supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

sj2512 scheme

Acta Cryst. (2008). E64, m1148-m1149    [ doi:10.1107/S1600536808023830 ]

catena-Poly[[[[mu]-cyanido-1:2[kappa]2C:N-tricyanido-1[kappa]3C-bis(ethylenediamine)-2[kappa]4N,N'-copper(II)iron(II)]-[mu]-cyanido-[kappa]2C:N-[bis(ethylenediamine-[kappa]2N,N')copper(II)]-[mu]-cyanido-[kappa]2N:C] 4.5-hydrate]

H. Liu and D. Wang

Abstract top

The asymmetric unit of the title compound, {[Cu2Fe(CN)6(C2H8N2)4]·4.5H2O}n, consists of two [Cu(C2H8N2)2]2+ cations, one [Fe(CN)6]4- anion, four water molecules and a half water molecule that lies on a twofold rotation axis. The FeII atom is coordinated by six C atoms from three terminal and three doubly bridging CN- ligands. The bridging CN- ligands connect the anion to a five-coordinate [Cu(C2H8N2)2]2+ cation and to two symmetry-related six-coordinate [Cu(C2H8N2)2]2+ cations, forming a one-dimensional polymer in the ab plane. Intermolecular hydrogen bonds connect the polymer units into a three-dimensional network.

Comment top

Hexacyanoferrate anions [Fe(CN)6]n- act as good building blocks to provide bimetallic assemblies exhibiting planar structures (Fu et al. 2005). In this paper we report the structure of the title compouund, (I), which forms linear polymer chains.

The asymmetric unit of the title compound, [Cu2(C2H8N2)4Fe(CN)64.5H2O]n, consists of two [Cu(C2H8N2]2+ cations, one [Fe(CN)6]4- anion, four water molecules and a half water molecule that lies on a two-fold rotation axis (Fig. 1). The Fe1 atom is coordinated by six nitrile C atoms from three terminal CN- ligands and three doubly bridging CN- ligands. Cu1 is coordinated by five N atoms from two chelating ethylenediamine (en) ligands and a doubly bridging CN1- ligand while Cu2 binds to six N atoms from two chelated en ligands and two doubly bridging CN- ligands (Fig. 2). The average Fe—C distance of the bridging CN1- ligands of 1.909 (6) Å (Table 1) is slightly shorter than that of the terminal CN- ligands, 1.937 Å. The average Cu—N bond distance involving the en ligands is 2.009 Å considerably shorter than the average Cu—N(nitrile) distance of 2.472 Å. These are similar to the corresponding N—Cu bonds in the compound [Cu2(C4N2S2)2(C2H8N2)2]n (Fu, et al., 2004). The coordination geometries about the Fe1 and Cu2 centers are distorted octahedral with Cu1 dispaying a distorted square-pyramidal geometry. The bridging CN- ligands connect the anion to the five coordinate Cu1 cation and to the Cu2 and Cu2i (I = x+1/2, y-1/2, z) cations to form a one dimensional polymer. In the crystal structure, the water O atoms and N atoms from the en and CN- ligands participate in intermolecular hydrogen bonds (Table 2), which further connect the polymer chains into a three-dimensional network (Fig. 3).

Related literature top

For the corresponding complex catena-poly-[bis(cyanido-C)iron(II)]-tetra (µ2cyanido-C: N)-bis[bis(ethylenediamine-N,N) cadmium(II)], see: Fu & Wang (2005). For related literature, see: Fu et al. (2004).

Experimental top

A solution (10 ml) of distilled water containing CuSO46H2O (1.0 mmol) was added slowly to aqueous mixture (20 ml)of K4[Fe(CN)6] (0.5 mmol) and NH3 (2 mmol). The mixture was stirred for 4 h and then filtered. crystals suitable for X-ray analysis were obtained by slow evaporation of a methanol/dichloromethane (1:2 v/v) solution over a period of three weeks. Elemental analysis found: C, 25.37%; H, 6.22%; N, 29.58%; calc. for C28 H82 Cu4 Fe2 N28O9: C, 25.45%; H, 6.26%; N, 29.69%.

Refinement top

Water H atoms were found in difference maps and were refined freely with isotropic displacement parameters. All other H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H = 0.97 Å and Uiso(H) = 1.2Ueq(C), N—H = 0.90 Å, and Uiso(H) = 1.2Ueq(N).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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
[Figure 1] Fig. 1. A view of the asymmetric unit of (I), with atom labels and 50% probability displacement ellipsoids.
[Figure 2] Fig. 2. The one-dimensional polymer chains of (I) with H bonds drawn as dashed lines.
[Figure 3] Fig. 3. Crystal packing of (I), showing the hydrogen-bonded interactions as dashed lines.
catena-Poly[[[µ-cyanido-1:2κ2C:N-tricyanido-1κ3C- bis(ethylenediamine)-2κ4N,N'-copper(II)iron(II)]-µ-cyanido-κ2C:N- [bis(ethylenediamine-κ2N,N')copper(II)]-µ-cyanido-κ2N:C] 4.5-hydrate] top
Crystal data top
[Cu2Fe(CN)6(C2H8N2)4]·4.5H2OF(000) = 2744
Mr = 660.56Dx = 1.555 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1697 reflections
a = 13.481 (7) Åθ = 2.3–20.2°
b = 13.497 (7) ŵ = 2.05 mm−1
c = 31.069 (15) ÅT = 298 K
β = 93.547 (8)°Block, blue
V = 5642 (5) Å30.25 × 0.15 × 0.09 mm
Z = 8
Data collection top
Bruker SMART CCD area detector
diffractometer		4993 independent reflections
Radiation source: fine-focus sealed tube2395 reflections with I > 2σ(I)
graphiteRint = 0.074
φ and ω scansθmax = 25.0°, θmin = 1.3°
Absorption correction: multi-scan
(SADABS; Bruker, 1997)		h = −16→16
Tmin = 0.628, Tmax = 0.837k = −11→16
14631 measured reflectionsl = −32→36
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)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.070H atoms treated by a mixture of independent and constrained refinement
S = 1.00 w = 1/[σ2(Fo2)]
where P = (Fo2 + 2Fc2)/3
4993 reflections(Δ/σ)max = 0.001
348 parametersΔρmax = 0.67 e Å−3
15 restraintsΔρmin = −0.47 e Å−3
Crystal data top
[Cu2Fe(CN)6(C2H8N2)4]·4.5H2OV = 5642 (5) Å3
Mr = 660.56Z = 8
Monoclinic, C2/cMo Kα radiation
a = 13.481 (7) ŵ = 2.05 mm−1
b = 13.497 (7) ÅT = 298 K
c = 31.069 (15) Å0.25 × 0.15 × 0.09 mm
β = 93.547 (8)°
Data collection top
Bruker SMART CCD area detector
diffractometer		4993 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1997)		2395 reflections with I > 2σ(I)
Tmin = 0.628, Tmax = 0.837Rint = 0.074
14631 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.047H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.070Δρmax = 0.67 e Å−3
S = 1.00Δρmin = −0.47 e Å−3
4993 reflectionsAbsolute structure: ?
348 parametersFlack parameter: ?
15 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.14883 (5)0.38885 (6)0.37321 (2)0.0446 (2)
Cu20.63210 (5)0.39053 (6)0.38794 (2)0.0494 (2)
Fe10.38981 (6)0.64597 (6)0.37999 (3)0.0328 (2)
N10.1742 (3)0.2994 (4)0.32332 (16)0.0728 (17)
H1A0.22530.25840.33050.087*
H1B0.12000.26240.31640.087*
N20.1342 (3)0.4945 (3)0.32725 (16)0.0562 (15)
H2A0.07910.53060.33070.067*
H2B0.18700.53540.32920.067*
N30.1608 (3)0.2829 (3)0.41874 (14)0.0465 (13)
H3A0.10940.24050.41530.056*
H3B0.21750.24860.41650.056*
N40.1050 (3)0.4741 (3)0.42098 (14)0.0552 (15)
H4A0.15310.51780.42890.066*
H4B0.05020.50820.41200.066*
N50.6854 (3)0.3574 (4)0.32995 (13)0.0538 (14)
H5A0.70420.41350.31700.065*
H5B0.73900.31800.33390.065*
N60.5073 (3)0.3308 (3)0.36175 (16)0.0625 (16)
H6A0.49700.27150.37390.075*
H6B0.45540.37020.36680.075*
N70.7606 (3)0.4297 (3)0.41861 (15)0.0624 (16)
H7C0.80850.38610.41280.075*
H7D0.77910.49010.40980.075*
N80.5739 (3)0.4383 (3)0.44283 (13)0.0483 (14)
H8A0.52450.48160.43640.058*
H8B0.54880.38670.45690.058*
N90.3237 (3)0.4320 (4)0.39355 (15)0.0531 (15)
N100.1843 (3)0.7038 (4)0.40890 (15)0.0539 (15)
N110.4716 (4)0.6769 (4)0.47419 (15)0.0568 (16)
N120.4435 (3)0.8605 (4)0.35978 (14)0.0488 (14)
N130.5947 (3)0.5724 (4)0.35587 (15)0.0535 (16)
N140.3119 (4)0.6286 (4)0.28505 (15)0.0665 (18)
O10.0188 (3)0.6836 (4)0.45869 (14)0.0775 (16)
O20.4258 (3)0.0620 (3)0.33942 (16)0.0716 (14)
O30.2555 (3)0.5748 (4)0.20204 (13)0.0963 (19)
O40.50000.7270 (5)0.25000.099 (2)
O50.3429 (3)0.1477 (5)0.41272 (18)0.1026 (18)
C10.1983 (5)0.3623 (6)0.2858 (2)0.091 (3)
H1C0.26610.38640.28930.109*
H1D0.19060.32480.25910.109*
C20.1274 (5)0.4455 (6)0.2852 (2)0.086 (3)
H2C0.14270.49230.26290.104*
H2D0.06040.42110.27890.104*
C30.1609 (4)0.3306 (5)0.46117 (18)0.064 (2)
H3C0.22570.35890.46890.076*
H3D0.14560.28240.48300.076*
C40.0834 (4)0.4102 (5)0.45824 (17)0.061 (2)
H4C0.01770.38130.45390.074*
H4D0.08600.44890.48460.074*
C50.6095 (5)0.3076 (6)0.3027 (2)0.106 (3)
H5C0.61120.33330.27360.127*
H5D0.62500.23750.30180.127*
C60.5141 (5)0.3190 (6)0.3164 (2)0.110 (3)
H6C0.47520.26150.30710.132*
H6D0.48400.37630.30200.132*
C70.7463 (5)0.4309 (5)0.46471 (19)0.072 (2)
H7A0.80210.46300.48020.087*
H7B0.74070.36390.47550.087*
C80.6534 (4)0.4868 (5)0.47051 (19)0.0606 (19)
H8C0.66100.55540.46200.073*
H8D0.63710.48510.50050.073*
C90.3514 (4)0.5131 (4)0.38950 (17)0.0385 (16)
C100.2612 (4)0.6829 (4)0.39777 (16)0.0361 (15)
C110.4408 (4)0.6643 (4)0.43898 (18)0.0357 (16)
C120.4243 (4)0.7784 (4)0.36780 (17)0.0343 (15)
C130.5186 (4)0.6004 (4)0.36404 (15)0.0350 (14)
C140.3402 (4)0.6327 (4)0.32031 (19)0.0421 (16)
H10.016 (4)0.718 (5)0.4802 (17)0.080*
H20.0778 (17)0.678 (4)0.4516 (17)0.080*
H30.372 (3)0.078 (3)0.3229 (15)0.080*
H40.4113 (17)−0.0018 (17)0.3443 (17)0.080*
H50.269 (4)0.598 (4)0.2280 (9)0.080*
H60.312 (2)0.575 (4)0.1913 (14)0.080*
H70.5503 (9)0.686 (2)0.249 (2)0.080*
H80.387 (3)0.173 (5)0.4315 (12)0.080*
H90.369 (4)0.145 (5)0.3890 (9)0.080*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0491 (5)0.0375 (5)0.0478 (5)−0.0015 (4)0.0080 (4)−0.0004 (4)
Cu20.0362 (5)0.0676 (7)0.0450 (5)0.0023 (4)0.0059 (4)−0.0024 (4)
Fe10.0277 (4)0.0340 (5)0.0373 (5)−0.0017 (4)0.0067 (4)−0.0016 (4)
N10.072 (4)0.060 (4)0.089 (5)−0.014 (3)0.025 (3)−0.027 (3)
N20.042 (3)0.051 (4)0.075 (4)−0.011 (3)0.007 (3)0.023 (3)
N30.028 (3)0.044 (4)0.067 (4)−0.009 (2)0.005 (3)0.005 (3)
N40.049 (3)0.048 (4)0.070 (4)−0.008 (3)0.013 (3)−0.014 (3)
N50.051 (3)0.056 (4)0.056 (4)0.013 (3)0.017 (3)0.014 (3)
N60.039 (3)0.059 (4)0.090 (4)0.011 (3)0.006 (3)−0.012 (3)
N70.037 (3)0.055 (4)0.097 (5)0.000 (3)0.017 (3)−0.020 (3)
N80.043 (3)0.051 (4)0.052 (3)0.003 (3)0.003 (3)0.011 (3)
N90.043 (3)0.039 (4)0.079 (4)−0.004 (3)0.012 (3)0.002 (3)
N100.037 (3)0.054 (4)0.073 (4)0.009 (3)0.022 (3)0.001 (3)
N110.062 (4)0.076 (5)0.032 (3)−0.014 (3)0.006 (3)−0.001 (3)
N120.043 (3)0.046 (4)0.058 (4)0.004 (3)0.008 (2)0.005 (3)
N130.029 (3)0.067 (4)0.066 (4)0.007 (3)0.020 (3)−0.005 (3)
N140.063 (4)0.099 (5)0.036 (3)−0.018 (3)−0.006 (3)−0.007 (3)
O10.062 (3)0.103 (5)0.071 (4)−0.024 (3)0.033 (3)−0.032 (3)
O20.061 (3)0.064 (4)0.089 (4)−0.001 (3)−0.003 (3)0.015 (3)
O30.064 (3)0.175 (6)0.052 (3)−0.048 (4)0.023 (3)−0.038 (3)
O40.085 (5)0.102 (7)0.116 (6)0.0000.043 (6)0.000
O50.068 (4)0.124 (5)0.115 (4)−0.002 (4)0.001 (3)−0.029 (4)
C10.094 (6)0.114 (8)0.068 (6)−0.029 (6)0.039 (5)−0.012 (5)
C20.087 (6)0.129 (9)0.041 (5)−0.038 (6)−0.010 (5)0.023 (5)
C30.056 (5)0.095 (7)0.039 (5)−0.018 (4)−0.002 (4)0.003 (4)
C40.060 (5)0.080 (6)0.046 (4)−0.020 (4)0.019 (4)−0.010 (4)
C50.058 (5)0.186 (10)0.072 (6)0.008 (6)−0.012 (5)−0.059 (6)
C60.081 (6)0.181 (10)0.068 (6)−0.022 (6)0.007 (5)−0.053 (6)
C70.060 (5)0.099 (7)0.057 (5)0.002 (4)−0.012 (4)−0.022 (4)
C80.072 (5)0.059 (5)0.054 (5)−0.008 (4)0.024 (4)−0.007 (4)
C90.022 (3)0.044 (5)0.050 (4)0.011 (3)0.004 (3)−0.010 (3)
C100.045 (4)0.028 (4)0.035 (4)−0.008 (3)0.004 (3)0.002 (3)
C110.024 (3)0.035 (4)0.050 (4)−0.003 (3)0.015 (3)0.006 (3)
C120.025 (3)0.038 (4)0.041 (4)0.009 (3)0.005 (3)−0.004 (3)
C130.044 (4)0.031 (4)0.031 (3)−0.014 (3)0.007 (3)0.007 (3)
C140.027 (4)0.043 (4)0.058 (4)−0.007 (3)0.014 (3)0.004 (4)
Geometric parameters (Å, °) top
Cu1—N41.996 (4)N8—C81.483 (6)
Cu1—N12.011 (5)N8—H8A0.9000
Cu1—N32.011 (4)N8—H8B0.9000
Cu1—N22.019 (4)N9—C91.166 (6)
Cu1—N92.472 (5)N10—C101.149 (5)
Cu2—N61.993 (4)N11—C111.158 (6)
Cu2—N71.996 (4)N12—C121.169 (6)
Cu2—N82.026 (4)N13—C131.137 (5)
Cu2—N52.030 (4)N14—C141.139 (6)
Cu2—N10i2.686 (5)O1—H10.81 (4)
Cu2—N132.686 (5)O1—H20.842 (14)
Fe1—C121.891 (6)O2—H30.888 (19)
Fe1—C91.895 (6)O2—H40.899 (18)
Fe1—C101.917 (5)O3—H50.873 (19)
Fe1—C111.933 (6)O3—H60.847 (19)
Fe1—C131.935 (6)O4—H70.879 (19)
Fe1—C141.940 (6)O5—H80.878 (19)
N1—C11.495 (7)O5—H90.839 (19)
N1—H1A0.9000C1—C21.474 (8)
N1—H1B0.9000C1—H1C0.9700
N2—C21.463 (7)C1—H1D0.9700
N2—H2A0.9000C2—H2C0.9700
N2—H2B0.9000C2—H2D0.9700
N3—C31.467 (6)C3—C41.497 (7)
N3—H3A0.9000C3—H3C0.9700
N3—H3B0.9000C3—H3D0.9700
N4—C41.487 (6)C4—H4C0.9700
N4—H4A0.9000C4—H4D0.9700
N4—H4B0.9000C5—C61.388 (7)
N5—C51.452 (7)C5—H5C0.9700
N5—H5A0.9000C5—H5D0.9700
N5—H5B0.9000C6—H6C0.9700
N6—C61.427 (7)C6—H6D0.9700
N6—H6A0.9000C7—C81.483 (7)
N6—H6B0.9000C7—H7A0.9700
N7—C71.457 (6)C7—H7B0.9700
N7—H7C0.9000C8—H8C0.9700
N7—H7D0.9000C8—H8D0.9700
N4—Cu1—N1172.59 (19)Cu2—N6—H6B109.6
N4—Cu1—N384.34 (19)H6A—N6—H6B108.1
N1—Cu1—N396.0 (2)C7—N7—Cu2107.9 (3)
N4—Cu1—N295.6 (2)C7—N7—H7C110.1
N1—Cu1—N283.9 (2)Cu2—N7—H7C110.1
N3—Cu1—N2178.96 (18)C7—N7—H7D110.1
N4—Cu1—N989.74 (17)Cu2—N7—H7D110.1
N1—Cu1—N997.67 (17)H7C—N7—H7D108.4
N3—Cu1—N987.37 (17)C8—N8—Cu2109.0 (3)
N2—Cu1—N993.67 (17)C8—N8—H8A109.9
N6—Cu2—N7171.0 (2)Cu2—N8—H8A109.9
N6—Cu2—N896.40 (19)C8—N8—H8B109.9
N7—Cu2—N883.32 (18)Cu2—N8—H8B109.9
N6—Cu2—N583.39 (19)H8A—N8—H8B108.3
N7—Cu2—N597.89 (18)C9—N9—Cu1120.0 (4)
N8—Cu2—N5173.55 (19)C13—N13—Cu2111.8 (4)
N6—Cu2—N10i85.50 (17)H1—O1—H2110 (4)
N7—Cu2—N10i85.77 (17)H3—O2—H498 (2)
N8—Cu2—N10i101.76 (16)H5—O3—H6103 (3)
N5—Cu2—N10i84.66 (16)H8—O5—H9107 (3)
N6—Cu2—N1394.80 (17)C2—C1—N1105.7 (5)
N7—Cu2—N1394.15 (17)C2—C1—H1C110.6
N8—Cu2—N1387.01 (16)N1—C1—H1C110.6
N5—Cu2—N1386.58 (16)C2—C1—H1D110.6
N10i—Cu2—N13171.15 (13)N1—C1—H1D110.6
C12—Fe1—C9177.1 (2)H1C—C1—H1D108.7
C12—Fe1—C1092.9 (2)N2—C2—C1109.2 (6)
C9—Fe1—C1086.6 (2)N2—C2—H2C109.8
C12—Fe1—C1189.5 (2)C1—C2—H2C109.8
C9—Fe1—C1193.3 (2)N2—C2—H2D109.8
C10—Fe1—C1188.2 (2)C1—C2—H2D109.8
C12—Fe1—C1390.8 (2)H2C—C2—H2D108.3
C9—Fe1—C1389.8 (2)N3—C3—C4107.4 (5)
C10—Fe1—C13176.2 (2)N3—C3—H3C110.2
C11—Fe1—C1390.6 (2)C4—C3—H3C110.2
C12—Fe1—C1488.3 (2)N3—C3—H3D110.2
C9—Fe1—C1488.9 (2)C4—C3—H3D110.2
C10—Fe1—C1492.0 (2)H3C—C3—H3D108.5
C11—Fe1—C14177.8 (2)N4—C4—C3107.1 (5)
C13—Fe1—C1489.3 (2)N4—C4—H4C110.3
C1—N1—Cu1108.4 (4)C3—C4—H4C110.3
C1—N1—H1A110.0N4—C4—H4D110.3
Cu1—N1—H1A110.0C3—C4—H4D110.3
C1—N1—H1B110.0H4C—C4—H4D108.5
Cu1—N1—H1B110.0C6—C5—N5113.8 (6)
H1A—N1—H1B108.4C6—C5—H5C108.8
C2—N2—Cu1108.1 (4)N5—C5—H5C108.8
C2—N2—H2A110.1C6—C5—H5D108.8
Cu1—N2—H2A110.1N5—C5—H5D108.8
C2—N2—H2B110.1H5C—C5—H5D107.7
Cu1—N2—H2B110.1C5—C6—N6115.6 (6)
H2A—N2—H2B108.4C5—C6—H6C108.4
C3—N3—Cu1108.4 (4)N6—C6—H6C108.4
C3—N3—H3A110.0C5—C6—H6D108.4
Cu1—N3—H3A110.0N6—C6—H6D108.4
C3—N3—H3B110.0H6C—C6—H6D107.4
Cu1—N3—H3B110.0N7—C7—C8106.9 (5)
H3A—N3—H3B108.4N7—C7—H7A110.4
C4—N4—Cu1109.0 (4)C8—C7—H7A110.4
C4—N4—H4A109.9N7—C7—H7B110.4
Cu1—N4—H4A109.9C8—C7—H7B110.4
C4—N4—H4B109.9H7A—C7—H7B108.6
Cu1—N4—H4B109.9C7—C8—N8106.9 (5)
H4A—N4—H4B108.3C7—C8—H8C110.4
C5—N5—Cu2110.1 (4)N8—C8—H8C110.4
C5—N5—H5A109.6C7—C8—H8D110.4
Cu2—N5—H5A109.6N8—C8—H8D110.4
C5—N5—H5B109.6H8C—C8—H8D108.6
Cu2—N5—H5B109.6N9—C9—Fe1176.3 (6)
H5A—N5—H5B108.2N10—C10—Fe1178.9 (5)
C6—N6—Cu2110.2 (4)N11—C11—Fe1178.9 (5)
C6—N6—H6A109.6N12—C12—Fe1178.4 (5)
Cu2—N6—H6A109.6N13—C13—Fe1178.0 (5)
C6—N6—H6B109.6N14—C14—Fe1177.4 (6)
N4—Cu1—N1—C1103.2 (16)N1—C1—C2—N254.8 (7)
N3—Cu1—N1—C1−164.2 (4)Cu1—N3—C3—C442.0 (5)
N2—Cu1—N1—C116.8 (4)Cu1—N4—C4—C339.0 (5)
N9—Cu1—N1—C1−76.1 (4)N3—C3—C4—N4−53.4 (6)
N4—Cu1—N2—C2−160.1 (4)Cu2—N5—C5—C617.3 (9)
N1—Cu1—N2—C212.5 (4)N5—C5—C6—N6−29.8 (11)
N3—Cu1—N2—C2−72 (11)Cu2—N6—C6—C527.0 (9)
N9—Cu1—N2—C2109.8 (4)Cu2—N7—C7—C8−47.8 (5)
N4—Cu1—N3—C3−16.3 (4)N7—C7—C8—N855.1 (6)
N1—Cu1—N3—C3171.1 (3)Cu2—N8—C8—C7−35.9 (6)
N2—Cu1—N3—C3−105 (11)Cu1—N9—C9—Fe1−27 (8)
N9—Cu1—N3—C373.7 (3)C12—Fe1—C9—N9−15 (11)
N1—Cu1—N4—C480.4 (17)C10—Fe1—C9—N964 (8)
N3—Cu1—N4—C4−12.9 (4)C11—Fe1—C9—N9152 (8)
N2—Cu1—N4—C4166.0 (4)C13—Fe1—C9—N9−118 (8)
N9—Cu1—N4—C4−100.3 (4)C14—Fe1—C9—N9−28 (8)
N6—Cu2—N5—C5−2.0 (5)C12—Fe1—C10—N10−146 (33)
N7—Cu2—N5—C5169.1 (5)C9—Fe1—C10—N1037 (33)
N8—Cu2—N5—C5−90.5 (17)C11—Fe1—C10—N10−57 (33)
N13—Cu2—N5—C5−97.2 (5)C13—Fe1—C10—N1016 (36)
N7—Cu2—N6—C6−111.6 (13)C14—Fe1—C10—N10126 (33)
N8—Cu2—N6—C6160.7 (5)C12—Fe1—C11—N117(26)
N5—Cu2—N6—C6−12.8 (5)C9—Fe1—C11—N11−173 (100)
N13—Cu2—N6—C673.2 (5)C10—Fe1—C11—N11−86 (26)
N6—Cu2—N7—C7−66.9 (13)C13—Fe1—C11—N1197 (26)
N8—Cu2—N7—C721.9 (4)C14—Fe1—C11—N119(30)
N5—Cu2—N7—C7−164.5 (4)C9—Fe1—C12—N1234 (23)
N13—Cu2—N7—C7108.4 (4)C10—Fe1—C12—N12−45 (20)
N6—Cu2—N8—C8179.1 (4)C11—Fe1—C12—N12−133 (20)
N7—Cu2—N8—C88.1 (4)C13—Fe1—C12—N12136 (20)
N5—Cu2—N8—C8−93.1 (17)C14—Fe1—C12—N1247 (20)
N13—Cu2—N8—C8−86.4 (4)Cu2—N13—C13—Fe141 (15)
N4—Cu1—N9—C9−66.4 (5)C12—Fe1—C13—N13122 (15)
N1—Cu1—N9—C9113.6 (5)C9—Fe1—C13—N13−61 (15)
N3—Cu1—N9—C9−150.7 (5)C10—Fe1—C13—N13−40 (17)
N2—Cu1—N9—C929.3 (5)C11—Fe1—C13—N1332 (15)
N6—Cu2—N13—C1353.0 (5)C14—Fe1—C13—N13−150 (15)
N7—Cu2—N13—C13−126.3 (5)C12—Fe1—C14—N14−3(12)
N8—Cu2—N13—C13−43.2 (5)C9—Fe1—C14—N14176 (100)
N5—Cu2—N13—C13136.1 (5)C10—Fe1—C14—N1490 (12)
Cu1—N1—C1—C2−42.4 (6)C11—Fe1—C14—N14−6(17)
Cu1—N2—C2—C1−40.4 (6)C13—Fe1—C14—N14−94 (12)
Symmetry codes: (i) x+1/2, y−1/2, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···O4ii0.902.593.316 (5)139.
N2—H2A···O2iii0.902.142.999 (6)159.
N2—H2B···N140.902.573.335 (6)144.
N3—H3B···O50.902.183.074 (7)172.
N4—H4A···N100.902.633.308 (7)133.
N5—H5A···O3iv0.902.333.214 (7)167.
N6—H6B···N90.902.173.044 (6)163.
N7—H7C···N12i0.902.553.293 (6)140.
N7—H7D···O5v0.902.293.153 (8)160.
N8—H8B···N11vi0.902.343.104 (6)143.
O1—H1···N11vii0.81 (4)2.01 (5)2.807 (6)167 (6)
O1—H2···N100.84 (1)2.04 (3)2.806 (6)150 (6)
O2—H3···O3viii0.89 (2)1.84 (3)2.697 (6)161 (4)
O2—H4···N12ix0.90 (2)1.96 (2)2.799 (7)155 (2)
O3—H5···N140.87 (2)1.88 (2)2.741 (6)170 (6)
O3—H6···N13iv0.85 (2)1.99 (2)2.787 (6)156 (5)
O4—H7···N14iv0.88 (2)2.33 (3)3.118 (6)149 (5)
O5—H8···O1i0.88 (2)1.92 (3)2.734 (7)153 (5)
O5—H9···O20.84 (2)2.09 (4)2.844 (7)150 (6)
Symmetry codes: (ii) x−1/2, y−1/2, z; (iii) x−1/2, y+1/2, z; (iv) −x+1, y, −z+1/2; (i) x+1/2, y−1/2, z; (v) x+1/2, y+1/2, z; (vi) −x+1, −y+1, −z+1; (vii) −x+1/2, −y+3/2, −z+1; (viii) −x+1/2, y−1/2, −z+1/2; (ix) x, y−1, z.
Table 1
Selected geometric parameters (Å, °) top
Cu1—N41.996 (4)Cu2—N52.030 (4)
Cu1—N12.011 (5)Cu2—N132.686 (5)
Cu1—N32.011 (4)Fe1—C121.891 (6)
Cu1—N22.019 (4)Fe1—C91.895 (6)
Cu1—N92.472 (5)Fe1—C101.917 (5)
Cu2—N61.993 (4)Fe1—C111.933 (6)
Cu2—N71.996 (4)Fe1—C131.935 (6)
Cu2—N82.026 (4)Fe1—C141.940 (6)
N4—Cu1—N1172.59 (19)N8—Cu2—N1387.01 (16)
N4—Cu1—N384.34 (19)N5—Cu2—N1386.58 (16)
N1—Cu1—N396.0 (2)C12—Fe1—C9177.1 (2)
N4—Cu1—N295.6 (2)C12—Fe1—C1092.9 (2)
N1—Cu1—N283.9 (2)C9—Fe1—C1086.6 (2)
N3—Cu1—N2178.96 (18)C12—Fe1—C1189.5 (2)
N4—Cu1—N989.74 (17)C9—Fe1—C1193.3 (2)
N1—Cu1—N997.67 (17)C10—Fe1—C1188.2 (2)
N3—Cu1—N987.37 (17)C12—Fe1—C1390.8 (2)
N2—Cu1—N993.67 (17)C9—Fe1—C1389.8 (2)
N6—Cu2—N7171.0 (2)C10—Fe1—C13176.2 (2)
N6—Cu2—N896.40 (19)C11—Fe1—C1390.6 (2)
N7—Cu2—N883.32 (18)C12—Fe1—C1488.3 (2)
N6—Cu2—N583.39 (19)C9—Fe1—C1488.9 (2)
N7—Cu2—N597.89 (18)C10—Fe1—C1492.0 (2)
N8—Cu2—N5173.55 (19)C11—Fe1—C14177.8 (2)
N6—Cu2—N1394.80 (17)C13—Fe1—C1489.3 (2)
N7—Cu2—N1394.15 (17)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···O4i0.902.593.316 (5)139.
N2—H2A···O2ii0.902.142.999 (6)159.
N2—H2B···N140.902.573.335 (6)144.
N3—H3B···O50.902.183.074 (7)172.
N4—H4A···N100.902.633.308 (7)133.
N5—H5A···O3iii0.902.333.214 (7)167.
N6—H6B···N90.902.173.044 (6)163.
N7—H7C···N12iv0.902.553.293 (6)140.
N7—H7D···O5v0.902.293.153 (8)160.
N8—H8B···N11vi0.902.343.104 (6)143.
O1—H1···N11vii0.81 (4)2.01 (5)2.807 (6)167 (6)
O1—H2···N100.84 (1)2.04 (3)2.806 (6)150 (6)
O2—H3···O3viii0.89 (2)1.84 (3)2.697 (6)161 (4)
O2—H4···N12ix0.90 (2)1.96 (2)2.799 (7)155 (2)
O3—H5···N140.87 (2)1.88 (2)2.741 (6)170 (6)
O3—H6···N13iii0.85 (2)1.99 (2)2.787 (6)156 (5)
O4—H7···N14iii0.88 (2)2.33 (3)3.118 (6)149 (5)
O5—H8···O1iv0.88 (2)1.92 (3)2.734 (7)153 (5)
O5—H9···O20.84 (2)2.09 (4)2.844 (7)150 (6)
Symmetry codes: (i) x−1/2, y−1/2, z; (ii) x−1/2, y+1/2, z; (iii) −x+1, y, −z+1/2; (iv) x+1/2, y−1/2, z; (v) x+1/2, y+1/2, z; (vi) −x+1, −y+1, −z+1; (vii) −x+1/2, −y+3/2, −z+1; (viii) −x+1/2, y−1/2, −z+1/2; (ix) x, y−1, z.
Acknowledgements top

We are grateful for financial support from the National Natural Science Foundation of China (No. 20771021), Shangdong Natural Science Foundation (No. Y2005B20).

references
References top

Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Fu, A.-Y. & Wang, D.-Q. (2005). Z. Kristallogr. New Cryst. Struct. Volume? 220.

Fu, A.-Y., Wang, D.-Q. & Sun, D.-Z. (2004). Acta Cryst. E60, m1869–m1871.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.