Poly[bis[3,10-bis(2-hydroxyethyl)-1,3,5,8,10,12-hexa­azacyclo­tetra­deca­ne]tetra-μ-cyanido-tetracyanidodicopper(II)molybdenum(IV)] tetra­hydrate]

Zhou, H.; Chen, Y.-Y.; Liu, W.-Y.; Yuan, A.-H.

doi:10.1107/S1600536808036131

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page m1528

doi:10.1107/S1600536808036131

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Poly[bis[3,10-bis(2-hydroxyethyl)-1,3,5,8,10,12-hexaazacyclotetradecane]tetra-μ-cyanido-tetracyanidodicopper(II)molybdenum(IV)] tetrahydrate]

Hu Zhou,^a Ying-Ying Chen,^a Wen-Yan Liu ^a and Ai-Hua Yuan ^a ^*

^aSchool of Materials Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, People's Republic of China
^*Correspondence e-mail: aihuayuan@163.com

(Received 11 October 2008; accepted 4 November 2008; online 13 November 2008)

In the title complex, {[Cu₂Mo(CN)₈(C₁₂H₃₀N₆O₂)₂]·4H₂O}_n, the polyhedron around Mo has site symmetry $[\overline1]$ with a distorted square-antiprismatic shape, while the Cu atom (2 symmetry) is in a distorted axially elongated octahedral coordination environment. The uncoordinated water molecule is disordered over three sites with occupancies of 0.445 (7), 0.340 (7) and 0.215 (7). Mo and Cu atoms acting as basic components are connected by an Mo—CN—Cu—NC—Mo— linkage to form a distorted diamond-like network. Additional hydrogen bonding between the N—H groups and the water molecules stabilizes this arrangement.

Related literature

For background information, see: Larionova et al. (2004 ); Przychodzeń et al. (2006 ). For related structures, see: Chen et al. (2007 ); Zhou et al. (2007 ; 2008 ). For literature related to the synthesis, see: Suh & Kang (1988 ); Leipoldt et al. (1974 ).

Experimental

Crystal data

[Cu₂Mo(CN)₈(C₁₂H₃₀N₆O₂)₂]·4H₂O
M_r = 1084.08
Tetragonal, I 4₁ /a
a = 20.0707 (10) Å
c = 15.4380 (17) Å
V = 6218.9 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.93 mm⁻¹
T = 293 (2) K
0.32 × 0.28 × 0.26 mm

Data collection

Bruker SMART APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.75, T_max = 0.79
16289 measured reflections
3053 independent reflections
2459 reflections with I > 2σ(I)
R_int = 0.058

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.103
S = 1.06
3053 reflections
165 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3C⋯N2ⁱ	0.93	2.44	3.261 (4)	147
N5—H5C⋯O2ⁱⁱ	0.93	2.38	3.291 (8)	165
O1—H1C⋯O4ⁱⁱⁱ	0.85	2.48	3.149 (7)	136
O4—H4D⋯N2^iv	0.85	2.11	2.729 (6)	129
O4—H4E⋯O2^v	0.85	2.47	3.279 (9)	159
Symmetry codes: (i) -x+2, -y+1, -z; (ii) $[y+{\script{3\over 4}}, -x+{\script{3\over 4}}, z-{\script{1\over 4}}]$ ; (iii) $[-y+{\script{5\over 4}}, x+{\script{1\over 4}}, -z+{\script{5\over 4}}]$ ; (iv) x-1, y, z+1; (v) $[y-{\script{1\over 4}}, -x+{\script{1\over 4}}, -z+{\script{5\over 4}}]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); 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, New_Global_Publ_Block. DOI: 10.1107/S1600536808036131/pv2114sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808036131/pv2114Isup2.hkl

checkCIF report

Comment top

Recently, octacyanometalates [M(CN)₈]^3-/4- (M = Mo, W and Nb) have been found to be versatile building blocks and investigated extensively (Larionova et al., 2004; Przychodzeń et al., 2006). For [CuL]²⁺/[M(CN)₈]^3-/4- (L = macrocyclic ligands) bimetallic systems, macrocyclic ligands block partly coordination sites of the metal ions and release their apical ones, which can be used to construct cyano-bridged bimetallic complexes with octacyanometalate [M(CN)₈]^3-/4- ions. In a recent study, we chose [CuL]²⁺ (L = 3,10-diethanol-1,3,5,8,10,12-hexaazacyclotetradecane) as building block to synthesize successfully an octacyanometalate-based bimetallic complex [CuL]₂[Mo(CN)₈].4H₂O, (I), with a distorted diamond network.

The title complex crystallizes in the tetragonal (I4₁/a) space group. As displayed in Fig. 1, the Mo atom is coordinated by eight CN groups in a distorted square antiprism. The Cu atom is in a distorted axially elongated octahedral coordination environment, in which four nitrogen atoms from the ligand (L) occupy the equatorial positions, while the axial sites are occupied by two nitrogen atoms from the bridging cyanide groups on different [Mo(CN)₈]^4- anions. The bonding parameters of the macrocyclic ligand L are reminiscent of those found in related complexes reported previously (Chen et al., 2007).

As shown in Fig. 2, Mo and Cu atoms acting as basic components (linker and connector, respectively) are connected by the Mo—CN—Cu—NC—Mo— linkages to form a three-dimensional structure. The network is composed of [CuL]²⁺ unit that is linked via cyanides to adjacent four-connected [Mo(CN)₈(µ-CN)₄]^4- centers. From a topological standpoint, each [Mo(CN)₈] unit is a tetrahedral four-connecting node. These nodes are linked to four adjacent [Mo(CN)₈] units by the [CuL] units, acting as linear two-connectors. The result is a distorted diamond network (Fig. 2), which is similar to octacyanometalate-based bimetallic complexes reported previously (Zhou et al., 2007; 2008).

Related literature top

For background information, see: Larionova et al. (2004); Przychodzeń et al. (2006). For related structures, see: Chen et al. (2007); Zhou et al. (2007; 2008). For literature related to the synthesis, see: Suh & Kang (1988); Leipoldt et al. (1974).

Experimental top

Well shaped brown crystals of the title complex suitable for X-ray single-crystal structure determination were grown at room temperature by slow diffusion of a DMF solution (15 ml) of [CuL](ClO₄)₂ (0.30 mmol) (Suh and Kang, 1988) and an aqueous solution (15 ml) of K₄[Mo(CN)₈].2H₂O (0.15 mmol) (Leipoldt et al., 1974) in a U-shaped tube containing agar for about one month. The resulting crystals were collected, washed with H₂O and dried in air.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SMART (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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. ORTEP drawing of the title complex, showing the atom labeling. Hydrogen atoms and water molecules are omitted for clarity. Symmetry codes: A: 2-x, 1-y, -z; B: 2-x, 0.5-y, z; C: 1.25-y, -0.75+x, 0.25-z.
	Fig. 2. Topological depiction of the title complex, where the Mo nodes and the Cu connectors are shown in pink and green colors, respectively.

Poly[[bis[3,10-bis(2-hydroxyethyl)-1,3,5,8,10,12-hexaazacyclotetradecane]tetra- µ-cyanido-tetracyanidodicopper(II)molybdenum(IV)] tetrahydrate] top

Crystal data top

[Cu₂Mo(CN)₈(C₁₂H₃₀N₆O₂)₂]·4H₂O	D_x = 1.158 Mg m⁻³
M_r = 1084.08	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4₁/a	Cell parameters from 3093 reflections
Hall symbol: -I 4ad	θ = 2.6–21.2°
a = 20.0707 (10) Å	µ = 0.93 mm⁻¹
c = 15.4380 (17) Å	T = 293 K
V = 6218.9 (8) Å³	Block, brown
Z = 4	0.32 × 0.28 × 0.26 mm
F(000) = 2256

Data collection top

Bruker SMART APEXII diffractometer	3053 independent reflections
Radiation source: sealed tube	2459 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.058
phi and ω scans	θ_max = 26.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −24→24
T_min = 0.75, T_max = 0.79	k = −19→24
16289 measured reflections	l = −16→19

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.103	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0515P)² + 3.1936P] where P = (F_o² + 2F_c²)/3
3053 reflections	(Δ/σ)_max < 0.001
165 parameters	Δρ_max = 0.23 e Å⁻³
1 restraint	Δρ_min = −0.38 e Å⁻³

Crystal data top

[Cu₂Mo(CN)₈(C₁₂H₃₀N₆O₂)₂]·4H₂O	Z = 4
M_r = 1084.08	Mo Kα radiation
Tetragonal, I4₁/a	µ = 0.93 mm⁻¹
a = 20.0707 (10) Å	T = 293 K
c = 15.4380 (17) Å	0.32 × 0.28 × 0.26 mm
V = 6218.9 (8) Å³

Data collection top

Bruker SMART APEXII diffractometer	3053 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	2459 reflections with I > 2σ(I)
T_min = 0.75, T_max = 0.79	R_int = 0.058
16289 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	1 restraint
wR(F²) = 0.103	H-atom parameters constrained
S = 1.06	Δρ_max = 0.23 e Å⁻³
3053 reflections	Δρ_min = −0.38 e Å⁻³
165 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	Occ. (<1)
C1	0.96688 (13)	0.34611 (15)	0.08263 (19)	0.0392 (6)
C2	1.06251 (16)	0.27104 (17)	0.0121 (2)	0.0485 (7)
C3	0.86789 (19)	0.5451 (2)	0.0135 (2)	0.0615 (9)
H3A	0.8364	0.5817	0.0269	0.074*
H3B	0.8476	0.5025	0.0322	0.074*
C4	0.92199 (19)	0.5426 (2)	0.1513 (2)	0.0610 (9)
H4A	0.8863	0.5716	0.1746	0.073*
H4B	0.9081	0.4957	0.1597	0.073*
C5	1.0360 (2)	0.5073 (2)	0.1850 (2)	0.0627 (10)
H5A	1.0195	0.4618	0.1971	0.075*
H5B	1.0715	0.5172	0.2277	0.075*
C6	1.1181 (2)	0.4567 (2)	0.0813 (2)	0.0649 (10)
H6A	1.1023	0.4126	0.1013	0.078*
H6B	1.1591	0.4682	0.1137	0.078*
C7	0.99694 (18)	0.62268 (18)	0.2106 (2)	0.0570 (9)
H7A	0.9623	0.6491	0.1805	0.068*
H7B	1.0397	0.6317	0.1808	0.068*
C8	1.0028 (2)	0.6495 (2)	0.3018 (3)	0.0694 (11)
H8A	1.0505	0.6519	0.3175	0.083*
H8B	0.9848	0.6954	0.3030	0.083*
Cu2	1.0000	0.5000	0.0000	0.04929 (18)
Mo1	1.0000	0.2500	0.1250	0.03165 (14)
N1	0.94948 (13)	0.39753 (13)	0.05790 (17)	0.0467 (6)
N2	1.09533 (14)	0.28414 (15)	−0.04505 (19)	0.0554 (7)
N3	0.92993 (13)	0.55566 (15)	0.05812 (19)	0.0539 (7)
H3C	0.9417	0.6002	0.0514	0.065*
N4	0.98158 (17)	0.55421 (16)	0.1980 (3)	0.0737 (9)
N5	1.06603 (14)	0.50813 (15)	0.09613 (16)	0.0500 (7)
H5C	1.0866	0.5493	0.0896	0.060*
O1	0.9722 (2)	0.6148 (2)	0.3594 (3)	0.1107 (12)
H1C	0.9917	0.5774	0.3651	0.133*
O2	0.1088 (4)	0.4119 (4)	0.3446 (5)	0.072 (3)	0.340 (7)
H2A	0.0857	0.4473	0.3454	0.087*	0.340 (7)
H2B	0.0994	0.3893	0.3896	0.087*	0.340 (7)
O3	0.2794 (8)	0.5343 (7)	0.0656 (10)	0.088 (6)	0.215 (7)
H3D	0.2957	0.5708	0.0836	0.105*	0.215 (7)
H3E	0.3107	0.5076	0.0526	0.105*	0.215 (7)
O4	0.2103 (3)	0.2935 (3)	0.8613 (3)	0.065 (2)	0.445 (7)
H4D	0.1814	0.3166	0.8882	0.078*	0.445 (7)
H4E	0.1970	0.2534	0.8577	0.078*	0.445 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0211 (12)	0.0461 (17)	0.0503 (17)	0.0025 (11)	−0.0005 (11)	0.0068 (13)
C2	0.0437 (17)	0.0534 (19)	0.0485 (18)	−0.0006 (14)	0.0066 (14)	−0.0020 (15)
C3	0.058 (2)	0.064 (2)	0.063 (2)	−0.0125 (18)	−0.0127 (17)	0.0055 (18)
C4	0.058 (2)	0.083 (3)	0.0428 (19)	−0.0050 (19)	0.0110 (15)	0.0042 (17)
C5	0.068 (2)	0.079 (3)	0.0419 (18)	0.0000 (19)	−0.0184 (17)	−0.0064 (17)
C6	0.072 (2)	0.079 (3)	0.044 (2)	−0.007 (2)	−0.0283 (18)	0.0000 (17)
C7	0.060 (2)	0.056 (2)	0.0550 (19)	−0.0147 (16)	0.0152 (16)	−0.0383 (16)
C8	0.071 (2)	0.068 (2)	0.069 (3)	−0.003 (2)	0.019 (2)	−0.024 (2)
Cu2	0.0514 (3)	0.0560 (3)	0.0405 (3)	−0.0020 (3)	−0.0059 (2)	0.0008 (2)
Mo1	0.01805 (15)	0.01805 (15)	0.0589 (3)	0.000	0.000	0.000
N1	0.0459 (14)	0.0452 (14)	0.0490 (15)	0.0031 (11)	−0.0036 (12)	0.0120 (12)
N2	0.0549 (17)	0.0586 (17)	0.0528 (17)	−0.0083 (14)	0.0019 (14)	0.0287 (14)
N3	0.0405 (14)	0.0671 (18)	0.0540 (16)	0.0017 (13)	0.0018 (12)	0.0123 (14)
N4	0.071 (2)	0.0478 (18)	0.103 (3)	−0.0030 (15)	0.018 (2)	−0.0012 (17)
N5	0.0521 (16)	0.0572 (17)	0.0406 (14)	0.0061 (13)	−0.0163 (12)	−0.0079 (12)
O1	0.115 (3)	0.113 (3)	0.104 (3)	0.004 (2)	0.011 (2)	0.006 (2)
O2	0.060 (5)	0.092 (6)	0.065 (5)	0.023 (4)	−0.024 (4)	−0.028 (4)
O3	0.097 (11)	0.063 (8)	0.103 (11)	−0.006 (7)	0.041 (9)	−0.006 (8)
O4	0.064 (4)	0.091 (5)	0.041 (3)	−0.014 (3)	0.016 (2)	0.009 (3)

Geometric parameters (Å, º) top

C1—N1	1.154 (4)	C8—O1	1.285 (5)
C1—Mo1	2.143 (3)	C8—H8A	0.9900
C2—N2	1.132 (4)	C8—H8B	0.9900
C2—Mo1	2.188 (3)	Cu2—N5ⁱ	1.996 (2)
C3—N3	1.439 (4)	Cu2—N5	1.996 (2)
C3—C6ⁱ	1.490 (5)	Cu2—N3	2.008 (3)
C3—H3A	0.9900	Cu2—N3ⁱ	2.008 (3)
C3—H3B	0.9900	Cu2—N1ⁱ	2.461 (3)
C4—N4	1.416 (5)	Cu2—N1	2.461 (3)
C4—N3	1.470 (5)	Mo1—C1ⁱⁱ	2.143 (3)
C4—H4A	0.9900	Mo1—C1ⁱⁱⁱ	2.143 (3)
C4—H4B	0.9900	Mo1—C1^iv	2.143 (3)
C5—N4	1.457 (5)	Mo1—C2ⁱⁱⁱ	2.188 (3)
C5—N5	1.499 (5)	Mo1—C2^iv	2.188 (3)
C5—H5A	0.9900	Mo1—C2ⁱⁱ	2.188 (3)
C5—H5B	0.9900	N3—H3C	0.9300
C6—N5	1.487 (5)	N5—H5C	0.9300
C6—C3ⁱ	1.490 (5)	O1—H1C	0.8501
C6—H6A	0.9900	O2—H2A	0.8500
C6—H6B	0.9900	O2—H2B	0.8500
C7—N4	1.422 (4)	O3—H3D	0.8500
C7—C8	1.512 (5)	O3—H3E	0.8500
C7—H7A	0.9900	O4—H4D	0.8498
C7—H7B	0.9900	O4—H4E	0.8498

N1—C1—Mo1	178.4 (3)	N3ⁱ—Cu2—N1	89.19 (10)
N2—C2—Mo1	177.5 (3)	N1ⁱ—Cu2—N1	180.00 (11)
N3—C3—C6ⁱ	108.1 (3)	C1ⁱⁱ—Mo1—C1ⁱⁱⁱ	95.35 (5)
N3—C3—H3A	110.1	C1ⁱⁱ—Mo1—C1	144.45 (16)
C6ⁱ—C3—H3A	110.1	C1ⁱⁱⁱ—Mo1—C1	95.35 (5)
N3—C3—H3B	110.1	C1ⁱⁱ—Mo1—C1^iv	95.35 (5)
C6ⁱ—C3—H3B	110.1	C1ⁱⁱⁱ—Mo1—C1^iv	144.45 (16)
H3A—C3—H3B	108.4	C1—Mo1—C1^iv	95.35 (5)
N4—C4—N3	112.2 (3)	C1ⁱⁱ—Mo1—C2ⁱⁱⁱ	145.00 (12)
N4—C4—H4A	109.2	C1ⁱⁱⁱ—Mo1—C2ⁱⁱⁱ	76.18 (12)
N3—C4—H4A	109.2	C1—Mo1—C2ⁱⁱⁱ	70.56 (12)
N4—C4—H4B	109.2	C1^iv—Mo1—C2ⁱⁱⁱ	75.69 (12)
N3—C4—H4B	109.2	C1ⁱⁱ—Mo1—C2^iv	70.56 (12)
H4A—C4—H4B	107.9	C1ⁱⁱⁱ—Mo1—C2^iv	75.69 (12)
N4—C5—N5	114.8 (3)	C1—Mo1—C2^iv	144.99 (12)
N4—C5—H5A	108.6	C1^iv—Mo1—C2^iv	76.18 (12)
N5—C5—H5A	108.6	C2ⁱⁱⁱ—Mo1—C2^iv	74.44 (17)
N4—C5—H5B	108.6	C1ⁱⁱ—Mo1—C2	75.69 (12)
N5—C5—H5B	108.6	C1ⁱⁱⁱ—Mo1—C2	144.99 (12)
H5A—C5—H5B	107.5	C1—Mo1—C2	76.17 (12)
N5—C6—C3ⁱ	107.5 (3)	C1^iv—Mo1—C2	70.55 (12)
N5—C6—H6A	110.2	C2ⁱⁱⁱ—Mo1—C2	129.35 (11)
C3ⁱ—C6—H6A	110.2	C2^iv—Mo1—C2	129.35 (11)
N5—C6—H6B	110.2	C1ⁱⁱ—Mo1—C2ⁱⁱ	76.17 (12)
C3ⁱ—C6—H6B	110.2	C1ⁱⁱⁱ—Mo1—C2ⁱⁱ	70.55 (12)
H6A—C6—H6B	108.5	C1—Mo1—C2ⁱⁱ	75.69 (12)
N4—C7—C8	119.2 (4)	C1^iv—Mo1—C2ⁱⁱ	144.99 (12)
N4—C7—H7A	107.5	C2ⁱⁱⁱ—Mo1—C2ⁱⁱ	129.36 (11)
C8—C7—H7A	107.5	C2^iv—Mo1—C2ⁱⁱ	129.35 (11)
N4—C7—H7B	107.5	C2—Mo1—C2ⁱⁱ	74.44 (17)
C8—C7—H7B	107.5	C1—N1—Cu2	137.9 (2)
H7A—C7—H7B	107.0	C3—N3—C4	110.4 (3)
O1—C8—C7	114.5 (4)	C3—N3—Cu2	108.1 (2)
O1—C8—H8A	108.6	C4—N3—Cu2	114.4 (2)
C7—C8—H8A	108.6	C3—N3—H3C	107.9
O1—C8—H8B	108.6	C4—N3—H3C	107.9
C7—C8—H8B	108.6	Cu2—N3—H3C	107.9
H8A—C8—H8B	107.6	C4—N4—C7	114.3 (3)
N5ⁱ—Cu2—N5	180.0	C4—N4—C5	117.2 (3)
N5ⁱ—Cu2—N3	84.99 (12)	C7—N4—C5	118.8 (3)
N5—Cu2—N3	95.01 (12)	C6—N5—C5	114.6 (3)
N5ⁱ—Cu2—N3ⁱ	95.01 (12)	C6—N5—Cu2	107.20 (19)
N5—Cu2—N3ⁱ	84.99 (12)	C5—N5—Cu2	114.4 (2)
N3—Cu2—N3ⁱ	180.0	C6—N5—H5C	106.7
N5ⁱ—Cu2—N1ⁱ	94.12 (11)	C5—N5—H5C	106.7
N5—Cu2—N1ⁱ	85.88 (11)	Cu2—N5—H5C	106.7
N3—Cu2—N1ⁱ	89.19 (10)	C8—O1—H1C	109.3
N3ⁱ—Cu2—N1ⁱ	90.81 (10)	H2A—O2—H2B	108.2
N5ⁱ—Cu2—N1	85.88 (11)	H3D—O3—H3E	109.5
N5—Cu2—N1	94.12 (11)	H4D—O4—H4E	109.5
N3—Cu2—N1	90.81 (10)

N4—C7—C8—O1	−22.2 (6)	N3—C4—N4—C5	−70.7 (4)
N5ⁱ—Cu2—N1—C1	129.7 (4)	C8—C7—N4—C4	120.0 (4)
N5—Cu2—N1—C1	−50.3 (4)	C8—C7—N4—C5	−94.9 (4)
N3—Cu2—N1—C1	−145.4 (4)	N5—C5—N4—C4	66.8 (4)
N3ⁱ—Cu2—N1—C1	34.6 (4)	N5—C5—N4—C7	−77.3 (4)
C6ⁱ—C3—N3—C4	−166.9 (3)	C3ⁱ—C6—N5—C5	168.3 (3)
C6ⁱ—C3—N3—Cu2	−41.1 (3)	C3ⁱ—C6—N5—Cu2	40.2 (3)
N4—C4—N3—C3	−178.4 (3)	N4—C5—N5—C6	−175.7 (3)
N4—C4—N3—Cu2	59.5 (4)	N4—C5—N5—Cu2	−51.3 (4)
N5ⁱ—Cu2—N3—C3	14.8 (2)	N3—Cu2—N5—C6	165.6 (2)
N5—Cu2—N3—C3	−165.2 (2)	N3ⁱ—Cu2—N5—C6	−14.4 (2)
N1ⁱ—Cu2—N3—C3	109.0 (2)	N1ⁱ—Cu2—N5—C6	−105.5 (2)
N1—Cu2—N3—C3	−71.0 (2)	N1—Cu2—N5—C6	74.5 (2)
N5ⁱ—Cu2—N3—C4	138.2 (3)	N3—Cu2—N5—C5	37.4 (3)
N5—Cu2—N3—C4	−41.8 (3)	N3ⁱ—Cu2—N5—C5	−142.6 (3)
N1ⁱ—Cu2—N3—C4	−127.6 (2)	N1ⁱ—Cu2—N5—C5	126.3 (3)
N1—Cu2—N3—C4	52.4 (2)	N1—Cu2—N5—C5	−53.7 (3)
N3—C4—N4—C7	75.0 (4)

Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+2, −y+1/2, z; (iii) −y+5/4, x−3/4, −z+1/4; (iv) y+3/4, −x+5/4, −z+1/4.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3C···N2ⁱ	0.93	2.44	3.261 (4)	147
N5—H5C···O2^v	0.93	2.38	3.291 (8)	165
O1—H1C···O4^vi	0.85	2.48	3.149 (7)	136
O4—H4D···N2^vii	0.85	2.11	2.729 (6)	129
O4—H4E···O2^viii	0.85	2.47	3.279 (9)	159

Symmetry codes: (i) −x+2, −y+1, −z; (v) y+3/4, −x+3/4, z−1/4; (vi) −y+5/4, x+1/4, −z+5/4; (vii) x−1, y, z+1; (viii) y−1/4, −x+1/4, −z+5/4.

Experimental details

Crystal data
Chemical formula	[Cu₂Mo(CN)₈(C₁₂H₃₀N₆O₂)₂]·4H₂O
M_r	1084.08
Crystal system, space group	Tetragonal, I4₁/a
Temperature (K)	293
a, c (Å)	20.0707 (10), 15.4380 (17)
V (Å³)	6218.9 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.93
Crystal size (mm)	0.32 × 0.28 × 0.26

Data collection
Diffractometer	Bruker SMART APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.75, 0.79
No. of measured, independent and observed [I > 2σ(I)] reflections	16289, 3053, 2459
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.103, 1.06
No. of reflections	3053
No. of parameters	165
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.38

Computer programs: APEX2 (Bruker, 2004), SMART (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3C···N2ⁱ	0.93	2.44	3.261 (4)	147.3
N5—H5C···O2ⁱⁱ	0.93	2.38	3.291 (8)	164.9
O1—H1C···O4ⁱⁱⁱ	0.85	2.48	3.149 (7)	136.0
O4—H4D···N2^iv	0.85	2.11	2.729 (6)	128.9
O4—H4E···O2^v	0.85	2.47	3.279 (9)	158.9

Symmetry codes: (i) −x+2, −y+1, −z; (ii) y+3/4, −x+3/4, z−1/4; (iii) −y+5/4, x+1/4, −z+5/4; (iv) x−1, y, z+1; (v) y−1/4, −x+1/4, −z+5/4.

Acknowledgements

This work is supported by the University Natural Science Foundation of Jiangsu Province (grant No. 07KJB150030).

References

Bruker (2002). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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Volume 64| Part 12| December 2008| Page m1528

doi:10.1107/S1600536808036131

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Poly[bis­[3,10-bis­(2-hydroxyethyl)-1,3,5,8,10,12-hexa­aza­cyclo­tetra­deca­ne]tetra-μ-cyanido-tetracyanidodicopper(II)molybdenum(IV)] tetra­hydrate]

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

Poly[bis[3,10-bis(2-hydroxyethyl)-1,3,5,8,10,12-hexaazacyclotetradecane]tetra-μ-cyanido-tetracyanidodicopper(II)molybdenum(IV)] tetrahydrate]