Bis[N,N-dimethyl-1-(10H-pyrido[3,2-b][1,4]benzothia-zin-10-yl)propan-2-aminium] tetrakis-(thio-cyanato-κN)cobaltate(II).

The asymmetric unit of the title salt, (C(16)H(20)N(3)S)(2)[Co(NCS)(4)], comprises one monovalent isothio-pendylium cation and one-half of a divalent thio-cyanatocobaltate(II) anion (2 symmetry). The central thia-zine ring of the cation is slightly twisted in a boat-like fashion, with r.m.s. deviations from the mean plane of 0.272 (1) and 0.2852 (8) Å for the N and S atoms. The mol-ecular structure of the cation is stabilized by an intra-molecular N-H⋯N hydrogen bond. Within the complex anion, the Co(II) atom is tetra-hedrally surrounded by four N atoms of the thio-cyanate ligands. π-π stacking, with a distance of 3.7615 (10) Å between the centroids of benzene and pyridine rings, helps to consolidate the packing.

Related literature

For general background to isothipendyl, cobalt(II) and thio­cyanate compounds, see: Kinnamon et al. (1994 ▶); Moreau et al. (1995 ▶); Scott et al. (1990 ▶); Hudson et al. (2005 ▶). For a related structure, see: Shi et al. (2005 ▶).

Experimental

Crystal data

(C16H20N3S)2[Co(NCS)4]

M = 864.07

Monoclinic,

a = 25.2420 (4) Å

b = 11.4357 (2) Å

c = 14.5939 (2) Å

β = 98.557 (1)°

V = 4165.78 (11) Å3

Z = 4

Mo Kα radiation

μ = 0.75 mm−1

T = 295 K

0.22 × 0.15 × 0.12 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: ψ scan (SADABS; Sheldrick, 2004 ▶) T min = 0.852, T max = 0.915

48347 measured reflections

6498 independent reflections

4566 reflections with I > 2σ(I)

R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.114

S = 1.01

6498 reflections

243 parameters

H-atom parameters constrained

Δρmax = 0.30 e Å−3

Δρmin = −0.37 e Å−3

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810021367/wm2356sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810021367/wm2356Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

(C16H20N3S)2[Co(NCS)4]	F(000) = 1796
Mr = 864.07	Dx = 1.378 Mg m−3
Monoclinic, C2/c	Melting point: 453 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 25.2420 (4) Å	Cell parameters from 6498 reflections
b = 11.4357 (2) Å	θ = 1.6–30.8°
c = 14.5939 (2) Å	µ = 0.75 mm−1
β = 98.557 (1)°	T = 295 K
V = 4165.78 (11) Å3	Plate, green
Z = 4	0.22 × 0.15 × 0.12 mm

Bruker APEXII CCD area-detector diffractometer	6498 independent reflections
Radiation source: fine-focus sealed tube	4566 reflections with I > 2σ(I)
graphite	Rint = 0.032
ω and φ scans	θmax = 30.8°, θmin = 1.6°
Absorption correction: ψ scan (SADABS; Sheldrick, 2004)	h = −36→36
Tmin = 0.852, Tmax = 0.915	k = −16→16
48347 measured reflections	l = −20→20

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.114	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.0516P)2 + 2.3179P] where P = (Fo2 + 2Fc2)/3
6498 reflections	(Δ/σ)max < 0.001
243 parameters	Δρmax = 0.30 e Å−3
0 restraints	Δρmin = −0.37 e Å−3

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.

	x	y	z	Uiso*/Ueq
Co1	0.0000	0.18800 (3)	0.2500	0.05395 (11)
S1	0.169598 (17)	0.36282 (5)	0.31347 (4)	0.06906 (15)
S2	0.09133 (3)	0.39599 (6)	0.04513 (5)	0.0913 (2)
S3	−0.09097 (2)	−0.11877 (5)	0.08464 (4)	0.06810 (15)
N1	0.30192 (5)	0.17216 (12)	0.37667 (10)	0.0479 (3)
N2	0.29026 (5)	0.36667 (11)	0.33141 (9)	0.0428 (3)
N3	0.40850 (5)	0.23282 (13)	0.40260 (9)	0.0503 (3)
H3A	0.3781	0.1888	0.3953	0.060*
N4	0.04020 (8)	0.28147 (18)	0.17318 (14)	0.0771 (5)
N5	−0.04823 (6)	0.08326 (15)	0.17017 (11)	0.0595 (4)
C2	0.28169 (8)	0.06803 (16)	0.39813 (13)	0.0589 (4)
H2	0.3049	0.0049	0.4101	0.071*
C3	0.22864 (9)	0.05145 (18)	0.40307 (14)	0.0663 (5)
H3	0.2161	−0.0205	0.4204	0.080*
C4	0.19412 (7)	0.14419 (19)	0.38174 (14)	0.0621 (5)
H4	0.1578	0.1352	0.3848	0.074*
C5	0.21316 (6)	0.24990 (16)	0.35591 (11)	0.0487 (4)
C6	0.26864 (5)	0.26126 (14)	0.35550 (10)	0.0413 (3)
C7	0.21115 (6)	0.48282 (17)	0.34832 (11)	0.0506 (4)
C8	0.18804 (8)	0.5880 (2)	0.36902 (13)	0.0653 (5)
H8	0.1513	0.5917	0.3700	0.078*
C9	0.21887 (10)	0.6863 (2)	0.38804 (14)	0.0729 (6)
H9	0.2030	0.7567	0.4007	0.087*
C10	0.27306 (10)	0.68031 (18)	0.38826 (14)	0.0693 (5)
H10	0.2939	0.7472	0.4000	0.083*
C11	0.29708 (8)	0.57504 (16)	0.37113 (12)	0.0562 (4)
H11	0.3341	0.5715	0.3736	0.067*
C12	0.26658 (6)	0.47499 (14)	0.35030 (10)	0.0443 (3)
C13	0.34445 (6)	0.36661 (15)	0.30759 (10)	0.0440 (3)
H13A	0.3491	0.4375	0.2732	0.053*
H13B	0.3476	0.3011	0.2666	0.053*
C14	0.39047 (6)	0.35898 (15)	0.38957 (11)	0.0459 (3)
H14	0.3763	0.3831	0.4456	0.055*
C15	0.43718 (7)	0.4390 (2)	0.37864 (16)	0.0689 (5)
H15A	0.4659	0.4254	0.4285	0.103*
H15B	0.4258	0.5190	0.3799	0.103*
H15C	0.4494	0.4230	0.3206	0.103*
C16	0.43609 (9)	0.2099 (2)	0.49819 (14)	0.0752 (6)
H16A	0.4490	0.1308	0.5024	0.113*
H16B	0.4114	0.2211	0.5414	0.113*
H16C	0.4657	0.2628	0.5125	0.113*
C17	0.44122 (9)	0.1896 (2)	0.33280 (17)	0.0764 (6)
H17A	0.4771	0.2191	0.3474	0.115*
H17B	0.4258	0.2162	0.2723	0.115*
H17C	0.4419	0.1057	0.3337	0.115*
C18	0.06195 (8)	0.32922 (17)	0.12044 (15)	0.0622 (5)
C19	−0.06629 (6)	−0.00127 (16)	0.13474 (12)	0.0492 (4)

	U11	U22	U33	U12	U13	U23
Co1	0.04465 (17)	0.0540 (2)	0.0604 (2)	0.000	−0.00135 (13)	0.000
S1	0.03187 (19)	0.0899 (4)	0.0813 (3)	0.0035 (2)	−0.00519 (19)	0.0002 (3)
S2	0.0961 (5)	0.0837 (4)	0.0981 (5)	−0.0315 (4)	0.0272 (4)	0.0016 (3)
S3	0.0596 (3)	0.0733 (3)	0.0717 (3)	−0.0168 (2)	0.0107 (2)	−0.0148 (2)
N1	0.0407 (6)	0.0498 (7)	0.0536 (7)	−0.0035 (5)	0.0078 (5)	0.0019 (6)
N2	0.0304 (5)	0.0487 (7)	0.0503 (7)	−0.0008 (5)	0.0087 (5)	0.0030 (6)
N3	0.0354 (6)	0.0617 (8)	0.0528 (7)	0.0017 (6)	0.0038 (5)	−0.0058 (6)
N4	0.0690 (11)	0.0815 (12)	0.0766 (11)	−0.0245 (9)	−0.0027 (9)	0.0100 (10)
N5	0.0439 (7)	0.0615 (9)	0.0701 (9)	−0.0001 (7)	−0.0014 (6)	−0.0029 (8)
C2	0.0628 (10)	0.0498 (9)	0.0644 (10)	−0.0054 (8)	0.0108 (8)	0.0037 (8)
C3	0.0728 (12)	0.0586 (11)	0.0709 (12)	−0.0233 (10)	0.0218 (10)	−0.0009 (9)
C4	0.0458 (8)	0.0757 (12)	0.0674 (11)	−0.0228 (9)	0.0172 (8)	−0.0099 (10)
C5	0.0332 (6)	0.0644 (10)	0.0484 (8)	−0.0073 (7)	0.0055 (6)	−0.0045 (7)
C6	0.0326 (6)	0.0525 (8)	0.0389 (7)	−0.0047 (6)	0.0054 (5)	−0.0021 (6)
C7	0.0433 (7)	0.0657 (10)	0.0418 (7)	0.0115 (7)	0.0031 (6)	0.0061 (7)
C8	0.0597 (10)	0.0838 (14)	0.0521 (9)	0.0296 (10)	0.0071 (8)	0.0072 (9)
C9	0.0941 (16)	0.0655 (13)	0.0572 (11)	0.0290 (12)	0.0056 (10)	0.0009 (9)
C10	0.0937 (16)	0.0514 (10)	0.0614 (11)	0.0053 (10)	0.0066 (10)	0.0023 (9)
C11	0.0585 (10)	0.0530 (10)	0.0565 (9)	−0.0007 (8)	0.0066 (8)	0.0047 (8)
C12	0.0431 (7)	0.0520 (9)	0.0375 (7)	0.0056 (6)	0.0046 (5)	0.0057 (6)
C13	0.0340 (6)	0.0550 (9)	0.0448 (7)	−0.0025 (6)	0.0115 (5)	0.0029 (6)
C14	0.0322 (6)	0.0567 (9)	0.0495 (8)	−0.0044 (6)	0.0085 (6)	−0.0045 (7)
C15	0.0421 (8)	0.0783 (13)	0.0871 (14)	−0.0189 (9)	0.0116 (9)	−0.0023 (11)
C16	0.0714 (13)	0.0858 (15)	0.0613 (11)	0.0179 (11)	−0.0133 (10)	−0.0035 (10)
C17	0.0584 (11)	0.0925 (16)	0.0811 (14)	0.0187 (11)	0.0194 (10)	−0.0162 (12)
C18	0.0510 (9)	0.0556 (10)	0.0757 (12)	−0.0121 (8)	−0.0049 (9)	−0.0033 (9)
C19	0.0310 (6)	0.0614 (10)	0.0546 (9)	0.0033 (6)	0.0048 (6)	0.0030 (8)

Co1—N4i	1.9411 (19)	C5—C6	1.4073 (19)
Co1—N4	1.9411 (19)	C7—C8	1.389 (3)
Co1—N5	1.9626 (16)	C7—C12	1.398 (2)
Co1—N5i	1.9626 (16)	C8—C9	1.372 (3)
S1—C5	1.7485 (18)	C8—H8	0.9300
S1—C7	1.756 (2)	C9—C10	1.369 (3)
S2—C18	1.607 (2)	C9—H9	0.9300
S3—C19	1.6102 (19)	C10—C11	1.387 (3)
N1—C6	1.328 (2)	C10—H10	0.9300
N1—C2	1.351 (2)	C11—C12	1.387 (2)
N2—C6	1.390 (2)	C11—H11	0.9300
N2—C12	1.420 (2)	C13—C14	1.541 (2)
N2—C13	1.4608 (18)	C13—H13A	0.9700
N3—C16	1.487 (2)	C13—H13B	0.9700
N3—C17	1.488 (2)	C14—C15	1.519 (2)
N3—C14	1.516 (2)	C14—H14	0.9800
N3—H3A	0.9100	C15—H15A	0.9600
N4—C18	1.148 (3)	C15—H15B	0.9600
N5—C19	1.157 (2)	C15—H15C	0.9600
C2—C3	1.365 (3)	C16—H16A	0.9600
C2—H2	0.9300	C16—H16B	0.9600
C3—C4	1.378 (3)	C16—H16C	0.9600
C3—H3	0.9300	C17—H17A	0.9600
C4—C5	1.374 (3)	C17—H17B	0.9600
C4—H4	0.9300	C17—H17C	0.9600
N4i—Co1—N4	113.17 (13)	C8—C9—H9	120.1
N4i—Co1—N5	110.33 (8)	C9—C10—C11	120.4 (2)
N4—Co1—N5	108.95 (7)	C9—C10—H10	119.8
N4i—Co1—N5i	108.95 (7)	C11—C10—H10	119.8
N4—Co1—N5i	110.33 (8)	C10—C11—C12	120.80 (19)
N5—Co1—N5i	104.78 (9)	C10—C11—H11	119.6
C5—S1—C7	99.06 (7)	C12—C11—H11	119.6
C6—N1—C2	118.85 (14)	C11—C12—C7	118.22 (16)
C6—N2—C12	121.00 (12)	C11—C12—N2	121.74 (14)
C6—N2—C13	118.47 (12)	C7—C12—N2	120.05 (15)
C12—N2—C13	118.87 (13)	N2—C13—C14	116.08 (12)
C16—N3—C17	110.70 (16)	N2—C13—H13A	108.3
C16—N3—C14	112.07 (14)	C14—C13—H13A	108.3
C17—N3—C14	114.63 (15)	N2—C13—H13B	108.3
C16—N3—H3A	106.3	C14—C13—H13B	108.3
C17—N3—H3A	106.3	H13A—C13—H13B	107.4
C14—N3—H3A	106.3	N3—C14—C15	111.28 (14)
C18—N4—Co1	172.97 (18)	N3—C14—C13	109.19 (13)
C19—N5—Co1	160.60 (14)	C15—C14—C13	113.05 (14)
N1—C2—C3	122.85 (19)	N3—C14—H14	107.7
N1—C2—H2	118.6	C15—C14—H14	107.7
C3—C2—H2	118.6	C13—C14—H14	107.7
C2—C3—C4	118.25 (18)	C14—C15—H15A	109.5
C2—C3—H3	120.9	C14—C15—H15B	109.5
C4—C3—H3	120.9	H15A—C15—H15B	109.5
C5—C4—C3	120.25 (16)	C14—C15—H15C	109.5
C5—C4—H4	119.9	H15A—C15—H15C	109.5
C3—C4—H4	119.9	H15B—C15—H15C	109.5
C4—C5—C6	118.11 (17)	N3—C16—H16A	109.5
C4—C5—S1	121.32 (13)	N3—C16—H16B	109.5
C6—C5—S1	120.26 (13)	H16A—C16—H16B	109.5
N1—C6—N2	117.76 (12)	N3—C16—H16C	109.5
N1—C6—C5	121.59 (15)	H16A—C16—H16C	109.5
N2—C6—C5	120.64 (14)	H16B—C16—H16C	109.5
C8—C7—C12	120.16 (18)	N3—C17—H17A	109.5
C8—C7—S1	119.17 (14)	N3—C17—H17B	109.5
C12—C7—S1	120.58 (13)	H17A—C17—H17B	109.5
C9—C8—C7	120.63 (19)	N3—C17—H17C	109.5
C9—C8—H8	119.7	H17A—C17—H17C	109.5
C7—C8—H8	119.7	H17B—C17—H17C	109.5
C10—C9—C8	119.72 (19)	N4—C18—S2	178.86 (19)
C10—C9—H9	120.1	N5—C19—S3	179.38 (17)
N4i—Co1—N5—C19	−126.5 (5)	S1—C7—C8—C9	−173.88 (15)
N4—Co1—N5—C19	108.7 (5)	C7—C8—C9—C10	−1.2 (3)
N5i—Co1—N5—C19	−9.4 (4)	C8—C9—C10—C11	−1.2 (3)
C6—N1—C2—C3	−3.0 (3)	C9—C10—C11—C12	2.3 (3)
N1—C2—C3—C4	2.5 (3)	C10—C11—C12—C7	−0.9 (3)
C2—C3—C4—C5	0.3 (3)	C10—C11—C12—N2	179.22 (16)
C3—C4—C5—C6	−2.4 (3)	C8—C7—C12—C11	−1.5 (2)
C3—C4—C5—S1	171.23 (15)	S1—C7—C12—C11	174.88 (12)
C7—S1—C5—C4	151.93 (15)	C8—C7—C12—N2	178.41 (14)
C7—S1—C5—C6	−34.59 (15)	S1—C7—C12—N2	−5.2 (2)
C2—N1—C6—N2	−178.41 (15)	C6—N2—C12—C11	147.52 (15)
C2—N1—C6—C5	0.7 (2)	C13—N2—C12—C11	−17.5 (2)
C12—N2—C6—N1	−149.64 (14)	C6—N2—C12—C7	−32.4 (2)
C13—N2—C6—N1	15.5 (2)	C13—N2—C12—C7	162.56 (14)
C12—N2—C6—C5	31.2 (2)	C6—N2—C13—C14	−77.11 (18)
C13—N2—C6—C5	−163.65 (14)	C12—N2—C13—C14	88.31 (17)
C4—C5—C6—N1	1.9 (2)	C16—N3—C14—C15	77.02 (19)
S1—C5—C6—N1	−171.75 (12)	C17—N3—C14—C15	−50.2 (2)
C4—C5—C6—N2	−178.98 (15)	C16—N3—C14—C13	−157.49 (15)
S1—C5—C6—N2	7.3 (2)	C17—N3—C14—C13	75.24 (17)
C5—S1—C7—C8	−150.12 (14)	N2—C13—C14—N3	96.79 (16)
C5—S1—C7—C12	33.45 (14)	N2—C13—C14—C15	−138.75 (16)
C12—C7—C8—C9	2.6 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N1	0.91	1.91	2.7494 (18)	152

Co1—N4	1.9411 (19)
Co1—N5	1.9626 (16)

N4i—Co1—N4	113.17 (13)
N4—Co1—N5	108.95 (7)
N4—Co1—N5i	110.33 (8)
N5—Co1—N5i	104.78 (9)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯N1	0.91	1.91	2.7494 (18)	152