Bis[2-(1H-pyrazol-3-yl-κN)pyridine-κN]dithio-cyanato-κN,κS-cadmium(II).

The mol-ecular structure of the mononuclear complex, [Cd(SCN)(2)(C(8)H(7)N(3))(2)], contains a Cd(II) atom in a distorted octa-hedral coordination defined by five N atoms from two bidentate chelate 2-(1H-pyrazol-3-yl)pyridine ligands and by one SCN(-) anion. The second SCN(-) anion provides its S atom for completion of the coordination sphere. The complex is linked to four others by N-H⋯N and N-H⋯S hydrogen-bonding inter-actions between the pyrazol N-H group and the terminal S and N atoms of neighbouring SCN(-) anions. This arrangement leads to the formation of sheets parallel to (100). Face-to-face π-π stacking inter-actions with shortest inter-planar distances of 3.805 (2) and 3.696 (2) Å help to consolidate the crystal packing.

Related literature

For background to self assembly in supra­molecular chemistry, see: Beatty (2003 ▶); Braga et al. (2003 ▶); Chen & Liu (2002 ▶); Zhang et al. (2004 ▶). For related structures, see: Hu et al. (2008 ▶).

Experimental

Crystal data

[Cd(NCS)2(C8H7N3)2]

M = 518.89

Monoclinic,

a = 14.4612 (19) Å

b = 9.6043 (12) Å

c = 14.9089 (19) Å

β = 99.290 (2)°

V = 2043.5 (5) Å3

Z = 4

Mo Kα radiation

μ = 1.30 mm−1

T = 296 K

0.32 × 0.26 × 0.22 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T min = 0.682, T max = 0.764

10166 measured reflections

3602 independent reflections

3119 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.023

wR(F 2) = 0.053

S = 1.05

3602 reflections

262 parameters

H-atom parameters constrained

Δρmax = 0.33 e Å−3

Δρmin = −0.24 e Å−3

Data collection: APEX2 (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2003 ▶); 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 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810034604/wm2396sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810034604/wm2396Isup2.hkl

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

[Cd(NCS)2(C8H7N3)2]	F(000) = 1032
Mr = 518.89	Dx = 1.687 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4275 reflections
a = 14.4612 (19) Å	θ = 2.5–27.4°
b = 9.6043 (12) Å	µ = 1.30 mm−1
c = 14.9089 (19) Å	T = 296 K
β = 99.290 (2)°	Block, colourless
V = 2043.5 (5) Å3	0.32 × 0.26 × 0.22 mm
Z = 4

Bruker APEXII CCD area-detector diffractometer	3602 independent reflections
Radiation source: fine-focus sealed tube	3119 reflections with I > 2σ(I)
graphite	Rint = 0.022
phi and ω scans	θmax = 25.0°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −17→9
Tmin = 0.682, Tmax = 0.764	k = −11→11
10166 measured reflections	l = −17→17

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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.053	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0226P)2 + 0.5639P] where P = (Fo2 + 2Fc2)/3
3602 reflections	(Δ/σ)max = 0.001
262 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.24 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
Cd1	0.229952 (12)	0.555357 (17)	0.337364 (11)	0.03567 (7)
S1	0.32477 (5)	1.02032 (7)	0.45051 (5)	0.05433 (19)
S2	0.12657 (5)	0.57892 (7)	0.46990 (5)	0.04796 (17)
N1	0.10594 (14)	0.5820 (2)	0.21453 (13)	0.0402 (5)
N2	0.18138 (14)	0.3329 (2)	0.27202 (13)	0.0413 (5)
N3	0.21610 (16)	0.2024 (2)	0.27632 (15)	0.0510 (6)
H3	0.2600	0.1737	0.3182	0.061*
N4	0.34659 (14)	0.42207 (19)	0.43362 (13)	0.0359 (5)
N5	0.36346 (15)	0.5293 (2)	0.26918 (14)	0.0419 (5)
N6	0.38935 (16)	0.5695 (2)	0.19073 (14)	0.0481 (5)
H6	0.3551	0.6189	0.1501	0.058*
N7	0.25827 (17)	0.7890 (2)	0.34656 (15)	0.0552 (6)
N8	0.26347 (18)	0.7180 (3)	0.59283 (16)	0.0653 (7)
C1	0.06579 (19)	0.7044 (3)	0.19052 (18)	0.0494 (7)
H1	0.0925	0.7850	0.2179	0.059*
C2	−0.0137 (2)	0.7152 (3)	0.12667 (19)	0.0589 (8)
H2	−0.0390	0.8020	0.1095	0.071*
C3	−0.0551 (2)	0.5966 (4)	0.0887 (2)	0.0681 (9)
H3A	−0.1102	0.6021	0.0470	0.082*
C4	−0.0156 (2)	0.4704 (4)	0.11192 (18)	0.0590 (8)
H4	−0.0435	0.3890	0.0868	0.071*
C5	0.06664 (17)	0.4655 (3)	0.17354 (16)	0.0421 (6)
C6	0.11593 (17)	0.3351 (3)	0.19786 (16)	0.0410 (6)
C7	0.1093 (2)	0.2035 (3)	0.15527 (19)	0.0589 (8)
H7	0.0693	0.1775	0.1027	0.071*
C8	0.1745 (2)	0.1224 (3)	0.2080 (2)	0.0586 (8)
H8	0.1874	0.0293	0.1981	0.070*
C9	0.33719 (18)	0.3731 (2)	0.51578 (16)	0.0415 (6)
H9	0.2809	0.3882	0.5368	0.050*
C10	0.40707 (19)	0.3014 (3)	0.57064 (17)	0.0454 (6)
H10	0.3983	0.2685	0.6273	0.054*
C11	0.4903 (2)	0.2798 (3)	0.53915 (18)	0.0485 (7)
H11	0.5389	0.2325	0.5749	0.058*
C12	0.50132 (17)	0.3284 (2)	0.45472 (17)	0.0413 (6)
H12	0.5573	0.3141	0.4329	0.050*
C13	0.42789 (16)	0.3990 (2)	0.40266 (16)	0.0354 (5)
C14	0.43478 (17)	0.4553 (2)	0.31247 (16)	0.0371 (6)
C15	0.5074 (2)	0.4489 (3)	0.26009 (18)	0.0475 (6)
H15	0.5648	0.4038	0.2746	0.057*
C16	0.4754 (2)	0.5230 (3)	0.18351 (18)	0.0510 (7)
H16	0.5072	0.5385	0.1350	0.061*
C17	0.28474 (18)	0.8847 (3)	0.39008 (17)	0.0411 (6)
C18	0.20761 (19)	0.6625 (3)	0.54154 (17)	0.0435 (6)

	U11	U22	U33	U12	U13	U23
Cd1	0.03330 (11)	0.03163 (10)	0.03974 (11)	0.00163 (8)	−0.00116 (7)	−0.00255 (8)
S1	0.0605 (5)	0.0379 (4)	0.0599 (4)	−0.0038 (3)	−0.0042 (4)	−0.0060 (3)
S2	0.0363 (4)	0.0557 (4)	0.0517 (4)	−0.0017 (3)	0.0065 (3)	−0.0062 (3)
N1	0.0355 (11)	0.0463 (13)	0.0389 (11)	0.0059 (10)	0.0061 (9)	0.0059 (9)
N2	0.0411 (12)	0.0385 (12)	0.0425 (12)	−0.0033 (10)	0.0012 (9)	−0.0049 (9)
N3	0.0541 (14)	0.0407 (13)	0.0558 (14)	0.0018 (11)	0.0014 (11)	0.0011 (11)
N4	0.0348 (11)	0.0334 (11)	0.0375 (11)	0.0022 (9)	−0.0002 (9)	0.0004 (8)
N5	0.0401 (12)	0.0405 (12)	0.0449 (12)	−0.0012 (10)	0.0063 (10)	0.0034 (9)
N6	0.0533 (14)	0.0481 (13)	0.0425 (12)	−0.0007 (11)	0.0067 (10)	0.0090 (10)
N7	0.0670 (16)	0.0360 (13)	0.0611 (15)	−0.0061 (12)	0.0062 (12)	−0.0068 (11)
N8	0.0662 (17)	0.0773 (18)	0.0530 (15)	−0.0144 (15)	0.0116 (13)	−0.0167 (13)
C1	0.0483 (16)	0.0484 (16)	0.0530 (16)	0.0079 (14)	0.0130 (13)	0.0077 (13)
C2	0.0558 (18)	0.070 (2)	0.0540 (17)	0.0284 (17)	0.0177 (14)	0.0211 (16)
C3	0.0472 (18)	0.105 (3)	0.0520 (18)	0.0130 (19)	0.0083 (14)	0.0102 (18)
C4	0.0439 (17)	0.086 (2)	0.0451 (16)	−0.0041 (16)	0.0013 (13)	0.0025 (15)
C5	0.0360 (14)	0.0607 (18)	0.0296 (12)	−0.0066 (13)	0.0052 (11)	0.0008 (12)
C6	0.0412 (15)	0.0465 (15)	0.0350 (13)	−0.0099 (12)	0.0050 (11)	−0.0022 (11)
C7	0.068 (2)	0.0604 (19)	0.0467 (16)	−0.0134 (17)	0.0038 (14)	−0.0142 (14)
C8	0.079 (2)	0.0358 (15)	0.0612 (18)	−0.0050 (16)	0.0124 (16)	−0.0120 (14)
C9	0.0458 (15)	0.0356 (13)	0.0418 (14)	−0.0009 (12)	0.0029 (11)	−0.0029 (11)
C10	0.0586 (18)	0.0360 (14)	0.0386 (14)	0.0024 (13)	−0.0011 (12)	0.0011 (11)
C11	0.0530 (17)	0.0361 (14)	0.0494 (16)	0.0057 (13)	−0.0131 (13)	−0.0012 (12)
C12	0.0359 (14)	0.0327 (13)	0.0529 (15)	0.0021 (11)	−0.0007 (11)	−0.0064 (11)
C13	0.0351 (13)	0.0251 (11)	0.0427 (13)	0.0004 (10)	−0.0037 (11)	−0.0081 (10)
C14	0.0370 (13)	0.0307 (13)	0.0423 (13)	−0.0029 (11)	0.0027 (11)	−0.0069 (11)
C15	0.0436 (15)	0.0455 (15)	0.0545 (16)	0.0038 (13)	0.0115 (13)	−0.0060 (13)
C16	0.0557 (18)	0.0499 (17)	0.0517 (17)	−0.0015 (14)	0.0213 (14)	−0.0015 (13)
C17	0.0398 (14)	0.0332 (13)	0.0495 (15)	0.0054 (12)	0.0052 (11)	0.0072 (12)
C18	0.0445 (15)	0.0479 (15)	0.0404 (14)	0.0025 (13)	0.0142 (12)	−0.0024 (12)

Cd1—N7	2.281 (2)	C2—C3	1.367 (4)
Cd1—N5	2.336 (2)	C2—H2	0.9300
Cd1—N1	2.361 (2)	C3—C4	1.360 (4)
Cd1—N4	2.4004 (18)	C3—H3A	0.9300
Cd1—N2	2.406 (2)	C4—C5	1.381 (4)
Cd1—S2	2.6730 (8)	C4—H4	0.9300
S1—C17	1.636 (3)	C5—C6	1.458 (4)
S2—C18	1.660 (3)	C6—C7	1.410 (4)
N1—C1	1.335 (3)	C7—C8	1.368 (4)
N1—C5	1.355 (3)	C7—H7	0.9300
N2—C6	1.335 (3)	C8—H8	0.9300
N2—N3	1.348 (3)	C9—C10	1.378 (3)
N3—C8	1.339 (3)	C9—H9	0.9300
N3—H3	0.8600	C10—C11	1.376 (4)
N4—C9	1.339 (3)	C10—H10	0.9300
N4—C13	1.349 (3)	C11—C12	1.376 (4)
N5—C14	1.331 (3)	C11—H11	0.9300
N5—N6	1.341 (3)	C12—C13	1.387 (3)
N6—C16	1.342 (3)	C12—H12	0.9300
N6—H6	0.8600	C13—C14	1.468 (3)
N7—C17	1.154 (3)	C14—C15	1.408 (4)
N8—C18	1.150 (3)	C15—C16	1.362 (4)
C1—C2	1.372 (4)	C15—H15	0.9300
C1—H1	0.9300	C16—H16	0.9300
N7—Cd1—N5	88.76 (8)	C2—C3—H3A	120.0
N7—Cd1—N1	92.68 (8)	C3—C4—C5	118.7 (3)
N5—Cd1—N1	104.58 (7)	C3—C4—H4	120.6
N7—Cd1—N4	112.75 (7)	C5—C4—H4	120.6
N5—Cd1—N4	69.68 (7)	N1—C5—C4	121.7 (3)
N1—Cd1—N4	153.36 (7)	N1—C5—C6	116.4 (2)
N7—Cd1—N2	159.38 (7)	C4—C5—C6	121.9 (3)
N5—Cd1—N2	86.36 (7)	N2—C6—C7	110.3 (2)
N1—Cd1—N2	69.29 (7)	N2—C6—C5	118.2 (2)
N4—Cd1—N2	84.23 (6)	C7—C6—C5	131.5 (2)
N7—Cd1—S2	89.35 (6)	C8—C7—C6	105.1 (2)
N5—Cd1—S2	158.58 (5)	C8—C7—H7	127.4
N1—Cd1—S2	96.82 (5)	C6—C7—H7	127.4
N4—Cd1—S2	91.50 (5)	N3—C8—C7	107.1 (2)
N2—Cd1—S2	102.30 (5)	N3—C8—H8	126.5
C18—S2—Cd1	95.48 (9)	C7—C8—H8	126.5
C1—N1—C5	118.3 (2)	N4—C9—C10	123.1 (2)
C1—N1—Cd1	123.13 (17)	N4—C9—H9	118.5
C5—N1—Cd1	118.12 (15)	C10—C9—H9	118.5
C6—N2—N3	105.2 (2)	C11—C10—C9	118.1 (2)
C6—N2—Cd1	116.32 (16)	C11—C10—H10	121.0
N3—N2—Cd1	136.43 (16)	C9—C10—H10	121.0
C8—N3—N2	112.3 (2)	C12—C11—C10	119.9 (2)
C8—N3—H3	123.9	C12—C11—H11	120.1
N2—N3—H3	123.9	C10—C11—H11	120.1
C9—N4—C13	118.5 (2)	C11—C12—C13	119.1 (2)
C9—N4—Cd1	124.66 (16)	C11—C12—H12	120.5
C13—N4—Cd1	116.77 (15)	C13—C12—H12	120.5
C14—N5—N6	105.9 (2)	N4—C13—C12	121.3 (2)
C14—N5—Cd1	118.45 (16)	N4—C13—C14	116.4 (2)
N6—N5—Cd1	135.67 (16)	C12—C13—C14	122.3 (2)
N5—N6—C16	111.5 (2)	N5—C14—C15	110.1 (2)
N5—N6—H6	124.2	N5—C14—C13	118.7 (2)
C16—N6—H6	124.2	C15—C14—C13	131.2 (2)
C17—N7—Cd1	149.0 (2)	C16—C15—C14	105.0 (2)
N1—C1—C2	122.1 (3)	C16—C15—H15	127.5
N1—C1—H1	118.9	C14—C15—H15	127.5
C2—C1—H1	118.9	N6—C16—C15	107.5 (2)
C3—C2—C1	119.1 (3)	N6—C16—H16	126.2
C3—C2—H2	120.5	C15—C16—H16	126.2
C1—C2—H2	120.5	N7—C17—S1	178.5 (3)
C4—C3—C2	120.0 (3)	N8—C18—S2	178.3 (3)
C4—C3—H3A	120.0
N7—Cd1—S2—C18	−51.87 (11)	N4—Cd1—N7—C17	−36.8 (5)
N5—Cd1—S2—C18	33.09 (17)	N2—Cd1—N7—C17	179.6 (3)
N1—Cd1—S2—C18	−144.49 (11)	S2—Cd1—N7—C17	54.5 (4)
N4—Cd1—S2—C18	60.87 (10)	C5—N1—C1—C2	0.5 (4)
N2—Cd1—S2—C18	145.29 (10)	Cd1—N1—C1—C2	−171.50 (19)
N7—Cd1—N1—C1	−14.5 (2)	N1—C1—C2—C3	2.4 (4)
N5—Cd1—N1—C1	−103.9 (2)	C1—C2—C3—C4	−2.4 (4)
N4—Cd1—N1—C1	−177.50 (17)	C2—C3—C4—C5	−0.4 (4)
N2—Cd1—N1—C1	175.8 (2)	C1—N1—C5—C4	−3.4 (4)
S2—Cd1—N1—C1	75.21 (19)	Cd1—N1—C5—C4	168.96 (19)
N7—Cd1—N1—C5	173.55 (18)	C1—N1—C5—C6	176.5 (2)
N5—Cd1—N1—C5	84.13 (18)	Cd1—N1—C5—C6	−11.2 (3)
N4—Cd1—N1—C5	10.5 (3)	C3—C4—C5—N1	3.4 (4)
N2—Cd1—N1—C5	3.83 (16)	C3—C4—C5—C6	−176.5 (3)
S2—Cd1—N1—C5	−96.78 (17)	N3—N2—C6—C7	0.3 (3)
N7—Cd1—N2—C6	−25.9 (3)	Cd1—N2—C6—C7	166.79 (17)
N5—Cd1—N2—C6	−102.57 (18)	N3—N2—C6—C5	−178.5 (2)
N1—Cd1—N2—C6	4.50 (16)	Cd1—N2—C6—C5	−12.0 (3)
N4—Cd1—N2—C6	−172.49 (18)	N1—C5—C6—N2	15.5 (3)
S2—Cd1—N2—C6	97.23 (17)	C4—C5—C6—N2	−164.6 (2)
N7—Cd1—N2—N3	135.1 (3)	N1—C5—C6—C7	−162.9 (3)
N5—Cd1—N2—N3	58.4 (2)	C4—C5—C6—C7	17.0 (4)
N1—Cd1—N2—N3	165.5 (2)	N2—C6—C7—C8	−0.1 (3)
N4—Cd1—N2—N3	−11.5 (2)	C5—C6—C7—C8	178.5 (3)
S2—Cd1—N2—N3	−101.8 (2)	N2—N3—C8—C7	0.4 (3)
C6—N2—N3—C8	−0.4 (3)	C6—C7—C8—N3	−0.2 (3)
Cd1—N2—N3—C8	−162.8 (2)	C13—N4—C9—C10	0.7 (3)
N7—Cd1—N4—C9	98.66 (19)	Cd1—N4—C9—C10	−177.48 (18)
N5—Cd1—N4—C9	178.3 (2)	N4—C9—C10—C11	0.2 (4)
N1—Cd1—N4—C9	−99.8 (2)	C9—C10—C11—C12	−0.6 (4)
N2—Cd1—N4—C9	−93.47 (18)	C10—C11—C12—C13	0.1 (4)
S2—Cd1—N4—C9	8.74 (18)	C9—N4—C13—C12	−1.1 (3)
N7—Cd1—N4—C13	−79.53 (17)	Cd1—N4—C13—C12	177.16 (16)
N5—Cd1—N4—C13	0.09 (15)	C9—N4—C13—C14	−179.73 (19)
N1—Cd1—N4—C13	82.1 (2)	Cd1—N4—C13—C14	−1.4 (2)
N2—Cd1—N4—C13	88.34 (16)	C11—C12—C13—N4	0.8 (3)
S2—Cd1—N4—C13	−169.45 (15)	C11—C12—C13—C14	179.3 (2)
N7—Cd1—N5—C14	116.27 (17)	N6—N5—C14—C15	0.1 (3)
N1—Cd1—N5—C14	−151.29 (16)	Cd1—N5—C14—C15	178.69 (15)
N4—Cd1—N5—C14	1.41 (16)	N6—N5—C14—C13	178.68 (19)
N2—Cd1—N5—C14	−83.78 (17)	Cd1—N5—C14—C13	−2.7 (3)
S2—Cd1—N5—C14	31.2 (3)	N4—C13—C14—N5	2.8 (3)
N7—Cd1—N5—N6	−65.6 (2)	C12—C13—C14—N5	−175.8 (2)
N1—Cd1—N5—N6	26.8 (2)	N4—C13—C14—C15	−179.0 (2)
N4—Cd1—N5—N6	179.5 (2)	C12—C13—C14—C15	2.4 (4)
N2—Cd1—N5—N6	94.3 (2)	N5—C14—C15—C16	0.0 (3)
S2—Cd1—N5—N6	−150.72 (17)	C13—C14—C15—C16	−178.4 (2)
C14—N5—N6—C16	−0.1 (3)	N5—N6—C16—C15	0.1 (3)
Cd1—N5—N6—C16	−178.39 (18)	C14—C15—C16—N6	−0.1 (3)
N5—Cd1—N7—C17	−104.2 (4)	Cd1—N7—C17—S1	107 (9)
N1—Cd1—N7—C17	151.3 (4)	Cd1—S2—C18—N8	−129 (9)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···S1i	0.86	2.52	3.310 (2)	153
N6—H6···N8ii	0.86	2.14	2.958 (3)	159

Table 1

Selected bond lengths (Å)

Cd1—N7	2.281 (2)
Cd1—N5	2.336 (2)
Cd1—N1	2.361 (2)
Cd1—N4	2.4004 (18)
Cd1—N2	2.406 (2)
Cd1—S2	2.6730 (8)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯S1i	0.86	2.52	3.310 (2)	153
N6—H6⋯N8ii	0.86	2.14	2.958 (3)	159

Symmetry codes: (i) ; (ii) .