catena-Poly[[bis­[[bis­(3-amino­prop­yl)amine-κ3N,N′,N′′](thio­cyanato-κN)cadmium]-μ4-sulfato-κ4O,O:O′,O′] methanol hemisolvate]

Boeckmann, J.; Näther, C.

doi:10.1107/S1600536811031163

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 9| September 2011| Pages m1201-m1202

doi:10.1107/S1600536811031163

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catena-Poly[[bis[[bis(3-aminopropyl)amine-κ³N,N′,N′′](thiocyanato-κN)cadmium]-μ₄-sulfato-κ⁴O,O:O′,O′] methanol hemisolvate]

Jan Boeckmann ^a ^* and Christian Näther ^a

^aInstitut für Anorganische Chemie, Christian-Albrechts-Universität Kiel, Max-Eyth Strasse 2, D-24098 Kiel, Germany
^*Correspondence e-mail: jboeckmann@ac.uni-kiel.de

(Received 29 July 2011; accepted 2 August 2011; online 6 August 2011)

The asymmetric unit of the title compound, {[Cd₂(NCS)₂(SO₄)(C₆H₁₇N₃)₂]·0.5CH₃OH}_n, consists of two Cd²⁺ cations, two thiocyanate and one sulfate anion, two bis(3-aminopropyl)amine co-ligands and one methanol molecule with half-occupancy. Each Cd²⁺ cation is coordinated by four N atoms of one terminal N-bonded thiocyanate anion and one bis(3-aminopropyl)amine co-ligand, and by two O atoms of two symmetry-related sulfate anions, defining a slightly distorted octahedral coordination polyhedron. Each two Cd²⁺ cations are connected into dimers, which are located on centres of inversion and which are further μ-1,1:3,3-bridged via the sulfate anions into polymeric zigzag chains along the a axis.

Related literature

For background information about thermal decomposition reactions and the resulting intermediates, see: Boeckmann & Näther (2010 , 2011 ); Boeckmann et al. (2011 ); Wöhlert et al. (2011 ); Wriedt et al. (2009a ,b ); Wriedt & Näther (2010 ).

Experimental

Crystal data

[Cd₂(NCS)₂(SO₄)(C₆H₁₇N₃)₂]·0.5CH₄O
M_r = 715.49
Triclinic, $[P \overline 1]$
a = 10.6648 (9) Å
b = 12.4441 (12) Å
c = 12.9240 (12) Å
α = 61.359 (10)°
β = 69.064 (10)°
γ = 68.772 (10)°
V = 1367.3 (2) Å³
Z = 2
Mo Kα radiation
μ = 1.82 mm⁻¹
T = 200 K
0.18 × 0.13 × 0.09 mm

Data collection

STOE IPDS-1 diffractometer
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008 ) T_min = 0.746, T_max = 0.841
12730 measured reflections
5736 independent reflections
4365 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.113
S = 1.07
5736 reflections
301 parameters
H-atom parameters constrained
Δρ_max = 1.07 e Å⁻³
Δρ_min = −0.87 e Å⁻³

Table 1
Selected bond lengths (Å)

Cd1—N11	2.248 (4)
Cd1—N13	2.250 (5)
Cd1—N1	2.347 (5)
Cd1—N12	2.351 (5)
Cd1—O1ⁱ	2.388 (3)
Cd1—O1	2.619 (3)
Cd2—N23	2.247 (5)
Cd2—N21	2.250 (5)
Cd2—N2	2.283 (6)
Cd2—N22	2.374 (4)
Cd2—O3	2.386 (3)
Cd2—O3ⁱⁱ	2.676 (4)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x, -y+1, -z+1.

Data collection: X-AREA (Stoe & Cie, 2008); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811031163/bt5596sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811031163/bt5596Isup2.hkl

checkCIF report

Comment top

Recently, we reported about the thermal decomposition reaction as a tool for the selective synthesis of one-dimensional and two-dimensional coordination compounds [Boeckmann & Näther (2010); Boeckmann & Näther (2011); Boeckmann et al. (2011); Wöhlert et al. (2011); Wriedt et al. (2009a,b); Wriedt & Näther (2010)]. In this approach precursors based on paramagnetic transition metal thio- and selenocyanates and bidentate and monodentate N-donor co-ligands are heated leading to a stepwise loss of the neutral co-ligands and the formation of higher condensed networks with modified magnetic exchange interactions. Unfortunately, structure determination of the ligand-deficient intermediates is very often difficult to achieve because most of them can only prepared by thermal decomposition which leads to powders of very poor crystallinity. This problem can be overcome by preparing similar compounds based on cadmium(II) thio- and selenocyanates, which can easily be crystallized from solution and which are very often isotypic to their paramagnetic counterparts. In this case the structures of the paramagnetic intermediates can simply be determined using the Rietveld method. In this connection, we tried to prepare a ligand-deficient intermediate on the basis of Cd(NCS)₂ and the tridentate co-ligand bis(3-aminopropyl)amine. Surprisingly a mixed anionic chain structure was obtained which was characterized by single crystal X-ray diffraction.

In the crystal structure of the title compound the cadmium(II) cations are coordinated by four nitrogen atoms of one terminal N-bonded thiocyanato anion, one tridentate co-ligand bis(3-aminopropyl)amine and two oxygen atoms of two symmetry related sulfate anions within a slightly distorted octahedral coordination geometry (Fig.1 and Tab.1). One of the Cd-O distances to Cd2 of 2.676 (4) Å is slightly elongated. These octahedra are bridged via the sulfur oxygen atoms into dimeric Cd²⁺ units that are located on centers of inversion. These units are further connected into zigzag chains that elongate in the direction of the crystallographic a axis (Fig.2).

Related literature top

For background information about thermal decomposition reactions and the resulting intermediates, see: Boeckmann & Näther (2010, 2011); Boeckmann et al. (2011a); Wöhlert et al. (2011); Wriedt et al. (2009a,b); Wriedt & Näther (2010).

Experimental top

The title compound was prepared by the reaction of 128.2 mg CdSO₄^.8/3H₂O (0.50 mmol), 153.8 mg Ba(NCS)₂^.3H₂O (0.50 mmol) and 35.2 µL bis(3-aminopropyl)amine (0.25 mmol) in 1.50 ml methanol at RT in a closed 3 ml snap cap vial. After two days colourless blocks of the title compound were obtained.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2008); cell refinement: X-AREA (Stoe & Cie, 2008); data reduction: X-AREA (Stoe & Cie, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. : Crystal structure of the title compound, showing the coordination around the Cd²⁺ cations with labelling and displacement ellipsoids drawn at the 50% probability level. The H-atoms are omitted for clarity.
	Fig. 2. : Packing diagram of the title compound with view along the crystallographic c axis (aqua = cadmium; yellow = sulfur; red = oxygen; blue = nitrogen; black = carbon; light-grey = hydrogen).

catena-Poly[[bis[[bis(3-aminopropyl)amine- κ³N,N',N''](thiocyanato-κN)cadmium]- µ₄-sulfato-κ⁴O,O:O',O'] methanol hemisolvate] top

Crystal data top

[Cd₂(NCS)₂(SO₄)(C₆H₁₇N₃)₂]·0.5CH₄O	Z = 2
M_r = 715.49	F(000) = 718
Triclinic, P1	D_x = 1.738 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.6648 (9) Å	Cell parameters from 13797 reflections
b = 12.4441 (12) Å	θ = 2.5–27.0°
c = 12.9240 (12) Å	µ = 1.82 mm⁻¹
α = 61.359 (10)°	T = 200 K
β = 69.064 (10)°	Block, colourless
γ = 68.772 (10)°	0.18 × 0.13 × 0.09 mm
V = 1367.3 (2) Å³

Data collection top

STOE IPDS-1 diffractometer	5736 independent reflections
Radiation source: fine-focus sealed tube	4365 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
Phi scans	θ_max = 27.0°, θ_min = 2.5°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	h = −13→13
T_min = 0.746, T_max = 0.841	k = −15→15
12730 measured reflections	l = −16→16

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.042	H-atom parameters constrained
wR(F²) = 0.113	w = 1/[σ²(F_o²) + (0.0508P)² + 3.6107P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
5736 reflections	Δρ_max = 1.07 e Å⁻³
301 parameters	Δρ_min = −0.87 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0113 (8)

Crystal data top

[Cd₂(NCS)₂(SO₄)(C₆H₁₇N₃)₂]·0.5CH₄O	γ = 68.772 (10)°
M_r = 715.49	V = 1367.3 (2) Å³
Triclinic, P1	Z = 2
a = 10.6648 (9) Å	Mo Kα radiation
b = 12.4441 (12) Å	µ = 1.82 mm⁻¹
c = 12.9240 (12) Å	T = 200 K
α = 61.359 (10)°	0.18 × 0.13 × 0.09 mm
β = 69.064 (10)°

Data collection top

STOE IPDS-1 diffractometer	5736 independent reflections
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	4365 reflections with I > 2σ(I)
T_min = 0.746, T_max = 0.841	R_int = 0.040
12730 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.113	H-atom parameters constrained
S = 1.07	Δρ_max = 1.07 e Å⁻³
5736 reflections	Δρ_min = −0.87 e Å⁻³
301 parameters

Special details top

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cd1	0.58718 (4)	0.60656 (4)	0.33218 (3)	0.02703 (13)
Cd2	0.13789 (4)	0.35828 (4)	0.45817 (4)	0.03022 (14)
N1	0.7929 (5)	0.6709 (5)	0.2127 (5)	0.0374 (12)
C1	0.8391 (7)	0.7302 (7)	0.1166 (7)	0.0464 (16)
S1	0.9043 (3)	0.8167 (3)	−0.0225 (2)	0.0857 (8)
N2	0.3704 (6)	0.2779 (6)	0.4148 (6)	0.0497 (15)
C2	0.4515 (6)	0.2311 (5)	0.3503 (6)	0.0344 (13)
S2	0.5669 (2)	0.1683 (2)	0.2620 (2)	0.0638 (6)
S3	0.23030 (13)	0.59733 (11)	0.45203 (11)	0.0225 (3)
O1	0.3696 (4)	0.5152 (3)	0.4693 (3)	0.0237 (7)
O2	0.1952 (4)	0.6886 (4)	0.5048 (4)	0.0341 (9)
O3	0.1277 (4)	0.5182 (3)	0.5148 (3)	0.0248 (7)
O4	0.2301 (4)	0.6606 (4)	0.3235 (3)	0.0358 (9)
N11	0.4780 (5)	0.7650 (4)	0.3937 (4)	0.0314 (10)
H11A	0.3903	0.7550	0.4365	0.038*
H11B	0.5233	0.7579	0.4461	0.038*
N12	0.4885 (5)	0.7225 (5)	0.1623 (4)	0.0335 (11)
H12	0.3988	0.7116	0.1897	0.040*
N13	0.6435 (5)	0.4318 (5)	0.2982 (4)	0.0328 (11)
H13A	0.7145	0.3756	0.3353	0.039*
H13B	0.5688	0.3957	0.3348	0.039*
C11	0.4672 (7)	0.8939 (6)	0.2973 (6)	0.0451 (16)
H11C	0.5611	0.9083	0.2545	0.054*
H11D	0.4176	0.9555	0.3346	0.054*
C12	0.3922 (7)	0.9159 (6)	0.2065 (6)	0.0490 (17)
H12A	0.3086	0.8818	0.2515	0.059*
H12B	0.3612	1.0079	0.1620	0.059*
C13	0.4749 (7)	0.8584 (6)	0.1151 (6)	0.0457 (16)
H13C	0.4304	0.9011	0.0455	0.055*
H13D	0.5684	0.8747	0.0847	0.055*
C14	0.5532 (7)	0.6788 (7)	0.0627 (5)	0.0433 (15)
H14A	0.6449	0.6991	0.0227	0.052*
H14B	0.4957	0.7254	0.0019	0.052*
C15	0.5708 (8)	0.5377 (7)	0.1047 (6)	0.0468 (17)
H15A	0.4827	0.5156	0.1590	0.056*
H15B	0.5865	0.5210	0.0330	0.056*
C16	0.6857 (8)	0.4500 (7)	0.1701 (6)	0.0454 (16)
H16A	0.7104	0.3676	0.1652	0.054*
H16B	0.7684	0.4857	0.1300	0.054*
N21	0.1109 (6)	0.4989 (5)	0.2712 (4)	0.0381 (12)
H21A	0.0189	0.5387	0.2760	0.046*
H21B	0.1585	0.5590	0.2463	0.046*
N22	0.0976 (5)	0.2022 (5)	0.4261 (5)	0.0375 (12)
H22	0.0022	0.2148	0.4444	0.045*
N23	0.0807 (5)	0.2394 (4)	0.6569 (4)	0.0324 (10)
H23A	0.1097	0.2661	0.6978	0.039*
H23B	−0.0140	0.2544	0.6804	0.039*
C21	0.1564 (8)	0.4493 (7)	0.1779 (6)	0.0502 (17)
H21C	0.2576	0.4155	0.1647	0.060*
H21D	0.1359	0.5191	0.1010	0.060*
C22	0.0864 (9)	0.3446 (8)	0.2112 (6)	0.057 (2)
H22A	−0.0130	0.3704	0.2459	0.068*
H22B	0.0938	0.3378	0.1358	0.068*
C23	0.1440 (7)	0.2160 (7)	0.2992 (7)	0.0475 (17)
H23C	0.1164	0.1521	0.2926	0.057*
H23D	0.2461	0.1990	0.2762	0.057*
C24	0.1475 (7)	0.0726 (6)	0.5072 (7)	0.0476 (17)
H24A	0.2490	0.0549	0.4933	0.057*
H24B	0.1265	0.0146	0.4869	0.057*
C25	0.0848 (8)	0.0459 (6)	0.6396 (7)	0.0489 (17)
H25A	0.1021	−0.0465	0.6857	0.059*
H25B	−0.0164	0.0789	0.6499	0.059*
C26	0.1370 (8)	0.1009 (6)	0.6962 (7)	0.0488 (17)
H26A	0.1094	0.0595	0.7855	0.059*
H26B	0.2391	0.0829	0.6728	0.059*
O31	0.1929 (15)	0.7375 (11)	0.0583 (11)	0.076 (4)	0.50
H31	0.2769	0.7008	0.0475	0.114*	0.50
C31	0.1801 (14)	0.8574 (13)	0.0413 (12)	0.050 (4)	0.50
H31A	0.1703	0.8593	0.1188	0.075*	0.50
H31B	0.0983	0.9125	0.0087	0.075*	0.50
H31C	0.2624	0.8868	−0.0158	0.075*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.0291 (2)	0.0297 (2)	0.0207 (2)	−0.00729 (16)	−0.00580 (15)	−0.00850 (15)
Cd2	0.0294 (3)	0.0346 (2)	0.0326 (2)	−0.00777 (17)	−0.00505 (17)	−0.01921 (18)
N1	0.031 (3)	0.052 (3)	0.033 (3)	−0.020 (2)	−0.010 (2)	−0.010 (2)
C1	0.044 (4)	0.062 (4)	0.051 (4)	−0.018 (3)	−0.005 (3)	−0.036 (4)
S1	0.119 (2)	0.107 (2)	0.0407 (11)	−0.0754 (18)	0.0075 (12)	−0.0195 (12)
N2	0.029 (3)	0.070 (4)	0.072 (4)	−0.004 (3)	−0.010 (3)	−0.052 (4)
C2	0.030 (3)	0.033 (3)	0.047 (3)	−0.009 (2)	−0.013 (3)	−0.016 (3)
S2	0.0483 (11)	0.0642 (12)	0.0892 (15)	−0.0107 (9)	0.0066 (10)	−0.0557 (12)
S3	0.0163 (6)	0.0281 (6)	0.0226 (6)	−0.0081 (5)	−0.0038 (4)	−0.0080 (5)
O1	0.0176 (19)	0.0311 (18)	0.0237 (17)	−0.0043 (15)	−0.0064 (14)	−0.0117 (15)
O2	0.023 (2)	0.035 (2)	0.051 (2)	−0.0062 (17)	−0.0077 (17)	−0.0233 (19)
O3	0.0214 (19)	0.0316 (19)	0.0236 (18)	−0.0142 (15)	0.0006 (14)	−0.0111 (15)
O4	0.022 (2)	0.050 (2)	0.0214 (18)	−0.0120 (18)	−0.0080 (15)	0.0009 (17)
N11	0.036 (3)	0.031 (2)	0.033 (2)	−0.012 (2)	−0.007 (2)	−0.015 (2)
N12	0.030 (3)	0.044 (3)	0.018 (2)	−0.017 (2)	−0.0042 (18)	−0.0005 (19)
N13	0.034 (3)	0.040 (3)	0.031 (2)	−0.015 (2)	−0.002 (2)	−0.018 (2)
C11	0.046 (4)	0.027 (3)	0.055 (4)	−0.014 (3)	−0.006 (3)	−0.011 (3)
C12	0.037 (4)	0.034 (3)	0.048 (4)	−0.004 (3)	−0.008 (3)	0.001 (3)
C13	0.044 (4)	0.042 (3)	0.033 (3)	−0.017 (3)	−0.010 (3)	0.004 (3)
C14	0.041 (4)	0.068 (4)	0.020 (3)	−0.027 (3)	−0.002 (2)	−0.010 (3)
C15	0.050 (4)	0.076 (5)	0.030 (3)	−0.031 (4)	−0.002 (3)	−0.026 (3)
C16	0.053 (4)	0.059 (4)	0.035 (3)	−0.025 (3)	0.003 (3)	−0.028 (3)
N21	0.038 (3)	0.046 (3)	0.030 (3)	−0.011 (2)	−0.002 (2)	−0.018 (2)
N22	0.026 (3)	0.045 (3)	0.057 (3)	−0.005 (2)	−0.007 (2)	−0.036 (3)
N23	0.029 (3)	0.035 (3)	0.034 (3)	−0.007 (2)	−0.009 (2)	−0.013 (2)
C21	0.044 (4)	0.070 (5)	0.029 (3)	−0.009 (3)	0.004 (3)	−0.026 (3)
C22	0.059 (5)	0.089 (6)	0.042 (4)	−0.018 (4)	−0.010 (3)	−0.041 (4)
C23	0.038 (4)	0.063 (4)	0.064 (4)	−0.005 (3)	−0.011 (3)	−0.048 (4)
C24	0.043 (4)	0.038 (3)	0.076 (5)	−0.008 (3)	−0.015 (3)	−0.033 (3)
C25	0.047 (4)	0.030 (3)	0.070 (5)	−0.005 (3)	−0.017 (3)	−0.020 (3)
C26	0.055 (5)	0.033 (3)	0.052 (4)	−0.003 (3)	−0.025 (3)	−0.008 (3)
O31	0.101 (11)	0.064 (7)	0.055 (7)	−0.020 (7)	−0.039 (7)	−0.001 (6)
C31	0.034 (8)	0.058 (9)	0.039 (7)	−0.020 (6)	−0.027 (6)	0.014 (6)

Geometric parameters (Å, º) top

Cd1—N11	2.248 (4)	C14—C15	1.528 (10)
Cd1—N13	2.250 (5)	C14—H14A	0.9900
Cd1—N1	2.347 (5)	C14—H14B	0.9900
Cd1—N12	2.351 (5)	C15—C16	1.515 (11)
Cd1—O1ⁱ	2.388 (3)	C15—H15A	0.9900
Cd1—O1	2.619 (3)	C15—H15B	0.9900
Cd2—N23	2.247 (5)	C16—H16A	0.9900
Cd2—N21	2.250 (5)	C16—H16B	0.9900
Cd2—N2	2.283 (6)	N21—C21	1.466 (8)
Cd2—N22	2.374 (4)	N21—H21A	0.9200
Cd2—O3	2.386 (3)	N21—H21B	0.9200
Cd2—O3ⁱⁱ	2.676 (4)	N22—C24	1.463 (9)
N1—C1	1.130 (8)	N22—C23	1.475 (8)
C1—S1	1.633 (8)	N22—H22	0.9300
N2—C2	1.169 (8)	N23—C26	1.489 (8)
C2—S2	1.607 (6)	N23—H23A	0.9200
S3—O4	1.458 (4)	N23—H23B	0.9200
S3—O2	1.465 (4)	C21—C22	1.542 (11)
S3—O3	1.485 (3)	C21—H21C	0.9900
S3—O1	1.490 (4)	C21—H21D	0.9900
O1—Cd1ⁱ	2.388 (3)	C22—C23	1.508 (11)
N11—C11	1.480 (7)	C22—H22A	0.9900
N11—H11A	0.9200	C22—H22B	0.9900
N11—H11B	0.9200	C23—H23C	0.9900
N12—C13	1.466 (8)	C23—H23D	0.9900
N12—C14	1.480 (8)	C24—C25	1.510 (10)
N12—H12	0.9300	C24—H24A	0.9900
N13—C16	1.476 (7)	C24—H24B	0.9900
N13—H13A	0.9200	C25—C26	1.537 (10)
N13—H13B	0.9200	C25—H25A	0.9900
C11—C12	1.515 (10)	C25—H25B	0.9900
C11—H11C	0.9900	C26—H26A	0.9900
C11—H11D	0.9900	C26—H26B	0.9900
C12—C13	1.515 (10)	O31—C31	1.362 (18)
C12—H12A	0.9900	O31—H31	0.8400
C12—H12B	0.9900	C31—H31A	0.9800
C13—H13C	0.9900	C31—H31B	0.9800
C13—H13D	0.9900	C31—H31C	0.9800

N11—Cd1—N13	164.76 (17)	C15—C14—H14A	108.9
N11—Cd1—N1	99.40 (18)	N12—C14—H14B	108.9
N13—Cd1—N1	95.82 (18)	C15—C14—H14B	108.9
N11—Cd1—N12	89.43 (18)	H14A—C14—H14B	107.7
N13—Cd1—N12	89.82 (18)	C16—C15—C14	117.0 (5)
N1—Cd1—N12	89.72 (17)	C16—C15—H15A	108.0
N11—Cd1—O1ⁱ	85.80 (15)	C14—C15—H15A	108.0
N13—Cd1—O1ⁱ	91.31 (15)	C16—C15—H15B	108.0
N1—Cd1—O1ⁱ	104.15 (15)	C14—C15—H15B	108.0
N12—Cd1—O1ⁱ	165.89 (14)	H15A—C15—H15B	107.3
N11—Cd1—O1	84.77 (14)	N13—C16—C15	111.0 (5)
N13—Cd1—O1	80.07 (14)	N13—C16—H16A	109.4
N1—Cd1—O1	175.20 (16)	C15—C16—H16A	109.4
N12—Cd1—O1	92.73 (14)	N13—C16—H16B	109.4
O1ⁱ—Cd1—O1	73.63 (13)	C15—C16—H16B	109.4
N23—Cd2—N21	159.07 (19)	H16A—C16—H16B	108.0
N23—Cd2—N2	101.4 (2)	C21—N21—Cd2	116.5 (4)
N21—Cd2—N2	99.3 (2)	C21—N21—H21A	108.2
N23—Cd2—N22	86.47 (18)	Cd2—N21—H21A	108.2
N21—Cd2—N22	90.32 (19)	C21—N21—H21B	108.2
N2—Cd2—N22	90.40 (18)	Cd2—N21—H21B	108.2
N23—Cd2—O3	86.86 (14)	H21A—N21—H21B	107.3
N21—Cd2—O3	92.16 (15)	C24—N22—C23	110.7 (5)
N2—Cd2—O3	101.23 (16)	C24—N22—Cd2	114.7 (4)
N22—Cd2—O3	167.55 (15)	C23—N22—Cd2	114.1 (4)
C1—N1—Cd1	140.6 (5)	C24—N22—H22	105.4
N1—C1—S1	179.4 (9)	C23—N22—H22	105.4
C2—N2—Cd2	138.6 (5)	Cd2—N22—H22	105.4
N2—C2—S2	178.1 (6)	C26—N23—Cd2	116.8 (4)
O4—S3—O2	111.1 (3)	C26—N23—H23A	108.1
O4—S3—O3	108.7 (2)	Cd2—N23—H23A	108.1
O2—S3—O3	109.5 (2)	C26—N23—H23B	108.1
O4—S3—O1	109.9 (2)	Cd2—N23—H23B	108.1
O2—S3—O1	108.6 (2)	H23A—N23—H23B	107.3
O3—S3—O1	109.1 (2)	N21—C21—C22	113.1 (5)
S3—O1—Cd1ⁱ	120.41 (19)	N21—C21—H21C	109.0
S3—O1—Cd1	118.74 (19)	C22—C21—H21C	109.0
Cd1ⁱ—O1—Cd1	106.37 (13)	N21—C21—H21D	109.0
S3—O3—Cd2	122.13 (19)	C22—C21—H21D	109.0
C11—N11—Cd1	116.2 (4)	H21C—C21—H21D	107.8
C11—N11—H11A	108.2	C23—C22—C21	115.7 (6)
Cd1—N11—H11A	108.2	C23—C22—H22A	108.4
C11—N11—H11B	108.2	C21—C22—H22A	108.4
Cd1—N11—H11B	108.2	C23—C22—H22B	108.4
H11A—N11—H11B	107.4	C21—C22—H22B	108.4
C13—N12—C14	110.3 (5)	H22A—C22—H22B	107.4
C13—N12—Cd1	113.1 (4)	N22—C23—C22	113.7 (5)
C14—N12—Cd1	115.7 (4)	N22—C23—H23C	108.8
C13—N12—H12	105.6	C22—C23—H23C	108.8
C14—N12—H12	105.6	N22—C23—H23D	108.8
Cd1—N12—H12	105.6	C22—C23—H23D	108.8
C16—N13—Cd1	115.9 (4)	H23C—C23—H23D	107.7
C16—N13—H13A	108.3	N22—C24—C25	113.7 (5)
Cd1—N13—H13A	108.3	N22—C24—H24A	108.8
C16—N13—H13B	108.3	C25—C24—H24A	108.8
Cd1—N13—H13B	108.3	N22—C24—H24B	108.8
H13A—N13—H13B	107.4	C25—C24—H24B	108.8
N11—C11—C12	112.4 (5)	H24A—C24—H24B	107.7
N11—C11—H11C	109.1	C24—C25—C26	116.3 (6)
C12—C11—H11C	109.1	C24—C25—H25A	108.2
N11—C11—H11D	109.1	C26—C25—H25A	108.2
C12—C11—H11D	109.1	C24—C25—H25B	108.2
H11C—C11—H11D	107.8	C26—C25—H25B	108.2
C13—C12—C11	115.7 (6)	H25A—C25—H25B	107.4
C13—C12—H12A	108.4	N23—C26—C25	111.9 (6)
C11—C12—H12A	108.4	N23—C26—H26A	109.2
C13—C12—H12B	108.4	C25—C26—H26A	109.2
C11—C12—H12B	108.4	N23—C26—H26B	109.2
H12A—C12—H12B	107.4	C25—C26—H26B	109.2
N12—C13—C12	114.5 (5)	H26A—C26—H26B	107.9
N12—C13—H13C	108.6	C31—O31—H31	109.5
C12—C13—H13C	108.6	O31—C31—H31A	109.5
N12—C13—H13D	108.6	O31—C31—H31B	109.5
C12—C13—H13D	108.6	H31A—C31—H31B	109.5
H13C—C13—H13D	107.6	O31—C31—H31C	109.5
N12—C14—C15	113.4 (5)	H31A—C31—H31C	109.5
N12—C14—H14A	108.9	H31B—C31—H31C	109.5

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

Experimental details

Crystal data
Chemical formula	[Cd₂(NCS)₂(SO₄)(C₆H₁₇N₃)₂]·0.5CH₄O
M_r	715.49
Crystal system, space group	Triclinic, P1
Temperature (K)	200
a, b, c (Å)	10.6648 (9), 12.4441 (12), 12.9240 (12)
α, β, γ (°)	61.359 (10), 69.064 (10), 68.772 (10)
V (Å³)	1367.3 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.82
Crystal size (mm)	0.18 × 0.13 × 0.09

Data collection
Diffractometer	STOE IPDS1 diffractometer
Absorption correction	Numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)
T_min, T_max	0.746, 0.841
No. of measured, independent and observed [I > 2σ(I)] reflections	12730, 5736, 4365
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.113, 1.07
No. of reflections	5736
No. of parameters	301
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.07, −0.87

Computer programs: X-AREA (Stoe & Cie, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011).

Selected bond lengths (Å) top

Cd1—N11	2.248 (4)	Cd2—N23	2.247 (5)
Cd1—N13	2.250 (5)	Cd2—N21	2.250 (5)
Cd1—N1	2.347 (5)	Cd2—N2	2.283 (6)
Cd1—N12	2.351 (5)	Cd2—N22	2.374 (4)
Cd1—O1ⁱ	2.388 (3)	Cd2—O3	2.386 (3)
Cd1—O1	2.619 (3)	Cd2—O3ⁱⁱ	2.676 (4)

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

Acknowledgements

We gratefully acknowledge financial support by the DFG (project number NA 720/3–1) and the State of Schleswig–Holstein. We thank Professor Dr Wolfgang Bensch for access to his experimental facilities. Special thanks go to Inke Jess for her support of the single-crystal measurements.

References

Boeckmann, J. & Näther, C. (2010). Dalton. Trans. 39, 11019–11026. CSD CrossRef CAS Google Scholar
Boeckmann, J. & Näther, C. (2011). Chem. Commun. 47, 7104–7106. Web of Science CSD CrossRef CAS Google Scholar
Boeckmann, J., Reinert, T. & Näther, C. (2011). Z. Anorg. Allg. Chem. 637, 940–946. CrossRef CAS Google Scholar
Brandenburg, K. (2011). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany. Google Scholar
Wöhlert, S., Boeckmann, J., Wriedt, M. & Näther, C. (2011). Angew. Chem. Int. Ed. 50, 6920–6923. Google Scholar
Wriedt, M. & Näther, C. (2010). Chem. Commun. 46, 4707–4709. Web of Science CSD CrossRef CAS Google Scholar
Wriedt, M., Sellmer, S. & Näther, C. (2009a). Dalton. Trans. pp. 7975–7984. CSD CrossRef Google Scholar
Wriedt, M., Sellmer, S. & Näther, C. (2009b). Inorg. Chem. 48, 6896–6903. Web of Science CSD CrossRef CAS PubMed Google Scholar

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