0.9279 (10)0.6661 (4)0.056 (2)
N40.6006 (7)1.0804 (10)0.6633 (4)0.0525 (19)
C10.0876 (8)0.8843 (10)0.3362 (5)0.046 (2)
H1A0.02470.95200.37130.056*
C20.1888 (8)0.9597 (10)0.2763 (5)0.050 (2)
H2A0.19311.07440.27080.059*
C30.2833 (8)0.8588 (10)0.2249 (5)0.042 (2)
C40.2708 (9)0.6913 (11)0.2340 (6)0.068 (3)
H4A0.33360.62130.20030.081*
C50.1640 (8)0.6267 (11)0.2936 (5)0.060 (3)
H5A0.15360.51230.29710.072*
C60.2540 (8)0.8884 (10)0.5123 (5)0.048 (2)
H6A0.18450.95500.48230.057*
C70.3652 (8)0.9648 (10)0.5625 (5)0.050 (2)
H7A0.36991.07960.56650.060*
C80.4689 (7)0.8682 (11)0.6067 (5)0.045 (2)
C90.4586 (9)0.6984 (11)0.5976 (6)0.073 (3)
H9A0.52800.62940.62590.087*
C100.3424 (8)0.6326 (11)0.5452 (6)0.069 (3)
H10A0.33630.51820.53860.083*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.0569 (4)0.0338 (3)0.0588 (4)0.0023 (3)0.0007 (3)0.0019 (3)
Cu10.0447 (6)0.0386 (6)0.0579 (7)0.0023 (5)0.0164 (5)0.0030 (5)
N10.041 (4)0.031 (4)0.047 (4)0.000 (3)0.001 (3)0.001 (3)
N20.039 (4)0.035 (4)0.052 (4)0.000 (3)0.010 (3)0.001 (3)
N30.041 (4)0.062 (5)0.063 (5)0.010 (4)0.005 (4)0.008 (4)
N40.043 (4)0.061 (5)0.050 (4)0.010 (4)0.005 (3)0.005 (4)
C10.045 (5)0.044 (6)0.046 (5)0.003 (4)0.008 (4)0.004 (4)
C20.054 (5)0.040 (5)0.052 (5)0.011 (4)0.000 (4)0.009 (4)
C30.044 (5)0.042 (5)0.036 (4)0.009 (4)0.004 (4)0.002 (4)
C40.058 (6)0.057 (6)0.074 (6)0.004 (5)0.035 (5)0.003 (5)
C50.061 (6)0.037 (5)0.072 (6)0.003 (4)0.020 (5)0.001 (4)
C60.048 (5)0.041 (6)0.049 (5)0.003 (4)0.008 (4)0.002 (4)
C70.051 (5)0.047 (6)0.048 (5)0.016 (4)0.005 (4)0.003 (4)
C80.030 (4)0.060 (6)0.044 (5)0.000 (4)0.001 (4)0.002 (4)
C90.058 (6)0.043 (6)0.102 (8)0.009 (5)0.035 (6)0.018 (5)
C100.053 (6)0.041 (6)0.101 (7)0.000 (4)0.032 (5)0.016 (5)
Geometric parameters (Å, º) top
I1—Cu12.6290 (13)C2—H2A0.9300
I1—Cu1i2.7495 (15)C3—C41.364 (11)
Cu1—N12.037 (6)C3—N4iii1.444 (9)
Cu1—N22.045 (6)C4—C51.379 (10)
N1—C11.330 (9)C4—H4A0.9300
N1—C51.338 (9)C5—H5A0.9300
N2—C101.326 (9)C6—C71.375 (9)
N2—C61.330 (9)C6—H6A0.9300
N3—N41.240 (9)C7—C81.370 (10)
N3—C81.435 (9)C7—H7A0.9300
N4—C3ii1.444 (9)C8—C91.381 (11)
C1—C21.382 (9)C9—C101.389 (10)
C1—H1A0.9300C9—H9A0.9300
C2—C31.383 (10)C10—H10A0.9300
Cu1—I1—Cu1i62.15 (4)C4—C3—C2119.0 (7)
N1—Cu1—N2123.7 (3)C4—C3—N4iii117.0 (7)
N1—Cu1—I1108.02 (18)C2—C3—N4iii124.0 (7)
N2—Cu1—I1106.82 (19)C3—C4—C5119.3 (7)
N1—Cu1—I1i100.64 (19)C3—C4—H4A120.3
N2—Cu1—I1i100.42 (19)C5—C4—H4A120.3
I1—Cu1—I1i117.85 (4)N1—C5—C4122.9 (8)
N1—Cu1—Cu1i118.39 (18)N1—C5—H5A118.5
N2—Cu1—Cu1i116.93 (18)C4—C5—H5A118.5
I1—Cu1—Cu1i61.05 (4)N2—C6—C7124.0 (7)
I1i—Cu1—Cu1i56.80 (4)N2—C6—H6A118.0
C1—N1—C5116.7 (6)C7—C6—H6A118.0
C1—N1—Cu1121.0 (5)C8—C7—C6118.6 (8)
C5—N1—Cu1121.5 (5)C8—C7—H7A120.7
C10—N2—C6116.9 (6)C6—C7—H7A120.7
C10—N2—Cu1121.5 (5)C7—C8—C9118.6 (7)
C6—N2—Cu1120.5 (5)C7—C8—N3125.5 (8)
N4—N3—C8113.1 (7)C9—C8—N3115.9 (7)
N3—N4—C3ii113.1 (7)C8—C9—C10118.6 (7)
N1—C1—C2124.2 (7)C8—C9—H9A120.7
N1—C1—H1A117.9C10—C9—H9A120.7
C2—C1—H1A117.9N2—C10—C9123.2 (8)
C1—C2—C3117.7 (7)N2—C10—H10A118.4
C1—C2—H2A121.1C9—C10—H10A118.4
C3—C2—H2A121.1
Cu1i—I1—Cu1—N1113.0 (2)Cu1—N1—C1—C2168.1 (6)
Cu1i—I1—Cu1—N2111.9 (2)N1—C1—C2—C30.8 (13)
Cu1i—I1—Cu1—I1i0.0C1—C2—C3—C41.5 (13)
N2—Cu1—N1—C137.0 (7)C1—C2—C3—N4iii176.3 (7)
I1—Cu1—N1—C1162.6 (6)C2—C3—C4—C50.4 (14)
I1i—Cu1—N1—C173.3 (6)N4iii—C3—C4—C5178.3 (8)
Cu1i—Cu1—N1—C1131.1 (6)C1—N1—C5—C43.8 (13)
N2—Cu1—N1—C5153.7 (6)Cu1—N1—C5—C4166.0 (7)
I1—Cu1—N1—C528.0 (7)C3—C4—C5—N13.2 (15)
I1i—Cu1—N1—C596.1 (6)C10—N2—C6—C72.2 (13)
Cu1i—Cu1—N1—C538.2 (7)Cu1—N2—C6—C7166.0 (6)
N1—Cu1—N2—C10152.1 (7)N2—C6—C7—C80.5 (13)
I1—Cu1—N2—C1026.0 (7)C6—C7—C8—C91.2 (13)
I1i—Cu1—N2—C1097.5 (7)C6—C7—C8—N3175.7 (8)
Cu1i—Cu1—N2—C1039.6 (8)N4—N3—C8—C711.7 (12)
N1—Cu1—N2—C640.2 (7)N4—N3—C8—C9171.4 (9)
I1—Cu1—N2—C6166.3 (6)C7—C8—C9—C101.0 (14)
I1i—Cu1—N2—C670.2 (6)N3—C8—C9—C10176.2 (9)
Cu1i—Cu1—N2—C6128.1 (6)C6—N2—C10—C92.4 (14)
C8—N3—N4—C3ii178.2 (6)Cu1—N2—C10—C9165.7 (8)
C5—N1—C1—C21.8 (12)C8—C9—C10—N20.8 (16)
Symmetry codes: (i) x, y+1, z+1; (ii) x+1, y+2, z+1/2; (iii) x1, y+2, z1/2.

Experimental details

Crystal data
Chemical formula[CuI(C10H8N4)]
Mr374.65
Crystal system, space groupMonoclinic, P2/c
Temperature (K)150
a, b, c (Å)9.7137 (19), 8.0745 (16), 15.396 (3)
β (°) 98.73 (3)
V3)1193.6 (4)
Z4
Radiation typeMo Kα
µ (mm1)4.39
Crystal size (mm)0.2 × 0.18 × 0.15
Data collection
DiffractometerRigaku Saturn724+ (2x2 bin mode)
diffractometer
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2008)
Tmin, Tmax0.795, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
6682, 2171, 1674
Rint0.053
(sin θ/λ)max1)0.602
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.060, 0.093, 1.17
No. of reflections2171
No. of parameters145
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.80, 0.63

Computer programs: CrystalClear (Rigaku, 2008), SHELXTL (Sheldrick, 2008).

 

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