trans-Bis(1,4-butane­di­amine)­bis­(iso­thio­cyanato)­cobalt(III) thio­cyanate

The title compound, [Co(NCS)₂(C₄H₁₂N₂)₂]NCS, (I), has an octahedral coordination geometry, in which one of the seven-membered chelate rings adopts the chair form and the other the twist-boat form.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.033
• wR factor = 0.094
• Data-to-parameter ratio = 27.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

Metal complexes of 1,4-butanediamine (tmd: putrescin or tetramethylenediamine) are of interest in the context of bioinorganic chemistry (Gasowska et al., 2000). Only a few structures have been reported for transition metal complexes of tmd (Sato et al., 1974; Shimoi et al., 1988; Kurachi & Ohba, 1992).

The two geometrical isomers of [Co^III(NCS)₂(tmd)₂]⁺ have been prepared and their geometrical configurations have been determined by the spectroscopic properties (Nagata & Kanamori, 2001). The present X-ray analysis confirms the trans configuration for one of the isomers, (I) (Fig. 1). In (I), the two seven-membered chelate rings adopt the different conformations (Fig. 2). The conformation of Fig. 2(a) corresponds to the chair form that has been found in trans-[Co(III)(NO₂)₂(tmd)₂]⁺ (Shimoi et al., 1988). The other chelate ring (Fig. 2 b) adopts approximately the twist-boat form. The coordination bond distances and angles are in the normal region.

S2. Experimental

The title compound, (I), was prepared by adapting the procedures described by Nagata et al. (1985) and Nagata & Kanamori (2001). Crystals of (I) were obtained by a spontaneous evaporation of an aqueous solution at room temperature.

S3. Refinement

H atoms bonded to C and N atoms were placed geometrically and refined using a riding model via SHELXL97 HFIX/AFIX 23 facility. The displacement parameter was set as 1.2 times that of the parent atom.

Computing details

Data collection: AFC-7R Diffractometer Control Software (Rigaku, 1999); cell refinement: AFC-7R Diffractometer Control Software; data reduction: AFC-7R Diffractometer Control Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

	Fig. 1. The molecular structure of (I) showing the labelling of the non-H atoms. Displacement ellipsoids are shown at 50% probability levels.
	Fig. 2. The conformation of the chelate rings. Projection is made along the bisector of the N—Co—N angle.

trans-bis(isothiocyanato)bis(1,4-butanediamine)cobalt(III) thiocyanate

Crystal data

[Co(NCS)2(C4H12N2)2]NCS	F(000) = 856
Mr = 409.48	Dx = 1.477 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.739 (2) Å	Cell parameters from 25 reflections
b = 13.647 (4) Å	θ = 14.8–15.0°
c = 14.5479 (19) Å	µ = 1.28 mm^−1
β = 107.790 (13)°	T = 296 K
V = 1841.2 (7) Å^3	Prism, brown
Z = 4	0.20 × 0.20 × 0.15 mm

Data collection

Rigaku AFC-7R diffractometer	4027 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.027
Graphite monochromator	θmax = 30.0°, θmin = 2.7°
ω–2θ scans	h = 0→13
Absorption correction: ψ scan (North et al., 1968)	k = 0→19
Tmin = 0.784, Tmax = 0.831	l = −20→19
5653 measured reflections	3 standard reflections every 60 min
5371 independent reflections	intensity decay: 1.8%

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.094	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0409P)^2 + 0.8638P] where P = (Fo^2 + 2Fc^2)/3
5371 reflections	(Δ/σ)max = 0.001
199 parameters	Δρmax = 0.42 e Å^−3
0 restraints	Δρmin = −0.56 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
Co	0.61578 (3)	0.727614 (19)	0.160813 (17)	0.02571 (7)
N1	0.45397 (18)	0.70888 (13)	0.03981 (12)	0.0329 (3)
H11A	0.4445	0.7651	0.0074	0.040*
H11B	0.4835	0.6646	0.0051	0.040*
N2	0.53694 (18)	0.85379 (12)	0.18814 (13)	0.0333 (3)
H12A	0.5351	0.8501	0.2488	0.040*
H12B	0.6027	0.8989	0.1876	0.040*
N3	0.78374 (18)	0.74681 (14)	0.27788 (12)	0.0356 (4)
H21A	0.7654	0.8002	0.3072	0.043*
H21B	0.7838	0.6966	0.3169	0.043*
N4	0.69300 (18)	0.59780 (12)	0.13768 (12)	0.0315 (3)
H22A	0.6176	0.5586	0.1134	0.038*
H22B	0.7345	0.6063	0.0916	0.038*
C1	0.3057 (2)	0.67895 (17)	0.03832 (17)	0.0393 (5)
H11C	0.3128	0.6360	0.0927	0.047*
H11D	0.2611	0.6422	−0.0203	0.047*
C2	0.2104 (2)	0.76543 (17)	0.04305 (17)	0.0400 (5)
H12C	0.1168	0.7404	0.0422	0.048*
H12D	0.1963	0.8042	−0.0150	0.048*
C3	0.2649 (2)	0.83303 (17)	0.12974 (17)	0.0394 (5)
H13A	0.2895	0.7934	0.1879	0.047*
H13B	0.1868	0.8762	0.1317	0.047*
C4	0.3952 (2)	0.89565 (15)	0.13133 (17)	0.0371 (4)
H14A	0.3957	0.9055	0.0654	0.044*
H14B	0.3845	0.9594	0.1578	0.044*
C5	0.9349 (2)	0.7570 (2)	0.27415 (19)	0.0500 (6)
H21C	1.0003	0.7547	0.3395	0.060*
H21D	0.9452	0.8208	0.2476	0.060*
C6	0.9802 (3)	0.6785 (2)	0.2143 (2)	0.0528 (6)
H22C	0.9296	0.6908	0.1467	0.063*
H22D	1.0824	0.6865	0.2230	0.063*
C7	0.9543 (3)	0.5728 (2)	0.2358 (2)	0.0531 (6)
H23A	1.0064	0.5598	0.3030	0.064*
H23B	0.9953	0.5311	0.1969	0.064*
C8	0.7979 (2)	0.54302 (17)	0.21793 (16)	0.0403 (5)
H24A	0.7886	0.4736	0.2032	0.048*
H24B	0.7727	0.5532	0.2768	0.048*
N5	0.70753 (19)	0.79497 (13)	0.08213 (13)	0.0361 (4)
N6	0.52243 (18)	0.66423 (13)	0.24127 (12)	0.0338 (4)
N7	0.4676 (3)	0.43263 (16)	0.10374 (15)	0.0497 (5)
C9	0.7676 (2)	0.84419 (15)	0.04234 (14)	0.0312 (4)
C10	0.4574 (2)	0.63575 (15)	0.29055 (14)	0.0308 (4)
C11	0.3473 (3)	0.43338 (16)	0.08874 (15)	0.0417 (5)
S1	0.85770 (7)	0.91171 (5)	−0.01093 (5)	0.04828 (16)
S2	0.36308 (7)	0.59482 (5)	0.35728 (5)	0.04567 (15)
S3	0.17016 (8)	0.43348 (6)	0.06252 (6)	0.06087 (19)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co	0.02639 (12)	0.02624 (13)	0.02650 (12)	−0.00079 (10)	0.01105 (9)	0.00022 (10)
N1	0.0335 (8)	0.0332 (8)	0.0318 (8)	0.0040 (7)	0.0096 (7)	−0.0048 (7)
N2	0.0351 (8)	0.0287 (8)	0.0380 (9)	−0.0010 (7)	0.0139 (7)	−0.0047 (7)
N3	0.0340 (9)	0.0371 (9)	0.0338 (8)	−0.0022 (7)	0.0078 (7)	−0.0027 (7)
N4	0.0337 (8)	0.0317 (8)	0.0318 (8)	0.0026 (7)	0.0138 (7)	−0.0003 (7)
C1	0.0326 (10)	0.0360 (11)	0.0461 (12)	−0.0045 (8)	0.0075 (9)	−0.0073 (9)
C2	0.0291 (9)	0.0439 (12)	0.0461 (12)	−0.0003 (9)	0.0101 (9)	−0.0029 (10)
C3	0.0326 (10)	0.0410 (11)	0.0472 (12)	0.0048 (9)	0.0163 (9)	−0.0019 (9)
C4	0.0363 (10)	0.0308 (10)	0.0442 (11)	0.0040 (8)	0.0123 (9)	−0.0028 (8)
C5	0.0311 (11)	0.0619 (16)	0.0518 (13)	−0.0101 (10)	0.0047 (10)	0.0020 (12)
C6	0.0307 (11)	0.0706 (18)	0.0598 (15)	0.0053 (11)	0.0176 (11)	0.0156 (13)
C7	0.0375 (12)	0.0639 (17)	0.0583 (15)	0.0160 (11)	0.0153 (11)	0.0145 (13)
C8	0.0452 (12)	0.0366 (11)	0.0399 (11)	0.0085 (9)	0.0140 (9)	0.0066 (9)
N5	0.0356 (9)	0.0378 (9)	0.0390 (9)	0.0001 (7)	0.0173 (7)	0.0060 (7)
N6	0.0347 (9)	0.0338 (8)	0.0366 (9)	0.0007 (7)	0.0165 (7)	0.0019 (7)
N7	0.0597 (14)	0.0483 (12)	0.0417 (11)	0.0024 (10)	0.0163 (10)	−0.0060 (9)
C9	0.0299 (9)	0.0323 (9)	0.0325 (9)	0.0027 (8)	0.0110 (8)	0.0033 (8)
C10	0.0309 (9)	0.0297 (9)	0.0336 (9)	0.0036 (7)	0.0124 (8)	−0.0003 (8)
C11	0.0656 (16)	0.0323 (10)	0.0300 (10)	−0.0012 (10)	0.0190 (10)	−0.0003 (8)
S1	0.0443 (3)	0.0522 (3)	0.0531 (3)	−0.0073 (3)	0.0218 (3)	0.0157 (3)
S2	0.0476 (3)	0.0504 (3)	0.0503 (3)	−0.0009 (3)	0.0317 (3)	0.0051 (3)
S3	0.0578 (4)	0.0584 (4)	0.0710 (5)	0.0028 (3)	0.0265 (4)	0.0117 (4)

Geometric parameters (Å, º)

Co—N1	1.9881 (17)	C2—C3	1.521 (3)
Co—N2	1.9747 (17)	C3—H13A	0.9700
Co—N3	1.9856 (17)	C3—H13B	0.9700
Co—N4	1.9930 (17)	C3—C4	1.525 (3)
Co—N5	1.8918 (17)	C4—H14A	0.9700
Co—N6	1.8961 (17)	C4—H14B	0.9700
N1—H11A	0.8900	C5—H21C	0.9700
N1—H11B	0.8900	C5—H21D	0.9700
N1—C1	1.494 (3)	C5—C6	1.528 (4)
N2—H12A	0.8900	C6—H22C	0.9700
N2—H12B	0.8900	C6—H22D	0.9700
N2—C4	1.489 (3)	C6—C7	1.514 (4)
N3—H21A	0.8900	C7—H23A	0.9700
N3—H21B	0.8900	C7—H23B	0.9700
N3—C5	1.496 (3)	C7—C8	1.520 (3)
N4—H22A	0.8900	C8—H24A	0.9700
N4—H22B	0.8900	C8—H24B	0.9700
N4—C8	1.496 (3)	N5—C9	1.155 (3)
C1—H11C	0.9700	N6—C10	1.159 (3)
C1—H11D	0.9700	N7—C11	1.124 (3)
C1—C2	1.516 (3)	C9—S1	1.624 (2)
C2—H12C	0.9700	C10—S2	1.626 (2)
C2—H12D	0.9700	C11—S3	1.649 (3)
Co···C1	3.074 (2)	N3···S3^ii	3.383 (2)
Co···C4	3.081 (2)	N4···C5	3.369 (3)
Co···C5	3.067 (2)	N4···C6	2.894 (3)
Co···C6	3.459 (2)	N4···N5	2.826 (3)
Co···C8	3.047 (2)	N4···N7	3.079 (3)
Co···C9	3.040 (2)	N4···N7^i	3.405 (3)
Co···C10	3.048 (2)	N4···C11^i	3.224 (3)
N1···N2	2.856 (2)	C1···C4	3.258 (3)
N1···C3	3.074 (3)	C1···N6	3.067 (3)
N1···C4	3.010 (3)	C1···C11	3.428 (3)
N1···N6	2.866 (2)	C3···N6	3.427 (3)
N1···N7^i	3.106 (3)	C5···C8	3.211 (4)
N2···C2	3.452 (3)	C5···N5	3.033 (3)
N2···N7^ii	3.226 (3)	C5···C9	3.477 (3)
N2···C11^ii	3.279 (3)	C6···N5	3.187 (3)
N3···N4	2.824 (2)	C8···N6	3.257 (3)
N3···C7	3.065 (3)	C8···N7	3.480 (3)
N3···C8	2.931 (3)
N1—Co—N2	92.21 (7)	C1—C2—H12D	108.2
N1—Co—N3	177.26 (7)	C1—C2—C3	116.53 (18)
N1—Co—N4	88.51 (7)	H12C—C2—H12D	107.3
N1—Co—N5	85.41 (8)	H12C—C2—C3	108.2
N1—Co—N6	95.05 (7)	H12D—C2—C3	108.2
N2—Co—N3	88.94 (7)	C2—C3—H13A	108.4
N2—Co—N4	177.64 (7)	C2—C3—H13B	108.4
N2—Co—N5	89.01 (8)	C2—C3—C4	115.47 (18)
N2—Co—N6	89.10 (7)	H13A—C3—H13B	107.5
N3—Co—N4	90.44 (7)	H13A—C3—C4	108.4
N3—Co—N5	92.13 (8)	H13B—C3—C4	108.4
N3—Co—N6	87.45 (8)	N2—C4—C3	114.81 (18)
N4—Co—N5	93.29 (8)	N2—C4—H14A	108.6
N4—Co—N6	88.60 (7)	N2—C4—H14B	108.6
N5—Co—N6	178.07 (8)	C3—C4—H14A	108.6
Co—N1—H11A	106.5	C3—C4—H14B	108.6
Co—N1—H11B	106.5	H14A—C4—H14B	107.5
Co—N1—C1	123.30 (14)	N3—C5—H21C	108.6
H11A—N1—H11B	106.5	N3—C5—H21D	108.6
H11A—N1—C1	106.5	N3—C5—C6	114.5 (2)
H11B—N1—C1	106.5	H21C—C5—H21D	107.6
Co—N2—H12A	106.1	H21C—C5—C6	108.6
Co—N2—H12B	106.1	H21D—C5—C6	108.6
Co—N2—C4	125.05 (13)	C5—C6—H22C	108.0
H12A—N2—H12B	106.3	C5—C6—H22D	108.0
H12A—N2—C4	106.1	C5—C6—C7	117.0 (2)
H12B—N2—C4	106.1	H22C—C6—H22D	107.3
Co—N3—H21A	106.6	H22C—C6—C7	108.0
Co—N3—H21B	106.6	H22D—C6—C7	108.0
Co—N3—C5	122.89 (14)	C6—C7—H23A	108.2
H21A—N3—H21B	106.6	C6—C7—H23B	108.2
H21A—N3—C5	106.6	C6—C7—C8	116.2 (2)
H21B—N3—C5	106.6	H23A—C7—H23B	107.4
Co—N4—H22A	107.1	H23A—C7—C8	108.2
Co—N4—H22B	107.1	H23B—C7—C8	108.2
Co—N4—C8	121.03 (13)	N4—C8—C7	114.20 (19)
H22A—N4—H22B	106.8	N4—C8—H24A	108.7
H22A—N4—C8	107.1	N4—C8—H24B	108.7
H22B—N4—C8	107.1	C7—C8—H24A	108.7
N1—C1—H11C	109.0	C7—C8—H24B	108.7
N1—C1—H11D	109.0	H24A—C8—H24B	107.6
N1—C1—C2	112.88 (18)	Co—N5—C9	172.11 (18)
H11C—C1—H11D	107.8	Co—N6—C10	172.07 (17)
H11C—C1—C2	109.0	N5—C9—S1	177.81 (19)
H11D—C1—C2	109.0	N6—C10—S2	178.6 (2)
C1—C2—H12C	108.2	N7—C11—S3	177.9 (2)
Co—N1—C1—C2	88.3 (2)	N4—Co—N3—C5	65.05 (19)
Co—N2—C4—C3	61.1 (2)	C1—C2—C3—C4	70.2 (3)
Co—N3—C5—C6	−49.0 (3)	C2—C3—C4—N2	−95.3 (2)
Co—N4—C8—C7	−85.0 (2)	C5—C6—C7—C8	62.9 (3)
N1—Co—N2—C4	5.81 (17)	C6—C7—C8—N4	31.0 (3)
N1—Co—N4—C8	−160.59 (16)	N5—Co—N1—C1	−164.02 (16)
N1—C1—C2—C3	−57.6 (3)	N5—Co—N2—C4	91.17 (17)
N2—Co—N1—C1	−75.19 (16)	N5—Co—N3—C5	−28.26 (19)
N2—Co—N3—C5	−117.23 (19)	N5—Co—N4—C8	114.09 (16)
N3—Co—N2—C4	−176.68 (17)	N6—Co—N1—C1	14.10 (16)
N3—Co—N4—C8	21.93 (16)	N6—Co—N2—C4	−89.21 (17)
N3—C5—C6—C7	−50.8 (3)	N6—Co—N3—C5	153.63 (19)
N4—Co—N1—C1	102.56 (16)	N6—Co—N4—C8	−65.50 (16)

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