Crystal structures of {[Cu(Lpn)2][Fe(CN)5(NO)]·H2O}n and {[Cu(Lpn)2]3[Cr(CN)6]2·5H2O}n [where Lpn = (R)-propane-1,2-di­amine]: two heterometallic chiral cyanide-bridged coordination polymers

Sereda, O.; Stoeckli-Evans, H.

doi:10.1107/S2056989015005253

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ISSN: 2056-9890

Volume 71| Part 4| April 2015| Pages 392-397

doi:10.1107/S2056989015005253

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Crystal structures of {[Cu(Lpn)₂][Fe(CN)₅(NO)]·H₂O}_n and {[Cu(Lpn)₂]₃[Cr(CN)₆]₂·5H₂O}_n [where Lpn = (R)-propane-1,2-diamine]: two heterometallic chiral cyanide-bridged coordination polymers

Olha Sereda ^a ‡ and Helen Stoeckli-Evans ^a ^*

^aInstitute of Physics, University of Neuchâtel, Rue Emile-Argand 11, CH-2000 Neuchâtel, Switzerland
^*Correspondence e-mail: helen.stoeckli-evans@unine.ch

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 28 February 2015; accepted 14 March 2015; online 21 March 2015)

The title compounds, catena-poly[[[bis[(R)-propane-1,2-diamine-κ²N,N′]copper(II)]-μ-cyanido-κ²N:C-[tris(cyanido-κC)(nitroso-κN)iron(III)]-μ-cyanido-κ²C:N] monohydrate], {[Cu(Lpn)₂][Fe(CN)₅(NO)]·H₂O}_n, (I), and poly[[hexa-μ-cyanido-κ¹²C:N-hexacyanido-κ⁶C-hexakis[(R)-propane-1,2-diamine-κ²N,N′]dichromium(III)tricopper(II)] pentahydrate], {[Cu(Lpn)₂]₃[Cr(CN)₆]₂·5H₂O}_n, (II) [where Lpn = (R)-propane-1,2-diamine, C₃H₁₀N₂], are new chiral cyanide-bridged bimetallic coordination polymers. The asymmetric unit of compound (I) is composed of two independent cation–anion units of {[Cu(Lpn)₂][Fe(CN)₅)(NO)]} and two water molecules. The Fe^III atoms have distorted octahedral geometries, while the Cu^II atoms can be considered to be pentacoordinate. In the crystal, however, the units align to form zigzag cyanide-bridged chains propagating along [101]. Hence, the Cu^II atoms have distorted octahedral coordination spheres with extremely long semicoordination Cu—N(cyanido) bridging bonds. The chains are linked by O—H⋯N and N—H⋯N hydrogen bonds, forming two-dimensional networks parallel to (010), and the networks are linked via N—H⋯O and N—H⋯N hydrogen bonds, forming a three-dimensional framework. Compound (II) is a two-dimensional cyanide-bridged coordination polymer. The asymmetric unit is composed of two chiral {[Cu(Lpn)₂][Cr(CN)₆]}⁻ anions bridged by a chiral [Cu(Lpn)₂]²⁺ cation and five water molecules of crystallization. Both the Cr^III atoms and the central Cu^II atom have distorted octahedral geometries. The coordination spheres of the outer Cu^II atoms of the asymmetric unit can be considered to be pentacoordinate. In the crystal, these units are bridged by long semicoordination Cu—N(cyanide) bridging bonds forming a two-dimensional network, hence these Cu^II atoms now have distorted octahedral geometries. The networks, which lie parallel to (10-1), are linked via O—H⋯O, O—H⋯N, N—H⋯O and N—H⋯N hydrogen bonds involving all five non-coordinating water molecules, the cyanide N atoms and the NH₂ groups of the Lpn ligands, forming a three-dimensional framework.

Keywords: crystal structure; chiral; bimetallic; cyanide-bridged; (R)-propane-1,2-diamine; coordination polymers; two-dimensional network; three-dimensional framework; hydrogen bonding.

CCDC references: 691330; 691331

1. Chemical context

The design of multi-dimensional molecular systems is closely linked to their unique bulk physicochemical properties, such as magnetism (Kahn, 1993 ). Examples of these systems include cyanide-bridged complexes, in which a cyanidometallate anion serves as the bridging moiety in a multi-dimensional structure with a second coordination centre (Fukita et al., 1998 ; Ohba et al., 1999 ; Tanase & Reedijk, 2006 ; Zhang & Luo, 2006 ). In this context, heterometallic and chiral frameworks are of particular interest (Cui et al., 2002 ; Mironov et al., 2004 ). A chiral network would allow selective binding of chiral guests, and the presence of different types of metal ions may enable specific tuning of the electronic properties. However, only a few examples of chiral cyanide-bridged bimetallic complexes have been published so far (Coronado et al., 2003 ; Imai et al., 2004 ; Kaneko et al., 2006 ). We report herein on the synthesis and crystal structures of two new chiral cyanide-bridged heterometallic coordination polymers, (I) and (II), synthesized using the chiral ligand (R)-propane-1,2-diamine. Compound (I) is isotypic with [Cu(1,2-pn)₂][Fe(CN)₅NO]·H₂O, synthesized using the racemic form of the same ligand propane-1,2-diamine (Smékal et al., 2000 ).

2. Structural commentary

The asymmetric unit of complex (I) (Fig. 1) is composed of two independent cation–anion units of [Cu(Lpn)₂]²⁺·[Fe(CN)₅)(NO)]²⁻·H₂O. Atoms Fe1 and Fe2 have distorted octahedral geometries being coordinated by five C atoms from the cyanide ligands (two cyanido groups are bridging and two terminal) and by one N atom, N2 and N12, respectively, from the nitrosyl group. The average Fe—N distance [1.657 (14) Å] is much shorter than the Fe—C distances, which are between 1.926 (5) and 1.954 (6) Å. These values are in good agreement with those reported for other polymeric structures involving nitroprusside (Shyu et al., 1997 ; Chen et al., 1995 ). Atoms Cu1 and Cu2 are pentacoordinate. Atom Cu1 has a perfect square-pyramidal geometry with a τ value of 0 (Addison et al., 1984 ), while atom Cu2 has a distorted square-pyramidal geometry with a τ value of 0.23. The Cu—N(Lpn) bond lengths vary between 1.998 (5) and 2.026 (5) Å, while the axial bond length Cu1—N1 is 2.333 (5) Å and Cu2—N11 is 2.290 (5) Å.

Figure 1
A view of the asymmetric unit of compound (I)

, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

The asymmetric unit of complex (II) (Fig. 2) consists of two chiral {[Cu(Lpn)₂][Cr(CN)₆]}⁻ anions bridged by a chiral [Cu(Lpn)₂]²⁺ cation. There are also five water molecules of crystallization present. The coordination sphere of the central Cu^II atom, Cu3, can be described as elongated octahedral, generated by four N atoms of the Lpn ligands and two cyanide N atoms. The outer atoms Cu1 and Cu2 are pentacoordinate; atom Cu1 has a distorted square-pyramidal geometry with a τ value of 0.14 (Addison et al., 1984), while atom Cu2 has an almost perfect square-pyramidal geometry with a τ value of 0.04. The Cu—N(Lpn) bond lengths vary between 1.960 (12) and 2.020 (10) Å, which is similar to the bond lengths observed in (I) and in a copper(II) complex involving (S)-propane-1,2-diamine (Higashikawa et al., 2007 ). The axial bond lengths Cu1—N2 and Cu2—N12 are 2.540 (12) and 2.490 (12) Å, respectively, while those for Cu3 are 2.465 (9) and 2.639 (12) Å for Cu3—N1 and Cu3—N11, respectively. Each Cr^III ion has an almost regular octahedral coordination geometry. The Cr—C bond lengths are in the range 2.047 (15)–2.081 (15) Å), and the Cr—C≡N bond angles vary over a small range, 174.5 (13)–179.6 (12)°.

Figure 2
A view of the asymmetric unit of compound (II)

, showing the atom labelling. Displacement ellipsoids are drawn at the 30% probability level. Water molecules and the C-bound H atoms have been omitted for clarity.

3. Supramolecular features

In the crystal of (I), the independent bimetallic units line up to form zigzag polymer chains propagating along [101] (see Fig. 3). The bridging axial bond lengths are 2.980 (9) and 3.112 (8) Å for Cu1—N13ⁱ and Cu2—N3ⁱⁱ, respectively [symmetry codes: (i) −x + 1, y − $[{1\over 2}]$ , −z + 1; (ii) −x, y + $[{1\over 2}]$ , −z]. This axial bonding results in distorted octahedral coordination spheres for the copper(II) atoms. The extremely long semi-coordination Cu—N bonds can be attributed to the co-existence of pseudo-Jahn–Teller elongation and electrostatic interactions in the infinite one dimensional chain. A similar geometry has been found in [Cu^IIL₂][M^II(CN)₄]·2H₂O [M^II = Ni^II, Pt^II; L = trans-cyclohexane-(1R,2R)-diamine] (Akitsu & Einaga, 2006 ). Neighbouring chains are linked via O—H⋯N and N—H⋯N hydrogen bonds (Table 1), forming sheets parallel to (010). The sheets are linked via N—H⋯O and further N—H⋯N hydrogen bonds, forming a three-dimensional framework (Table 1 and Fig. 4).

Table 1
Hydrogen-bond geometry (Å, °) for (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N7—H7X⋯N15ⁱ	0.89	2.39	3.257 (8)	166
N7—H7Y⋯N14ⁱⁱ	0.89	2.12	3.008 (8)	173
N8—H8X⋯N14ⁱⁱⁱ	0.89	2.27	3.120 (8)	160
N8—H8Y⋯N15	0.89	2.45	3.209 (7)	144
N9—H9X⋯O1W	0.89	2.52	3.207 (7)	135
N9—H9Y⋯N16ⁱⁱⁱ	0.89	2.39	3.157 (7)	144
N10—H10X⋯N16ⁱⁱ	0.89	2.52	3.189 (7)	132
N10—H10Y⋯O1Wⁱ	0.89	2.11	2.962 (7)	159
N17—H17X⋯N4^iv	0.89	2.22	3.051 (8)	155
N17—H17Y⋯N5^v	0.89	2.32	3.197 (7)	169
N18—H18X⋯N5	0.89	2.37	3.224 (8)	161
N18—H18Y⋯N4^vi	0.89	2.27	3.080 (8)	151
N19—H19X⋯N6^vi	0.89	2.44	3.295 (8)	160
N19—H19Y⋯O2Wⁱ	0.89	2.30	3.142 (8)	159
N20—H20X⋯O2W	0.89	2.11	2.990 (8)	172
O1W—H1WB⋯N15	0.84 (3)	2.11 (3)	2.928 (7)	163 (6)
O2W—H2WA⋯N13	0.83 (3)	2.65 (4)	3.419 (9)	155 (6)
Symmetry codes: (i) x-1, y, z; (ii) $[-x, y-{\script{1\over 2}}, -z+1]$ ; (iii) $[-x+1, y-{\script{1\over 2}}, -z+1]$ ; (iv) $[-x+1, y+{\script{1\over 2}}, -z]$ ; (v) x+1, y, z; (vi) $[-x, y+{\script{1\over 2}}, -z]$ .

Figure 3
A partial view along the a axis of the crystal packing of compound (I)

, showing the one-dimensional polymer structure (Cu atoms are green, Fe atoms are orange, and bridging Cu—N bonds are thin dashed cyan lines). Water molecules and the C-bound H atoms have been omitted for clarity.

Figure 4
Crystal packing of compound (I)

, viewed along the a axis. Hydrogen bonds are shown as dashed lines (see Table 1

for details) and C-bound H atoms have been omitted for clarity.

In the crystal of (II), the cation-anion units are linked to form two-dimensional networks lying parallel to (10 $[\overline{1}]$ ) (see Fig. 5). The bridging Cu—N(cyanido) bond lengths, Cu1—N3ⁱⁱⁱ and Cu2—N13^iv, are 2.698 (14) and 2.860 (14) Å, respectively [symmetry codes: (iii) −x + 1, y − $[{1\over 2}]$ , −z; (iv) −x + 2, y + $[{1\over 2}]$ , −z + 1]. Thus, as for complex (I), atoms Cu1 and Cu2 have octahedral coordination spheres with a strong pseudo-Jahn–Teller effect. Closely related two-dimensional bimetallic systems have been found in iron(III) analogues, where [Fe(CN)₆]³⁻ anions binds to three adjacent nickel atoms (Kou et al., 1999 , 2000 ). The two-dimensional networks of (II) (Fig. 5) are linked by a series of O—H⋯O, O—H⋯N, N—H⋯O and N—H⋯N hydrogen bonds, involving the water molecules, the cyanide N atoms and the NH₂ groups of the Lpn ligands, forming a three-dimensional framework (Fig. 6 and Table 2).

Table 2
Hydrogen-bond geometry (Å, °) for (II)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4X⋯N19ⁱ	0.89	2.27	3.153 (16)	171
N5—H5X⋯O5WAⁱⁱ	0.89	2.24	3.04 (4)	150
N5—H5X⋯O5WBⁱⁱ	0.89	2.22	2.89 (3)	133
N5—H5Y⋯O4W	0.89	2.50	3.177 (17)	133
N6—H6X⋯N18ⁱ	0.89	2.56	3.373 (17)	152
N7—H7X⋯N1ⁱⁱ	0.89	2.49	3.219 (15)	139
N14—H14Y⋯N9ⁱⁱⁱ	0.89	2.62	3.360 (16)	142
N15—H15Y⋯N11^iv	0.89	2.27	3.156 (15)	177
N16—H16Y⋯O1W^v	0.89	2.32	3.159 (16)	158
N17—H17X⋯O2W	0.89	2.33	3.132 (18)	150
N17—H17Y⋯N13^iv	0.89	2.69	3.166 (19)	115
N17—H17Y⋯O4W^vi	0.89	2.60	3.361 (18)	145
N21—H21X⋯O5WA	0.89	2.16	3.04 (5)	170
N21—H21X⋯O5WB	0.89	2.02	2.88 (3)	163
N21—H21Y⋯N12	0.89	2.51	3.376 (17)	164
N22—H22X⋯N18ⁱ	0.89	2.43	3.262 (17)	155
N23—H23X⋯N20	0.89	2.68	3.445 (18)	144
N23—H23Y⋯N9ⁱⁱⁱ	0.89	2.20	3.086 (17)	172
N24—H24Y⋯O3W	0.89	2.09	2.969 (18)	167
O1W—H1WA⋯N19^vii	0.85 (3)	2.14 (5)	2.972 (16)	167 (16)
O1W—H1WB⋯N20	0.84 (3)	2.00 (5)	2.822 (15)	164 (14)
O2W—H2WA⋯N10^viii	0.85 (3)	2.09 (10)	2.811 (17)	143 (15)
O2W—H2WB⋯O5WA	0.85 (3)	1.78 (9)	2.56 (6)	153 (16)
O2W—H2WB⋯O5WB	0.85 (3)	2.01 (8)	2.85 (7)	169 (20)
O3W—H3WA⋯N18ⁱ	0.85 (3)	2.27 (14)	2.982 (19)	142 (20)
O3W—H3WB⋯O1W^ix	0.85 (3)	1.92 (10)	2.712 (17)	156 (21)
O4W—H4WA⋯N10ⁱⁱ	0.84 (3)	2.53 (18)	3.104 (17)	126 (18)
O4W—H4WB⋯N8^x	0.84 (3)	2.16 (13)	2.883 (16)	145 (19)
Symmetry codes: (i) $[-x+2, y-{\script{1\over 2}}, -z+1]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z]$ ; (iii) $[-x+1, y+{\script{1\over 2}}, -z]$ ; (iv) $[-x+2, y+{\script{1\over 2}}, -z+1]$ ; (v) x+1, y, z; (vi) x+1, y+1, z; (vii) x-1, y, z; (viii) $[-x+2, y+{\script{1\over 2}}, -z]$ ; (ix) $[-x+1, y-{\script{1\over 2}}, -z+1]$ ; (x) $[-x, y-{\script{1\over 2}}, -z]$ .

Figure 5
A partial view approximately along [101] of the crystal packing of compound (II)

, showing the two-dimensional polymer structure (Cu atoms are green, Cr atoms are violet, and bridging Cu—N bonds are thin dashed cyan lines). Water molecules and the C-bound H atoms have been omitted for clarity.

Figure 6
Crystal packing of compound (II)

, viewed along the a axis. Hydrogen bonds are shown as dashed lines (see Table 2

for details) and C-bound H atoms have been omitted for clarity.

4. Database survey

A search of the Cambridge Structural Database (Version 5.36, last update November 2014; Groom & Allen, 2014 ) gave 49 hits for bimetallic cyanide-bridged complexes involving transition metals and the ligand propane-1,2-diamine. Of these, only two complexes involved (R)-propane-1,2-diamine, viz. catena-[tris(μ₂-cyanido)cyanido[(R)-1,2-diaminopropane]copper(II)nickel(II) hemihydrate clathrate] (IZEPOS; Imai et al., 2003 ) and catena-[heptadecakis(μ₂-cyanido-κ²C:N)tetraaquapentadecacyanidohexakis[(R)-propane-1,2-diamine-κ²N,N′]hexacopper(II)tetratungsten(V) hydrate] (YIMBEC; Higashikawa et al., 2007). Two complexes involved (S)-propane-1,2-diamine, viz. catena-[potassium (S)-1-amino-2-ammoniopropane tetrakis(μ₂-cyanido)dicyanido[(S)-1,2-diaminopropane-κ²N,N′]chromiummanganese(II) (S)-1,2-diaminopropane] (IDEBOI; Inoue et al., 2001 ) and catena-[heptadecakis(μ₂-cyanido-κ²C:N)tetraaquapentadecacyanidohexakis[(S)-propane-1,2-diamine-κ²N,N′]hexacopper(II)tetratungsten(V) hydrate] (YIMBAY; Higashikawa et al., 2007). They were studied principally for their magnetic properties, compound IDEBOI being a ferrimagnet, while the other three compounds have one- or two-dimensional antiferromagnetic properties.

5. Synthesis and crystallization

Compound (I): (R)-propane-1,2-diamine (Lpn) was synthesized according to a reported procedure (Bernauer, 1971 ). The pH of an aqueous solution of Lpn·HCl (0.1 mmol in 1 ml of water) was adjusted to 7–8 by the addition of an aqueous solution of KOH (0.12 mmol in 0.3 ml of water). To this mixture, a solution of CuSO₄·5H₂O (0.1 mmol) in 0.8 ml of water was added under an argon atmosphere. A glass tube (ca 8 mm diameter, ca 20 cm long) was charged with this solution, and a mixture of methanol and H₂O (1:2, 1.5 ml) was gently added as a buffer layer. A solution of Na₂[Fe(CN)₅NO] (0.07 mmol) in methanol/H₂O (1:1, 1 ml) was then added carefully as a third layer under an argon atmosphere, and then the tube was sealed. Crystals of complex (I) grew as violet blocks after several weeks. Elemental analysis for C₁₁H₂₂N₁₀CuFeO₂, found: C, 29.86; H, 5.07; N, 31.93%. calc: C, 29.64; H, 4.97 N, 31.42%.

Compound (II): Dark-blue block-like crystals of compound (II) were prepared in a similar manner to those of (I), but this time using K₃[Cr(CN)₆] instead of Na₂[Fe(CN)₅NO]. Elemental analysis for C₃₀H₇₀N₂₄Cu₃Cr₂O₅, found: C, 30.87; H, 5.80; N, 28.41%. calc: C, 31.56; H, 6.18 N, 29.44%.

6. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 3. For both compounds, the water molecule H atoms were located in difference Fourier maps and refined with distance restraints of O—H = 0.84 (2) Å and with U_iso(H) = 1.5U_eq(O). The N- and C-bound H atoms were included in calculated positions and treated as riding atoms: N—H = 0.89 Å, C—H = 0.98–1.00 Å with U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(N,C) for other H atoms. It was not possible to locate the H atoms of the disordered water molecule, OW5A/OW5B, in compound (II).

Table 3
Experimental details

	(I)	(II)
Crystal data
Chemical formula	[CuFe(C₃H₁₀N₂)₂(CN)₅(NO)]·H₂O	[Cr₂Cu₃(CN)₁₂(C₃H₁₀N₂)₆]·5H₂O
M_r	445.77	1141.72
Crystal system, space group	Monoclinic, P2₁	Monoclinic, P2₁
Temperature (K)	173	173
a, b, c (Å)	6.7987 (3), 17.891 (1), 15.7161 (8)	10.1474 (10), 17.6136 (10), 15.5376 (14)
β (°)	100.482 (4)	103.973 (11)
V (Å³)	1879.73 (17)	2694.9 (4)
Z	4	2
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	1.93	1.61
Crystal size (mm)	0.45 × 0.38 × 0.35	0.40 × 0.30 × 0.30

Data collection
Diffractometer	Stoe IPDS 2	Stoe IPDS 2
Absorption correction	Multi-scan (MULABS in PLATON; Spek, 2009 )	Multi-scan (MULABS in PLATON; Spek, 2009)
T_min, T_max	0.572, 0.740	0.583, 0.678
No. of measured, independent and observed [I > 2σ(I)] reflections	22802, 9961, 8537	21461, 10308, 4948
R_int	0.033	0.085
(sin θ/λ)_max (Å⁻¹)	0.688	0.620

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.078, 1.03	0.052, 0.131, 0.79
No. of reflections	9961	10308
No. of parameters	467	594
No. of restraints	7	14
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.44	0.61, −1.05
Absolute structure	Flack x determined using 3691 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 ).	Flack x determined using 1754 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013)
Absolute structure parameter	0.038 (15)	0.00 (3)
Computer programs: X-AREA and X-RED32 (Stoe & Cie, 2009 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), PLATON (Spek, 2009), Mercury (Macrae et al., 2008 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC references: 691330; 691331

Crystal structure: contains datablocks I, II, Global. DOI: 10.1107/S2056989015005253/hb7374sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015005253/hb7374Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S2056989015005253/hb7374IIsup3.hkl

checkCIF report

Computing details top

For both compounds, data collection: X-AREA (Stoe & Cie, 2009); cell refinement: X-AREA (Stoe & Cie, 2009); data reduction: X-RED32 (Stoe & Cie, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

(I) catena-Poly[[[bis[(R)-propane-1,2-diamine-κ²N,N']copper(II)]-µ-cyanido-κ²N:C-[tris(cyanido-κC)(nitroso-κN)iron(III)]-µ-cyanido-κ²C:N] monohydrate] top

Crystal data top

[CuFe(C₃H₁₀N₂)₂(CN)₅(NO)]·H₂O	F(000) = 916
M_r = 445.77	D_x = 1.575 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 6.7987 (3) Å	Cell parameters from 22904 reflections
b = 17.891 (1) Å	θ = 1.8–29.3°
c = 15.7161 (8) Å	µ = 1.93 mm⁻¹
β = 100.482 (4)°	T = 173 K
V = 1879.73 (17) Å³	Plate, violet
Z = 4	0.45 × 0.38 × 0.35 mm

Data collection top

Stoe IPDS 2 diffractometer	9961 independent reflections
Radiation source: fine-focus sealed tube	8537 reflections with I > 2σ(I)
Plane graphite monochromator	R_int = 0.033
φ + ω scans	θ_max = 29.3°, θ_min = 1.7°
Absorption correction: multi-scan (MULABS in PLATON; Spek, 2009)	h = −8→9
T_min = 0.572, T_max = 0.740	k = −24→24
22802 measured reflections	l = −21→21

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.078	w = 1/[σ²(F_o²) + (0.0453P)² + 0.0779P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
9961 reflections	Δρ_max = 0.55 e Å⁻³
467 parameters	Δρ_min = −0.44 e Å⁻³
7 restraints	Absolute structure: Flack x determined using 3691 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013).
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.038 (15)

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0.10706 (10)	0.11302 (3)	0.41868 (5)	0.02243 (16)
Fe1	0.07542 (12)	0.24094 (3)	0.11676 (5)	0.01767 (16)
O1	0.4628 (7)	0.2972 (2)	0.1620 (3)	0.0346 (11)
N1	0.0460 (9)	0.1979 (3)	0.3043 (4)	0.0298 (12)
N2	0.3065 (8)	0.2752 (2)	0.1432 (3)	0.0231 (10)
N3	−0.3427 (9)	0.1681 (4)	0.0694 (5)	0.0452 (16)
N4	0.2137 (9)	0.0800 (3)	0.0924 (5)	0.0362 (14)
N5	−0.1151 (9)	0.3962 (3)	0.1278 (4)	0.0329 (12)
N6	0.0371 (9)	0.2626 (3)	−0.0800 (4)	0.0387 (12)
N7	−0.0285 (8)	0.1791 (3)	0.4932 (4)	0.0295 (11)
H7X	−0.1059	0.2120	0.4603	0.035*
H7Y	−0.1057	0.1516	0.5210	0.035*
N8	0.3547 (7)	0.1695 (2)	0.4694 (4)	0.0257 (10)
H8X	0.4323	0.1415	0.5087	0.031*
H8Y	0.4234	0.1817	0.4283	0.031*
N9	0.2476 (8)	0.0400 (3)	0.3514 (3)	0.0279 (10)
H9X	0.2753	0.0621	0.3042	0.033*
H9Y	0.3622	0.0253	0.3839	0.033*
N10	−0.1344 (8)	0.0507 (3)	0.3756 (4)	0.0317 (11)
H10X	−0.1620	0.0221	0.4183	0.038*
H10Y	−0.2395	0.0800	0.3574	0.038*
C1	0.0529 (8)	0.2162 (3)	0.2339 (4)	0.0215 (11)
C2	−0.1916 (9)	0.1970 (3)	0.0875 (4)	0.0253 (12)
C3	0.1650 (8)	0.1403 (3)	0.1026 (4)	0.0233 (12)
C4	−0.0513 (9)	0.3374 (3)	0.1251 (4)	0.0246 (12)
C5	0.0524 (9)	0.2554 (3)	−0.0071 (4)	0.0278 (12)
C6	0.1233 (9)	0.2186 (3)	0.5568 (3)	0.0363 (11)
H6	0.1732	0.1842	0.6061	0.044*
C7	0.2936 (7)	0.2377 (2)	0.5113 (3)	0.0310 (9)
H7A	0.2510	0.2768	0.4672	0.037*
H7B	0.4079	0.2573	0.5536	0.037*
C8	0.0405 (14)	0.2889 (4)	0.5915 (6)	0.058 (2)
H8A	−0.0820	0.2766	0.6131	0.087*
H8B	0.0102	0.3259	0.5450	0.087*
H8C	0.1398	0.3094	0.6388	0.087*
C9	0.1164 (7)	−0.0257 (2)	0.3268 (3)	0.0310 (9)
H9	0.1262	−0.0588	0.3786	0.037*
C10	−0.0953 (7)	0.0037 (3)	0.3051 (4)	0.0341 (10)
H10A	−0.1128	0.0330	0.2508	0.041*
H10B	−0.1908	−0.0386	0.2964	0.041*
C11	0.1796 (12)	−0.0705 (4)	0.2547 (5)	0.0423 (15)
H11A	0.3156	−0.0895	0.2739	0.063*
H11B	0.1765	−0.0384	0.2039	0.063*
H11C	0.0876	−0.1126	0.2396	0.063*
Cu2	0.39302 (11)	0.55505 (3)	0.08355 (5)	0.02290 (16)
Fe2	0.41932 (12)	0.43450 (3)	0.38348 (5)	0.01729 (16)
O2	0.0342 (6)	0.3768 (2)	0.3377 (3)	0.0317 (10)
N11	0.4582 (9)	0.4728 (3)	0.1969 (4)	0.0273 (11)
N12	0.1918 (7)	0.4003 (2)	0.3562 (3)	0.0191 (9)
N13	0.8371 (9)	0.5054 (3)	0.4342 (4)	0.0370 (13)
N14	0.2910 (8)	0.5974 (3)	0.4029 (4)	0.0330 (12)
N15	0.6236 (9)	0.2807 (3)	0.3783 (4)	0.0333 (13)
N16	0.4194 (8)	0.4211 (3)	0.5782 (4)	0.0325 (11)
N17	0.5330 (7)	0.4883 (3)	0.0108 (3)	0.0251 (10)
H17X	0.5716	0.5147	−0.0313	0.030*
H17Y	0.6413	0.4685	0.0433	0.030*
N18	0.1419 (8)	0.5031 (3)	0.0242 (4)	0.0304 (12)
H18X	0.0998	0.4716	0.0609	0.036*
H18Y	0.0454	0.5363	0.0069	0.036*
N19	0.2644 (9)	0.6247 (3)	0.1572 (4)	0.0346 (12)
H19X	0.1798	0.6553	0.1241	0.041*
H19Y	0.1969	0.5989	0.1908	0.041*
N20	0.6299 (9)	0.6241 (3)	0.1114 (4)	0.0320 (11)
H20X	0.7298	0.6010	0.1460	0.038*
H20Y	0.6719	0.6371	0.0631	0.038*
C12	0.4471 (9)	0.4562 (3)	0.2656 (4)	0.0222 (12)
C13	0.6835 (10)	0.4773 (3)	0.4159 (4)	0.0252 (12)
C14	0.3364 (9)	0.5368 (3)	0.3945 (4)	0.0242 (12)
C15	0.5529 (9)	0.3388 (3)	0.3807 (4)	0.0205 (11)
C16	0.4259 (8)	0.4240 (3)	0.5064 (4)	0.0231 (11)
C17	0.3943 (8)	0.4284 (2)	−0.0270 (4)	0.0328 (10)
H17	0.3918	0.3890	0.0180	0.039*
C18	0.1901 (8)	0.4623 (3)	−0.0496 (3)	0.0361 (10)
H18A	0.1852	0.4967	−0.0992	0.043*
H18B	0.0898	0.4224	−0.0668	0.043*
C19	0.4588 (15)	0.3922 (4)	−0.1060 (6)	0.055 (2)
H19A	0.4664	0.4306	−0.1498	0.082*
H19B	0.3608	0.3541	−0.1302	0.082*
H19C	0.5903	0.3689	−0.0885	0.082*
C20	0.4301 (9)	0.6681 (3)	0.2113 (3)	0.0406 (11)
H20	0.5033	0.6338	0.2565	0.049*
C21	0.5683 (9)	0.6910 (3)	0.1547 (4)	0.0433 (13)
H21A	0.6871	0.7156	0.1892	0.052*
H21B	0.5018	0.7271	0.1110	0.052*
C22	0.3594 (13)	0.7349 (4)	0.2563 (6)	0.053 (2)
H22A	0.2714	0.7181	0.2955	0.080*
H22B	0.2858	0.7690	0.2131	0.080*
H22C	0.4751	0.7609	0.2897	0.080*
O1W	0.5517 (7)	0.1452 (3)	0.2726 (4)	0.0378 (11)
H1WA	0.630 (9)	0.142 (3)	0.239 (4)	0.057*
H1WB	0.568 (10)	0.189 (2)	0.293 (4)	0.057*
O2W	0.9350 (8)	0.5353 (2)	0.2311 (3)	0.0369 (11)
H2WA	0.953 (10)	0.526 (3)	0.284 (2)	0.055*
H2WB	0.890 (10)	0.576 (2)	0.219 (4)	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0191 (3)	0.0216 (3)	0.0265 (4)	0.0003 (2)	0.0040 (3)	0.0021 (3)
Fe1	0.0175 (4)	0.0162 (3)	0.0195 (4)	−0.0007 (3)	0.0038 (3)	−0.0003 (3)
O1	0.029 (2)	0.0278 (19)	0.046 (3)	−0.0116 (17)	0.002 (2)	−0.0036 (18)
N1	0.034 (3)	0.026 (2)	0.031 (3)	0.005 (2)	0.008 (2)	0.006 (2)
N2	0.028 (3)	0.0141 (17)	0.027 (3)	−0.0008 (17)	0.005 (2)	−0.0002 (17)
N3	0.028 (3)	0.050 (3)	0.059 (4)	−0.015 (3)	0.012 (3)	−0.011 (3)
N4	0.032 (3)	0.023 (2)	0.056 (4)	−0.0056 (19)	0.013 (3)	−0.013 (2)
N5	0.032 (3)	0.027 (2)	0.042 (3)	0.0061 (19)	0.012 (2)	0.003 (2)
N6	0.041 (3)	0.049 (3)	0.026 (2)	−0.007 (2)	0.0034 (19)	−0.0001 (19)
N7	0.031 (3)	0.026 (2)	0.035 (3)	−0.0009 (19)	0.015 (2)	0.002 (2)
N8	0.021 (2)	0.023 (2)	0.033 (3)	0.0003 (17)	0.005 (2)	0.0030 (18)
N9	0.032 (2)	0.0208 (18)	0.032 (2)	0.0047 (16)	0.0090 (19)	0.0027 (16)
N10	0.027 (2)	0.028 (2)	0.037 (3)	−0.0066 (18)	−0.001 (2)	0.0047 (19)
C1	0.018 (3)	0.018 (2)	0.029 (3)	0.0020 (18)	0.005 (2)	0.002 (2)
C2	0.019 (3)	0.027 (2)	0.031 (3)	0.0014 (19)	0.008 (2)	−0.004 (2)
C3	0.014 (2)	0.022 (2)	0.035 (3)	−0.0017 (18)	0.010 (2)	−0.007 (2)
C4	0.027 (3)	0.021 (2)	0.025 (3)	−0.001 (2)	0.004 (2)	−0.0014 (19)
C5	0.032 (3)	0.025 (2)	0.026 (3)	−0.0048 (19)	0.006 (2)	−0.0023 (19)
C6	0.052 (3)	0.031 (2)	0.029 (2)	−0.009 (2)	0.013 (2)	−0.0021 (18)
C7	0.035 (2)	0.0229 (18)	0.036 (2)	−0.0059 (16)	0.0075 (19)	−0.0023 (17)
C8	0.072 (5)	0.048 (4)	0.067 (5)	−0.018 (3)	0.044 (4)	−0.021 (3)
C9	0.041 (2)	0.0195 (17)	0.030 (2)	0.0031 (16)	−0.0007 (18)	0.0028 (15)
C10	0.027 (2)	0.032 (2)	0.040 (3)	0.0008 (17)	−0.003 (2)	−0.0026 (19)
C11	0.050 (3)	0.036 (3)	0.036 (3)	0.011 (2)	−0.002 (3)	−0.008 (2)
Cu2	0.0230 (4)	0.0224 (3)	0.0236 (4)	0.0011 (2)	0.0049 (3)	0.0016 (3)
Fe2	0.0186 (4)	0.0160 (3)	0.0179 (4)	−0.0002 (3)	0.0050 (3)	−0.0009 (3)
O2	0.016 (2)	0.035 (2)	0.042 (3)	−0.0022 (16)	0.0003 (19)	−0.0019 (19)
N11	0.034 (3)	0.026 (2)	0.023 (3)	0.006 (2)	0.006 (2)	0.0050 (19)
N12	0.021 (2)	0.0192 (18)	0.018 (2)	0.0023 (16)	0.0054 (19)	0.0003 (16)
N13	0.030 (3)	0.040 (3)	0.041 (3)	−0.006 (2)	0.004 (3)	−0.006 (2)
N14	0.031 (3)	0.026 (2)	0.044 (3)	0.0030 (19)	0.013 (2)	−0.003 (2)
N15	0.040 (3)	0.024 (2)	0.039 (3)	0.0061 (19)	0.015 (3)	0.005 (2)
N16	0.035 (2)	0.036 (2)	0.028 (2)	−0.0027 (17)	0.0111 (19)	−0.0032 (16)
N17	0.024 (2)	0.026 (2)	0.027 (2)	0.0036 (18)	0.008 (2)	0.0051 (18)
N18	0.025 (3)	0.032 (2)	0.032 (3)	−0.0036 (19)	−0.001 (2)	0.009 (2)
N19	0.042 (3)	0.026 (2)	0.039 (3)	0.0089 (18)	0.016 (2)	0.0073 (18)
N20	0.032 (3)	0.027 (2)	0.036 (3)	−0.0015 (17)	0.004 (2)	0.0051 (18)
C12	0.029 (3)	0.0151 (19)	0.022 (3)	0.0019 (19)	0.005 (2)	0.0004 (19)
C13	0.030 (3)	0.024 (2)	0.022 (3)	−0.006 (2)	0.008 (2)	−0.002 (2)
C14	0.029 (3)	0.022 (2)	0.022 (3)	−0.003 (2)	0.006 (2)	−0.0006 (19)
C15	0.021 (3)	0.023 (2)	0.019 (3)	0.0004 (18)	0.009 (2)	0.0044 (18)
C16	0.024 (2)	0.022 (2)	0.024 (3)	−0.0032 (16)	0.006 (2)	−0.0024 (17)
C17	0.043 (3)	0.0188 (19)	0.038 (3)	0.0012 (17)	0.010 (2)	0.0024 (17)
C18	0.042 (2)	0.031 (2)	0.032 (2)	−0.0077 (19)	−0.003 (2)	0.0015 (18)
C19	0.082 (6)	0.039 (3)	0.048 (4)	0.003 (3)	0.022 (4)	−0.016 (3)
C20	0.061 (3)	0.028 (2)	0.032 (2)	0.007 (2)	0.005 (2)	−0.0031 (19)
C21	0.058 (3)	0.022 (2)	0.043 (3)	−0.005 (2)	−0.008 (3)	0.0010 (19)
C22	0.066 (5)	0.044 (3)	0.050 (4)	0.013 (3)	0.009 (3)	−0.005 (3)
O1W	0.028 (2)	0.038 (2)	0.047 (3)	0.0050 (17)	0.005 (2)	0.0024 (19)
O2W	0.036 (2)	0.0306 (19)	0.042 (3)	0.0019 (16)	0.002 (2)	−0.0006 (17)

Geometric parameters (Å, º) top

Cu1—N10	1.998 (5)	Cu2—N20	2.013 (6)
Cu1—N8	2.001 (5)	Cu2—N18	2.017 (5)
Cu1—N7	2.003 (5)	Cu2—N11	2.290 (5)
Cu1—N9	2.026 (5)	Cu2—N3ⁱⁱ	3.112 (8)
Cu1—N1	2.333 (5)	Fe2—N12	1.646 (5)
Cu1—N13ⁱ	2.980 (9)	Fe2—C14	1.933 (5)
Fe1—N2	1.667 (5)	Fe2—C13	1.933 (6)
Fe1—C3	1.926 (5)	Fe2—C16	1.933 (6)
Fe1—C1	1.927 (6)	Fe2—C12	1.936 (6)
Fe1—C5	1.941 (6)	Fe2—C15	1.942 (5)
Fe1—C4	1.945 (5)	O2—N12	1.139 (6)
Fe1—C2	1.954 (6)	N11—C12	1.135 (8)
O1—N2	1.121 (6)	N13—C13	1.148 (8)
N1—C1	1.162 (8)	N14—C14	1.141 (8)
N3—C2	1.139 (8)	N15—C15	1.150 (7)
N4—C3	1.148 (7)	N16—C16	1.139 (8)
N5—C4	1.141 (7)	N17—C17	1.478 (7)
N6—C5	1.140 (8)	N17—H17X	0.8900
N7—C6	1.479 (7)	N17—H17Y	0.8900
N7—H7X	0.8900	N18—C18	1.457 (8)
N7—H7Y	0.8900	N18—H18X	0.8900
N8—C7	1.482 (6)	N18—H18Y	0.8900
N8—H8X	0.8900	N19—C20	1.498 (8)
N8—H8Y	0.8900	N19—H19X	0.8900
N9—C9	1.484 (6)	N19—H19Y	0.8900
N9—H9X	0.8900	N20—C21	1.475 (8)
N9—H9Y	0.8900	N20—H20X	0.8900
N10—C10	1.454 (8)	N20—H20Y	0.8900
N10—H10X	0.8900	C17—C18	1.497 (7)
N10—H10Y	0.8900	C17—C19	1.534 (9)
C6—C7	1.506 (7)	C17—H17	1.0000
C6—C8	1.519 (9)	C18—H18A	0.9900
C6—H6	1.0000	C18—H18B	0.9900
C7—H7A	0.9900	C19—H19A	0.9800
C7—H7B	0.9900	C19—H19B	0.9800
C8—H8A	0.9800	C19—H19C	0.9800
C8—H8B	0.9800	C20—C21	1.465 (8)
C8—H8C	0.9800	C20—C22	1.513 (9)
C9—C10	1.511 (6)	C20—H20	1.0000
C9—C11	1.512 (8)	C21—H21A	0.9900
C9—H9	1.0000	C21—H21B	0.9900
C10—H10A	0.9900	C22—H22A	0.9800
C10—H10B	0.9900	C22—H22B	0.9800
C11—H11A	0.9800	C22—H22C	0.9800
C11—H11B	0.9800	O1W—H1WA	0.82 (3)
C11—H11C	0.9800	O1W—H1WB	0.84 (3)
Cu2—N19	2.006 (6)	O2W—H2WA	0.83 (3)
Cu2—N17	2.009 (5)	O2W—H2WB	0.80 (3)

N10—Cu1—N8	175.5 (2)	N19—Cu2—N20	84.8 (2)
N10—Cu1—N7	95.2 (2)	N17—Cu2—N20	92.6 (2)
N8—Cu1—N7	85.0 (2)	N19—Cu2—N18	97.6 (3)
N10—Cu1—N9	84.3 (2)	N17—Cu2—N18	84.9 (2)
N8—Cu1—N9	95.2 (2)	N20—Cu2—N18	163.6 (2)
N7—Cu1—N9	175.3 (2)	N19—Cu2—N11	89.6 (2)
N10—Cu1—N1	94.7 (2)	N17—Cu2—N11	90.9 (2)
N8—Cu1—N1	89.8 (2)	N20—Cu2—N11	101.0 (2)
N7—Cu1—N1	91.7 (2)	N18—Cu2—N11	95.2 (2)
N9—Cu1—N1	93.0 (2)	N12—Fe2—C14	95.8 (2)
N2—Fe1—C3	94.0 (2)	N12—Fe2—C13	178.5 (2)
N2—Fe1—C1	94.7 (3)	C14—Fe2—C13	82.7 (3)
C3—Fe1—C1	88.7 (3)	N12—Fe2—C16	94.3 (2)
N2—Fe1—C5	95.8 (3)	C14—Fe2—C16	87.5 (2)
C3—Fe1—C5	88.8 (3)	C13—Fe2—C16	85.6 (3)
C1—Fe1—C5	169.4 (2)	N12—Fe2—C12	94.3 (2)
N2—Fe1—C4	93.7 (2)	C14—Fe2—C12	88.7 (2)
C3—Fe1—C4	172.2 (3)	C13—Fe2—C12	85.7 (3)
C1—Fe1—C4	91.5 (2)	C16—Fe2—C12	170.9 (2)
C5—Fe1—C4	89.6 (3)	N12—Fe2—C15	95.0 (2)
N2—Fe1—C2	177.8 (2)	C14—Fe2—C15	169.2 (3)
C3—Fe1—C2	84.1 (2)	C13—Fe2—C15	86.5 (2)
C1—Fe1—C2	84.3 (3)	C16—Fe2—C15	90.6 (2)
C5—Fe1—C2	85.2 (3)	C12—Fe2—C15	91.6 (2)
C4—Fe1—C2	88.2 (2)	C12—N11—Cu2	150.5 (5)
C1—N1—Cu1	152.2 (5)	O2—N12—Fe2	179.6 (5)
O1—N2—Fe1	178.7 (5)	C17—N17—Cu2	109.0 (3)
C6—N7—Cu1	109.8 (4)	C17—N17—H17X	109.9
C6—N7—H7X	110.1	Cu2—N17—H17X	109.9
Cu1—N7—H7X	109.6	C17—N17—H17Y	110.0
C6—N7—H7Y	109.6	Cu2—N17—H17Y	109.8
Cu1—N7—H7Y	109.6	H17X—N17—H17Y	108.2
H7X—N7—H7Y	108.2	C18—N18—Cu2	107.7 (4)
C7—N8—Cu1	108.0 (3)	C18—N18—H18X	110.0
C7—N8—H8X	109.6	Cu2—N18—H18X	109.8
Cu1—N8—H8X	109.9	C18—N18—H18Y	110.5
C7—N8—H8Y	110.4	Cu2—N18—H18Y	110.4
Cu1—N8—H8Y	110.4	H18X—N18—H18Y	108.4
H8X—N8—H8Y	108.5	C20—N19—Cu2	106.7 (4)
C9—N9—Cu1	109.2 (4)	C20—N19—H19X	110.6
C9—N9—H9X	110.1	Cu2—N19—H19X	110.4
Cu1—N9—H9X	109.8	C20—N19—H19Y	110.3
C9—N9—H9Y	109.7	Cu2—N19—H19Y	110.2
Cu1—N9—H9Y	109.7	H19X—N19—H19Y	108.5
H9X—N9—H9Y	108.3	C21—N20—Cu2	108.4 (4)
C10—N10—Cu1	109.1 (4)	C21—N20—H20X	110.1
C10—N10—H10X	109.5	Cu2—N20—H20X	109.9
Cu1—N10—H10X	109.7	C21—N20—H20Y	110.0
C10—N10—H10Y	110.1	Cu2—N20—H20Y	110.1
Cu1—N10—H10Y	110.0	H20X—N20—H20Y	108.4
H10X—N10—H10Y	108.3	N11—C12—Fe2	176.0 (5)
N1—C1—Fe1	176.2 (5)	N13—C13—Fe2	177.3 (5)
N3—C2—Fe1	176.4 (6)	N14—C14—Fe2	178.3 (6)
N4—C3—Fe1	178.1 (6)	N15—C15—Fe2	176.9 (5)
N5—C4—Fe1	175.3 (6)	N16—C16—Fe2	175.4 (5)
N6—C5—Fe1	178.6 (6)	N17—C17—C18	107.4 (4)
N7—C6—C7	106.9 (4)	N17—C17—C19	112.0 (5)
N7—C6—C8	112.3 (6)	C18—C17—C19	111.6 (5)
C7—C6—C8	110.5 (5)	N17—C17—H17	108.6
N7—C6—H6	109.0	C18—C17—H17	108.6
C7—C6—H6	109.0	C19—C17—H17	108.6
C8—C6—H6	109.0	N18—C18—C17	110.3 (4)
N8—C7—C6	109.0 (4)	N18—C18—H18A	109.6
N8—C7—H7A	109.9	C17—C18—H18A	109.6
C6—C7—H7A	109.9	N18—C18—H18B	109.6
N8—C7—H7B	109.9	C17—C18—H18B	109.6
C6—C7—H7B	109.9	H18A—C18—H18B	108.1
H7A—C7—H7B	108.3	C17—C19—H19A	109.5
C6—C8—H8A	109.5	C17—C19—H19B	109.5
C6—C8—H8B	109.5	H19A—C19—H19B	109.5
H8A—C8—H8B	109.5	C17—C19—H19C	109.5
C6—C8—H8C	109.5	H19A—C19—H19C	109.5
H8A—C8—H8C	109.5	H19B—C19—H19C	109.5
H8B—C8—H8C	109.5	C21—C20—N19	107.5 (4)
N9—C9—C10	106.6 (4)	C21—C20—C22	110.8 (5)
N9—C9—C11	112.1 (5)	N19—C20—C22	113.9 (5)
C10—C9—C11	113.8 (4)	C21—C20—H20	108.2
N9—C9—H9	108.1	N19—C20—H20	108.2
C10—C9—H9	108.1	C22—C20—H20	108.2
C11—C9—H9	108.1	C20—C21—N20	108.6 (4)
N10—C10—C9	109.1 (4)	C20—C21—H21A	110.0
N10—C10—H10A	109.9	N20—C21—H21A	110.0
C9—C10—H10A	109.9	C20—C21—H21B	110.0
N10—C10—H10B	109.9	N20—C21—H21B	110.0
C9—C10—H10B	109.9	H21A—C21—H21B	108.4
H10A—C10—H10B	108.3	C20—C22—H22A	109.5
C9—C11—H11A	109.5	C20—C22—H22B	109.5
C9—C11—H11B	109.5	H22A—C22—H22B	109.5
H11A—C11—H11B	109.5	C20—C22—H22C	109.5
C9—C11—H11C	109.5	H22A—C22—H22C	109.5
H11A—C11—H11C	109.5	H22B—C22—H22C	109.5
H11B—C11—H11C	109.5	H1WA—O1W—H1WB	105 (4)
N19—Cu2—N17	177.4 (2)	H2WA—O2W—H2WB	114 (4)

Cu1—N7—C6—C7	37.2 (5)	Cu2—N17—C17—C18	37.3 (5)
Cu1—N7—C6—C8	158.6 (5)	Cu2—N17—C17—C19	160.2 (5)
Cu1—N8—C7—C6	39.8 (5)	Cu2—N18—C18—C17	38.5 (5)
N7—C6—C7—N8	−50.9 (6)	N17—C17—C18—N18	−50.7 (5)
C8—C6—C7—N8	−173.3 (6)	C19—C17—C18—N18	−173.9 (5)
Cu1—N9—C9—C10	37.3 (5)	Cu2—N19—C20—C21	44.0 (5)
Cu1—N9—C9—C11	162.4 (4)	Cu2—N19—C20—C22	167.2 (5)
Cu1—N10—C10—C9	40.4 (5)	N19—C20—C21—N20	−54.1 (6)
N9—C9—C10—N10	−51.3 (5)	C22—C20—C21—N20	−179.1 (5)
C11—C9—C10—N10	−175.4 (5)	Cu2—N20—C21—C20	37.2 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N7—H7X···N15ⁱⁱⁱ	0.89	2.39	3.257 (8)	166
N7—H7Y···N14^iv	0.89	2.12	3.008 (8)	173
N8—H8X···N14ⁱ	0.89	2.27	3.120 (8)	160
N8—H8Y···N15	0.89	2.45	3.209 (7)	144
N9—H9X···O1W	0.89	2.52	3.207 (7)	135
N9—H9Y···N16ⁱ	0.89	2.39	3.157 (7)	144
N10—H10X···N16^iv	0.89	2.52	3.189 (7)	132
N10—H10Y···O1Wⁱⁱⁱ	0.89	2.11	2.962 (7)	159
C11—H11A···N16ⁱ	0.98	2.68	3.427 (9)	134
N17—H17X···N4^v	0.89	2.22	3.051 (8)	155
N17—H17Y···N5^vi	0.89	2.32	3.197 (7)	169
N18—H18X···N5	0.89	2.37	3.224 (8)	161
N18—H18Y···N4ⁱⁱ	0.89	2.27	3.080 (8)	151
N19—H19X···N6ⁱⁱ	0.89	2.44	3.295 (8)	160
N19—H19Y···O2Wⁱⁱⁱ	0.89	2.30	3.142 (8)	159
N20—H20X···O2W	0.89	2.11	2.990 (8)	172
O1W—H1WB···N15	0.84 (3)	2.11 (3)	2.928 (7)	163 (6)
O2W—H2WA···N13	0.83 (3)	2.65 (4)	3.419 (9)	155 (6)
O2W—H2WB···N20	0.80 (3)	2.37 (5)	2.990 (8)	135 (6)

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

(II) Poly[[hexa-µ-cyanido-κ¹²C:N-hexacyanido-κ⁶C-hexakis[(R)-propane-1,2-diamine-κ²N,N']dichromiun(III)tricopper(II)] pentahydrate] top

Crystal data top

[Cr₂Cu₃(CN)₁₂(C₃H₁₀N₂)₆]·5H₂O	F(000) = 1186
M_r = 1141.72	D_x = 1.407 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 10.1474 (10) Å	Cell parameters from 21484 reflections
b = 17.6136 (10) Å	θ = 0.1–24.9°
c = 15.5376 (14) Å	µ = 1.61 mm⁻¹
β = 103.973 (11)°	T = 173 K
V = 2694.9 (4) Å³	Block, blue
Z = 2	0.40 × 0.30 × 0.30 mm

Data collection top

Stoe IPDS 2 diffractometer	10308 independent reflections
Radiation source: fine-focus sealed tube	4948 reflections with I > 2σ(I)
Plane graphite monochromator	R_int = 0.085
φ + ω scans	θ_max = 26.1°, θ_min = 2.1°
Absorption correction: multi-scan (MULABS in PLATON; Spek, 2009)	h = −12→12
T_min = 0.583, T_max = 0.678	k = −21→21
21461 measured reflections	l = −18→19

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.052	w = 1/[σ²(F_o²) + (0.0562P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.131	(Δ/σ)_max < 0.001
S = 0.79	Δρ_max = 0.61 e Å⁻³
10308 reflections	Δρ_min = −1.05 e Å⁻³
594 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
14 restraints	Extinction coefficient: 0.0020 (3)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack x determined using 1754 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.00 (3)

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cu1	0.51532 (17)	−0.16435 (9)	0.17076 (10)	0.0541 (5)
Cu2	1.02528 (15)	0.55090 (9)	0.33881 (9)	0.0478 (5)
Cu3	0.73882 (16)	0.20223 (11)	0.24976 (12)	0.0445 (4)
Cr1	0.48267 (17)	0.07601 (10)	−0.02939 (11)	0.0342 (5)
Cr2	0.99071 (17)	0.31948 (10)	0.52845 (11)	0.0338 (5)
N1	0.5975 (11)	0.2178 (7)	0.0977 (7)	0.051 (3)
N2	0.5099 (12)	−0.0213 (7)	0.1496 (8)	0.058 (3)
N3	0.4666 (13)	0.1845 (8)	−0.1992 (8)	0.065 (4)
N4	0.4687 (12)	−0.1554 (8)	0.2882 (7)	0.068 (4)
H4X	0.5307	−0.1793	0.3296	0.081*
H4Y	0.4676	−0.1068	0.3035	0.081*
N5	0.3166 (13)	−0.1839 (9)	0.1257 (8)	0.085 (4)
H5X	0.2834	−0.1534	0.0799	0.102*
H5Y	0.3041	−0.2317	0.1067	0.102*
N6	0.7170 (11)	−0.1651 (7)	0.2205 (7)	0.060 (3)
H6X	0.7447	−0.1195	0.2423	0.071*
H6Y	0.7387	−0.1988	0.2643	0.071*
N7	0.5640 (11)	−0.1689 (7)	0.0541 (7)	0.057 (3)
H7X	0.5495	−0.2157	0.0321	0.068*
H7Y	0.5112	−0.1372	0.0163	0.068*
N8	0.1712 (12)	0.1231 (8)	−0.0411 (10)	0.065 (4)
N9	0.3824 (11)	−0.0737 (7)	−0.1487 (8)	0.057 (3)
N10	0.7910 (13)	0.0303 (7)	−0.0181 (9)	0.063 (4)
N11	0.8801 (12)	0.1718 (7)	0.4122 (8)	0.059 (4)
N12	1.0084 (10)	0.4105 (7)	0.3515 (8)	0.047 (3)
N13	0.9876 (12)	0.2109 (8)	0.6935 (8)	0.059 (3)
N14	0.8281 (10)	0.5536 (7)	0.2720 (7)	0.052 (3)
H14X	0.8091	0.5980	0.2443	0.063*
H14Y	0.8114	0.5169	0.2315	0.063*
N15	0.9496 (11)	0.5592 (7)	0.4455 (7)	0.057 (3)
H15X	0.9528	0.5141	0.4717	0.068*
H15Y	0.9992	0.5916	0.4840	0.068*
N16	1.2223 (12)	0.5567 (8)	0.4047 (9)	0.081 (4)
H16X	1.2309	0.5868	0.4518	0.098*
H16Y	1.2520	0.5107	0.4237	0.098*
N17	1.1002 (11)	0.5557 (7)	0.2339 (8)	0.067 (3)
H17X	1.0659	0.5180	0.1971	0.081*
H17Y	1.0762	0.5994	0.2057	0.081*
N18	1.0917 (12)	0.4670 (7)	0.6493 (8)	0.056 (3)
N19	1.3045 (12)	0.2783 (7)	0.5541 (8)	0.056 (3)
N20	0.6777 (12)	0.3732 (7)	0.4901 (8)	0.060 (3)
N21	0.8943 (12)	0.2578 (8)	0.2240 (8)	0.066 (4)
H21X	0.8677	0.2831	0.1731	0.079*
H21Y	0.9267	0.2910	0.2670	0.079*
N22	0.8271 (12)	0.1100 (8)	0.2148 (8)	0.063 (4)
H22X	0.8629	0.0825	0.2629	0.075*
H22Y	0.7650	0.0817	0.1785	0.075*
N23	0.6505 (12)	0.2948 (7)	0.2834 (7)	0.059 (3)
H23X	0.6979	0.3120	0.3356	0.071*
H23Y	0.6481	0.3310	0.2431	0.071*
N24	0.5846 (11)	0.1492 (8)	0.2809 (8)	0.059 (3)
H24X	0.5273	0.1325	0.2318	0.071*
H24Y	0.6150	0.1093	0.3151	0.071*
C1	0.5538 (12)	0.1684 (8)	0.0494 (9)	0.042 (3)
C2	0.4959 (12)	0.0149 (8)	0.0868 (9)	0.042 (3)
C3	0.4714 (13)	0.1428 (8)	−0.1401 (10)	0.046 (3)
C4	0.336 (2)	−0.1892 (14)	0.2814 (12)	0.111 (4)
H4A	0.2984	−0.1705	0.3307	0.133*
H4B	0.3454	−0.2450	0.2871	0.133*
C5	0.241 (2)	−0.1708 (17)	0.1968 (12)	0.111 (4)
H5	0.1592	−0.2044	0.1870	0.133*
C6	0.199 (2)	−0.0890 (13)	0.1930 (13)	0.111 (4)
H6A	0.1438	−0.0772	0.1336	0.166*
H6B	0.2802	−0.0567	0.2061	0.166*
H6C	0.1459	−0.0795	0.2368	0.166*
C7	0.7840 (14)	−0.1851 (9)	0.1491 (9)	0.064 (4)
H7A	0.7844	−0.2409	0.1417	0.076*
H7B	0.8793	−0.1672	0.1647	0.076*
C8	0.7079 (15)	−0.1482 (9)	0.0637 (9)	0.064 (4)
H8	0.7168	−0.0919	0.0706	0.077*
C9	0.7626 (17)	−0.1715 (12)	−0.0140 (12)	0.083 (5)
H9A	0.7148	−0.1437	−0.0669	0.124*
H9B	0.7489	−0.2262	−0.0242	0.124*
H9C	0.8599	−0.1600	−0.0014	0.124*
C10	0.2848 (15)	0.1048 (8)	−0.0364 (10)	0.048 (4)
C11	0.4177 (13)	−0.0199 (9)	−0.1051 (9)	0.045 (3)
C12	0.6798 (14)	0.0468 (9)	−0.0239 (8)	0.045 (3)
C13	0.9223 (11)	0.2246 (8)	0.4512 (7)	0.038 (3)
C14	1.0025 (12)	0.3780 (8)	0.4143 (10)	0.040 (3)
C15	0.9862 (12)	0.2523 (8)	0.6373 (9)	0.044 (3)
C16	0.7459 (13)	0.5435 (9)	0.3339 (9)	0.058 (4)
H16A	0.7401	0.4888	0.3472	0.070*
H16B	0.6528	0.5622	0.3077	0.070*
C17	0.8058 (14)	0.5863 (9)	0.4186 (9)	0.059 (4)
H17	0.8077	0.6413	0.4032	0.071*
C18	0.7343 (17)	0.5794 (11)	0.4909 (11)	0.080 (5)
H18A	0.7916	0.6002	0.5459	0.120*
H18B	0.7153	0.5258	0.4997	0.120*
H18C	0.6487	0.6077	0.4750	0.120*
C19	1.3002 (18)	0.5853 (13)	0.3487 (14)	0.108 (7)
H19A	1.3973	0.5731	0.3732	0.130*
H19B	1.2905	0.6411	0.3440	0.130*
C20	1.2512 (16)	0.5496 (11)	0.2590 (14)	0.089 (6)
H20	1.2880	0.5796	0.2155	0.107*
C21	1.2885 (19)	0.4656 (13)	0.2508 (12)	0.112 (7)
H21C	1.3869	0.4591	0.2722	0.169*
H21B	1.2603	0.4499	0.1886	0.169*
H21A	1.2421	0.4342	0.2865	0.169*
C22	1.0531 (12)	0.4149 (8)	0.6067 (8)	0.041 (3)
C23	1.1914 (14)	0.2903 (7)	0.5443 (8)	0.041 (3)
C24	0.7905 (14)	0.3520 (8)	0.5069 (8)	0.044 (3)
C25	1.0019 (17)	0.2019 (12)	0.2175 (12)	0.087 (3)
H25A	1.0575	0.1892	0.2773	0.104*
H25B	1.0623	0.2234	0.1823	0.104*
C26	0.9301 (17)	0.1304 (12)	0.1719 (12)	0.087 (3)
H26	0.8884	0.1416	0.1080	0.104*
C27	1.0398 (15)	0.0766 (11)	0.1785 (11)	0.087 (3)
H27A	1.0745	0.0616	0.2406	0.130*
H27B	1.1130	0.1002	0.1566	0.130*
H27C	1.0063	0.0317	0.1427	0.130*
C28	0.5164 (19)	0.2764 (10)	0.2887 (11)	0.084 (6)
H28A	0.4552	0.2768	0.2285	0.101*
H28B	0.4836	0.3149	0.3250	0.101*
C29	0.5137 (17)	0.2017 (11)	0.3283 (11)	0.078 (5)
H29	0.5714	0.2055	0.3902	0.094*
C30	0.3779 (18)	0.1714 (12)	0.3362 (13)	0.111 (7)
H30A	0.3882	0.1185	0.3564	0.166*
H30B	0.3130	0.1739	0.2782	0.166*
H30C	0.3444	0.2020	0.3791	0.166*
O1W	0.4077 (9)	0.4169 (5)	0.4832 (7)	0.065 (3)
H1WA	0.387 (13)	0.379 (6)	0.511 (10)	0.098*
H1WB	0.485 (8)	0.407 (8)	0.475 (10)	0.098*
O2W	0.9673 (10)	0.4758 (7)	0.0537 (9)	0.087 (3)
H2WA	1.028 (14)	0.477 (10)	0.025 (11)	0.130*
H2WB	0.931 (17)	0.432 (5)	0.046 (13)	0.130*
O3W	0.6417 (16)	0.0077 (9)	0.3872 (9)	0.116 (5)
H3WA	0.726 (5)	−0.001 (15)	0.404 (14)	0.174*
H3WB	0.606 (18)	−0.012 (15)	0.426 (12)	0.174*
O4W	0.1006 (11)	−0.3169 (7)	0.0730 (9)	0.095 (4)
H4WA	0.114 (15)	−0.338 (12)	0.027 (8)	0.143*
H4WB	0.016 (4)	−0.314 (12)	0.066 (11)	0.143*
O5WA	0.815 (4)	0.362 (3)	0.064 (3)	0.056 (14)	0.43 (17)
O5WB	0.857 (12)	0.327 (7)	0.052 (4)	0.13 (4)	0.57 (17)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0756 (11)	0.0442 (11)	0.0307 (8)	−0.0028 (8)	−0.0101 (7)	−0.0017 (7)
Cu2	0.0593 (10)	0.0442 (10)	0.0313 (8)	−0.0020 (8)	−0.0058 (7)	−0.0040 (7)
Cu3	0.0575 (9)	0.0389 (8)	0.0291 (6)	−0.0067 (7)	−0.0051 (6)	0.0014 (6)
Cr1	0.0428 (10)	0.0268 (12)	0.0283 (10)	−0.0036 (8)	−0.0008 (8)	0.0002 (9)
Cr2	0.0452 (10)	0.0256 (12)	0.0250 (10)	−0.0010 (8)	−0.0026 (8)	0.0009 (8)
N1	0.068 (7)	0.043 (8)	0.024 (5)	0.001 (6)	−0.023 (5)	0.002 (5)
N2	0.102 (10)	0.032 (7)	0.037 (7)	0.000 (6)	0.012 (6)	0.007 (6)
N3	0.106 (10)	0.040 (8)	0.045 (7)	0.012 (7)	0.008 (7)	0.012 (6)
N4	0.080 (8)	0.064 (9)	0.047 (7)	0.013 (7)	−0.008 (6)	−0.002 (6)
N5	0.097 (9)	0.085 (11)	0.060 (8)	−0.029 (9)	−0.007 (7)	−0.007 (8)
N6	0.085 (8)	0.038 (7)	0.040 (6)	−0.003 (6)	−0.016 (6)	0.005 (6)
N7	0.078 (8)	0.040 (7)	0.040 (6)	−0.005 (7)	−0.010 (5)	0.004 (6)
N8	0.049 (7)	0.052 (8)	0.088 (10)	−0.002 (6)	0.007 (6)	0.004 (7)
N9	0.064 (7)	0.043 (8)	0.049 (7)	−0.003 (6)	−0.015 (6)	−0.010 (6)
N10	0.064 (8)	0.042 (8)	0.084 (10)	−0.008 (6)	0.018 (7)	−0.002 (7)
N11	0.086 (8)	0.028 (7)	0.045 (7)	−0.001 (6)	−0.023 (6)	−0.012 (6)
N12	0.061 (7)	0.041 (8)	0.036 (7)	−0.003 (5)	0.008 (5)	0.001 (6)
N13	0.089 (8)	0.050 (8)	0.041 (7)	0.005 (7)	0.020 (6)	0.020 (7)
N14	0.070 (7)	0.038 (7)	0.041 (6)	−0.005 (6)	−0.003 (5)	−0.001 (6)
N15	0.079 (7)	0.029 (7)	0.046 (7)	−0.001 (6)	−0.016 (5)	−0.008 (6)
N16	0.067 (8)	0.062 (9)	0.099 (11)	−0.003 (7)	−0.010 (7)	0.010 (8)
N17	0.081 (8)	0.053 (8)	0.064 (8)	0.009 (7)	0.007 (6)	0.012 (6)
N18	0.077 (8)	0.026 (7)	0.054 (7)	−0.006 (6)	−0.007 (6)	−0.010 (6)
N19	0.058 (8)	0.050 (8)	0.056 (8)	−0.003 (6)	0.009 (6)	−0.001 (6)
N20	0.056 (7)	0.060 (8)	0.061 (8)	0.011 (6)	0.006 (6)	0.013 (6)
N21	0.097 (9)	0.055 (8)	0.032 (7)	−0.029 (7)	−0.008 (6)	0.000 (6)
N22	0.069 (8)	0.063 (9)	0.039 (7)	−0.005 (6)	−0.018 (6)	0.005 (6)
N23	0.078 (9)	0.061 (9)	0.031 (6)	0.003 (6)	0.000 (6)	0.005 (6)
N24	0.079 (8)	0.060 (9)	0.032 (6)	−0.005 (6)	−0.001 (6)	0.001 (6)
C1	0.047 (7)	0.036 (8)	0.035 (7)	0.005 (6)	−0.008 (6)	0.018 (7)
C2	0.045 (7)	0.041 (9)	0.037 (8)	−0.006 (6)	0.005 (6)	−0.006 (7)
C3	0.054 (8)	0.028 (8)	0.049 (9)	−0.003 (6)	−0.001 (6)	−0.011 (7)
C4	0.123 (9)	0.132 (11)	0.079 (7)	0.000 (9)	0.028 (6)	−0.008 (9)
C5	0.123 (9)	0.132 (11)	0.079 (7)	0.000 (9)	0.028 (6)	−0.008 (9)
C6	0.123 (9)	0.132 (11)	0.079 (7)	0.000 (9)	0.028 (6)	−0.008 (9)
C7	0.072 (9)	0.055 (10)	0.054 (9)	0.005 (8)	−0.004 (7)	0.009 (8)
C8	0.093 (11)	0.049 (10)	0.048 (8)	−0.009 (8)	0.014 (7)	0.007 (7)
C9	0.112 (12)	0.058 (11)	0.086 (12)	0.002 (10)	0.039 (10)	0.012 (10)
C10	0.068 (9)	0.027 (8)	0.046 (9)	−0.009 (7)	0.004 (7)	0.001 (6)
C11	0.051 (8)	0.037 (9)	0.042 (8)	0.011 (6)	0.002 (6)	0.015 (7)
C12	0.047 (8)	0.046 (9)	0.038 (7)	−0.016 (7)	0.005 (6)	−0.004 (7)
C13	0.048 (7)	0.037 (9)	0.020 (6)	0.013 (6)	−0.011 (5)	0.009 (6)
C14	0.045 (7)	0.023 (8)	0.046 (9)	0.009 (5)	0.000 (6)	−0.005 (7)
C15	0.055 (8)	0.040 (9)	0.036 (8)	−0.005 (6)	0.007 (6)	−0.015 (7)
C16	0.045 (8)	0.053 (10)	0.069 (10)	0.002 (7)	−0.003 (7)	0.009 (8)
C17	0.080 (10)	0.042 (9)	0.061 (9)	0.008 (7)	0.030 (8)	0.002 (7)
C18	0.108 (13)	0.061 (12)	0.081 (12)	0.011 (10)	0.045 (10)	−0.002 (10)
C19	0.080 (13)	0.104 (16)	0.121 (17)	−0.026 (11)	−0.015 (12)	0.039 (14)
C20	0.061 (10)	0.077 (13)	0.144 (18)	0.011 (10)	0.050 (11)	0.026 (13)
C21	0.105 (14)	0.15 (2)	0.084 (13)	0.036 (14)	0.020 (10)	0.028 (13)
C22	0.055 (8)	0.033 (8)	0.030 (7)	0.010 (6)	0.000 (6)	0.013 (6)
C23	0.053 (8)	0.033 (8)	0.028 (7)	−0.010 (6)	−0.007 (6)	0.008 (6)
C24	0.068 (9)	0.031 (8)	0.032 (7)	0.000 (7)	0.007 (6)	0.001 (6)
C25	0.077 (7)	0.105 (9)	0.074 (7)	0.009 (6)	0.012 (5)	0.006 (6)
C26	0.077 (7)	0.105 (9)	0.074 (7)	0.009 (6)	0.012 (5)	0.006 (6)
C27	0.077 (7)	0.105 (9)	0.074 (7)	0.009 (6)	0.012 (5)	0.006 (6)
C28	0.108 (15)	0.086 (14)	0.059 (10)	0.040 (11)	0.023 (9)	−0.010 (9)
C29	0.087 (12)	0.087 (14)	0.065 (10)	0.012 (11)	0.028 (9)	0.012 (10)
C30	0.104 (14)	0.135 (18)	0.115 (16)	−0.022 (13)	0.066 (12)	−0.006 (13)
O1W	0.053 (6)	0.052 (6)	0.092 (8)	0.005 (5)	0.018 (5)	0.015 (5)
O2W	0.047 (7)	0.091 (9)	0.123 (10)	0.004 (6)	0.020 (6)	0.018 (8)
O3W	0.155 (13)	0.102 (11)	0.098 (10)	0.047 (10)	0.046 (9)	0.047 (8)
O4W	0.090 (8)	0.076 (9)	0.131 (11)	−0.023 (7)	0.050 (7)	−0.041 (7)
O5WA	0.06 (2)	0.04 (2)	0.057 (17)	0.009 (18)	−0.007 (11)	−0.006 (16)
O5WB	0.17 (5)	0.11 (6)	0.09 (2)	−0.10 (5)	−0.04 (3)	0.06 (3)

Geometric parameters (Å, º) top

Cu1—N7	1.992 (12)	N21—H21Y	0.8900
Cu1—N5	1.998 (12)	N22—C26	1.42 (2)
Cu1—N4	1.999 (12)	N22—H22X	0.8900
Cu1—N6	2.006 (10)	N22—H22Y	0.8900
Cu1—N2	2.540 (12)	N23—C28	1.42 (2)
Cu1—N3ⁱ	2.698 (14)	N23—H23X	0.8900
Cu2—N17	1.960 (12)	N23—H23Y	0.8900
Cu2—N15	1.993 (12)	N24—C29	1.47 (2)
Cu2—N16	2.017 (11)	N24—H24X	0.8900
Cu2—N14	2.020 (10)	N24—H24Y	0.8900
Cu2—N12	2.490 (12)	C4—C5	1.47 (2)
Cu2—N13ⁱⁱ	2.860 (14)	C4—H4A	0.9900
Cu3—N21	1.978 (12)	C4—H4B	0.9900
Cu3—N24	1.981 (12)	C5—C6	1.50 (3)
Cu3—N23	1.990 (13)	C5—H5	1.0000
Cu3—N22	1.993 (14)	C6—H6A	0.9800
Cu3—N1	2.465 (9)	C6—H6B	0.9800
Cu3—N11	2.639 (12)	C6—H6C	0.9800
Cr1—C12	2.047 (15)	C7—C8	1.512 (18)
Cr1—C10	2.049 (16)	C7—H7A	0.9900
Cr1—C1	2.060 (14)	C7—H7B	0.9900
Cr1—C3	2.065 (16)	C8—C9	1.50 (2)
Cr1—C11	2.073 (16)	C8—H8	1.0000
Cr1—C2	2.078 (15)	C9—H9A	0.9800
Cr2—C23	2.057 (15)	C9—H9B	0.9800
Cr2—C24	2.059 (15)	C9—H9C	0.9800
Cr2—C15	2.074 (16)	C16—C17	1.511 (19)
Cr2—C13	2.077 (13)	C16—H16A	0.9900
Cr2—C14	2.080 (16)	C16—H16B	0.9900
Cr2—C22	2.081 (15)	C17—C18	1.48 (2)
N1—C1	1.163 (16)	C17—H17	1.0000
N2—C2	1.146 (16)	C18—H18A	0.9800
N3—C3	1.168 (17)	C18—H18B	0.9800
N4—C4	1.45 (2)	C18—H18C	0.9800
N4—H4X	0.8900	C19—C20	1.50 (3)
N4—H4Y	0.8900	C19—H19A	0.9900
N5—C5	1.51 (2)	C19—H19B	0.9900
N5—H5X	0.8900	C20—C21	1.54 (3)
N5—H5Y	0.8900	C20—H20	1.0000
N6—C7	1.476 (18)	C21—H21C	0.9800
N6—H6X	0.8900	C21—H21B	0.9800
N6—H6Y	0.8900	C21—H21A	0.9800
N7—C8	1.478 (17)	C25—C26	1.54 (3)
N7—H7X	0.8900	C25—H25A	0.9900
N7—H7Y	0.8900	C25—H25B	0.9900
N8—C10	1.182 (17)	C26—C27	1.45 (2)
N9—C11	1.171 (18)	C26—H26	1.0000
N10—C12	1.148 (16)	C27—H27A	0.9800
N11—C13	1.136 (16)	C27—H27B	0.9800
N12—C14	1.145 (16)	C27—H27C	0.9800
N13—C15	1.135 (17)	C28—C29	1.46 (2)
N14—C16	1.429 (17)	C28—H28A	0.9900
N14—H14X	0.8900	C28—H28B	0.9900
N14—H14Y	0.8900	C29—C30	1.51 (2)
N15—C17	1.496 (17)	C29—H29	1.0000
N15—H15X	0.8900	C30—H30A	0.9800
N15—H15Y	0.8900	C30—H30B	0.9800
N16—C19	1.40 (2)	C30—H30C	0.9800
N16—H16X	0.8900	O1W—H1WA	0.85 (3)
N16—H16Y	0.8900	O1W—H1WB	0.84 (3)
N17—C20	1.491 (18)	O2W—H2WA	0.85 (3)
N17—H17X	0.8900	O2W—H2WB	0.85 (3)
N17—H17Y	0.8900	O3W—H3WA	0.85 (3)
N18—C22	1.143 (17)	O3W—H3WB	0.85 (3)
N19—C23	1.140 (15)	O4W—H4WA	0.84 (3)
N20—C24	1.172 (15)	O4W—H4WB	0.84 (3)
N21—C25	1.49 (2)	O5WA—O5WB	0.80 (16)
N21—H21X	0.8900

N7—Cu1—N5	97.2 (5)	N1—C1—Cr1	176.1 (10)
N7—Cu1—N4	177.7 (6)	N2—C2—Cr1	175.7 (12)
N5—Cu1—N4	83.8 (5)	N3—C3—Cr1	175.7 (12)
N7—Cu1—N6	84.1 (5)	N4—C4—C5	111.8 (17)
N5—Cu1—N6	169.5 (6)	N4—C4—H4A	109.2
N4—Cu1—N6	95.3 (5)	C5—C4—H4A	109.2
N17—Cu2—N15	173.3 (5)	N4—C4—H4B	109.2
N17—Cu2—N16	83.4 (6)	C5—C4—H4B	109.2
N15—Cu2—N16	96.2 (5)	H4A—C4—H4B	107.9
N17—Cu2—N14	96.1 (5)	C4—C5—C6	112 (2)
N15—Cu2—N14	83.9 (4)	C4—C5—N5	106.4 (16)
N16—Cu2—N14	175.7 (6)	C6—C5—N5	107.9 (19)
N21—Cu3—N24	177.3 (6)	C4—C5—H5	110.3
N21—Cu3—N23	94.6 (6)	C6—C5—H5	110.3
N24—Cu3—N23	83.7 (6)	N5—C5—H5	110.3
N21—Cu3—N22	85.1 (6)	C5—C6—H6A	109.5
N24—Cu3—N22	96.6 (5)	C5—C6—H6B	109.5
N23—Cu3—N22	179.4 (6)	H6A—C6—H6B	109.5
N21—Cu3—N1	93.4 (4)	C5—C6—H6C	109.5
N24—Cu3—N1	88.6 (4)	H6A—C6—H6C	109.5
N23—Cu3—N1	88.1 (4)	H6B—C6—H6C	109.5
N22—Cu3—N1	91.4 (4)	N6—C7—C8	109.1 (12)
C12—Cr1—C10	179.4 (6)	N6—C7—H7A	109.9
C12—Cr1—C1	88.6 (5)	C8—C7—H7A	109.9
C10—Cr1—C1	91.9 (5)	N6—C7—H7B	109.9
C12—Cr1—C3	92.0 (5)	C8—C7—H7B	109.9
C10—Cr1—C3	87.6 (6)	H7A—C7—H7B	108.3
C1—Cr1—C3	89.2 (5)	N7—C8—C9	113.6 (12)
C12—Cr1—C11	89.6 (5)	N7—C8—C7	105.4 (11)
C10—Cr1—C11	89.9 (5)	C9—C8—C7	112.3 (14)
C1—Cr1—C11	177.5 (5)	N7—C8—H8	108.5
C3—Cr1—C11	92.6 (5)	C9—C8—H8	108.5
C12—Cr1—C2	88.6 (5)	C7—C8—H8	108.5
C10—Cr1—C2	91.8 (5)	C8—C9—H9A	109.5
C1—Cr1—C2	87.3 (5)	C8—C9—H9B	109.5
C3—Cr1—C2	176.4 (5)	H9A—C9—H9B	109.5
C11—Cr1—C2	90.9 (5)	C8—C9—H9C	109.5
C23—Cr2—C24	177.0 (5)	H9A—C9—H9C	109.5
C23—Cr2—C15	88.6 (5)	H9B—C9—H9C	109.5
C24—Cr2—C15	94.4 (5)	N8—C10—Cr1	178.5 (13)
C23—Cr2—C13	92.9 (5)	N9—C11—Cr1	178.9 (14)
C24—Cr2—C13	87.2 (5)	N10—C12—Cr1	178.0 (12)
C15—Cr2—C13	86.7 (5)	N11—C13—Cr2	175.9 (13)
C23—Cr2—C14	88.1 (5)	N12—C14—Cr2	179.6 (12)
C24—Cr2—C14	88.9 (5)	N13—C15—Cr2	174.5 (13)
C15—Cr2—C14	174.6 (5)	N14—C16—C17	110.3 (11)
C13—Cr2—C14	89.2 (5)	N14—C16—H16A	109.6
C23—Cr2—C22	88.8 (5)	C17—C16—H16A	109.6
C24—Cr2—C22	91.1 (5)	N14—C16—H16B	109.6
C15—Cr2—C22	92.7 (5)	C17—C16—H16B	109.6
C13—Cr2—C22	178.2 (5)	H16A—C16—H16B	108.1
C14—Cr2—C22	91.5 (5)	C18—C17—N15	112.7 (12)
C1—N1—Cu3	125.3 (10)	C18—C17—C16	116.9 (14)
C4—N4—Cu1	108.7 (9)	N15—C17—C16	104.1 (10)
C4—N4—H4X	109.9	C18—C17—H17	107.6
Cu1—N4—H4X	109.9	N15—C17—H17	107.6
C4—N4—H4Y	110.0	C16—C17—H17	107.6
Cu1—N4—H4Y	109.9	C17—C18—H18A	109.5
H4X—N4—H4Y	108.3	C17—C18—H18B	109.5
C5—N5—Cu1	111.5 (10)	H18A—C18—H18B	109.5
C5—N5—H5X	109.3	C17—C18—H18C	109.5
Cu1—N5—H5X	109.3	H18A—C18—H18C	109.5
C5—N5—H5Y	109.3	H18B—C18—H18C	109.5
Cu1—N5—H5Y	109.3	N16—C19—C20	108.4 (15)
H5X—N5—H5Y	108.0	N16—C19—H19A	110.0
C7—N6—Cu1	108.9 (8)	C20—C19—H19A	110.0
C7—N6—H6X	109.9	N16—C19—H19B	110.0
Cu1—N6—H6X	109.9	C20—C19—H19B	110.0
C7—N6—H6Y	109.9	H19A—C19—H19B	108.4
Cu1—N6—H6Y	109.9	N17—C20—C19	107.6 (14)
H6X—N6—H6Y	108.3	N17—C20—C21	107.8 (15)
C8—N7—Cu1	110.8 (8)	C19—C20—C21	116.5 (17)
C8—N7—H7X	109.5	N17—C20—H20	108.2
Cu1—N7—H7X	109.5	C19—C20—H20	108.2
C8—N7—H7Y	109.5	C21—C20—H20	108.2
Cu1—N7—H7Y	109.5	C20—C21—H21C	109.5
H7X—N7—H7Y	108.1	C20—C21—H21B	109.5
C16—N14—Cu2	108.5 (8)	H21C—C21—H21B	109.5
C16—N14—H14X	110.0	C20—C21—H21A	109.5
Cu2—N14—H14X	110.0	H21C—C21—H21A	109.5
C16—N14—H14Y	110.0	H21B—C21—H21A	109.5
Cu2—N14—H14Y	110.0	N18—C22—Cr2	177.7 (13)
H14X—N14—H14Y	108.4	N19—C23—Cr2	176.2 (12)
C17—N15—Cu2	109.7 (7)	N20—C24—Cr2	175.8 (12)
C17—N15—H15X	109.7	N21—C25—C26	107.4 (13)
Cu2—N15—H15X	109.7	N21—C25—H25A	110.2
C17—N15—H15Y	109.7	C26—C25—H25A	110.2
Cu2—N15—H15Y	109.7	N21—C25—H25B	110.2
H15X—N15—H15Y	108.2	C26—C25—H25B	110.2
C19—N16—Cu2	110.0 (11)	H25A—C25—H25B	108.5
C19—N16—H16X	109.7	N22—C26—C27	116.4 (17)
Cu2—N16—H16X	109.7	N22—C26—C25	108.2 (15)
C19—N16—H16Y	109.7	C27—C26—C25	103.5 (14)
Cu2—N16—H16Y	109.7	N22—C26—H26	109.5
H16X—N16—H16Y	108.2	C27—C26—H26	109.5
C20—N17—Cu2	111.1 (10)	C25—C26—H26	109.5
C20—N17—H17X	109.4	C26—C27—H27A	109.5
Cu2—N17—H17X	109.4	C26—C27—H27B	109.5
C20—N17—H17Y	109.4	H27A—C27—H27B	109.5
Cu2—N17—H17Y	109.4	C26—C27—H27C	109.5
H17X—N17—H17Y	108.0	H27A—C27—H27C	109.5
C25—N21—Cu3	108.7 (11)	H27B—C27—H27C	109.5
C25—N21—H21X	109.9	N23—C28—C29	110.3 (13)
Cu3—N21—H21X	109.9	N23—C28—H28A	109.6
C25—N21—H21Y	110.0	C29—C28—H28A	109.6
Cu3—N21—H21Y	110.0	N23—C28—H28B	109.6
H21X—N21—H21Y	108.4	C29—C28—H28B	109.6
C26—N22—Cu3	110.7 (11)	H28A—C28—H28B	108.1
C26—N22—H22X	109.5	C28—C29—N24	107.1 (13)
Cu3—N22—H22X	109.5	C28—C29—C30	117.7 (16)
C26—N22—H22Y	109.5	N24—C29—C30	112.6 (16)
Cu3—N22—H22Y	109.5	C28—C29—H29	106.2
H22X—N22—H22Y	108.1	N24—C29—H29	106.2
C28—N23—Cu3	109.1 (10)	C30—C29—H29	106.2
C28—N23—H23X	109.9	C29—C30—H30A	109.5
Cu3—N23—H23X	109.9	C29—C30—H30B	109.5
C28—N23—H23Y	109.9	H30A—C30—H30B	109.5
Cu3—N23—H23Y	109.9	C29—C30—H30C	109.5
H23X—N23—H23Y	108.3	H30A—C30—H30C	109.5
C29—N24—Cu3	109.7 (10)	H30B—C30—H30C	109.5
C29—N24—H24X	109.7	H1WA—O1W—H1WB	106 (5)
Cu3—N24—H24X	109.7	H2WA—O2W—H2WB	107 (5)
C29—N24—H24Y	109.7	H3WA—O3W—H3WB	106 (5)
Cu3—N24—H24Y	109.8	H4WA—O4W—H4WB	106 (5)
H24X—N24—H24Y	108.2

Cu1—N4—C4—C5	−40 (2)	Cu2—N16—C19—C20	−41.6 (19)
N4—C4—C5—C6	−71 (2)	Cu2—N17—C20—C19	−31.8 (17)
N4—C4—C5—N5	46 (3)	Cu2—N17—C20—C21	94.5 (15)
Cu1—N5—C5—C4	−31 (2)	N16—C19—C20—N17	48 (2)
Cu1—N5—C5—C6	89.2 (15)	N16—C19—C20—C21	−73 (2)
Cu1—N6—C7—C8	38.0 (14)	Cu3—N21—C25—C26	37.3 (16)
Cu1—N7—C8—C9	163.4 (11)	Cu3—N22—C26—C27	153.0 (12)
Cu1—N7—C8—C7	40.1 (14)	Cu3—N22—C26—C25	37.1 (16)
N6—C7—C8—N7	−50.8 (15)	N21—C25—C26—N22	−49.1 (19)
N6—C7—C8—C9	−174.9 (13)	N21—C25—C26—C27	−173.1 (13)
Cu2—N14—C16—C17	39.5 (14)	Cu3—N23—C28—C29	39.2 (15)
Cu2—N15—C17—C18	168.7 (12)	N23—C28—C29—N24	−49.8 (18)
Cu2—N15—C17—C16	41.0 (13)	N23—C28—C29—C30	−177.9 (14)
N14—C16—C17—C18	−178.1 (13)	Cu3—N24—C29—C28	36.3 (15)
N14—C16—C17—N15	−53.1 (15)	Cu3—N24—C29—C30	167.2 (12)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4X···N19ⁱⁱⁱ	0.89	2.27	3.153 (16)	171
N5—H5X···O5WAⁱ	0.89	2.24	3.04 (4)	150
N5—H5X···O5WBⁱ	0.89	2.22	2.89 (3)	133
N5—H5Y···O4W	0.89	2.50	3.177 (17)	133
N6—H6X···N18ⁱⁱⁱ	0.89	2.56	3.373 (17)	152
N7—H7X···N1ⁱ	0.89	2.49	3.219 (15)	139
N14—H14Y···N9^iv	0.89	2.62	3.360 (16)	142
N15—H15Y···N11ⁱⁱ	0.89	2.27	3.156 (15)	177
N16—H16Y···O1W^v	0.89	2.32	3.159 (16)	158
N17—H17X···O2W	0.89	2.33	3.132 (18)	150
N17—H17Y···N13ⁱⁱ	0.89	2.69	3.166 (19)	115
N17—H17Y···O4W^vi	0.89	2.60	3.361 (18)	145
N21—H21X···O5WA	0.89	2.16	3.04 (5)	170
N21—H21X···O5WB	0.89	2.02	2.88 (3)	163
N21—H21Y···N12	0.89	2.51	3.376 (17)	164
N22—H22X···N18ⁱⁱⁱ	0.89	2.43	3.262 (17)	155
N23—H23X···N20	0.89	2.68	3.445 (18)	144
N23—H23Y···N9^iv	0.89	2.20	3.086 (17)	172
N24—H24Y···O3W	0.89	2.09	2.969 (18)	167
O1W—H1WA···N19^vii	0.85 (3)	2.14 (5)	2.972 (16)	167 (16)
O1W—H1WB···N20	0.84 (3)	2.00 (5)	2.822 (15)	164 (14)
O2W—H2WA···N10^viii	0.85 (3)	2.09 (10)	2.811 (17)	143 (15)
O2W—H2WB···O5WA	0.85 (3)	1.78 (9)	2.56 (6)	153 (16)
O2W—H2WB···O5WB	0.85 (3)	2.01 (8)	2.85 (7)	169 (20)
O3W—H3WA···N18ⁱⁱⁱ	0.85 (3)	2.27 (14)	2.982 (19)	142 (20)
O3W—H3WB···O1W^ix	0.85 (3)	1.92 (10)	2.712 (17)	156 (21)
O4W—H4WA···N10ⁱ	0.84 (3)	2.53 (18)	3.104 (17)	126 (18)
O4W—H4WB···N8^x	0.84 (3)	2.16 (13)	2.883 (16)	145 (19)

Symmetry codes: (i) −x+1, y−1/2, −z; (ii) −x+2, y+1/2, −z+1; (iii) −x+2, y−1/2, −z+1; (iv) −x+1, y+1/2, −z; (v) x+1, y, z; (vi) x+1, y+1, z; (vii) x−1, y, z; (viii) −x+2, y+1/2, −z; (ix) −x+1, y−1/2, −z+1; (x) −x, y−1/2, −z.

Footnotes

‡Current address: Characterization & Quality Assurance, Micosystems Division, Swiss Center for Electronics and Microelectronics, rue Jaquet-Droz 1, CH-2001 Neuchâtel, Switzerland.

Acknowledgements

This work was financed by the Swiss National Science Foundation (grant No. 111732). We thank Professor K. Bernaur, University of Neuchâtel, for the gift of the ligand (R)-propane-1,2-diamine.

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