A novel thio­cyanate-bridged dinuclear cadmium(II) complex: di-[mu]-thio­cyanato-bis­((methanol){4-nitro-2-[2-(dimethyl­amino)ethyl­imino­meth­yl]phenolato}cadmium(II))

The title complex, [Cd₂(C₁₁H₁₄N₃O₃)₂(NCS)₂(CH₄O)₂], is an inter­esting thio­cyanate-bridged dinuclear cadmium(II) compound. It is located on a crystallographic inversion center. The Cd^II atom is six-coordinated in an octa­hedral configuration by one O and two N atoms of one Schiff base ligand and by the terminal N atom of a bridging thio­cyanate ligand, defining the basal plane, and by the terminal S atom of another bridging thio­cyanate ligand and by the O atom of a coordi­nated methanol mol­ecule, occupying the axial positions. The mol­ecules are linked through inter­molecular O-H...O hydrogen bonds, forming chains running along the b axis.

S1. Comment

Metal-organic complexes containing bridging ligands are of current interest because of their interesting molecular topologies and crystal-packing motifs, as well as the fact that they may be designed with specific functionalities (Batten & Robson, 1998; Abourahma et al., 2002; Konar et al., 2002). In addition to being robust and thermally stable, some possess photoluminescent properties, a feature that has contributed to d¹⁰ metal polynuclear complexes being investigated in the search for new materials (Weidenbruch et al., 1989; Kunkely & Vogler, 1990; Bertoncello et al., 1992). Among the Cd^II coordination polymers featuring interesting supramolecular structures, such as one-dimensional helical ribbons or molecular zippers, two-dimensional molecular square or triangular grids, and interpenetrating/non-interpenetrating three-dimensional networks (Dai et al., 2002; Chen et al., 2003; Luo et al., 2003), most of them possess photoluminescent properties (Xiong et al., 2000; Wang et al., 2003).

Owing to the versatile coordination modes of the ambidentate thiocyanate ligand, this pseudohalide ligand has become one of the most extensively studied building blocks in the multi-dimensional complexes (Sailaja et al., 2003; Dey et al., 2004). Thiocyanate complexes of various dimensionalities have been obtained (Zurowska et al., 2002; Zhang et al., 2003; You, 2005a). A major obstacle to a more comprehensive study of such thiocyanate-based polymeric coordination complexes is the lack of rational synthetic procedures, since with the present state of knowledge it is hardly possible to determine which coordination mode will be adopted by the thiocyanate ligand and whether the sought-after alternating chain structure will finally be formed (Tercero et al., 2002; Ribas et al., 1999; Liu et al., 2003).

Our work is aimed at obtaining multi-dimensional polymetallic complexes. Based on the above considerations, we designed and synthesized a tridentate ligand, 4-nitro-2-(2-dimethylaminoethyliminomethyl)phenol (NDAP). The reason we use NDAP as ligand is that it could adopt an almost fixed coordination mode through the three donor atoms (You, 2005b; Yue et al., 2005). The second ligand, viz. thiocyanate, is a well known bridging group. It readily bridges different metal ions through the terminal donor atoms, forming polynuclear complexes (Kuang et al., 2001). Cd^II is a good candidate for octahedral coordination geometry. We report here the dinuclear structure of the title compound, (I), formed by the reaction of the NDAP ligand, ammonium thiocyanate and Cd^II acetate.

Complex (I) (Fig. 1) contains two Cd(NDAP) units connected to each other by two bridging thiocyanate anions. The Cd^II atom is in an octahedral coordination environment and is six-coordinated by one O and two N atoms of one Schiff base ligand and by one teminal N atom of a bridging thiocyanate ligand, defining the basal plane, and by one terminal S atom of another bridging thiocyanate ligand, together with one O atom of a coordinated MeOH molecule, occupying the axial positions. The Schiff base ligand acts as a tridentate ligand and ligates to the metal via three O– and N-donor atoms. The thiocyanate anion acts as a bridging ligand and ligates to two different but symmetry-related Cd^II atoms via the terminal N and S atoms.

The three trans angles at the Cd^II atom lie in the range 151.7 (3)–170.90 (4)° (Table 1). The other angles subtended at the Cd^II atom range from 74.5 (3) to 109.81 (7)°, indicating a somewhat distorted octahedral geometry. The bond lengths subtended at Cd1 are comparable to those observed in other Schiff base–cadmium(II) complexes (You et al., 2004) and, as expected, the bond involving amine atom N3 [2.419 (13) Å] is longer than that involving imine atom N2 [2.296 (2) Å] (Mondal et al., 2001). The Cd1—S1ⁱ bond [symmetry code: (i) 1 − x, 1 − y, 1 − z] is much longer than the other bonds, indicating that the Cd—S bond is not very strong. The bridging thiocyanate group is nearly linear and shows bent coordination modes with the metal atoms [N4—C13—S1 = 179.3 (2)°, Cd1—N4—C13 = 160.4 (2)° and Cd1ⁱ—S1—C13 = 100.71 (8)°]. The N2—Cd1—N3(or N3') bond angle [mean 75.3 (3)°] of the five-membered chelate ring is much smaller than 90°, as a result of the strain created by the five-membered chelate rings Cd1/N2/C8/C9/N3 and Cd1/N2/C8'/C9'/N3'.

The C7═N2 bond length [1.280 (3) Å] conforms to the normal value for a double bond, while the C8—N2 bond length [1.458 (3) Å] conforms to the normal value for a single bond. The O1/N1/O2 plane and the C1–C6 phenyl ring are not coplanar, having a dihedral angle of 14.7 (3)°.

In the crystal structure, the molecules are linked by the intermolecular O—H···O hydrogen bonds, forming chains running along the b axis (Table 2 and Fig. 2).

S2. Experimental

5-Nitrosalicylaldehyde (0.1 mmol, 16.7 mg) and N,N-dimethylethane-1,2-diamine (0.1 mmol, 8.8 mg) were dissolved in MeOH (10 ml). The mixture was stirred at room temperature for 10 min to give a yellow solution. To the solution was added an MeOH solution (5 ml) of Cd(CH₃COO)₂·4H₂O (0.1 mmol, 30.3 mg), with stirring. The mixture was stirred for another 10 min at room temperature. After keeping the filtrate in air for 3 d, colorless block-shaped crystals were formed.

S3. Refinement

Atom H4 was located in a difference Fourier map and refined isotropically, with the O—H distance restrained to 0.88 (1) Å. The other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances in the range 0.93–0.97 Å, and with U_iso(H) = 1.2 or 1.5U_eq(C). The C9/N3/C10/C11 moieties are disordered over two distinct sites, with occupancies of 0.535 (5) and 0.465 (5).

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Atoms labelled with the suffix A are at the symmetry position (1 − x, 1 − y, 1 − z). Only the major component of the disordered moiety is shown.
	Fig. 2. The crystal packing of (I). Dashed lines show the intermolecular O—H···O hydrogen bonds.

di-µ-thiocyanato-bis((methanol){4-nitro-2-[2- (dimethylamino)ethyliminomethyl]phenolato}cadmium(II)]

Crystal data

[Cd2(C11H14N3O2)2(NCS)2(CH4O)2]	Z = 1
Mr = 877.55	F(000) = 440
Triclinic, P1	Dx = 1.751 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.286 (1) Å	Cell parameters from 5707 reflections
b = 8.946 (1) Å	θ = 2.4–28.3°
c = 11.971 (2) Å	µ = 1.46 mm^−1
α = 110.019 (2)°	T = 298 K
β = 92.705 (2)°	Block, colorless
γ = 91.482 (2)°	0.32 × 0.21 × 0.11 mm
V = 832.0 (2) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	3686 independent reflections
Radiation source: fine-focus sealed tube	3559 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.016
ω scans	θmax = 27.5°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
Tmin = 0.652, Tmax = 0.856	k = −11→11
7155 measured reflections	l = −15→15

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.062	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ^2(Fo^2) + (0.034P)^2 + 0.1681P] where P = (Fo^2 + 2Fc^2)/3
3686 reflections	(Δ/σ)max < 0.001
253 parameters	Δρmax = 0.34 e Å^−3
21 restraints	Δρmin = −0.55 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	Occ. (<1)
Cd1	0.404413 (17)	0.167141 (16)	0.357952 (12)	0.03278 (7)
S1	0.40874 (8)	0.64051 (7)	0.72641 (6)	0.04685 (15)
O1	0.7429 (3)	−0.5691 (2)	−0.11703 (18)	0.0644 (5)
O2	0.8870 (2)	−0.6258 (2)	0.01713 (19)	0.0596 (5)
O3	0.61049 (18)	0.00293 (17)	0.33886 (13)	0.0372 (3)
O4	0.2822 (2)	−0.00646 (18)	0.44507 (13)	0.0406 (4)
N1	0.7969 (3)	−0.5386 (2)	−0.01447 (19)	0.0458 (5)
N2	0.3463 (2)	0.0052 (2)	0.16408 (16)	0.0378 (4)
N3	0.1300 (15)	0.2208 (12)	0.3100 (12)	0.0328 (15)	0.535 (6)
N4	0.4184 (3)	0.3495 (2)	0.54200 (18)	0.0498 (5)
C1	0.6517 (2)	−0.1192 (2)	0.25131 (17)	0.0302 (4)
C2	0.5694 (2)	−0.1759 (2)	0.13573 (17)	0.0319 (4)
C3	0.6226 (3)	−0.3127 (2)	0.04980 (18)	0.0348 (4)
H3	0.5702	−0.3500	−0.0257	0.042*
C4	0.7505 (3)	−0.3927 (2)	0.0748 (2)	0.0370 (5)
C5	0.8340 (3)	−0.3390 (3)	0.1858 (2)	0.0395 (5)
H5	0.9210	−0.3937	0.2019	0.047*
C6	0.7861 (3)	−0.2049 (3)	0.27064 (19)	0.0374 (5)
H6	0.8437	−0.1678	0.3442	0.045*
C7	0.4265 (3)	−0.1102 (3)	0.09989 (18)	0.0363 (4)
H7	0.3884	−0.1573	0.0208	0.044*
C8	0.1994 (3)	0.0455 (4)	0.1107 (2)	0.0578 (7)	0.535 (6)
H8A	0.1555	−0.0475	0.0461	0.069*	0.535 (6)
H8B	0.2249	0.1281	0.0781	0.069*	0.535 (6)
C9	0.0783 (5)	0.1013 (6)	0.1999 (4)	0.0489 (14)	0.535 (6)
H9A	−0.0104	0.1417	0.1644	0.059*	0.535 (6)
H9B	0.0356	0.0100	0.2170	0.059*	0.535 (6)
C10	0.0231 (10)	0.2286 (12)	0.4068 (7)	0.0613 (19)	0.535 (6)
H10A	−0.0832	0.2551	0.3865	0.092*	0.535 (6)
H10B	0.0655	0.3087	0.4793	0.092*	0.535 (6)
H10C	0.0176	0.1272	0.4177	0.092*	0.535 (6)
C11	0.1338 (12)	0.3849 (11)	0.2984 (8)	0.064 (2)	0.535 (6)
H11A	0.2093	0.3881	0.2407	0.096*	0.535 (6)
H11B	0.1665	0.4638	0.3741	0.096*	0.535 (6)
H11C	0.0280	0.4064	0.2730	0.096*	0.535 (6)
C12	0.2508 (3)	−0.1696 (3)	0.3773 (2)	0.0488 (6)
H12A	0.1748	−0.1794	0.3118	0.073*
H12B	0.2065	−0.2232	0.4268	0.073*
H12C	0.3497	−0.2169	0.3472	0.073*
C13	0.4147 (3)	0.4694 (3)	0.61719 (19)	0.0350 (4)
N3'	0.1515 (18)	0.2586 (12)	0.3043 (13)	0.0303 (16)	0.465 (6)
C8'	0.1994 (3)	0.0455 (4)	0.1107 (2)	0.0578 (7)	0.465 (6)
H8'1	0.2172	0.0339	0.0288	0.069*	0.465 (6)
H8'2	0.1131	−0.0304	0.1096	0.069*	0.465 (6)
C9'	0.1470 (7)	0.2038 (6)	0.1707 (5)	0.0492 (16)	0.465 (6)
H9'1	0.0370	0.2099	0.1416	0.059*	0.465 (6)
H9'2	0.2141	0.2780	0.1481	0.059*	0.465 (6)
C10'	0.0161 (12)	0.1761 (15)	0.3407 (10)	0.078 (3)	0.465 (6)
H10D	0.0131	0.2161	0.4259	0.117*	0.465 (6)
H10E	0.0322	0.0637	0.3140	0.117*	0.465 (6)
H10F	−0.0844	0.1952	0.3056	0.117*	0.465 (6)
C11'	0.1396 (15)	0.4252 (12)	0.3517 (8)	0.060 (2)	0.465 (6)
H11D	0.0406	0.4544	0.3214	0.090*	0.465 (6)
H11E	0.2296	0.4760	0.3291	0.090*	0.465 (6)
H11F	0.1406	0.4587	0.4370	0.090*	0.465 (6)
H4	0.319 (4)	0.002 (4)	0.5179 (15)	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.03754 (10)	0.02599 (9)	0.03024 (10)	0.00490 (6)	−0.00079 (6)	0.00391 (6)
S1	0.0591 (4)	0.0338 (3)	0.0398 (3)	−0.0032 (3)	0.0132 (3)	0.0016 (2)
O1	0.0731 (14)	0.0526 (11)	0.0471 (11)	0.0072 (10)	0.0118 (10)	−0.0105 (9)
O2	0.0618 (12)	0.0351 (9)	0.0772 (13)	0.0146 (8)	0.0211 (10)	0.0103 (9)
O3	0.0443 (8)	0.0329 (8)	0.0263 (7)	0.0097 (6)	−0.0024 (6)	−0.0002 (6)
O4	0.0586 (10)	0.0318 (8)	0.0289 (7)	0.0019 (7)	0.0001 (7)	0.0076 (6)
N1	0.0452 (11)	0.0335 (10)	0.0490 (12)	−0.0013 (9)	0.0183 (9)	0.0000 (9)
N2	0.0389 (10)	0.0368 (10)	0.0336 (9)	0.0052 (8)	−0.0058 (7)	0.0076 (8)
N4	0.0737 (15)	0.0333 (10)	0.0365 (11)	−0.0067 (10)	0.0074 (10)	0.0046 (9)
C1	0.0346 (10)	0.0269 (9)	0.0276 (9)	0.0022 (8)	0.0046 (7)	0.0072 (8)
C2	0.0353 (10)	0.0305 (10)	0.0271 (10)	0.0005 (8)	0.0039 (8)	0.0061 (8)
C3	0.0405 (11)	0.0323 (10)	0.0265 (10)	−0.0025 (8)	0.0051 (8)	0.0032 (8)
C4	0.0405 (12)	0.0279 (10)	0.0377 (11)	0.0018 (9)	0.0141 (9)	0.0035 (9)
C5	0.0409 (12)	0.0380 (11)	0.0410 (12)	0.0113 (9)	0.0085 (9)	0.0137 (10)
C6	0.0401 (11)	0.0393 (11)	0.0306 (10)	0.0073 (9)	0.0007 (8)	0.0087 (9)
C7	0.0436 (12)	0.0351 (11)	0.0256 (10)	−0.0003 (9)	−0.0021 (8)	0.0050 (8)
C12	0.0606 (16)	0.0351 (12)	0.0447 (13)	−0.0042 (11)	−0.0018 (11)	0.0072 (10)
C13	0.0385 (11)	0.0343 (11)	0.0321 (10)	−0.0029 (9)	0.0025 (8)	0.0117 (9)
N3	0.035 (4)	0.018 (4)	0.050 (3)	−0.002 (3)	0.001 (2)	0.019 (3)
C8	0.0540 (15)	0.0682 (18)	0.0445 (14)	0.0200 (13)	−0.0129 (11)	0.0115 (13)
C9	0.043 (3)	0.050 (3)	0.053 (3)	0.003 (2)	−0.008 (2)	0.017 (2)
C10	0.042 (3)	0.082 (5)	0.072 (4)	0.021 (3)	0.021 (4)	0.038 (4)
C11	0.065 (4)	0.050 (5)	0.082 (6)	0.014 (4)	−0.003 (5)	0.028 (5)
N3'	0.032 (4)	0.013 (4)	0.050 (3)	−0.003 (3)	0.005 (2)	0.016 (3)
C8'	0.0540 (15)	0.0682 (18)	0.0445 (14)	0.0200 (13)	−0.0129 (11)	0.0115 (13)
C9'	0.055 (3)	0.042 (3)	0.049 (3)	0.014 (2)	−0.011 (2)	0.015 (2)
C10'	0.044 (4)	0.106 (9)	0.113 (9)	0.021 (5)	0.018 (6)	0.070 (8)
C11'	0.074 (5)	0.038 (5)	0.062 (5)	0.028 (4)	−0.002 (5)	0.010 (4)

Geometric parameters (Å, º)

Cd1—N4	2.244 (2)	C12—H12A	0.96
Cd1—O3	2.250 (2)	C12—H12B	0.96
Cd1—N2	2.296 (2)	C12—H12C	0.96
Cd1—O4	2.378 (2)	N3—C9	1.421 (13)
Cd1—N3'	2.408 (15)	N3—C10	1.476 (13)
Cd1—N3	2.419 (13)	N3—C11	1.521 (12)
Cd1—S1^i	2.7527 (8)	C8—C9	1.469 (5)
S1—C13	1.642 (2)	C8—H8A	0.97
O1—N1	1.222 (3)	C8—H8B	0.9700
O2—N1	1.231 (3)	C9—H9A	0.9700
O3—C1	1.295 (2)	C9—H9B	0.9700
O4—C12	1.417 (3)	C10—H10A	0.96
O4—H4	0.887 (10)	C10—H10B	0.96
N1—C4	1.450 (3)	C10—H10C	0.96
N2—C7	1.280 (3)	C11—H11A	0.96
N2—C8	1.458 (3)	C11—H11B	0.96
N4—C13	1.142 (3)	C11—H11C	0.96
C1—C6	1.422 (3)	N3'—C11'	1.410 (14)
C1—C2	1.431 (3)	N3'—C10'	1.489 (13)
C2—C3	1.400 (3)	N3'—C9'	1.502 (16)
C2—C7	1.446 (3)	C9'—H9'1	0.9700
C3—C4	1.371 (3)	C9'—H9'2	0.9700
C3—H3	0.93	C10'—H10D	0.9600
C4—C5	1.392 (3)	C10'—H10E	0.9600
C5—C6	1.363 (3)	C10'—H10F	0.9600
C5—H5	0.93	C11'—H11D	0.9600
C6—H6	0.93	C11'—H11E	0.9600
C7—H7	0.93	C11'—H11F	0.9600
N4—Cd1—O3	109.81 (7)	C1—C6—H6	118.6
N4—Cd1—N2	168.91 (7)	N2—C7—C2	127.71 (19)
O3—Cd1—N2	81.28 (6)	N2—C7—H7	116.1
N4—Cd1—O4	85.89 (6)	C2—C7—H7	116.1
O3—Cd1—O4	83.00 (6)	O4—C12—H12A	109.5
N2—Cd1—O4	95.72 (6)	O4—C12—H12B	109.5
N4—Cd1—N3'	92.9 (4)	H12A—C12—H12B	109.5
O3—Cd1—N3'	156.8 (3)	O4—C12—H12C	109.5
N2—Cd1—N3'	76.0 (4)	H12A—C12—H12C	109.5
O4—Cd1—N3'	94.4 (2)	H12B—C12—H12C	109.5
N4—Cd1—N3	94.8 (3)	N4—C13—S1	179.3 (2)
O3—Cd1—N3	151.7 (3)	C9—N3—C10	113.1 (7)
N2—Cd1—N3	74.5 (3)	C9—N3—C11	110.9 (9)
O4—Cd1—N3	85.14 (18)	C10—N3—C11	106.5 (10)
N3'—Cd1—N3	9.6 (2)	C9—N3—Cd1	107.1 (7)
N4—Cd1—S1^i	91.83 (6)	C10—N3—Cd1	111.7 (7)
O3—Cd1—S1^i	89.50 (4)	C11—N3—Cd1	107.3 (6)
N2—Cd1—S1^i	88.20 (5)	N2—C8—C9	110.6 (3)
O4—Cd1—S1^i	170.90 (4)	N2—C8—H8A	109.5
N3'—Cd1—S1^i	94.5 (2)	C9—C8—H8A	109.5
N3—Cd1—S1^i	103.85 (17)	N2—C8—H8B	109.5
C13—S1—Cd1^i	100.71 (8)	C9—C8—H8B	109.5
C1—O3—Cd1	132.37 (13)	H8A—C8—H8B	108.1
C12—O4—Cd1	120.30 (14)	N3—C9—C8	117.3 (6)
C12—O4—H4	109 (2)	N3—C9—H9A	108.0
Cd1—O4—H4	117 (2)	C8—C9—H9A	108.0
O1—N1—O2	123.5 (2)	N3—C9—H9B	108.0
O1—N1—C4	118.1 (2)	C8—C9—H9B	108.0
O2—N1—C4	118.4 (2)	H9A—C9—H9B	107.2
C7—N2—C8	118.3 (2)	C11'—N3'—C10'	110.9 (12)
C7—N2—Cd1	128.37 (15)	C11'—N3'—C9'	110.2 (8)
C8—N2—Cd1	113.35 (15)	C10'—N3'—C9'	108.9 (10)
C13—N4—Cd1	160.4 (2)	C11'—N3'—Cd1	113.7 (9)
O3—C1—C6	118.39 (18)	C10'—N3'—Cd1	109.1 (7)
O3—C1—C2	124.34 (18)	C9'—N3'—Cd1	103.7 (8)
C6—C1—C2	117.26 (18)	N3'—C9'—H9'1	108.2
C3—C2—C1	118.78 (19)	N3'—C9'—H9'2	108.2
C3—C2—C7	115.31 (18)	H9'1—C9'—H9'2	107.3
C1—C2—C7	125.78 (18)	N3'—C10'—H10D	109.5
C4—C3—C2	121.3 (2)	N3'—C10'—H10E	109.5
C4—C3—H3	119.4	H10D—C10'—H10E	109.5
C2—C3—H3	119.4	N3'—C10'—H10F	109.5
C3—C4—C5	121.13 (19)	H10D—C10'—H10F	109.5
C3—C4—N1	119.7 (2)	H10E—C10'—H10F	109.5
C5—C4—N1	119.1 (2)	N3'—C11'—H11D	109.5
C6—C5—C4	118.8 (2)	N3'—C11'—H11E	109.5
C6—C5—H5	120.6	H11D—C11'—H11E	109.5
C4—C5—H5	120.6	N3'—C11'—H11F	109.5
C5—C6—C1	122.7 (2)	H11D—C11'—H11F	109.5
C5—C6—H6	118.6	H11E—C11'—H11F	109.5
N4—Cd1—O3—C1	179.25 (18)	C2—C1—C6—C5	−2.3 (3)
N2—Cd1—O3—C1	−0.73 (18)	C8—N2—C7—C2	−176.3 (2)
O4—Cd1—O3—C1	96.19 (18)	Cd1—N2—C7—C2	4.7 (4)
N3'—Cd1—O3—C1	11.3 (6)	C3—C2—C7—N2	173.8 (2)
N3—Cd1—O3—C1	30.3 (6)	C1—C2—C7—N2	−2.1 (4)
S1^i—Cd1—O3—C1	−88.99 (18)	N4—Cd1—N3—C9	−171.3 (4)
N4—Cd1—O4—C12	−172.50 (18)	O3—Cd1—N3—C9	−20.5 (8)
O3—Cd1—O4—C12	−61.95 (17)	N2—Cd1—N3—C9	11.4 (4)
N2—Cd1—O4—C12	18.51 (18)	O4—Cd1—N3—C9	−85.9 (4)
N3'—Cd1—O4—C12	94.9 (4)	N3'—Cd1—N3—C9	110 (4)
N3—Cd1—O4—C12	92.3 (4)	S1^i—Cd1—N3—C9	95.6 (4)
N4—Cd1—N2—C7	177.1 (3)	N4—Cd1—N3—C10	−47.0 (7)
O3—Cd1—N2—C7	−3.0 (2)	O3—Cd1—N3—C10	103.9 (9)
O4—Cd1—N2—C7	−85.0 (2)	N2—Cd1—N3—C10	135.8 (7)
N3'—Cd1—N2—C7	−178.2 (3)	O4—Cd1—N3—C10	38.5 (6)
N3—Cd1—N2—C7	−168.3 (3)	N3'—Cd1—N3—C10	−126 (4)
S1^i—Cd1—N2—C7	86.8 (2)	S1^i—Cd1—N3—C10	−140.1 (6)
N4—Cd1—N2—C8	−1.9 (4)	N4—Cd1—N3—C11	69.4 (7)
O3—Cd1—N2—C8	178.03 (19)	O3—Cd1—N3—C11	−139.7 (4)
O4—Cd1—N2—C8	96.03 (18)	N2—Cd1—N3—C11	−107.8 (8)
N3'—Cd1—N2—C8	2.9 (3)	O4—Cd1—N3—C11	154.9 (8)
N3—Cd1—N2—C8	12.7 (2)	N3'—Cd1—N3—C11	−10 (3)
S1^i—Cd1—N2—C8	−92.20 (18)	S1^i—Cd1—N3—C11	−23.6 (8)
O3—Cd1—N4—C13	137.5 (6)	C7—N2—C8—C9	146.1 (3)
N2—Cd1—N4—C13	−42.7 (8)	Cd1—N2—C8—C9	−34.8 (3)
O4—Cd1—N4—C13	−141.5 (6)	C10—N3—C9—C8	−159.6 (7)
N3'—Cd1—N4—C13	−47.3 (7)	C11—N3—C9—C8	80.8 (10)
N3—Cd1—N4—C13	−56.7 (6)	Cd1—N3—C9—C8	−36.1 (6)
S1^i—Cd1—N4—C13	47.3 (6)	N2—C8—C9—N3	49.4 (6)
Cd1—O3—C1—C6	−176.20 (14)	N4—Cd1—N3'—C11'	37.3 (9)
Cd1—O3—C1—C2	3.0 (3)	O3—Cd1—N3'—C11'	−154.1 (6)
O3—C1—C2—C3	−177.82 (19)	N2—Cd1—N3'—C11'	−141.8 (10)
C6—C1—C2—C3	1.4 (3)	O4—Cd1—N3'—C11'	123.4 (9)
O3—C1—C2—C7	−2.1 (3)	N3—Cd1—N3'—C11'	139 (5)
C6—C1—C2—C7	177.11 (19)	S1^i—Cd1—N3'—C11'	−54.8 (9)
C1—C2—C3—C4	0.3 (3)	N4—Cd1—N3'—C10'	−87.1 (9)
C7—C2—C3—C4	−175.86 (19)	O3—Cd1—N3'—C10'	81.5 (12)
C2—C3—C4—C5	−1.2 (3)	N2—Cd1—N3'—C10'	93.8 (9)
C2—C3—C4—N1	176.80 (19)	O4—Cd1—N3'—C10'	−1.0 (9)
O1—N1—C4—C3	14.7 (3)	N3—Cd1—N3'—C10'	14 (3)
O2—N1—C4—C3	−164.6 (2)	S1^i—Cd1—N3'—C10'	−179.2 (9)
O1—N1—C4—C5	−167.2 (2)	N4—Cd1—N3'—C9'	156.9 (4)
O2—N1—C4—C5	13.5 (3)	O3—Cd1—N3'—C9'	−34.4 (8)
C3—C4—C5—C6	0.3 (3)	N2—Cd1—N3'—C9'	−22.2 (4)
N1—C4—C5—C6	−177.7 (2)	O4—Cd1—N3'—C9'	−117.0 (4)
C4—C5—C6—C1	1.5 (3)	N3—Cd1—N3'—C9'	−102 (4)
O3—C1—C6—C5	176.9 (2)	S1^i—Cd1—N3'—C9'	64.9 (4)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O3^ii	0.89 (1)	1.80 (1)	2.685 (2)	174 (3)

Symmetry code: (ii) −x+1, −y, −z+1.