Bis(benzo-15-crown-5-κ5O)barium tetrakis­(isothio­cyanato-κN)cobaltate(II)

Cao, Z.; Liu, K.; Niu, M.; Wang, D.

doi:10.1107/S1600536809053471

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page m68

doi:10.1107/S1600536809053471

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Bis(benzo-15-crown-5-κ⁵O)barium tetrakis(isothiocyanato-κN)cobaltate(II)

Zhiqiang Cao,^a Kai Liu,^a Meiju Niu ^a ^* and Daqi Wang ^a

^aCollege of Chemistry and Chemical Engineering, Liaocheng University, Shandong 252059, People's Republic of China
^*Correspondence e-mail: niumeiju@163.com

(Received 26 November 2009; accepted 11 December 2009; online 16 December 2009)

In the title compound, [Ba(C₁₄H₂₀O₅)₂][Co(NCS)₄], the Ba^II and Co^II ions are situated on twofold rotational axes, so asymmetric unit contains half each of the complex cations and anions. The Co^II ion is coordinated by four N atoms [Co—N 1.83 (2), 1.95 (3) Å] in a distorted tetrahedral geometry. The Ba^II ion is coordinated by ten O atoms [Ba—O 2.766 (19)–2.859 (19) Å] from two benzo-15-crown-5 ligands in a sandwich-like configuration.

Related literature

For related structures, see: Drew et al. (1983 ); Owen (1983 ); Nunez & Rogers (1993 ).

Experimental

Crystal data

[Ba(C₁₄H₂₀O₅)₂][Co(NCS)₄]
M_r = 965.19
Trigonal, P 3₁ 21
a = 12.5772 (13) Å
c = 23.758 (3) Å
V = 3254.7 (6) Å³
Z = 3
Mo Kα radiation
μ = 1.53 mm⁻¹
T = 298 K
0.43 × 0.40 × 0.28 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.559, T_max = 0.674
14488 measured reflections
3786 independent reflections
2749 reflections with I > 2σ(I)
R_int = 0.059

Refinement

R[F² > 2σ(F²)] = 0.068
wR(F²) = 0.196
S = 1.00
3786 reflections
236 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 1.68 e Å⁻³
Δρ_min = −1.38 e Å⁻³
Absolute structure: Flack (1983 ), 1623 Friedel pairs
Flack parameter: −0.01 (12)

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809053471/cv2669sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809053471/cv2669Isup2.hkl

checkCIF report

Comment top

In continuation of structural study of benzo-15-crown-5 ligands and their barium(II) complexes (Nunez et al., 1993), we report here the synthesis and crystal structure of the title compound, (I).

In (I) (Fig. 1), the Ba^II ions are sandwiched between the 15-crown-5 rings from two ligands (Owen, 1983). The Co^II ions are coordinated by four N atoms from the thiocyanate ligands in a distorted tetrahedal geometry. The Ba—O and Co—N coordinating bond lengths are comparable with those observed in other Ba^II (Nunez et al., 1993) and Co^II complexes (Drew et al., 1983).

Related literature top

For related structures, see: Drew et al. (1983); Owen (1983); Nunez et al. (1993).

Experimental top

Potassium thiocyanate (1 mmol, 97.18 mg) and cobalt(II) dichloride (0.25 mmol, 59.49 mg) were dissolved and stirred at 293 K in H₂O solution (10 ml) for 0.5 h and then added dropwise to a 1,2-dichloroethane solution (10 ml) of benzo-15-crown-5 (0.5 mmol,134.16 mg). The mixture was then stirred at 293 K for 0.5 h. An aqueous solution (2 ml) of barium(II) chloride (0.25 mmol, 52.07 mg) was then added dropwise and the mixture stirred for another 5 h. The lower clear liquid was held at room temperature for about one week, whereupon blue square block crystal suitable for X-ray diffraction analysis were obtained.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids and atomic numbering for non-C atoms [symmetry codes: (A) -x, -x + y, 4/3 - z; (B)1 + x-y,2 - y, 5/3 - z]. H atoms omitted for clarity.

Bis(benzo-15-crown-5-κ⁵O)barium tetrakis(isothiocyanato-κN)cobaltate(II) top

Crystal data top

[Ba(C₁₄H₂₀O₅)₂][Co(NCS)₄]	D_x = 1.477 Mg m⁻³
M_r = 965.19	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3₁21	Cell parameters from 2944 reflections
a = 12.5772 (13) Å	θ = 2.5–18.7°
c = 23.758 (3) Å	µ = 1.53 mm⁻¹
V = 3254.7 (6) Å³	T = 298 K
Z = 3	Block, blue
F(000) = 1461	0.43 × 0.40 × 0.28 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	3786 independent reflections
Radiation source: fine-focus sealed tube	2749 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.059
phi and ω scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→14
T_min = 0.559, T_max = 0.674	k = −14→14
14488 measured reflections	l = −28→26

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)] = 0.068	H-atom parameters constrained
wR(F²) = 0.196	w = 1/[σ²(F_o²) + (0.1148P)²] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max = 0.001
3786 reflections	Δρ_max = 1.68 e Å⁻³
236 parameters	Δρ_min = −1.38 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1623 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.01 (12)

Crystal data top

[Ba(C₁₄H₂₀O₅)₂][Co(NCS)₄]	Z = 3
M_r = 965.19	Mo Kα radiation
Trigonal, P3₁21	µ = 1.53 mm⁻¹
a = 12.5772 (13) Å	T = 298 K
c = 23.758 (3) Å	0.43 × 0.40 × 0.28 mm
V = 3254.7 (6) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	3786 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2749 reflections with I > 2σ(I)
T_min = 0.559, T_max = 0.674	R_int = 0.059
14488 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.068	H-atom parameters constrained
wR(F²) = 0.196	Δρ_max = 1.68 e Å⁻³
S = 1.00	Δρ_min = −1.38 e Å⁻³
3786 reflections	Absolute structure: Flack (1983), 1623 Friedel pairs
236 parameters	Absolute structure parameter: −0.01 (12)
1 restraint

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

	x	y	z	U_iso*/U_eq
Ba1	0.0000	0.58989 (14)	0.6667	0.0538 (6)
Co1	0.5798 (5)	1.0000	0.8333	0.1076 (17)
N1	0.553 (2)	1.113 (2)	0.7970 (9)	0.069 (6)
N2	0.615 (3)	0.900 (3)	0.7820 (13)	0.119 (9)
O1	−0.0086 (19)	0.409 (2)	0.7422 (9)	0.087 (6)
O2	0.1988 (19)	0.561 (2)	0.6987 (9)	0.097 (7)
O3	0.222 (2)	0.794 (2)	0.6989 (9)	0.102 (6)
O4	0.002 (2)	0.773 (2)	0.7356 (9)	0.096 (6)
O5	−0.130 (2)	0.530 (2)	0.7666 (9)	0.111 (7)
S1	0.5021 (12)	1.3067 (13)	0.7753 (4)	0.127 (4)
S2	0.6535 (14)	0.7424 (14)	0.7203 (5)	0.147 (5)
C1	0.068 (3)	0.364 (3)	0.7324 (14)	0.094 (9)
C2	0.028 (4)	0.241 (4)	0.7438 (16)	0.118 (13)
H2	−0.0487	0.1890	0.7594	0.141*
C3	0.110 (5)	0.201 (4)	0.7304 (16)	0.126 (14)
H3	0.0906	0.1213	0.7385	0.151*
C4	0.218 (4)	0.281 (4)	0.7053 (15)	0.108 (11)
H4	0.2689	0.2499	0.6954	0.129*
C5	0.260 (4)	0.403 (4)	0.6928 (14)	0.111 (12)
H5	0.3340	0.4523	0.6743	0.133*
C6	0.182 (3)	0.445 (4)	0.7105 (13)	0.090 (9)
C7	0.300 (4)	0.651 (4)	0.7258 (19)	0.124 (13)
H7A	0.3695	0.6377	0.7202	0.149*
H7B	0.2846	0.6482	0.7659	0.149*
C8	0.329 (4)	0.774 (4)	0.7017 (17)	0.131 (13)
H8A	0.3927	0.8380	0.7245	0.157*
H8B	0.3617	0.7808	0.6640	0.157*
C9	0.228 (4)	0.877 (4)	0.7402 (16)	0.119 (13)
H9A	0.3014	0.9570	0.7355	0.143*
H9B	0.2281	0.8470	0.7777	0.143*
C10	0.113 (4)	0.884 (4)	0.7295 (17)	0.121 (13)
H10A	0.1125	0.9438	0.7553	0.145*
H10B	0.1171	0.9148	0.6916	0.145*
C11	−0.059 (4)	0.743 (3)	0.7883 (14)	0.106 (11)
H11A	−0.0932	0.7958	0.7956	0.128*
H11B	−0.0013	0.7552	0.8182	0.128*
C12	−0.160 (3)	0.610 (4)	0.7861 (14)	0.101 (11)
H12A	−0.1920	0.5849	0.8239	0.121*
H12B	−0.2261	0.6048	0.7631	0.121*
C13	−0.126 (3)	0.453 (4)	0.8075 (13)	0.102 (10)
H13A	−0.2086	0.3862	0.8149	0.122*
H13B	−0.0935	0.4983	0.8422	0.122*
C14	−0.047 (5)	0.401 (4)	0.7888 (16)	0.128 (14)
H14A	0.0241	0.4360	0.8134	0.154*
H14B	−0.0929	0.3136	0.7974	0.154*
C15	0.529 (3)	1.183 (2)	0.7886 (11)	0.098 (11)
C16	0.639 (3)	0.835 (3)	0.7554 (14)	0.094 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ba1	0.0643 (13)	0.0576 (9)	0.0417 (9)	0.0321 (6)	−0.0018 (10)	−0.0009 (5)
Co1	0.101 (3)	0.091 (4)	0.128 (5)	0.045 (2)	−0.003 (2)	−0.007 (4)
N1	0.088 (16)	0.076 (14)	0.078 (14)	0.067 (13)	−0.009 (11)	−0.004 (11)
N2	0.13 (2)	0.12 (2)	0.11 (2)	0.06 (2)	0.010 (17)	−0.002 (18)
O1	0.094 (14)	0.119 (17)	0.072 (12)	0.070 (14)	0.009 (11)	0.025 (12)
O2	0.081 (14)	0.130 (19)	0.082 (14)	0.053 (14)	−0.005 (11)	0.012 (13)
O3	0.104 (15)	0.099 (16)	0.094 (14)	0.044 (14)	−0.009 (12)	−0.020 (13)
O4	0.116 (18)	0.092 (15)	0.087 (14)	0.059 (15)	0.003 (13)	−0.021 (11)
O5	0.133 (19)	0.126 (18)	0.083 (13)	0.070 (17)	0.038 (14)	0.007 (14)
S1	0.159 (9)	0.182 (11)	0.091 (5)	0.123 (8)	0.024 (6)	0.023 (7)
S2	0.170 (11)	0.177 (12)	0.150 (9)	0.129 (10)	0.032 (9)	0.023 (9)
C1	0.12 (3)	0.11 (3)	0.08 (2)	0.08 (2)	−0.021 (19)	−0.01 (2)
C2	0.14 (3)	0.13 (4)	0.10 (3)	0.08 (3)	−0.03 (2)	0.00 (2)
C3	0.15 (4)	0.14 (4)	0.10 (3)	0.08 (4)	−0.03 (3)	−0.01 (3)
C4	0.14 (3)	0.14 (3)	0.10 (2)	0.11 (3)	−0.02 (2)	−0.02 (2)
C5	0.13 (3)	0.14 (3)	0.10 (2)	0.09 (3)	−0.03 (2)	−0.01 (2)
C6	0.11 (3)	0.13 (3)	0.081 (18)	0.09 (3)	−0.009 (18)	−0.004 (19)
C7	0.12 (3)	0.13 (3)	0.12 (3)	0.06 (3)	−0.01 (3)	0.00 (3)
C8	0.11 (3)	0.13 (3)	0.11 (3)	0.03 (3)	−0.01 (2)	−0.01 (3)
C9	0.12 (3)	0.11 (3)	0.11 (3)	0.04 (2)	0.00 (2)	−0.01 (2)
C10	0.14 (4)	0.10 (3)	0.12 (3)	0.05 (2)	−0.01 (2)	−0.03 (2)
C11	0.13 (3)	0.13 (3)	0.09 (2)	0.09 (3)	0.01 (2)	−0.010 (19)
C12	0.12 (3)	0.13 (3)	0.09 (2)	0.09 (3)	0.035 (19)	0.01 (2)
C13	0.11 (2)	0.14 (3)	0.061 (17)	0.06 (2)	0.019 (17)	0.02 (2)
C14	0.16 (4)	0.13 (3)	0.09 (3)	0.07 (3)	0.00 (3)	0.01 (3)
C15	0.062 (17)	0.15 (3)	0.056 (16)	0.031 (19)	0.008 (14)	−0.024 (19)
C16	0.10 (2)	0.11 (2)	0.10 (2)	0.063 (19)	0.011 (18)	0.018 (18)

Geometric parameters (Å, º) top

Ba1—O5	2.766 (19)	C1—C2	1.39 (5)
Ba1—O5ⁱ	2.766 (19)	C2—C3	1.39 (6)
Ba1—O3	2.79 (2)	C2—H2	0.9300
Ba1—O3ⁱ	2.79 (2)	C3—C4	1.36 (5)
Ba1—O2	2.81 (2)	C3—H3	0.9300
Ba1—O2ⁱ	2.81 (2)	C4—C5	1.38 (5)
Ba1—O4	2.816 (18)	C4—H4	0.9300
Ba1—O4ⁱ	2.816 (18)	C5—C6	1.40 (4)
Ba1—O1	2.859 (19)	C5—H5	0.9300
Ba1—O1ⁱ	2.859 (19)	C7—C8	1.51 (6)
Co1—N1	1.834 (19)	C7—H7A	0.9700
Co1—N1ⁱⁱ	1.83 (2)	C7—H7B	0.9700
Co1—N2	1.95 (3)	C8—H8A	0.9700
Co1—N2ⁱⁱ	1.95 (3)	C8—H8B	0.9700
N1—C15	1.07 (3)	C9—C10	1.52 (5)
N2—C16	1.19 (4)	C9—H9A	0.9700
O1—C14	1.19 (4)	C9—H9B	0.9700
O1—C1	1.36 (4)	C10—H10A	0.9700
O2—C7	1.37 (4)	C10—H10B	0.9700
O2—C6	1.39 (4)	C11—C12	1.52 (5)
O3—C9	1.41 (4)	C11—H11A	0.9700
O3—C8	1.49 (5)	C11—H11B	0.9700
O4—C10	1.40 (5)	C12—H12A	0.9700
O4—C11	1.42 (4)	C12—H12B	0.9700
O5—C12	1.32 (4)	C13—C14	1.51 (5)
O5—C13	1.40 (4)	C13—H13A	0.9700
S1—C15	1.79 (2)	C13—H13B	0.9700
S2—C16	1.51 (4)	C14—H14A	0.9700
C1—C6	1.38 (5)	C14—H14B	0.9700

O5—Ba1—O5ⁱ	177.1 (11)	O1—C1—C6	117 (3)
O5—Ba1—O3	101.4 (7)	O1—C1—C2	120 (4)
O5ⁱ—Ba1—O3	77.3 (7)	C6—C1—C2	124 (3)
O5—Ba1—O3ⁱ	77.3 (7)	C3—C2—C1	116 (4)
O5ⁱ—Ba1—O3ⁱ	101.4 (7)	C3—C2—H2	122.0
O3—Ba1—O3ⁱ	130.4 (10)	C1—C2—H2	122.0
O5—Ba1—O2	100.2 (7)	C4—C3—C2	119 (4)
O5ⁱ—Ba1—O2	81.5 (7)	C4—C3—H3	120.5
O3—Ba1—O2	59.9 (8)	C2—C3—H3	120.5
O3ⁱ—Ba1—O2	169.6 (7)	C3—C4—C5	127 (4)
O5—Ba1—O2ⁱ	81.5 (7)	C3—C4—H4	116.7
O5ⁱ—Ba1—O2ⁱ	100.2 (7)	C5—C4—H4	116.7
O3—Ba1—O2ⁱ	169.6 (7)	C4—C5—C6	114 (4)
O3ⁱ—Ba1—O2ⁱ	59.9 (8)	C4—C5—H5	123.0
O2—Ba1—O2ⁱ	109.9 (11)	C6—C5—H5	123.0
O5—Ba1—O4	59.0 (7)	C1—C6—O2	114 (3)
O5ⁱ—Ba1—O4	118.2 (8)	C1—C6—C5	120 (3)
O3—Ba1—O4	59.4 (7)	O2—C6—C5	125 (4)
O3ⁱ—Ba1—O4	80.0 (7)	O2—C7—C8	108 (3)
O2—Ba1—O4	107.6 (7)	O2—C7—H7A	110.1
O2ⁱ—Ba1—O4	129.2 (7)	C8—C7—H7A	110.1
O5—Ba1—O4ⁱ	118.2 (8)	O2—C7—H7B	110.1
O5ⁱ—Ba1—O4ⁱ	59.0 (7)	C8—C7—H7B	110.1
O3—Ba1—O4ⁱ	80.0 (7)	H7A—C7—H7B	108.4
O3ⁱ—Ba1—O4ⁱ	59.4 (7)	O3—C8—C7	115 (3)
O2—Ba1—O4ⁱ	129.2 (7)	O3—C8—H8A	108.6
O2ⁱ—Ba1—O4ⁱ	107.6 (7)	C7—C8—H8A	108.6
O4—Ba1—O4ⁱ	71.1 (9)	O3—C8—H8B	108.6
O5—Ba1—O1	57.6 (7)	C7—C8—H8B	108.6
O5ⁱ—Ba1—O1	125.1 (7)	H8A—C8—H8B	107.6
O3—Ba1—O1	100.5 (6)	O3—C9—C10	103 (3)
O3ⁱ—Ba1—O1	118.0 (6)	O3—C9—H9A	111.1
O2—Ba1—O1	53.7 (6)	C10—C9—H9A	111.1
O2ⁱ—Ba1—O1	72.4 (7)	O3—C9—H9B	111.1
O4—Ba1—O1	105.6 (6)	C10—C9—H9B	111.1
O4ⁱ—Ba1—O1	175.9 (7)	H9A—C9—H9B	109.1
O5—Ba1—O1ⁱ	125.1 (7)	O4—C10—C9	115 (3)
O5ⁱ—Ba1—O1ⁱ	57.6 (7)	O4—C10—H10A	108.4
O3—Ba1—O1ⁱ	118.0 (6)	C9—C10—H10A	108.4
O3ⁱ—Ba1—O1ⁱ	100.5 (6)	O4—C10—H10B	108.4
O2—Ba1—O1ⁱ	72.4 (7)	C9—C10—H10B	108.4
O2ⁱ—Ba1—O1ⁱ	53.7 (6)	H10A—C10—H10B	107.5
O4—Ba1—O1ⁱ	175.9 (7)	O4—C11—C12	108 (3)
O4ⁱ—Ba1—O1ⁱ	105.6 (6)	O4—C11—H11A	110.1
O1—Ba1—O1ⁱ	77.9 (9)	C12—C11—H11A	110.1
N1—Co1—N1ⁱⁱ	110.4 (15)	O4—C11—H11B	110.1
N1—Co1—N2	113.2 (12)	C12—C11—H11B	110.1
N1ⁱⁱ—Co1—N2	103.5 (11)	H11A—C11—H11B	108.4
N1—Co1—N2ⁱⁱ	103.5 (11)	O5—C12—C11	117 (3)
N1ⁱⁱ—Co1—N2ⁱⁱ	113.2 (12)	O5—C12—H12A	108.1
N2—Co1—N2ⁱⁱ	113.2 (19)	C11—C12—H12A	108.1
C15—N1—Co1	162 (3)	O5—C12—H12B	108.1
C16—N2—Co1	173 (3)	C11—C12—H12B	108.1
C14—O1—C1	118 (3)	H12A—C12—H12B	107.3
C14—O1—Ba1	120 (3)	O5—C13—C14	111 (3)
C1—O1—Ba1	118.2 (19)	O5—C13—H13A	109.4
C7—O2—C6	111 (3)	C14—C13—H13A	109.4
C7—O2—Ba1	123 (2)	O5—C13—H13B	109.4
C6—O2—Ba1	120.6 (19)	C14—C13—H13B	109.4
C9—O3—C8	112 (3)	H13A—C13—H13B	108.0
C9—O3—Ba1	122 (2)	O1—C14—C13	124 (4)
C8—O3—Ba1	115 (2)	O1—C14—H14A	106.2
C10—O4—C11	119 (3)	C13—C14—H14A	106.2
C10—O4—Ba1	110.8 (19)	O1—C14—H14B	106.2
C11—O4—Ba1	120.9 (19)	C13—C14—H14B	106.2
C12—O5—C13	114 (2)	H14A—C14—H14B	106.4
C12—O5—Ba1	117 (2)	N1—C15—S1	176 (3)
C13—O5—Ba1	124 (2)	N2—C16—S2	173 (3)

N1ⁱⁱ—Co1—N1—C15	55 (8)	O5—Ba1—O4—C11	4 (2)
N2—Co1—N1—C15	171 (8)	O5ⁱ—Ba1—O4—C11	−178 (2)
N2ⁱⁱ—Co1—N1—C15	−66 (9)	O3—Ba1—O4—C11	−125 (3)
N1—Co1—N2—C16	174 (26)	O3ⁱ—Ba1—O4—C11	85 (2)
N1ⁱⁱ—Co1—N2—C16	−66 (26)	O2—Ba1—O4—C11	−88 (2)
N2ⁱⁱ—Co1—N2—C16	57 (26)	O2ⁱ—Ba1—O4—C11	48 (3)
O5—Ba1—O1—C14	−13 (3)	O4ⁱ—Ba1—O4—C11	146 (3)
O5ⁱ—Ba1—O1—C14	166 (3)	O1—Ba1—O4—C11	−32 (2)
O3—Ba1—O1—C14	84 (3)	O1ⁱ—Ba1—O4—C11	−178 (9)
O3ⁱ—Ba1—O1—C14	−64 (3)	O5ⁱ—Ba1—O5—C12	2 (2)
O2—Ba1—O1—C14	123 (3)	O3—Ba1—O5—C12	66 (2)
O2ⁱ—Ba1—O1—C14	−104 (3)	O3ⁱ—Ba1—O5—C12	−63 (2)
O4—Ba1—O1—C14	23 (3)	O2—Ba1—O5—C12	127 (2)
O4ⁱ—Ba1—O1—C14	−13 (12)	O2ⁱ—Ba1—O5—C12	−124 (3)
O1ⁱ—Ba1—O1—C14	−160 (4)	O4—Ba1—O5—C12	23 (2)
O5—Ba1—O1—C1	−170 (2)	O4ⁱ—Ba1—O5—C12	−18 (3)
O5ⁱ—Ba1—O1—C1	8 (3)	O1—Ba1—O5—C12	162 (3)
O3—Ba1—O1—C1	−74 (2)	O1ⁱ—Ba1—O5—C12	−157 (2)
O3ⁱ—Ba1—O1—C1	139 (2)	O5ⁱ—Ba1—O5—C13	−152 (3)
O2—Ba1—O1—C1	−34 (2)	O3—Ba1—O5—C13	−88 (3)
O2ⁱ—Ba1—O1—C1	99 (2)	O3ⁱ—Ba1—O5—C13	143 (3)
O4—Ba1—O1—C1	−134 (2)	O2—Ba1—O5—C13	−27 (3)
O4ⁱ—Ba1—O1—C1	−170 (9)	O2ⁱ—Ba1—O5—C13	82 (3)
O1ⁱ—Ba1—O1—C1	43 (2)	O4—Ba1—O5—C13	−131 (3)
O5—Ba1—O2—C7	−83 (3)	O4ⁱ—Ba1—O5—C13	−173 (2)
O5ⁱ—Ba1—O2—C7	94 (3)	O1—Ba1—O5—C13	7 (2)
O3—Ba1—O2—C7	14 (3)	O1ⁱ—Ba1—O5—C13	49 (3)
O3ⁱ—Ba1—O2—C7	−159 (4)	C14—O1—C1—C6	−123 (4)
O2ⁱ—Ba1—O2—C7	−168 (3)	Ba1—O1—C1—C6	35 (4)
O4—Ba1—O2—C7	−23 (3)	C14—O1—C1—C2	58 (5)
O4ⁱ—Ba1—O2—C7	57 (3)	Ba1—O1—C1—C2	−144 (3)
O1—Ba1—O2—C7	−119 (3)	O1—C1—C2—C3	177 (3)
O1ⁱ—Ba1—O2—C7	153 (3)	C6—C1—C2—C3	−2 (5)
O5—Ba1—O2—C6	69 (2)	C1—C2—C3—C4	−3 (5)
O5ⁱ—Ba1—O2—C6	−114 (2)	C2—C3—C4—C5	3 (6)
O3—Ba1—O2—C6	166 (2)	C3—C4—C5—C6	2 (5)
O3ⁱ—Ba1—O2—C6	−7 (5)	O1—C1—C6—O2	−3 (4)
O2ⁱ—Ba1—O2—C6	−15.7 (18)	C2—C1—C6—O2	176 (3)
O4—Ba1—O2—C6	129 (2)	O1—C1—C6—C5	−172 (3)
O4ⁱ—Ba1—O2—C6	−151.0 (19)	C2—C1—C6—C5	7 (5)
O1—Ba1—O2—C6	32.7 (19)	C7—O2—C6—C1	124 (3)
O1ⁱ—Ba1—O2—C6	−55 (2)	Ba1—O2—C6—C1	−31 (3)
O5—Ba1—O3—C9	−33 (3)	C7—O2—C6—C5	−67 (4)
O5ⁱ—Ba1—O3—C9	144 (3)	Ba1—O2—C6—C5	137 (3)
O3ⁱ—Ba1—O3—C9	50 (2)	C4—C5—C6—C1	−7 (5)
O2—Ba1—O3—C9	−128 (3)	C4—C5—C6—O2	−174 (3)
O2ⁱ—Ba1—O3—C9	−138 (4)	C6—O2—C7—C8	168 (3)
O4—Ba1—O3—C9	10 (2)	Ba1—O2—C7—C8	−37 (4)
O4ⁱ—Ba1—O3—C9	84 (3)	C9—O3—C8—C7	106 (4)
O1—Ba1—O3—C9	−92 (2)	Ba1—O3—C8—C7	−40 (4)
O1ⁱ—Ba1—O3—C9	−173 (2)	O2—C7—C8—O3	50 (5)
O5—Ba1—O3—C8	109 (2)	C8—O3—C9—C10	180 (3)
O5ⁱ—Ba1—O3—C8	−73 (2)	Ba1—O3—C9—C10	−37 (4)
O3ⁱ—Ba1—O3—C8	−168 (2)	C11—O4—C10—C9	92 (4)
O2—Ba1—O3—C8	14 (2)	Ba1—O4—C10—C9	−55 (4)
O2ⁱ—Ba1—O3—C8	4 (5)	O3—C9—C10—O4	61 (4)
O4—Ba1—O3—C8	153 (2)	C10—O4—C11—C12	−169 (3)
O4ⁱ—Ba1—O3—C8	−134 (2)	Ba1—O4—C11—C12	−25 (4)
O1—Ba1—O3—C8	51 (2)	C13—O5—C12—C11	109 (3)
O1ⁱ—Ba1—O3—C8	−31 (2)	Ba1—O5—C12—C11	−48 (4)
O5—Ba1—O4—C10	151 (2)	O4—C11—C12—O5	48 (5)
O5ⁱ—Ba1—O4—C10	−31 (2)	C12—O5—C13—C14	−158 (3)
O3—Ba1—O4—C10	22 (2)	Ba1—O5—C13—C14	−3 (4)
O3ⁱ—Ba1—O4—C10	−128 (2)	C1—O1—C14—C13	176 (4)
O2—Ba1—O4—C10	59 (2)	Ba1—O1—C14—C13	19 (6)
O2ⁱ—Ba1—O4—C10	−165 (2)	O5—C13—C14—O1	−11 (6)
O4ⁱ—Ba1—O4—C10	−67 (2)	Co1—N1—C15—S1	95 (36)
O1—Ba1—O4—C10	115 (2)	Co1—N2—C16—S2	105 (33)
O1ⁱ—Ba1—O4—C10	−31 (11)

Symmetry codes: (i) −x, −x+y, −z+4/3; (ii) x−y+1, −y+2, −z+5/3.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12B···S2ⁱⁱⁱ	0.97	2.99	3.83 (4)	145
C8—H8B···S1^iv	0.97	2.97	3.93 (4)	170

Symmetry codes: (iii) x−1, y, z; (iv) −x+1, −x+y, −z+4/3.

Experimental details

Crystal data
Chemical formula	[Ba(C₁₄H₂₀O₅)₂][Co(NCS)₄]
M_r	965.19
Crystal system, space group	Trigonal, P3₁21
Temperature (K)	298
a, c (Å)	12.5772 (13), 23.758 (3)
V (Å³)	3254.7 (6)
Z	3
Radiation type	Mo Kα
µ (mm⁻¹)	1.53
Crystal size (mm)	0.43 × 0.40 × 0.28

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.559, 0.674
No. of measured, independent and observed [I > 2σ(I)] reflections	14488, 3786, 2749
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.068, 0.196, 1.00
No. of reflections	3786
No. of parameters	236
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.68, −1.38
Absolute structure	Flack (1983), 1623 Friedel pairs
Absolute structure parameter	−0.01 (12)

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

References

Drew, B. G. M., Esho, S. F. & Nelson, M. S. (1983). J. Chem. Soc. Dalton Trans. pp. 1653–1659. CSD CrossRef Web of Science Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Nunez, L. & Rogers, D. R. (1993). J. Coord. Chem. 28, 347–354. CrossRef CAS Web of Science Google Scholar
Owen, J. D. (1983). J. Chem. Soc. Perkin Trans. 2, pp. 407–415. CrossRef Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar