cis-(1,4,8,11-Tetra-aza-cyclo-tetra-decane-κN (4))bis(-thio-cyanato-κN)chromium(III) thio-cyanate.

The crystal structure of [Cr(NCS)2(cyclam)]NCS (cyclam = 1,4,8,11-tetra-aza-cyclo-tetra-deca-ne, C10H24N4) has been determined by using synchrotron radiation at 98 K. The Cr(III) atom is in a slightly distorted octa-hedral environment with four N atoms of the macrocyclic ligand and two N-coordinated NCS(-) anions in cis positions. The average Cr-N(cyclam) and Cr-NCS bond lengths are 2.085 (5) and 1.996 (15) Å, respectively. In the crystal, the uncoordinating SCN(-) anion is hydrogen bonded through N-H⋯S and N-H⋯N inter-actions to neighbouring complex cations.

Related literature

For the synthesis, see: Ferguson & Tobe (1970 ▶); For spectroscopic studies, see: Choi & Park (2003 ▶); Poon & Pun (1980 ▶). For related structures, see: Forsellini et al. (1986 ▶); Friesen et al. (1997 ▶); Meyer et al. (1998 ▶); Choi et al. (2004a ▶,b ▶, 2009 ▶); Subhan et al. (2011 ▶).

Experimental

Crystal data

[Cr(NCS)2(C10H24N4)]NCS

M = 426.57

Monoclinic,

a = 10.590 (2) Å

b = 7.6970 (15) Å

c = 23.750 (5) Å

β = 94.70 (3)°

V = 1929.4 (7) Å3

Z = 4

Synchrotron radiation

λ = 0.740 Å

μ = 1.03 mm−1

T = 98 K

0.01 × 0.01 × 0.01 mm

Data collection

ADSC Q210 CCD area-detector diffractometer

Absorption correction: empirical (HKL-3000 SCALEPACK; Otwinowski & Minor, 1997 ▶) T min = 0.988, T max = 0.989

16587 measured reflections

4727 independent reflections

3998 reflections with I > 2σ(I)

R int = 0.038

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.085

S = 1.07

4727 reflections

234 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.38 e Å−3

Δρmin = −0.46 e Å−3

Data collection: ADSC Quantum-210 ADX (Arvai & Nielsen, 1983 ▶); cell refinement: HKL-3000 (Otwinowski & Minor, 1997 ▶); data reduction: HKL-3000; program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008) ▶; program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008) ▶; molecular graphics: DIAMOND (Brandenburg, 2007 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536813015456/lr2107sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813015456/lr2107Isup2.hkl

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

[Cr(NCS)2(C10H24N4)]NCS	F(000) = 89
Mr = 426.57	Dx = 1.469 Mg m−3
Monoclinic, P21/c	Synchrotron radiation, λ = 0.740 Å
a = 10.590 (2) Å	Cell parameters from 39021 reflections
b = 7.6970 (15) Å	θ = 1.9–33.1°
c = 23.750 (5) Å	µ = 1.03 mm−1
β = 94.70 (3)°	T = 98 K
V = 1929.4 (7) Å3	Block, pink
Z = 4	0.01 × 0.01 × 0.01 mm

ADSC Q210 CCD area-detector diffractometer	3998 reflections with I > 2σ(I)
Radiation source: PLSII 2D bending magnet	Rint = 0.038
ω scan	θmax = 29.5°, θmin = 2.0°
Absorption correction: empirical (using intensity measurements) (HKL-3000SCALEPACK; Otwinowski & Minor, 1997)	h = −14→14
Tmin = 0.988, Tmax = 0.989	k = −10→10
16587 measured reflections	l = −31→31
4727 independent reflections

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.030	w = 1/[σ2(Fo2) + (0.0543P)2 + 0.0369P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.085	(Δ/σ)max = 0.001
S = 1.07	Δρmax = 0.38 e Å−3
4727 reflections	Δρmin = −0.46 e Å−3
234 parameters	Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraints	Extinction coefficient: 0.0149 (11)

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.

	x	y	z	Uiso*/Ueq
Cr1	0.78572 (2)	0.65230 (3)	0.13425 (2)	0.01445 (9)
S2	0.80594 (3)	1.01716 (5)	0.29372 (2)	0.02043 (10)
S3	1.17137 (4)	0.91514 (6)	0.09132 (2)	0.03337 (12)
N1	0.87142 (12)	0.48585 (16)	0.19523 (5)	0.0176 (3)
H1N1	0.949 (2)	0.521 (2)	0.2008 (8)	0.030 (5)*
N2	0.60770 (11)	0.58345 (16)	0.15912 (5)	0.0158 (2)
H1N2	0.5895 (18)	0.494 (3)	0.1465 (8)	0.026 (5)*
N3	0.80817 (12)	0.44123 (17)	0.08083 (5)	0.0194 (3)
H1N3	0.7441 (18)	0.378 (2)	0.0769 (8)	0.024 (5)*
N4	0.67930 (12)	0.78077 (18)	0.06965 (5)	0.0193 (3)
H1N4	0.6773 (17)	0.888 (2)	0.0783 (8)	0.024 (5)*
N5	0.95059 (12)	0.74035 (17)	0.11200 (5)	0.0216 (3)
N6	0.78208 (12)	0.85015 (16)	0.18914 (5)	0.0203 (3)
C1	0.82134 (14)	0.4809 (2)	0.25209 (6)	0.0199 (3)
H1A	0.8357	0.5954	0.2705	0.024*
H1B	0.8694	0.3932	0.2756	0.024*
C2	0.68044 (14)	0.4373 (2)	0.25004 (6)	0.0203 (3)
H2A	0.6664	0.3245	0.2305	0.024*
H2B	0.6569	0.4225	0.2892	0.024*
C3	0.59240 (14)	0.5705 (2)	0.22082 (6)	0.0195 (3)
H3A	0.5037	0.5387	0.2263	0.023*
H3B	0.6094	0.6855	0.2385	0.023*
C4	0.88174 (15)	0.30950 (19)	0.17019 (7)	0.0224 (3)
H4A	0.8016	0.2449	0.1728	0.027*
H4B	0.9509	0.2437	0.1911	0.027*
C5	0.90900 (15)	0.3290 (2)	0.10901 (7)	0.0248 (3)
H5A	0.9932	0.3830	0.1064	0.030*
H5B	0.9089	0.2138	0.0905	0.030*
C6	0.51544 (14)	0.7103 (2)	0.13191 (6)	0.0215 (3)
H6A	0.5239	0.8239	0.1514	0.026*
H6B	0.4278	0.6677	0.1341	0.026*
C7	0.54392 (14)	0.7294 (2)	0.07095 (6)	0.0228 (3)
H7A	0.5283	0.6180	0.0507	0.027*
H7B	0.4884	0.8191	0.0521	0.027*
C8	0.83850 (16)	0.4808 (2)	0.02215 (6)	0.0266 (3)
H8A	0.8490	0.3703	0.0017	0.032*
H8B	0.9201	0.5441	0.0235	0.032*
C9	0.73707 (17)	0.5890 (2)	−0.01027 (7)	0.0295 (4)
H9A	0.7568	0.5952	−0.0503	0.035*
H9B	0.6548	0.5286	−0.0093	0.035*
C10	0.72283 (16)	0.7724 (2)	0.01150 (6)	0.0257 (3)
H10A	0.8054	0.8326	0.0114	0.031*
H10B	0.6614	0.8356	−0.0147	0.031*
C11	1.04332 (14)	0.81402 (19)	0.10314 (6)	0.0200 (3)
C12	0.79292 (13)	0.92117 (18)	0.23267 (6)	0.0172 (3)
S4	0.56857 (4)	0.72414 (6)	0.36233 (2)	0.03051 (12)
N7	0.37447 (15)	0.65647 (19)	0.43301 (7)	0.0338 (3)
C13	0.45576 (15)	0.68218 (19)	0.40360 (7)	0.0235 (3)

	U11	U22	U33	U12	U13	U23
Cr1	0.01319 (12)	0.01531 (13)	0.01455 (13)	−0.00352 (8)	−0.00060 (8)	0.00023 (8)
S2	0.01916 (18)	0.02155 (19)	0.02016 (19)	−0.00004 (13)	−0.00094 (14)	−0.00355 (14)
S3	0.0250 (2)	0.0448 (3)	0.0303 (2)	−0.01871 (19)	0.00255 (17)	0.00597 (19)
N1	0.0142 (6)	0.0178 (6)	0.0205 (6)	−0.0020 (5)	−0.0012 (5)	0.0014 (5)
N2	0.0142 (6)	0.0153 (6)	0.0176 (6)	−0.0019 (5)	0.0005 (5)	−0.0001 (5)
N3	0.0170 (6)	0.0210 (6)	0.0205 (6)	−0.0036 (5)	0.0031 (5)	−0.0031 (5)
N4	0.0183 (6)	0.0204 (6)	0.0184 (6)	−0.0053 (5)	−0.0028 (5)	0.0018 (5)
N5	0.0183 (6)	0.0244 (7)	0.0218 (6)	−0.0068 (5)	0.0002 (5)	0.0017 (5)
N6	0.0216 (6)	0.0171 (6)	0.0217 (6)	−0.0036 (5)	−0.0012 (5)	−0.0002 (5)
C1	0.0212 (7)	0.0209 (7)	0.0171 (7)	−0.0012 (6)	−0.0019 (6)	0.0035 (6)
C2	0.0213 (7)	0.0213 (7)	0.0183 (7)	−0.0019 (6)	0.0022 (6)	0.0036 (6)
C3	0.0176 (7)	0.0223 (7)	0.0190 (7)	−0.0020 (6)	0.0045 (6)	−0.0001 (6)
C4	0.0208 (7)	0.0177 (7)	0.0282 (8)	0.0016 (6)	0.0000 (6)	0.0006 (6)
C5	0.0219 (7)	0.0231 (8)	0.0298 (8)	0.0023 (6)	0.0042 (6)	−0.0043 (6)
C6	0.0154 (7)	0.0230 (7)	0.0256 (8)	0.0005 (6)	−0.0006 (6)	0.0038 (6)
C7	0.0172 (7)	0.0275 (8)	0.0228 (7)	−0.0041 (6)	−0.0045 (6)	0.0043 (6)
C8	0.0293 (8)	0.0320 (9)	0.0195 (7)	−0.0042 (7)	0.0077 (6)	−0.0062 (6)
C9	0.0340 (9)	0.0378 (9)	0.0167 (7)	−0.0073 (8)	0.0013 (7)	−0.0040 (7)
C10	0.0284 (8)	0.0323 (9)	0.0160 (7)	−0.0071 (7)	−0.0006 (6)	0.0049 (6)
C11	0.0211 (7)	0.0234 (7)	0.0150 (7)	−0.0028 (6)	−0.0019 (6)	0.0004 (6)
C12	0.0146 (6)	0.0146 (6)	0.0218 (7)	−0.0024 (5)	−0.0017 (6)	0.0028 (5)
S4	0.0347 (2)	0.0333 (2)	0.0235 (2)	0.01233 (18)	0.00211 (17)	0.00132 (17)
N7	0.0297 (8)	0.0263 (7)	0.0453 (9)	0.0070 (6)	0.0013 (7)	0.0027 (6)
C13	0.0260 (8)	0.0160 (7)	0.0267 (8)	0.0081 (6)	−0.0087 (7)	−0.0027 (6)

Cr1—N5	1.9846 (13)	C2—C3	1.515 (2)
Cr1—N6	2.0071 (13)	C2—H2A	0.9900
Cr1—N4	2.0781 (14)	C2—H2B	0.9900
Cr1—N1	2.0849 (13)	C3—H3A	0.9900
Cr1—N3	2.0868 (13)	C3—H3B	0.9900
Cr1—N2	2.0895 (13)	C4—C5	1.512 (2)
S2—C12	1.6231 (15)	C4—H4A	0.9900
S3—C11	1.6081 (16)	C4—H4B	0.9900
N1—C4	1.4895 (19)	C5—H5A	0.9900
N1—C1	1.4913 (19)	C5—H5B	0.9900
N1—H1N1	0.86 (2)	C6—C7	1.510 (2)
N2—C6	1.4904 (19)	C6—H6A	0.9900
N2—C3	1.4909 (18)	C6—H6B	0.9900
N2—H1N2	0.77 (2)	C7—H7A	0.9900
N3—C8	1.4871 (19)	C7—H7B	0.9900
N3—C5	1.489 (2)	C8—C9	1.518 (2)
N3—H1N3	0.834 (19)	C8—H8A	0.9900
N4—C7	1.4901 (19)	C8—H8B	0.9900
N4—C10	1.4928 (19)	C9—C10	1.515 (2)
N4—H1N4	0.851 (19)	C9—H9A	0.9900
N5—C11	1.168 (2)	C9—H9B	0.9900
N6—C12	1.1666 (19)	C10—H10A	0.9900
C1—C2	1.526 (2)	C10—H10B	0.9900
C1—H1A	0.9900	S4—C13	1.6384 (19)
C1—H1B	0.9900	N7—C13	1.169 (2)
N5—Cr1—N6	88.74 (6)	H2A—C2—H2B	107.5
N5—Cr1—N4	94.39 (5)	N2—C3—C2	112.52 (12)
N6—Cr1—N4	94.61 (6)	N2—C3—H3A	109.1
N5—Cr1—N1	93.01 (5)	C2—C3—H3A	109.1
N6—Cr1—N1	92.61 (5)	N2—C3—H3B	109.1
N4—Cr1—N1	169.77 (5)	C2—C3—H3B	109.1
N5—Cr1—N3	87.56 (6)	H3A—C3—H3B	107.8
N6—Cr1—N3	174.14 (5)	N1—C4—C5	108.61 (12)
N4—Cr1—N3	90.20 (5)	N1—C4—H4A	110.0
N1—Cr1—N3	83.06 (5)	C5—C4—H4A	110.0
N5—Cr1—N2	174.70 (5)	N1—C4—H4B	110.0
N6—Cr1—N2	86.73 (5)	C5—C4—H4B	110.0
N4—Cr1—N2	83.23 (5)	H4A—C4—H4B	108.3
N1—Cr1—N2	89.96 (5)	N3—C5—C4	107.65 (12)
N3—Cr1—N2	97.17 (5)	N3—C5—H5A	110.2
C4—N1—C1	112.42 (11)	C4—C5—H5A	110.2
C4—N1—Cr1	108.95 (9)	N3—C5—H5B	110.2
C1—N1—Cr1	118.54 (9)	C4—C5—H5B	110.2
C4—N1—H1N1	104.3 (13)	H5A—C5—H5B	108.5
C1—N1—H1N1	105.8 (13)	N2—C6—C7	107.70 (12)
Cr1—N1—H1N1	105.6 (13)	N2—C6—H6A	110.2
C6—N2—C3	110.46 (12)	C7—C6—H6A	110.2
C6—N2—Cr1	106.62 (9)	N2—C6—H6B	110.2
C3—N2—Cr1	117.91 (9)	C7—C6—H6B	110.2
C6—N2—H1N2	106.5 (14)	H6A—C6—H6B	108.5
C3—N2—H1N2	106.1 (14)	N4—C7—C6	108.29 (12)
Cr1—N2—H1N2	108.7 (14)	N4—C7—H7A	110.0
C8—N3—C5	109.76 (12)	C6—C7—H7A	110.0
C8—N3—Cr1	117.03 (10)	N4—C7—H7B	110.0
C5—N3—Cr1	106.96 (10)	C6—C7—H7B	110.0
C8—N3—H1N3	104.5 (13)	H7A—C7—H7B	108.4
C5—N3—H1N3	105.0 (12)	N3—C8—C9	112.93 (13)
Cr1—N3—H1N3	113.0 (13)	N3—C8—H8A	109.0
C7—N4—C10	112.23 (12)	C9—C8—H8A	109.0
C7—N4—Cr1	108.83 (9)	N3—C8—H8B	109.0
C10—N4—Cr1	118.20 (10)	C9—C8—H8B	109.0
C7—N4—H1N4	102.1 (12)	H8A—C8—H8B	107.8
C10—N4—H1N4	106.4 (12)	C10—C9—C8	115.10 (13)
Cr1—N4—H1N4	107.8 (12)	C10—C9—H9A	108.5
C11—N5—Cr1	170.02 (13)	C8—C9—H9A	108.5
C12—N6—Cr1	157.72 (12)	C10—C9—H9B	108.5
N1—C1—C2	113.34 (12)	C8—C9—H9B	108.5
N1—C1—H1A	108.9	H9A—C9—H9B	107.5
C2—C1—H1A	108.9	N4—C10—C9	113.77 (13)
N1—C1—H1B	108.9	N4—C10—H10A	108.8
C2—C1—H1B	108.9	C9—C10—H10A	108.8
H1A—C1—H1B	107.7	N4—C10—H10B	108.8
C3—C2—C1	115.42 (12)	C9—C10—H10B	108.8
C3—C2—H2A	108.4	H10A—C10—H10B	107.7
C1—C2—H2A	108.4	N5—C11—S3	179.66 (15)
C3—C2—H2B	108.4	N6—C12—S2	178.82 (14)
C1—C2—H2B	108.4	N7—C13—S4	178.35 (14)
C4—N1—C1—C2	−72.13 (15)	C3—N2—C6—C7	174.88 (12)
Cr1—N1—C1—C2	56.50 (15)	Cr1—N2—C6—C7	45.63 (13)
N1—C1—C2—C3	−64.97 (17)	C10—N4—C7—C6	169.85 (13)
C6—N2—C3—C2	177.56 (12)	Cr1—N4—C7—C6	37.10 (15)
Cr1—N2—C3—C2	−59.54 (15)	N2—C6—C7—N4	−55.65 (16)
C1—C2—C3—N2	66.51 (17)	C5—N3—C8—C9	177.66 (13)
C1—N1—C4—C5	169.43 (12)	Cr1—N3—C8—C9	−60.26 (16)
Cr1—N1—C4—C5	35.94 (14)	N3—C8—C9—C10	66.73 (19)
C8—N3—C5—C4	173.69 (12)	C7—N4—C10—C9	−71.42 (17)
Cr1—N3—C5—C4	45.79 (14)	Cr1—N4—C10—C9	56.52 (16)
N1—C4—C5—N3	−54.89 (16)	C8—C9—C10—N4	−64.47 (18)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···S2i	0.86 (2)	2.59 (2)	3.4138 (15)	160.1 (17)
N2—H1N2···S4ii	0.77 (2)	2.66 (2)	3.3521 (14)	149.8 (18)
N3—H1N3···N7ii	0.834 (19)	2.119 (19)	2.9238 (19)	162.0 (17)
N4—H1N4···N7iii	0.851 (19)	2.150 (19)	2.947 (2)	155.9 (17)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯S2i	0.86 (2)	2.59 (2)	3.4138 (15)	160.1 (17)
N2—H1N2⋯S4ii	0.77 (2)	2.66 (2)	3.3521 (14)	149.8 (18)
N3—H1N3⋯N7ii	0.834 (19)	2.119 (19)	2.9238 (19)	162.0 (17)
N4—H1N4⋯N7iii	0.851 (19)	2.150 (19)	2.947 (2)	155.9 (17)

Symmetry codes: (i) ; (ii) ; (iii) .