A cyano-bridged dinuclear 4f–3d array

A cyano-bridged bimetallic 4f–3d complex, tri­aqua-1κ³O-μ-cyano-1:2κ²N:C-penta­cyano-2κ⁵C-tetrakis(2-pyrrolidone-1κO)­chromium(III)­dysprosium(III) dihydrate, [CrDy(C₄H₇NO)₄(CN)₆(H₂O)₃]·2H₂O, has been prepared and characterized by X-ray crystallographic analysis. The structure consists of a neutral cyano-bridged Dy–Cr dimer. A hydrogen-bonded three-dimensional architecture is formed through N—H...O, O—H...N and O—H...O hydrogen bonds.

S1. Comment

Recently, there has been considerable interest in lanthanide(III) hexacyanoferrates, and the analogous cobalt(III) and chromium(III) complexes, because of their potential as catalytic, semiconductor and magnetic materials (Hulliger et al., 1976). Also, some of these cyanides can form semipermeable membranes, which are very important in connection with the desalination of sea water. In particular, a series of three-dimensional cyano-bridged 4f-3 d complexes, Ln[M(CN)₆].nH₂O (M is Cr^III or Fe^III), exhibit magnetic ordering (Hulliger et al., 1976). Incorporation of organic ligands into these three-dimensional 4f-3 d adducts may reduce the dimensionality of the parent complexes and give various molecular structures. Along this line, we have employed the simple ligand dimethylformamide (dmf) to prepare cyano-bridged 4f-3 d dimers, [Ln(dmf)₄(H₂O)₄Fe(CN)₆]·H₂O (Kou et al., 1998; Kautz et al., 2000) and [Pr(dmf)₄(H₂O)₃Cr(CN)₆]·H₂O (Combs et al., 2000), a one-dimensional zigzag chain, [Sm(dmf)₄(H₂O)₂Cr(CN)₆]·H₂O (Kou, Gao & Jin, 2001), and two-dimensional brick-wall-like complexes, [Ln(dmf)₂(H₂O)₃Cr(CN)₆]·H₂O (Ln is Sm or Gd; Kou, Gao & Jin, 2001; Kou, Gao, Sun & Zhang, 2001). In the present study, we used 2-pyrrolidone (pyr) to synthesize the cyano-bridged bimetallic complex [Dy(pyr)₄(H₂O)₃Cr(CN)₆]·2H₂O, (I).

A perspective view of (I) is shown in Fig. 1, and selected bond distances and angles are listed in Table 1. The crystal structure of (I) consists of a neutral cyano-bridged bimetallic fragment. The lanthanide ion is eight-coordinate and the coordination polyhedron can be described as a distorted square antiprism. Seven O atoms of three water molecules and four pyr molecules, and one N atom of the bridging CN ligand, coordinate to Dy^III. The bridging cyanide coordinates to the Dy^III ion in a bent fashion, with a bond angle of 162.4 (3)° for C1—N1—Dy. The Cr···Dy metal–metal distance is 5.592 (2) Å.

The N1—Dy—O(H₂O) angles range from 83.68 (13) to 141.33 (11)°, generally larger than the average value for N1—Dy—O(pyr) [96.36 (6)°]. This reflects the fact that small water molecules are more polar than bulky 2-pyrrolidone ligands, and the electrostatic repulsion force may be significant.

The Cr—C—N bond angles are nearly linear and range from 174.2 (4) to 179.5 (5)°, indicative of directional bonding involving the π orbitals of the metal centre. The Cr—C bond distances are in the range 2.061 (4)–2.088 (4) Å, consistent with the corresponding literature values (Combs et al., 2000; Kou, Gao & Jin, 2001; Kou, Gao, Sun & Zhang, 2001).

The coordinated and uncoordinated water molecules are hydrogen bonded to the non-bridging cyanide N atom and to water molecules to produce a hydrogen-bonded three-dimensional network; details are available in Table 2.

S2. Experimental

Complex (I) was obtained as yellow crystals by the reaction between an aqueous solution (10 ml) of K₃[Cr(CN)₆] (0.2 mmol), 2-pyrrolidone (0.4 mmol) and an aqueous solution (10 ml) of [Dy(H2O)₆]Cl₃ (0.2 mmol) at room tempetature.

S3. Refinement

The coordinates of the water H atoms were found from difference Fourier maps and were normalized to have O—H distances of 0.88 Å. H atoms bound to C and N atoms were also visible in difference maps and were placed using the HFIX commands in SHELXL97 (Sheldrick, 1997). All H atoms were allowed for as riding atoms (C—H = 0.97 Å and N—H 0.86 Å). Residual peaks in the final Fourier map shows were adjacent (1.12 Å) to the Dy atom.

Computing details

Data collection: COLLECT (Nonius, 1998); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2002); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. A view of (I) with the atom-labelling scheme. Displacement ellipsoids are drawn at the 20% probability level. Hydrogen bonds within the asymmetric unit are indicated by dashed lines.

triaqua-1κ³O-µ-cyano-1:2κ²N:C-pentacyano-2κ⁵C-tetrakis -(2-pyrrolidone-1κO)chromium(III)dysprosium(III) dihydrate

Crystal data

[CrDy(C4H7NO)4(CN)6(H2O)3]·2H2O	Z = 2
Mr = 801.12	F(000) = 804
Triclinic, P1	Dx = 1.612 Mg m^−3
a = 9.1442 (18) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.448 (3) Å	θ = 3.5–25.0°
c = 14.518 (3) Å	µ = 2.64 mm^−1
α = 90.19 (3)°	T = 293 K
β = 92.40 (3)°	Platelet, yellow
γ = 91.10 (3)°	0.20 × 0.10 × 0.08 mm
V = 1650.8 (6) Å^3

Data collection

Nonius KappaCCD area-detector diffractometer	5798 independent reflections
Radiation source: fine-focus sealed tube	5457 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
Detector resolution: 0.76 pixels mm^-1	θmax = 25.0°, θmin = 3.5°
CCD scans	h = −10→10
Absorption correction: empirical (using intensity measurements) (Blessing, 1995, 1997)	k = −14→14
Tmin = 0.625, Tmax = 0.812	l = 0→17
9078 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.074	H-atom parameters constrained
S = 1.13	w = 1/[σ^2(Fo^2) + (0.0281P)^2 + 3.8796P] where P = (Fo^2 + 2Fc^2)/3
5798 reflections	(Δ/σ)max = 0.001
389 parameters	Δρmax = 2.25 e Å^−3
0 restraints	Δρmin = −0.95 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Dy	0.557981 (18)	0.234345 (14)	0.249405 (11)	0.02406 (7)
Cr	0.21126 (6)	−0.14059 (5)	0.25114 (4)	0.02209 (13)
O1	0.6484 (4)	0.3850 (3)	0.3299 (2)	0.0543 (9)
O2	0.4831 (3)	0.2048 (3)	0.40197 (19)	0.0375 (7)
O3	0.4588 (4)	0.1971 (3)	0.1015 (2)	0.0594 (10)
O4	0.3229 (3)	0.3073 (3)	0.2551 (2)	0.0525 (9)
O5	0.5930 (4)	0.3839 (2)	0.1488 (2)	0.0404 (7)
O6	0.7567 (3)	0.1824 (3)	0.15911 (19)	0.0429 (8)
O7	0.7513 (3)	0.1570 (3)	0.33933 (19)	0.0483 (9)
N1	0.4533 (4)	0.0510 (3)	0.2503 (2)	0.0379 (8)
N2	0.2270 (5)	−0.1762 (4)	0.0324 (3)	0.0589 (12)
N3	0.4579 (5)	−0.3197 (4)	0.2634 (4)	0.0635 (13)
N4	−0.0446 (5)	−0.3199 (4)	0.2494 (4)	0.0711 (14)
N5	0.2279 (4)	−0.1323 (3)	0.4716 (2)	0.0460 (10)
N6	−0.0214 (4)	0.0515 (4)	0.2428 (3)	0.0498 (10)
N7	0.6979 (7)	0.3761 (4)	0.4842 (3)	0.0765 (17)
H7	0.6722	0.3097	0.4904	0.092*
N8	0.2384 (5)	0.1669 (4)	0.4150 (3)	0.0611 (12)
H8	0.2140	0.1765	0.3578	0.073*
N9	0.4174 (5)	0.1295 (4)	−0.0435 (3)	0.0669 (13)
H9	0.5077	0.1254	−0.0572	0.080*
N10	0.2623 (5)	0.4325 (4)	0.1488 (4)	0.0658 (13)
H10	0.3499	0.4475	0.1330	0.079*
C1	0.3725 (4)	−0.0196 (3)	0.2497 (3)	0.0301 (8)
C2	0.2162 (4)	−0.1592 (4)	0.1088 (3)	0.0343 (9)
C3	0.3696 (5)	−0.2561 (4)	0.2593 (3)	0.0361 (9)
C4	0.0467 (5)	−0.2566 (4)	0.2520 (3)	0.0392 (10)
C5	0.2190 (4)	−0.1334 (3)	0.3934 (3)	0.0310 (9)
C6	0.0582 (4)	−0.0182 (3)	0.2442 (3)	0.0315 (9)
C7	0.6885 (6)	0.4252 (4)	0.4049 (3)	0.0439 (11)
C8	0.7326 (9)	0.5391 (5)	0.4202 (4)	0.076 (2)
H8A	0.6529	0.5861	0.4025	0.092*
H8B	0.8167	0.5578	0.3845	0.092*
C9	0.7704 (11)	0.5489 (5)	0.5221 (4)	0.094 (3)
H9A	0.8700	0.5757	0.5323	0.112*
H9B	0.7048	0.5980	0.5509	0.112*
C10	0.7544 (10)	0.4410 (5)	0.5609 (4)	0.087 (2)
H10A	0.8481	0.4149	0.5843	0.104*
H10B	0.6866	0.4407	0.6106	0.104*
C11	0.3786 (5)	0.1633 (4)	0.0389 (3)	0.0444 (11)
C12	0.2172 (7)	0.1542 (7)	0.0380 (5)	0.087 (2)
H12A	0.1865	0.1097	0.0887	0.105*
H12B	0.1751	0.2246	0.0442	0.105*
C13	0.1688 (7)	0.1051 (6)	−0.0504 (5)	0.078 (2)
H13A	0.0939	0.1480	−0.0809	0.093*
H13B	0.1288	0.0334	−0.0409	0.093*
C14	0.3018 (7)	0.1005 (6)	−0.1074 (4)	0.0719 (17)
H14A	0.3145	0.0288	−0.1318	0.086*
H14B	0.2955	0.1510	−0.1581	0.086*
C15	0.3774 (5)	0.1777 (4)	0.4476 (3)	0.0382 (10)
C16	0.3847 (7)	0.1514 (6)	0.5458 (4)	0.0732 (18)
H16A	0.4335	0.2084	0.5817	0.088*
H16B	0.4360	0.0848	0.5568	0.088*
C17	0.2227 (10)	0.1398 (6)	0.5695 (6)	0.105 (3)
H17A	0.2067	0.0737	0.6031	0.126*
H17B	0.1952	0.1995	0.6077	0.126*
C18	0.1333 (8)	0.1383 (6)	0.4817 (6)	0.089 (2)
H18A	0.0908	0.0675	0.4692	0.107*
H18B	0.0556	0.1902	0.4829	0.107*
C19	0.2340 (5)	0.3613 (4)	0.2112 (3)	0.0444 (11)
C20	0.0706 (6)	0.3554 (6)	0.2217 (5)	0.0748 (19)
H20A	0.0443	0.3868	0.2799	0.090*
H20B	0.0346	0.2816	0.2186	0.090*
C21	0.0094 (7)	0.4198 (6)	0.1412 (6)	0.096 (3)
H21A	−0.0302	0.3722	0.0929	0.115*
H21B	−0.0679	0.4658	0.1608	0.115*
C22	0.1335 (7)	0.4852 (6)	0.1074 (6)	0.087 (2)
H22A	0.1346	0.4837	0.0406	0.105*
H22B	0.1287	0.5592	0.1280	0.105*
O8	0.6882 (4)	0.5915 (3)	0.1705 (2)	0.0501 (8)
O9	0.5662 (5)	0.3900 (3)	−0.0407 (3)	0.0655 (10)
H51	0.6268	0.4488	0.1630	0.094*
H52	0.5930	0.3796	0.0883	0.094*
H61	0.8331	0.1428	0.1731	0.094*
H62	0.7616	0.1791	0.0988	0.094*
H71	0.8299	0.1203	0.3281	0.094*
H72	0.7396	0.1295	0.3943	0.094*
H81	0.6266	0.6097	0.2125	0.094*
H82	0.7803	0.6054	0.1870	0.094*
H91	0.6286	0.3406	−0.0556	0.094*
H92	0.4758	0.3928	−0.0638	0.094*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Dy	0.02291 (10)	0.02860 (11)	0.02033 (10)	−0.00276 (7)	−0.00165 (6)	0.00127 (7)
Cr	0.0228 (3)	0.0265 (3)	0.0170 (3)	−0.0005 (2)	0.0011 (2)	−0.0005 (2)
O1	0.086 (3)	0.0430 (19)	0.0316 (17)	−0.0200 (17)	−0.0101 (16)	−0.0031 (14)
O2	0.0334 (16)	0.0525 (19)	0.0269 (15)	−0.0011 (13)	0.0069 (12)	0.0020 (13)
O3	0.076 (3)	0.061 (2)	0.0371 (18)	−0.0250 (19)	−0.0300 (17)	0.0049 (16)
O4	0.0336 (17)	0.081 (3)	0.0438 (19)	0.0156 (17)	0.0037 (14)	0.0176 (17)
O5	0.060 (2)	0.0311 (16)	0.0298 (15)	−0.0085 (14)	0.0007 (13)	0.0047 (12)
O6	0.0421 (17)	0.068 (2)	0.0195 (14)	0.0189 (15)	0.0055 (12)	0.0020 (14)
O7	0.0387 (17)	0.086 (3)	0.0212 (15)	0.0286 (17)	0.0023 (12)	0.0089 (15)
N1	0.042 (2)	0.036 (2)	0.035 (2)	−0.0107 (17)	0.0027 (15)	−0.0006 (15)
N2	0.054 (3)	0.099 (4)	0.024 (2)	0.015 (2)	0.0051 (17)	−0.004 (2)
N3	0.061 (3)	0.056 (3)	0.075 (3)	0.026 (2)	0.003 (2)	−0.001 (2)
N4	0.054 (3)	0.071 (3)	0.087 (4)	−0.031 (3)	0.012 (2)	−0.012 (3)
N5	0.053 (2)	0.064 (3)	0.022 (2)	0.011 (2)	0.0007 (16)	0.0024 (17)
N6	0.045 (2)	0.057 (3)	0.048 (2)	0.020 (2)	−0.0014 (18)	−0.001 (2)
N7	0.143 (5)	0.042 (3)	0.041 (3)	−0.024 (3)	−0.021 (3)	0.006 (2)
N8	0.039 (2)	0.082 (3)	0.063 (3)	−0.006 (2)	0.007 (2)	−0.007 (2)
N9	0.046 (3)	0.084 (4)	0.070 (3)	−0.007 (2)	0.007 (2)	−0.017 (3)
N10	0.041 (2)	0.066 (3)	0.091 (4)	0.006 (2)	−0.006 (2)	0.029 (3)
C1	0.032 (2)	0.034 (2)	0.024 (2)	−0.0005 (17)	0.0030 (15)	−0.0003 (16)
C2	0.030 (2)	0.046 (3)	0.026 (2)	0.0054 (17)	0.0020 (16)	0.0004 (18)
C3	0.040 (2)	0.037 (2)	0.032 (2)	0.0067 (19)	−0.0008 (17)	−0.0026 (18)
C4	0.035 (2)	0.045 (3)	0.037 (2)	−0.009 (2)	0.0049 (18)	−0.004 (2)
C5	0.028 (2)	0.036 (2)	0.030 (2)	0.0031 (16)	0.0022 (16)	0.0031 (17)
C6	0.031 (2)	0.039 (2)	0.023 (2)	0.0025 (18)	−0.0003 (15)	−0.0021 (16)
C7	0.060 (3)	0.038 (3)	0.033 (2)	−0.009 (2)	−0.005 (2)	0.0003 (19)
C8	0.132 (6)	0.046 (3)	0.048 (3)	−0.022 (3)	−0.021 (3)	0.001 (3)
C9	0.163 (8)	0.060 (4)	0.055 (4)	−0.025 (4)	−0.021 (4)	−0.015 (3)
C10	0.147 (7)	0.071 (4)	0.040 (3)	−0.022 (4)	−0.025 (4)	−0.001 (3)
C11	0.055 (3)	0.038 (3)	0.038 (3)	−0.008 (2)	−0.012 (2)	0.005 (2)
C12	0.061 (4)	0.125 (6)	0.076 (4)	−0.016 (4)	0.009 (3)	−0.039 (4)
C13	0.050 (3)	0.104 (5)	0.077 (4)	0.000 (3)	−0.023 (3)	−0.025 (4)
C14	0.080 (4)	0.089 (5)	0.045 (3)	−0.015 (3)	−0.009 (3)	−0.019 (3)
C15	0.040 (2)	0.037 (2)	0.039 (2)	0.0035 (18)	0.0153 (19)	−0.0013 (19)
C16	0.076 (4)	0.112 (5)	0.033 (3)	0.019 (4)	0.011 (3)	0.011 (3)
C17	0.146 (8)	0.083 (5)	0.093 (6)	−0.018 (5)	0.096 (6)	0.003 (4)
C18	0.060 (4)	0.071 (4)	0.140 (7)	−0.003 (3)	0.052 (4)	0.011 (4)
C19	0.035 (2)	0.050 (3)	0.049 (3)	0.007 (2)	0.001 (2)	−0.003 (2)
C20	0.031 (3)	0.109 (5)	0.085 (5)	0.012 (3)	0.001 (3)	0.010 (4)
C21	0.051 (4)	0.087 (5)	0.148 (8)	0.019 (3)	−0.021 (4)	0.023 (5)
C22	0.069 (4)	0.081 (5)	0.112 (6)	0.027 (4)	−0.018 (4)	0.034 (4)
O8	0.0438 (19)	0.0431 (19)	0.063 (2)	−0.0055 (14)	0.0020 (16)	−0.0070 (16)
O9	0.090 (3)	0.063 (2)	0.043 (2)	0.007 (2)	0.0016 (19)	−0.0001 (18)

Geometric parameters (Å, º)

Dy—O1	2.326 (3)	N10—H10	0.86
Dy—O3	2.337 (3)	C7—C8	1.480 (7)
Dy—O4	2.354 (3)	C8—C9	1.510 (8)
Dy—O2	2.373 (3)	C8—H8A	0.97
Dy—O7	2.374 (3)	C8—H8B	0.97
Dy—O6	2.383 (3)	C9—C10	1.465 (9)
Dy—O5	2.394 (3)	C9—H9A	0.97
Dy—N1	2.458 (4)	C9—H9B	0.97
Cr—C3	2.061 (4)	C10—H10A	0.97
Cr—C5	2.064 (4)	C10—H10B	0.97
Cr—C4	2.066 (4)	C11—C12	1.478 (8)
Cr—C2	2.081 (4)	C12—C13	1.467 (8)
Cr—C1	2.088 (4)	C12—H12A	0.97
Cr—C6	2.088 (4)	C12—H12B	0.97
O1—C7	1.236 (5)	C13—C14	1.502 (9)
O2—C15	1.237 (5)	C13—H13A	0.97
O3—C11	1.213 (5)	C13—H13B	0.97
O4—C19	1.224 (6)	C14—H14A	0.97
O5—H51	0.88	C14—H14B	0.97
O5—H52	0.88	C15—C16	1.463 (7)
O6—H61	0.88	C16—C17	1.539 (10)
O6—H62	0.88	C16—H16A	0.97
O7—H71	0.88	C16—H16B	0.97
O7—H72	0.88	C17—C18	1.485 (12)
N1—C1	1.138 (5)	C17—H17A	0.97
N2—C2	1.137 (6)	C17—H17B	0.97
N3—C3	1.141 (6)	C18—H18A	0.97
N4—C4	1.137 (6)	C18—H18B	0.97
N5—C5	1.136 (5)	C19—C20	1.509 (7)
N6—C6	1.142 (6)	C20—C21	1.513 (9)
N7—C7	1.306 (6)	C20—H20A	0.97
N7—C10	1.446 (7)	C20—H20B	0.97
N7—H7	0.86	C21—C22	1.486 (10)
N8—C15	1.341 (6)	C21—H21A	0.97
N8—C18	1.434 (8)	C21—H21B	0.97
N8—H8	0.86	C22—H22A	0.97
N9—C11	1.331 (7)	C22—H22B	0.97
N9—C14	1.417 (7)	O8—H81	0.88
N9—H9	0.86	O8—H82	0.88
N10—C19	1.300 (7)	O9—H91	0.88
N10—C22	1.467 (7)	O9—H92	0.88
O1—Dy—O3	136.65 (12)	C7—C8—H8B	110.7
O1—Dy—O4	88.05 (14)	C9—C8—H8B	110.7
O3—Dy—O4	77.80 (14)	H8A—C8—H8B	108.8
O1—Dy—O2	76.31 (11)	C10—C9—C8	106.7 (5)
O3—Dy—O2	135.47 (12)	C10—C9—H9A	110.4
O4—Dy—O2	74.29 (11)	C8—C9—H9A	110.4
O1—Dy—O7	79.61 (13)	C10—C9—H9B	110.4
O3—Dy—O7	132.63 (13)	C8—C9—H9B	110.4
O4—Dy—O7	144.12 (11)	H9A—C9—H9B	108.6
O2—Dy—O7	70.10 (10)	N7—C10—C9	104.2 (5)
O1—Dy—O6	103.88 (13)	N7—C10—H10A	110.9
O3—Dy—O6	73.53 (13)	C9—C10—H10A	110.9
O4—Dy—O6	148.46 (11)	N7—C10—H10B	110.9
O2—Dy—O6	136.60 (10)	C9—C10—H10B	110.9
O7—Dy—O6	67.39 (10)	H10A—C10—H10B	108.9
O1—Dy—O5	68.44 (11)	O3—C11—N9	127.2 (5)
O3—Dy—O5	69.05 (11)	O3—C11—C12	126.7 (5)
O4—Dy—O5	81.61 (12)	N9—C11—C12	106.1 (4)
O2—Dy—O5	137.63 (11)	C13—C12—C11	107.2 (5)
O7—Dy—O5	123.17 (12)	C13—C12—H12A	110.3
O6—Dy—O5	76.14 (11)	C11—C12—H12A	110.3
O1—Dy—N1	149.59 (12)	C13—C12—H12B	110.3
O3—Dy—N1	72.28 (12)	C11—C12—H12B	110.3
O4—Dy—N1	90.87 (13)	H12A—C12—H12B	108.5
O2—Dy—N1	74.17 (12)	C12—C13—C14	106.4 (5)
O7—Dy—N1	83.68 (13)	C12—C13—H13A	110.5
O6—Dy—N1	92.71 (13)	C14—C13—H13A	110.5
O5—Dy—N1	141.33 (11)	C12—C13—H13B	110.5
C3—Cr—C5	88.60 (16)	C14—C13—H13B	110.5
C3—Cr—C4	91.26 (18)	H13A—C13—H13B	108.6
C5—Cr—C4	90.87 (17)	N9—C14—C13	103.0 (5)
C3—Cr—C2	86.29 (17)	N9—C14—H14A	111.2
C5—Cr—C2	174.87 (16)	C13—C14—H14A	111.2
C4—Cr—C2	88.73 (17)	N9—C14—H14B	111.2
C3—Cr—C1	90.55 (17)	C13—C14—H14B	111.2
C5—Cr—C1	89.26 (16)	H14A—C14—H14B	109.1
C4—Cr—C1	178.18 (17)	O2—C15—N8	125.6 (4)
C2—Cr—C1	91.30 (16)	O2—C15—C16	125.1 (5)
C3—Cr—C6	177.40 (17)	N8—C15—C16	109.2 (4)
C5—Cr—C6	90.80 (16)	C15—C16—C17	103.3 (5)
C4—Cr—C6	91.27 (17)	C15—C16—H16A	111.1
C2—Cr—C6	94.32 (16)	C17—C16—H16A	111.1
C1—Cr—C6	86.91 (16)	C15—C16—H16B	111.1
C7—O1—Dy	147.6 (3)	C17—C16—H16B	111.1
C15—O2—Dy	143.3 (3)	H16A—C16—H16B	109.1
C11—O3—Dy	161.8 (4)	C18—C17—C16	108.0 (5)
C19—O4—Dy	142.7 (3)	C18—C17—H17A	110.1
Dy—O5—H51	128.3	C16—C17—H17A	110.1
Dy—O5—H52	124.8	C18—C17—H17B	110.1
H51—O5—H52	105.7	C16—C17—H17B	110.1
Dy—O6—H61	130.8	H17A—C17—H17B	108.4
Dy—O6—H62	129.2	N8—C18—C17	102.7 (5)
H61—O6—H62	97.5	N8—C18—H18A	111.2
Dy—O7—H71	135.9	C17—C18—H18A	111.2
Dy—O7—H72	123.2	N8—C18—H18B	111.2
H71—O7—H72	95.2	C17—C18—H18B	111.2
C1—N1—Dy	162.4 (3)	H18A—C18—H18B	109.1
C7—N7—C10	115.3 (5)	O4—C19—N10	126.8 (5)
C7—N7—H7	122.3	O4—C19—C20	124.7 (5)
C10—N7—H7	122.3	N10—C19—C20	108.5 (5)
C15—N8—C18	115.7 (6)	C19—C20—C21	104.0 (5)
C15—N8—H8	122.2	C19—C20—H20A	111.0
C18—N8—H8	122.2	C21—C20—H20A	111.0
C11—N9—C14	116.4 (5)	C19—C20—H20B	111.0
C11—N9—H9	121.8	C21—C20—H20B	111.0
C14—N9—H9	121.8	H20A—C20—H20B	109.0
C19—N10—C22	115.0 (5)	C22—C21—C20	106.3 (5)
C19—N10—H10	122.5	C22—C21—H21A	110.5
C22—N10—H10	122.5	C20—C21—H21A	110.5
N1—C1—Cr	175.4 (4)	C22—C21—H21B	110.5
N2—C2—Cr	174.2 (4)	C20—C21—H21B	110.5
N3—C3—Cr	179.5 (5)	H21A—C21—H21B	108.7
N4—C4—Cr	177.7 (5)	N10—C22—C21	103.1 (5)
N5—C5—Cr	177.2 (4)	N10—C22—H22A	111.1
N6—C6—Cr	177.0 (4)	C21—C22—H22A	111.1
O1—C7—N7	126.6 (4)	N10—C22—H22B	111.1
O1—C7—C8	125.3 (4)	C21—C22—H22B	111.1
N7—C7—C8	108.1 (4)	H22A—C22—H22B	109.1
C7—C8—C9	105.4 (5)	H81—O8—H82	113.3
C7—C8—H8A	110.7	H91—O9—H92	123.8
C9—C8—H8A	110.7
O3—Dy—O1—C7	168.0 (6)	Dy—O1—C7—C8	−175.6 (5)
O4—Dy—O1—C7	98.2 (7)	C10—N7—C7—O1	177.4 (6)
O2—Dy—O1—C7	23.9 (7)	C10—N7—C7—C8	−3.5 (9)
O7—Dy—O1—C7	−48.0 (7)	O1—C7—C8—C9	179.4 (6)
O6—Dy—O1—C7	−111.4 (7)	N7—C7—C8—C9	0.3 (8)
O5—Dy—O1—C7	179.9 (7)	C7—C8—C9—C10	2.8 (9)
N1—Dy—O1—C7	9.8 (9)	C7—N7—C10—C9	5.2 (10)
O1—Dy—O2—C15	133.1 (5)	C8—C9—C10—N7	−4.5 (10)
O3—Dy—O2—C15	−11.9 (6)	Dy—O3—C11—N9	−145.2 (10)
O4—Dy—O2—C15	41.3 (5)	Dy—O3—C11—C12	36.7 (16)
O7—Dy—O2—C15	−143.2 (5)	C14—N9—C11—O3	−175.8 (6)
O6—Dy—O2—C15	−131.1 (5)	C14—N9—C11—C12	2.7 (8)
O5—Dy—O2—C15	99.0 (5)	O3—C11—C12—C13	−177.7 (6)
N1—Dy—O2—C15	−54.3 (5)	N9—C11—C12—C13	3.8 (8)
O1—Dy—O3—C11	−131.5 (12)	C11—C12—C13—C14	−8.3 (9)
O4—Dy—O3—C11	−57.7 (12)	C11—N9—C14—C13	−7.8 (8)
O2—Dy—O3—C11	−5.7 (13)	C12—C13—C14—N9	9.4 (8)
O7—Dy—O3—C11	100.3 (12)	Dy—O2—C15—N8	−10.6 (8)
O6—Dy—O3—C11	135.6 (12)	Dy—O2—C15—C16	168.7 (4)
O5—Dy—O3—C11	−143.3 (13)	C18—N8—C15—O2	−177.9 (5)
N1—Dy—O3—C11	37.2 (12)	C18—N8—C15—C16	2.7 (7)
O1—Dy—O4—C19	95.0 (6)	O2—C15—C16—C17	172.2 (5)
O3—Dy—O4—C19	−43.7 (6)	N8—C15—C16—C17	−8.4 (7)
O2—Dy—O4—C19	171.4 (6)	C15—C16—C17—C18	11.1 (8)
O7—Dy—O4—C19	164.3 (5)	C15—N8—C18—C17	4.5 (8)
O6—Dy—O4—C19	−18.8 (7)	C16—C17—C18—N8	−9.5 (8)
O5—Dy—O4—C19	26.6 (6)	Dy—O4—C19—N10	−26.1 (10)
N1—Dy—O4—C19	−115.4 (6)	Dy—O4—C19—C20	154.1 (5)
O1—Dy—N1—C1	91.9 (11)	C22—N10—C19—O4	−179.9 (6)
O3—Dy—N1—C1	−72.6 (11)	C22—N10—C19—C20	−0.1 (8)
O4—Dy—N1—C1	4.3 (11)	O4—C19—C20—C21	−169.4 (6)
O2—Dy—N1—C1	77.7 (11)	N10—C19—C20—C21	10.8 (7)
O7—Dy—N1—C1	148.7 (11)	C19—C20—C21—C22	−17.1 (8)
O6—Dy—N1—C1	−144.4 (11)	C19—N10—C22—C21	−10.8 (9)
O5—Dy—N1—C1	−73.3 (11)	C20—C21—C22—N10	16.8 (9)
Dy—O1—C7—N7	3.4 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N7—H7···O2	0.86	2.46	3.075 (6)	129
N7—H7···N5^i	0.86	2.46	3.183 (7)	142
N8—H8···O4	0.86	2.44	3.028 (6)	126
N9—H9···N2^ii	0.86	2.51	3.290 (7)	152
N10—H10···O5	0.86	2.38	3.096 (6)	141
N10—H10···O9^iii	0.86	2.55	3.147 (6)	127
O5—H51···O8	0.88	1.85	2.724 (4)	170
O5—H52···O9	0.88	1.88	2.754 (5)	169
O6—H61···N6^iv	0.88	2.01	2.861 (5)	162
O6—H62···N2^ii	0.88	1.91	2.792 (5)	178
O7—H71···N6^iv	0.88	2.07	2.890 (5)	154
O7—H72···N5^i	0.88	1.96	2.762 (5)	152
O8—H81···N3^v	0.88	1.96	2.792 (6)	157
O8—H82···N4^vi	0.88	2.02	2.855 (6)	159
O9—H91···N2^ii	0.88	2.47	3.294 (6)	156
O9—H92···O8^iii	0.88	2.12	2.945 (5)	155

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