A twofold interwoven two-dimen-sional!two-dimensional (2-D!2-D)cluster–organic network based on the[Cu2I2] cluster and the 4,4000-(diazene-diyl)dipyridine ligand: poly[[l2-4,4

000-(diazenediyl)dipyridine]-l2-iodido-copper(I)]

Wenjiang Huang,a Jinfang Zhang,b Jianghua Lib and Chi

Zhanga,b*

aInstitute of Molecular Engineering and Advanced Materials, School of Chemical

Engineering, Nanjing University of Science and Technology, 200 Xiaolingwei,

Nanjing 210094, Jiangsu, People’s Republic of China, and bInstitute of Science and

Technology, Jiangsu University, 301 Xuefu Road, Zhenjiang 212013, People’s

Republic of China

Correspondence e-mail: chizhang@mail.njust.edu.cn

Received 31 December 2012

Accepted 10 January 2013

Online 22 January 2013

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 4,40-

(diazenediyl)dipyridine (4,40-azpy) ligands. Two �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) A and the Cu—I bond lengths are

2.6290 (13) and 2.7495 (15) A. The bridging 4,40-azpy ligands

connect the [Cu2I2] clusters into a two-dimensional (2-D)

double-layered grid-like network [parallel to the (102) plane],

with a (4,4)-connected topology. Two 2-D grid-like networks

interweave each other by long 4,40-azpy bridging ligands to

form a dense 2-D double-layered network. To the best of our

knowledge, this interwoven 2-D!2-D network is observed for

the first time in [Cu2I2]–organic compounds.

Comment

In recent years, the construction of multidimensional cluster-

based coordination polymers has been a major focus of

research in the field of chemistry and materials science, due

not only to 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

metal-organic compounds

Acta Cryst. (2013). C69, 123–126 doi:10.1107/S0108270113000942 # 2013 International Union of Crystallography 123

Acta Crystallographica Section C

Crystal StructureCommunications

ISSN 0108-2701

Figure 1The structure of a portion of the title compound, showing the atom-labelling scheme and 50% probability displacement ellipsoids. All H atoms have beenomitted. [Symmetry codes: (i) �x, �y + 1, �z + 1; (ii) x + 1, �y + 2, z + 1

2.]

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 used in constructing CuX-based coor-

dination polymers (Peng et al., 2010). Herein, we have used

4,40-(diazenediyl)dipyridine (4,40-azpy) ligands as long bridges

to construct the CuI-based coordination polymer poly[[�-4,40-

(diazenediyl)dipyridine]-�2-iodido-copper(I)], (I), which is

formed by [Cu2I2] clusters and single 4,40-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 4,40-

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 4,40-azpy ligands, forming a

four-coordinated tetrahedral geometry. The Cu1—N1 and

Cu1—N2 bond lengths are 2.037 (6) and 2.045 (6) A, respec-

tively, and the N1—Cu1—N2 angle is 123.7 (3)�. The centro-

symmetric planar rhomboid [Cu2I2] cluster is formed by two

�2-I atoms linking two CuI atoms. In the [Cu2I2] cluster, the

distance between two CuI atoms is 2.7781 (15) A and the

Cu—I bonds lengths are 2.6290 (13) and 2.7495 (15) A. The

I—Cu—I and Cu—I—Cu angles are 117.85 (4) and 62.15 (4)�,

respectively.

In the 4,40-azpy ligands, the N N bond length is

1.240 (9) A and the average distances between the C and N

atoms of the pyridine rings is 1.331 (9) A. In the (4,4) network,

the [Cu2I2] clusters shows a unique ABAB arrangement

(Fig. 2) and the 4,40-azpy ligand is slightly distorted because

the angle between the planes of the two pyridine rings is

metal-organic compounds

124 Huang et al. � [CuI(C10H8N4)] Acta Cryst. (2013). C69, 123–126

Figure 2A fragment of the two-dimensional (4,4) network showing the [Cu2I2]clusters in a unique ABAB arrangement. The diagonal distances betweenthe centres of the [Cu2I2] clusters are d1 = 16.149 (2) A and d2 =22.883 (3) A.

Figure 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 aregreen, I atoms are purple, C atoms are grey and N atoms are blue.) (b) The novel two-dimensional twofold interwoven networks. (In the electronicversion of the paper, the different layers layers are highlighted in red and blue.)

8.9 (4)�. Interestingly, the 2-D net exhibits a rare double-

layered structure (Fig. 3a), which is probably 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 4,40-azpy bridges, are 16.149 (2)

and 22.883 (3) A (Fig. 2). Each layer has enough empty space

to allow two layers to interweave by long 4,40-azpy bridging

ligands and thus 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 poly-

mers. 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), a 2-D polycatenane network is formed by inter-

locking 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, our 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 4,40-azpy

ligands to form a cubane-shaped W/S/Cu cluster-based coor-

dination polymer. However, in the second step, the W/S/Cu

clusters were decomposed by water present in 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 2-D!2-D network in

(I) is found for the first time in [Cu2I2]–organic compounds.

Experimental

(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, isopropanol (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 4,40-(di-

azenediyl)dipyridine (0.0183 g, 0.1 mmol) were added to acetonitrile

(2 ml) and DMF (1 ml), and the resulting solution was stirred thor-

oughly 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).

Crystal data

[CuI(C10H8N4)]Mr = 374.65Monoclinic, P2=ca = 9.7137 (19) Ab = 8.0745 (16) Ac = 15.396 (3) A� = 98.73 (3)�

V = 1193.6 (4) A3

Z = 4Mo K� radiation� = 4.39 mm�1

T = 150 K0.2 � 0.18 � 0.15 mm

Data collection

Rigaku Saturn724+ diffractometerAbsorption correction: multi-scan

(CrystalClear; Rigaku, 2008)Tmin = 0.795, Tmax = 1.000

6682 measured reflections2171 independent reflections1674 reflections with I > 2�(I)Rint = 0.053

Refinement

R[F 2 > 2�(F 2)] = 0.060wR(F 2) = 0.093S = 1.172171 reflections

145 parametersH-atom parameters constrained��max = 0.80 e A�3

��min = �0.63 e A�3

H atoms were positioned geometrically and refined using a riding

model, with C—H = 0.93 A and Uiso(H) = 1.2Ueq(C).

Data collection: CrystalClear (Rigaku, 2008); cell refinement:

CrystalClear; data reduction: CrystalClear; program(s) used to solve

structure: SHELXTL (Sheldrick, 2008); program(s) used to refine

structure: SHELXTL; molecular graphics: SHELXTL; software used

to prepare material for publication: SHELXTL.

This work was supported by the National Natural Science

Foundation of China (No. 50472048) and the Program for New

Century Excellent Talents in University (NCET-05–0499).

Supplementary data for this paper are available from the IUCr electronicarchives (Reference: SK3470). Services for accessing these data aredescribed at the back of the journal.

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126 Huang et al. � [CuI(C10H8N4)] Acta Cryst. (2013). C69, 123–126

supplementary materials

sup-1Acta Cryst. (2013). C69, 123-126

supplementary materials

Acta Cryst. (2013). C69, 123-126 [doi:10.1107/S0108270113000942]

A twofold interwoven two-dimensional→two-dimensional (2-D→2-D) cluster–

organic network based on the [Cu2I2] cluster and the 4,4′-(diazenediyl)di-

pyridine ligand: poly[[µ2-4,4′-(diazenediyl)dipyridine]-µ2-iodido-copper(I)]

Wenjiang Huang, Jinfang Zhang, Jianghua Li and Chi Zhang

poly[[µ-4,4′-(diazenediyl)dipyridine]-µ2-iodido-copper(I)]

Crystal data

[CuI(C10H8N4)]Mr = 374.65Monoclinic, P2/cHall symbol: -P 2yca = 9.7137 (19) Åb = 8.0745 (16) Åc = 15.396 (3) Åβ = 98.73 (3)°V = 1193.6 (4) Å3

Z = 4

F(000) = 712Dx = 2.085 Mg m−3

Mo Kα radiation, λ = 0.71073 ÅCell parameters from 3410 reflectionsθ = 2.5–28.9°µ = 4.39 mm−1

T = 150 KBlock, brown0.2 × 0.18 × 0.15 mm

Data collection

Rigaku Saturn724+ (2x2 bin mode) diffractometer

Radiation source: fine-focus sealed tubeGraphite monochromatorω scansAbsorption correction: multi-scan

(CrystalClear; Rigaku, 2008)Tmin = 0.795, Tmax = 1.000

6682 measured reflections2171 independent reflections1674 reflections with I > 2σ(I)Rint = 0.053θmax = 25.3°, θmin = 2.9°h = −11→9k = −9→8l = −17→18

Refinement

Refinement on F2

Least-squares matrix: fullR[F2 > 2σ(F2)] = 0.060wR(F2) = 0.093S = 1.172171 reflections145 parameters0 restraintsPrimary atom site location: structure-invariant

direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrainedw = 1/[σ2(Fo

2) + (0.0198P)2 + 2.6592P] where P = (Fo

2 + 2Fc2)/3

(Δ/σ)max < 0.001Δρmax = 0.80 e Å−3

Δρmin = −0.63 e Å−3

supplementary materials

sup-2Acta Cryst. (2013). C69, 123-126

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 (Å2)

x y z Uiso*/Ueq

I1 0.10063 (6) 0.31252 (6) 0.41593 (4) 0.0507 (2)Cu1 0.05260 (10) 0.62373 (12) 0.45162 (7) 0.0496 (3)N1 −0.0745 (6) 0.7213 (8) 0.3467 (4) 0.0404 (16)N2 0.2398 (6) 0.7250 (8) 0.5042 (4) 0.0440 (17)N3 0.5868 (7) 0.9279 (10) 0.6661 (4) 0.056 (2)N4 0.6006 (7) 1.0804 (10) 0.6633 (4) 0.0525 (19)C1 −0.0876 (8) 0.8843 (10) 0.3362 (5) 0.046 (2)H1A −0.0247 0.9520 0.3713 0.056*C2 −0.1888 (8) 0.9597 (10) 0.2763 (5) 0.050 (2)H2A −0.1931 1.0744 0.2708 0.059*C3 −0.2833 (8) 0.8588 (10) 0.2249 (5) 0.042 (2)C4 −0.2708 (9) 0.6913 (11) 0.2340 (6) 0.068 (3)H4A −0.3336 0.6213 0.2003 0.081*C5 −0.1640 (8) 0.6267 (11) 0.2936 (5) 0.060 (3)H5A −0.1536 0.5123 0.2971 0.072*C6 0.2540 (8) 0.8884 (10) 0.5123 (5) 0.048 (2)H6A 0.1845 0.9550 0.4823 0.057*C7 0.3652 (8) 0.9648 (10) 0.5625 (5) 0.050 (2)H7A 0.3699 1.0796 0.5665 0.060*C8 0.4689 (7) 0.8682 (11) 0.6067 (5) 0.045 (2)C9 0.4586 (9) 0.6984 (11) 0.5976 (6) 0.073 (3)H9A 0.5280 0.6294 0.6259 0.087*C10 0.3424 (8) 0.6326 (11) 0.5452 (6) 0.069 (3)H10A 0.3363 0.5182 0.5386 0.083*

Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23

I1 0.0569 (4) 0.0338 (3) 0.0588 (4) 0.0023 (3) 0.0007 (3) −0.0019 (3)Cu1 0.0447 (6) 0.0386 (6) 0.0579 (7) −0.0023 (5) −0.0164 (5) 0.0030 (5)N1 0.041 (4) 0.031 (4) 0.047 (4) 0.000 (3) −0.001 (3) −0.001 (3)N2 0.039 (4) 0.035 (4) 0.052 (4) 0.000 (3) −0.010 (3) 0.001 (3)N3 0.041 (4) 0.062 (5) 0.063 (5) −0.010 (4) −0.005 (4) −0.008 (4)N4 0.043 (4) 0.061 (5) 0.050 (4) −0.010 (4) −0.005 (3) −0.005 (4)C1 0.045 (5) 0.044 (6) 0.046 (5) −0.003 (4) −0.008 (4) −0.004 (4)C2 0.054 (5) 0.040 (5) 0.052 (5) 0.011 (4) 0.000 (4) 0.009 (4)C3 0.044 (5) 0.042 (5) 0.036 (4) 0.009 (4) −0.004 (4) 0.002 (4)

supplementary materials

sup-3Acta Cryst. (2013). C69, 123-126

C4 0.058 (6) 0.057 (6) 0.074 (6) 0.004 (5) −0.035 (5) −0.003 (5)C5 0.061 (6) 0.037 (5) 0.072 (6) 0.003 (4) −0.020 (5) −0.001 (4)C6 0.048 (5) 0.041 (6) 0.049 (5) −0.003 (4) −0.008 (4) 0.002 (4)C7 0.051 (5) 0.047 (6) 0.048 (5) −0.016 (4) −0.005 (4) −0.003 (4)C8 0.030 (4) 0.060 (6) 0.044 (5) 0.000 (4) −0.001 (4) −0.002 (4)C9 0.058 (6) 0.043 (6) 0.102 (8) 0.009 (5) −0.035 (6) −0.018 (5)C10 0.053 (6) 0.041 (6) 0.101 (7) 0.000 (4) −0.032 (5) −0.016 (5)

Geometric parameters (Å, º)

I1—Cu1 2.6290 (13) C2—H2A 0.9300I1—Cu1i 2.7495 (15) C3—C4 1.364 (11)Cu1—N1 2.037 (6) C3—N4iii 1.444 (9)Cu1—N2 2.045 (6) C4—C5 1.379 (10)N1—C1 1.330 (9) C4—H4A 0.9300N1—C5 1.338 (9) C5—H5A 0.9300N2—C10 1.326 (9) C6—C7 1.375 (9)N2—C6 1.330 (9) C6—H6A 0.9300N3—N4 1.240 (9) C7—C8 1.370 (10)N3—C8 1.435 (9) C7—H7A 0.9300N4—C3ii 1.444 (9) C8—C9 1.381 (11)C1—C2 1.382 (9) C9—C10 1.389 (10)C1—H1A 0.9300 C9—H9A 0.9300C2—C3 1.383 (10) C10—H10A 0.9300

Cu1—I1—Cu1i 62.15 (4) C4—C3—C2 119.0 (7)N1—Cu1—N2 123.7 (3) C4—C3—N4iii 117.0 (7)N1—Cu1—I1 108.02 (18) C2—C3—N4iii 124.0 (7)N2—Cu1—I1 106.82 (19) C3—C4—C5 119.3 (7)N1—Cu1—I1i 100.64 (19) C3—C4—H4A 120.3N2—Cu1—I1i 100.42 (19) C5—C4—H4A 120.3I1—Cu1—I1i 117.85 (4) N1—C5—C4 122.9 (8)N1—Cu1—Cu1i 118.39 (18) N1—C5—H5A 118.5N2—Cu1—Cu1i 116.93 (18) C4—C5—H5A 118.5I1—Cu1—Cu1i 61.05 (4) N2—C6—C7 124.0 (7)I1i—Cu1—Cu1i 56.80 (4) N2—C6—H6A 118.0C1—N1—C5 116.7 (6) C7—C6—H6A 118.0C1—N1—Cu1 121.0 (5) C8—C7—C6 118.6 (8)C5—N1—Cu1 121.5 (5) C8—C7—H7A 120.7C10—N2—C6 116.9 (6) C6—C7—H7A 120.7C10—N2—Cu1 121.5 (5) C7—C8—C9 118.6 (7)C6—N2—Cu1 120.5 (5) C7—C8—N3 125.5 (8)N4—N3—C8 113.1 (7) C9—C8—N3 115.9 (7)N3—N4—C3ii 113.1 (7) C8—C9—C10 118.6 (7)N1—C1—C2 124.2 (7) C8—C9—H9A 120.7N1—C1—H1A 117.9 C10—C9—H9A 120.7C2—C1—H1A 117.9 N2—C10—C9 123.2 (8)C1—C2—C3 117.7 (7) N2—C10—H10A 118.4C1—C2—H2A 121.1 C9—C10—H10A 118.4C3—C2—H2A 121.1

supplementary materials

sup-4Acta Cryst. (2013). C69, 123-126

Cu1i—I1—Cu1—N1 −113.0 (2) Cu1—N1—C1—C2 −168.1 (6)Cu1i—I1—Cu1—N2 111.9 (2) N1—C1—C2—C3 0.8 (13)Cu1i—I1—Cu1—I1i 0.0 C1—C2—C3—C4 −1.5 (13)N2—Cu1—N1—C1 −37.0 (7) C1—C2—C3—N4iii 176.3 (7)I1—Cu1—N1—C1 −162.6 (6) C2—C3—C4—C5 −0.4 (14)I1i—Cu1—N1—C1 73.3 (6) N4iii—C3—C4—C5 −178.3 (8)Cu1i—Cu1—N1—C1 131.1 (6) C1—N1—C5—C4 −3.8 (13)N2—Cu1—N1—C5 153.7 (6) Cu1—N1—C5—C4 166.0 (7)I1—Cu1—N1—C5 28.0 (7) C3—C4—C5—N1 3.2 (15)I1i—Cu1—N1—C5 −96.1 (6) C10—N2—C6—C7 −2.2 (13)Cu1i—Cu1—N1—C5 −38.2 (7) Cu1—N2—C6—C7 166.0 (6)N1—Cu1—N2—C10 −152.1 (7) N2—C6—C7—C8 0.5 (13)I1—Cu1—N2—C10 −26.0 (7) C6—C7—C8—C9 1.2 (13)I1i—Cu1—N2—C10 97.5 (7) C6—C7—C8—N3 −175.7 (8)Cu1i—Cu1—N2—C10 39.6 (8) N4—N3—C8—C7 −11.7 (12)N1—Cu1—N2—C6 40.2 (7) N4—N3—C8—C9 171.4 (9)I1—Cu1—N2—C6 166.3 (6) C7—C8—C9—C10 −1.0 (14)I1i—Cu1—N2—C6 −70.2 (6) N3—C8—C9—C10 176.2 (9)Cu1i—Cu1—N2—C6 −128.1 (6) C6—N2—C10—C9 2.4 (14)C8—N3—N4—C3ii 178.2 (6) Cu1—N2—C10—C9 −165.7 (8)C5—N1—C1—C2 1.8 (12) C8—C9—C10—N2 −0.8 (16)

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