(5,7,7,12,14,14-Hexamethyl-1,4,8,11-tetra­azacyclo­tetra­deca-4,11-diene-κ4N1,N4,N8,N11)(thio­cyanato-κS)nickel(II) perchlorate monohydrate

Bi, J.-H.

doi:10.1107/S1600536809018091

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page m668

doi:10.1107/S1600536809018091

Open

access

(5,7,7,12,14,14-Hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene-κ⁴N¹,N⁴,N⁸,N¹¹)(thiocyanato-κS)nickel(II) perchlorate monohydrate

Jian-Hong Bi ^a ^*

^aDeparment of Chemistry and Chemical Engineering, Hefei Teachers College, Hefei 230061, People's Republic of China
^*Correspondence e-mail: bi010101@126.com

(Received 5 May 2009; accepted 13 May 2009; online 20 May 2009)

In the title compound, [Ni(SCN)(C₁₆H₃₂N₄)]ClO₄·H₂O, the Ni^II ion is coordinated by the four N atoms of the tetraazacyclotetradeca-4,11-diene macrocyclic ligand and by the S atom of a thiocyanate anion. The perchlorate anion is rotationally disordered around one Cl—O bond between two orientations; the occupancies refined to 0.61 (4) and 0.39 (4). Intermolecular O—H⋯N, N—H⋯O and N—H⋯N hydrogen bonds link two cations, two anions and two solvent water molecules into a centrosymmetric cluster. The crystal packing is further stabilized by weak intermolecular C—H⋯O hydrogen bonds.

Related literature

For the crystal structures of related complexes, see: Bienko et al. (2007 ); Shen et al. (1999 ); Szalda & Fujita (1992 ).

Experimental

Crystal data

[Ni(NCS)(C₁₆H₃₂N₄)]ClO₄·H₂O
M_r = 514.71
Triclinic, $[P \overline 1]$
a = 7.2678 (11) Å
b = 8.9998 (13) Å
c = 19.513 (2) Å
α = 84.1430 (10)°
β = 87.005 (2)°
γ = 67.3480 (10)°
V = 1171.6 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.07 mm⁻¹
T = 291 K
0.49 × 0.40 × 0.39 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.623, T_max = 0.681
6103 measured reflections
4062 independent reflections
3247 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.109
S = 1.03
4062 reflections
299 parameters
H-atom parameters constrained
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.90 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O2	0.91	2.28	3.16 (3)	162
N4—H4⋯N5	0.91	2.33	3.241 (5)	175
O5—H5F⋯N5	0.85	2.09	2.942 (6)	178
O5—H5G⋯N5ⁱ	0.85	2.15	2.997 (6)	178
C3—H3A⋯O4ⁱⁱ	0.97	2.49	3.450 (16)	172
C3—H3B⋯O2	0.97	2.48	3.26 (3)	137
C15—H15A⋯O1ⁱⁱⁱ	0.97	2.37	3.155 (6)	138
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) -x+1, -y+1, -z+2; (iii) x-1, y+1, z.

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809018091/cv2562sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809018091/cv2562Isup2.hkl

checkCIF report

Comment top

A number of researches study azamacrocyclic systems (Bienko et al., 2007; Shen et al., 1999; Szalda et al., 1992). Szalda reported a crystal structure of metal complex derived from tetraazacyclotetradeca-4,11-diene macrocycles (Szalda et al., 1992). To investigate whether the potentially explosive perchlorate anions in this complex can be replaced by other anions to facilitate its further application, NCS^- anion was used and the title complex was obtained.

The coordination geometry of Ni^II center is shown in Fig.1. The Ni^II center adopts a square-pyramidal coordination geometry, where four N atoms from macrocyclic ligand form an equatorial plane and one S atom from the thiocyanate anion occupies an apical position. The Ni–S bond length of 3.298 (13) Å is slightly longer than those of 3.171 (14) Å observed and discussed by Bienko et al. (2007).

The crystal packing is stabilized by intermolecular hydrogen bonding interactions (Table 1).

Related literature top

For the crystal structures of related complexes, see: Bienko et al. (2007); Shen et al. (1999); Szalda et al. (1992)

Experimental top

All solvents and chemicals were of analytical grade and were used without further purification. The mononuclear nickel(II)-diperchlorate macrocycle complex (0.538 g, 0.1 mmol), which was prepared via similar method as reported previously (Szalda et al., 1992), was dissolved in acetonitrile (30 ml) and NH₄(NCS)(0.152 g, 0.2 mmol) was added. The mixture was refluxed for 2 h, and then cooled to room temperature. The green precipitate was collected, washed with a small amount of acetonitrile and dried in vacuo. Single crystals suitable for X-ray analysis were grown from the mother solution by slow evaporation at room temperature in air. Elemental analysis calculated for C₁₇H₃₄ClN₅NiO₅S: C 39.67, H 6.66, N 13.61%; found: C 39.71, H 6.70, N 13.57%.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. Molecular structure of the cation of the title compound showing 30% probability displacement ellipsoids and the atomic numbering.

(5,7,7,12,14,14-Hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene- κ⁴N¹,N⁴,N⁸,N¹¹)(thiocyanato- κS)nickel(II) perchlorate monohydrate top

Crystal data top

[Ni(NCS)(C₁₆H₃₂N₄)]ClO₄·H₂O	Z = 2
M_r = 514.71	F(000) = 544
Triclinic, P1	D_x = 1.459 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2678 (11) Å	Cell parameters from 2923 reflections
b = 8.9998 (13) Å	θ = 2.5–27.7°
c = 19.513 (2) Å	µ = 1.07 mm⁻¹
α = 84.143 (1)°	T = 291 K
β = 87.005 (2)°	Block, green
γ = 67.348 (1)°	0.49 × 0.40 × 0.39 mm
V = 1171.6 (3) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	4062 independent reflections
Radiation source: fine-focus sealed tube	3247 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −8→8
T_min = 0.623, T_max = 0.681	k = −10→8
6103 measured reflections	l = −23→16

Refinement top

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.109	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0501P)² + 0.9082P] where P = (F_o² + 2F_c²)/3
4062 reflections	(Δ/σ)_max = 0.001
299 parameters	Δρ_max = 0.53 e Å⁻³
0 restraints	Δρ_min = −0.90 e Å⁻³

Crystal data top

[Ni(NCS)(C₁₆H₃₂N₄)]ClO₄·H₂O	γ = 67.348 (1)°
M_r = 514.71	V = 1171.6 (3) Å³
Triclinic, P1	Z = 2
a = 7.2678 (11) Å	Mo Kα radiation
b = 8.9998 (13) Å	µ = 1.07 mm⁻¹
c = 19.513 (2) Å	T = 291 K
α = 84.143 (1)°	0.49 × 0.40 × 0.39 mm
β = 87.005 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	4062 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	3247 reflections with I > 2σ(I)
T_min = 0.623, T_max = 0.681	R_int = 0.019
6103 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.109	H-atom parameters constrained
S = 1.03	Δρ_max = 0.53 e Å⁻³
4062 reflections	Δρ_min = −0.90 e Å⁻³
299 parameters

Special details top

Experimental. The structure was solved by direct methods (Bruker, 2000) and successive difference Fourier syntheses.

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 (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ni1	0.30773 (6)	0.73405 (4)	0.74822 (2)	0.03298 (14)
S1	0.77119 (17)	0.55310 (15)	0.69389 (7)	0.0742 (3)
Cl1	0.83588 (13)	0.23413 (11)	0.87389 (5)	0.0488 (2)
N1	0.3810 (4)	0.8445 (3)	0.81175 (14)	0.0369 (6)
N2	0.3265 (4)	0.5584 (3)	0.81554 (13)	0.0358 (6)
H2	0.4585	0.5040	0.8246	0.043*
N3	0.2600 (4)	0.6153 (3)	0.68168 (14)	0.0370 (6)
N4	0.2731 (4)	0.9145 (3)	0.68173 (13)	0.0358 (6)
H4	0.3769	0.8812	0.6512	0.043*
N5	0.6503 (6)	0.7714 (6)	0.5780 (2)	0.0895 (13)
O1	1.0226 (5)	0.1857 (5)	0.8446 (3)	0.1262 (16)
O2	0.758 (4)	0.401 (3)	0.8792 (15)	0.103 (6)	0.61 (4)
O3	0.698 (3)	0.198 (3)	0.8398 (14)	0.115 (7)	0.61 (4)
O4	0.889 (5)	0.1340 (19)	0.9359 (6)	0.151 (8)	0.61 (4)
O2'	0.765 (6)	0.150 (3)	0.9228 (18)	0.125 (11)	0.39 (4)
O3'	0.724 (6)	0.244 (5)	0.8153 (16)	0.132 (12)	0.39 (4)
O4'	0.774 (7)	0.381 (6)	0.9037 (19)	0.101 (10)	0.39 (4)
O5	0.4522 (5)	0.8714 (5)	0.44382 (19)	0.1003 (11)
H5F	0.5099	0.8396	0.4824	0.120*
H5G	0.4217	0.9727	0.4365	0.120*
C1	0.4568 (6)	0.9196 (5)	0.9214 (2)	0.0567 (10)
H1A	0.5602	0.9470	0.8977	0.085*
H1B	0.5066	0.8575	0.9642	0.085*
H1C	0.3455	1.0168	0.9303	0.085*
C2	0.3917 (5)	0.8227 (4)	0.87771 (17)	0.0393 (7)
C3	0.3413 (5)	0.6913 (4)	0.91705 (18)	0.0470 (8)
H3A	0.2667	0.7355	0.9579	0.056*
H3B	0.4658	0.6070	0.9327	0.056*
C4	0.2248 (5)	0.6103 (4)	0.88317 (17)	0.0423 (8)
C5	0.0098 (5)	0.7264 (5)	0.8714 (2)	0.0587 (10)
H5A	0.0078	0.8222	0.8442	0.088*
H5B	−0.0551	0.7550	0.9150	0.088*
H5C	−0.0589	0.6753	0.8476	0.088*
C6	0.2333 (6)	0.4619 (5)	0.9316 (2)	0.0595 (10)
H6A	0.1473	0.4156	0.9148	0.089*
H6B	0.1902	0.4942	0.9770	0.089*
H6C	0.3676	0.3832	0.9332	0.089*
C7	0.2598 (6)	0.4456 (4)	0.78297 (19)	0.0482 (9)
H7A	0.1158	0.4814	0.7863	0.058*
H7B	0.3180	0.3379	0.8063	0.058*
C8	0.3252 (6)	0.4434 (4)	0.70907 (19)	0.0493 (9)
H8A	0.4689	0.3895	0.7052	0.059*
H8B	0.2635	0.3874	0.6840	0.059*
C9	0.2099 (7)	0.5436 (5)	0.5678 (2)	0.0617 (11)
H9A	0.3387	0.4569	0.5687	0.093*
H9B	0.1862	0.5996	0.5226	0.093*
H9C	0.1092	0.5004	0.5794	0.093*
C10	0.2029 (5)	0.6592 (4)	0.61938 (17)	0.0404 (8)
C11	0.1245 (5)	0.8328 (4)	0.59141 (17)	0.0432 (8)
H11A	0.0002	0.8546	0.5685	0.052*
H11B	0.2179	0.8455	0.5562	0.052*
C12	0.0857 (5)	0.9639 (4)	0.64053 (16)	0.0394 (7)
C13	−0.0909 (5)	0.9766 (4)	0.68875 (18)	0.0466 (8)
H13A	−0.0751	0.8710	0.7093	0.070*
H13B	−0.2121	1.0222	0.6631	0.070*
H13C	−0.0965	1.0448	0.7242	0.070*
C14	0.0433 (6)	1.1253 (4)	0.5974 (2)	0.0554 (10)
H14A	0.0124	1.2101	0.6275	0.083*
H14B	−0.0678	1.1476	0.5680	0.083*
H14C	0.1587	1.1194	0.5698	0.083*
C15	0.2952 (6)	1.0464 (4)	0.71649 (18)	0.0473 (9)
H15A	0.1677	1.1145	0.7353	0.057*
H15B	0.3427	1.1128	0.6838	0.057*
C16	0.4423 (6)	0.9688 (4)	0.77314 (19)	0.0487 (9)
H16A	0.5759	0.9194	0.7542	0.058*
H16B	0.4409	1.0486	0.8032	0.058*
C17	0.7045 (6)	0.6772 (5)	0.6252 (3)	0.0621 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0374 (2)	0.0284 (2)	0.0350 (2)	−0.01414 (17)	0.00074 (17)	−0.00531 (16)
S1	0.0542 (6)	0.0768 (8)	0.0868 (9)	−0.0221 (6)	−0.0052 (6)	0.0040 (6)
Cl1	0.0432 (5)	0.0483 (5)	0.0450 (5)	−0.0061 (4)	0.0094 (4)	−0.0117 (4)
N1	0.0370 (14)	0.0317 (14)	0.0435 (16)	−0.0140 (12)	0.0022 (12)	−0.0078 (12)
N2	0.0340 (14)	0.0309 (14)	0.0409 (15)	−0.0111 (11)	−0.0024 (11)	−0.0012 (11)
N3	0.0396 (15)	0.0305 (14)	0.0428 (16)	−0.0149 (12)	0.0008 (12)	−0.0070 (12)
N4	0.0425 (15)	0.0315 (14)	0.0356 (15)	−0.0164 (12)	0.0068 (12)	−0.0078 (11)
N5	0.071 (3)	0.098 (3)	0.082 (3)	−0.017 (2)	0.000 (2)	0.007 (3)
O1	0.070 (2)	0.144 (4)	0.160 (4)	−0.029 (2)	0.041 (2)	−0.062 (3)
O2	0.083 (7)	0.074 (6)	0.143 (16)	−0.012 (5)	−0.027 (11)	−0.026 (10)
O3	0.078 (5)	0.119 (9)	0.169 (19)	−0.053 (6)	−0.008 (9)	−0.040 (11)
O4	0.158 (16)	0.151 (8)	0.071 (5)	0.013 (9)	−0.002 (7)	0.027 (5)
O2'	0.13 (2)	0.110 (13)	0.125 (17)	−0.050 (13)	0.048 (15)	−0.002 (11)
O3'	0.121 (19)	0.15 (2)	0.081 (13)	0.002 (13)	−0.035 (11)	−0.040 (12)
O4'	0.10 (2)	0.10 (2)	0.104 (17)	−0.026 (15)	0.031 (14)	−0.071 (17)
O5	0.106 (3)	0.114 (3)	0.085 (3)	−0.045 (2)	−0.019 (2)	−0.004 (2)
C1	0.063 (2)	0.063 (2)	0.049 (2)	−0.026 (2)	−0.0088 (19)	−0.0173 (19)
C2	0.0320 (16)	0.0397 (18)	0.0408 (19)	−0.0060 (14)	0.0001 (14)	−0.0115 (15)
C3	0.051 (2)	0.052 (2)	0.0383 (19)	−0.0191 (17)	0.0002 (16)	−0.0057 (16)
C4	0.0389 (18)	0.0453 (19)	0.0405 (19)	−0.0151 (15)	0.0031 (15)	0.0002 (15)
C5	0.042 (2)	0.065 (3)	0.061 (3)	−0.0130 (18)	0.0071 (18)	−0.003 (2)
C6	0.063 (2)	0.065 (3)	0.053 (2)	−0.032 (2)	0.0009 (19)	0.0119 (19)
C7	0.058 (2)	0.0326 (18)	0.058 (2)	−0.0216 (17)	−0.0078 (18)	0.0007 (16)
C8	0.063 (2)	0.0290 (17)	0.058 (2)	−0.0171 (16)	−0.0087 (18)	−0.0095 (16)
C9	0.080 (3)	0.054 (2)	0.054 (2)	−0.024 (2)	−0.001 (2)	−0.0235 (19)
C10	0.0436 (19)	0.0434 (19)	0.0402 (19)	−0.0219 (16)	0.0069 (15)	−0.0135 (15)
C11	0.0467 (19)	0.049 (2)	0.0362 (18)	−0.0204 (17)	0.0019 (15)	−0.0068 (15)
C12	0.0427 (18)	0.0382 (18)	0.0333 (17)	−0.0118 (15)	0.0022 (14)	−0.0020 (14)
C13	0.0398 (18)	0.049 (2)	0.044 (2)	−0.0088 (16)	0.0031 (15)	−0.0065 (16)
C14	0.066 (2)	0.044 (2)	0.049 (2)	−0.0161 (19)	−0.0030 (19)	0.0058 (17)
C15	0.067 (2)	0.0337 (18)	0.047 (2)	−0.0252 (17)	0.0034 (17)	−0.0061 (15)
C16	0.061 (2)	0.045 (2)	0.053 (2)	−0.0321 (18)	0.0022 (18)	−0.0107 (17)
C17	0.041 (2)	0.066 (3)	0.075 (3)	−0.015 (2)	0.006 (2)	−0.016 (2)

Geometric parameters (Å, º) top

Ni1—N1	1.880 (3)	C4—C5	1.522 (5)
Ni1—N3	1.888 (3)	C4—C6	1.538 (5)
Ni1—N2	1.916 (2)	C5—H5A	0.9600
Ni1—N4	1.917 (2)	C5—H5B	0.9600
Ni1—S1	3.2979 (13)	C5—H5C	0.9600
S1—C17	1.620 (5)	C6—H6A	0.9600
Cl1—O2'	1.359 (18)	C6—H6B	0.9600
Cl1—O1	1.369 (4)	C6—H6C	0.9600
Cl1—O3	1.385 (18)	C7—C8	1.494 (5)
Cl1—O2	1.40 (3)	C7—H7A	0.9700
Cl1—O4'	1.40 (4)	C7—H7B	0.9700
Cl1—O4	1.408 (11)	C8—H8A	0.9700
Cl1—O3'	1.41 (3)	C8—H8B	0.9700
N1—C2	1.284 (4)	C9—C10	1.505 (5)
N1—C16	1.482 (4)	C9—H9A	0.9600
N2—C7	1.487 (4)	C9—H9B	0.9600
N2—C4	1.505 (4)	C9—H9C	0.9600
N2—H2	0.9100	C10—C11	1.495 (5)
N3—C10	1.278 (4)	C11—C12	1.529 (4)
N3—C8	1.482 (4)	C11—H11A	0.9700
N4—C15	1.489 (4)	C11—H11B	0.9700
N4—C12	1.508 (4)	C12—C13	1.526 (4)
N4—H4	0.9100	C12—C14	1.531 (4)
N5—C17	1.159 (5)	C13—H13A	0.9600
O5—H5F	0.8500	C13—H13B	0.9600
O5—H5G	0.8500	C13—H13C	0.9600
C1—C2	1.491 (5)	C14—H14A	0.9600
C1—H1A	0.9600	C14—H14B	0.9600
C1—H1B	0.9600	C14—H14C	0.9600
C1—H1C	0.9600	C15—C16	1.498 (5)
C2—C3	1.496 (5)	C15—H15A	0.9700
C3—C4	1.523 (5)	C15—H15B	0.9700
C3—H3A	0.9700	C16—H16A	0.9700
C3—H3B	0.9700	C16—H16B	0.9700

N1—Ni1—N3	174.53 (11)	C3—C4—C6	107.2 (3)
N1—Ni1—N2	92.60 (11)	C4—C5—H5A	109.5
N3—Ni1—N2	88.02 (11)	C4—C5—H5B	109.5
N1—Ni1—N4	87.93 (11)	H5A—C5—H5B	109.5
N3—Ni1—N4	91.75 (11)	C4—C5—H5C	109.5
N2—Ni1—N4	176.80 (11)	H5A—C5—H5C	109.5
N1—Ni1—S1	92.86 (8)	H5B—C5—H5C	109.5
N3—Ni1—S1	81.67 (8)	C4—C6—H6A	109.5
N2—Ni1—S1	92.88 (8)	C4—C6—H6B	109.5
N4—Ni1—S1	90.25 (8)	H6A—C6—H6B	109.5
C17—S1—Ni1	85.87 (14)	C4—C6—H6C	109.5
O2'—Cl1—O1	127.9 (17)	H6A—C6—H6C	109.5
O2'—Cl1—O3	75.5 (14)	H6B—C6—H6C	109.5
O1—Cl1—O3	115.2 (10)	N2—C7—C8	108.2 (3)
O2'—Cl1—O2	113.7 (19)	N2—C7—H7A	110.0
O1—Cl1—O2	110.6 (14)	C8—C7—H7A	110.0
O3—Cl1—O2	107.7 (14)	N2—C7—H7B	110.0
O2'—Cl1—O4'	99 (2)	C8—C7—H7B	110.0
O1—Cl1—O4'	115 (2)	H7A—C7—H7B	108.4
O3—Cl1—O4'	119 (2)	N3—C8—C7	105.6 (3)
O2—Cl1—O4'	21 (2)	N3—C8—H8A	110.6
O2'—Cl1—O4	38.1 (9)	C7—C8—H8A	110.6
O1—Cl1—O4	97.2 (13)	N3—C8—H8B	110.6
O3—Cl1—O4	109.6 (11)	C7—C8—H8B	110.6
O2—Cl1—O4	116.7 (11)	H8A—C8—H8B	108.7
O4'—Cl1—O4	96.2 (18)	C10—C9—H9A	109.5
O2'—Cl1—O3'	103.0 (12)	C10—C9—H9B	109.5
O1—Cl1—O3'	99.4 (17)	H9A—C9—H9B	109.5
O3—Cl1—O3'	27.7 (17)	C10—C9—H9C	109.5
O2—Cl1—O3'	94.5 (16)	H9A—C9—H9C	109.5
O4'—Cl1—O3'	113 (2)	H9B—C9—H9C	109.5
O4—Cl1—O3'	136.4 (14)	N3—C10—C11	122.0 (3)
C2—N1—C16	120.5 (3)	N3—C10—C9	123.9 (3)
C2—N1—Ni1	130.8 (2)	C11—C10—C9	114.1 (3)
C16—N1—Ni1	108.6 (2)	C10—C11—C12	119.3 (3)
C7—N2—C4	114.5 (3)	C10—C11—H11A	107.5
C7—N2—Ni1	107.9 (2)	C12—C11—H11A	107.5
C4—N2—Ni1	114.08 (19)	C10—C11—H11B	107.5
C7—N2—H2	106.6	C12—C11—H11B	107.5
C4—N2—H2	106.6	H11A—C11—H11B	107.0
Ni1—N2—H2	106.6	N4—C12—C13	109.9 (3)
C10—N3—C8	120.7 (3)	N4—C12—C11	106.1 (3)
C10—N3—Ni1	129.9 (2)	C13—C12—C11	111.4 (3)
C8—N3—Ni1	109.0 (2)	N4—C12—C14	111.4 (3)
C15—N4—C12	115.1 (2)	C13—C12—C14	109.8 (3)
C15—N4—Ni1	109.0 (2)	C11—C12—C14	108.3 (3)
C12—N4—Ni1	112.87 (18)	C12—C13—H13A	109.5
C15—N4—H4	106.4	C12—C13—H13B	109.5
C12—N4—H4	106.4	H13A—C13—H13B	109.5
Ni1—N4—H4	106.4	C12—C13—H13C	109.5
H5F—O5—H5G	108.3	H13A—C13—H13C	109.5
C2—C1—H1A	109.5	H13B—C13—H13C	109.5
C2—C1—H1B	109.5	C12—C14—H14A	109.5
H1A—C1—H1B	109.5	C12—C14—H14B	109.5
C2—C1—H1C	109.5	H14A—C14—H14B	109.5
H1A—C1—H1C	109.5	C12—C14—H14C	109.5
H1B—C1—H1C	109.5	H14A—C14—H14C	109.5
N1—C2—C1	124.5 (3)	H14B—C14—H14C	109.5
N1—C2—C3	121.1 (3)	N4—C15—C16	107.5 (3)
C1—C2—C3	114.4 (3)	N4—C15—H15A	110.2
C2—C3—C4	120.4 (3)	C16—C15—H15A	110.2
C2—C3—H3A	107.2	N4—C15—H15B	110.2
C4—C3—H3A	107.2	C16—C15—H15B	110.2
C2—C3—H3B	107.2	H15A—C15—H15B	108.5
C4—C3—H3B	107.2	N1—C16—C15	106.6 (3)
H3A—C3—H3B	106.9	N1—C16—H16A	110.4
N2—C4—C5	110.3 (3)	C15—C16—H16A	110.4
N2—C4—C3	107.6 (3)	N1—C16—H16B	110.4
C5—C4—C3	110.8 (3)	C15—C16—H16B	110.4
N2—C4—C6	110.3 (3)	H16A—C16—H16B	108.6
C5—C4—C6	110.7 (3)	N5—C17—S1	176.7 (4)

N1—Ni1—S1—C17	−106.07 (18)	Ni1—N1—C2—C3	−0.1 (5)
N3—Ni1—S1—C17	73.60 (18)	N1—C2—C3—C4	−16.4 (5)
N2—Ni1—S1—C17	161.18 (18)	C1—C2—C3—C4	164.7 (3)
N4—Ni1—S1—C17	−18.13 (18)	C7—N2—C4—C5	−72.0 (3)
N3—Ni1—N1—C2	−110.1 (12)	Ni1—N2—C4—C5	53.0 (3)
N2—Ni1—N1—C2	−13.6 (3)	C7—N2—C4—C3	167.1 (3)
N4—Ni1—N1—C2	163.2 (3)	Ni1—N2—C4—C3	−67.9 (3)
S1—Ni1—N1—C2	−106.7 (3)	C7—N2—C4—C6	50.5 (4)
N3—Ni1—N1—C16	66.7 (12)	Ni1—N2—C4—C6	175.5 (2)
N2—Ni1—N1—C16	163.1 (2)	C2—C3—C4—N2	50.8 (4)
N4—Ni1—N1—C16	−20.1 (2)	C2—C3—C4—C5	−69.8 (4)
S1—Ni1—N1—C16	70.1 (2)	C2—C3—C4—C6	169.4 (3)
N1—Ni1—N2—C7	175.6 (2)	C4—N2—C7—C8	163.6 (3)
N3—Ni1—N2—C7	−9.8 (2)	Ni1—N2—C7—C8	35.4 (3)
N4—Ni1—N2—C7	76 (2)	C10—N3—C8—C7	−145.6 (3)
S1—Ni1—N2—C7	−91.4 (2)	Ni1—N3—C8—C7	41.0 (3)
N1—Ni1—N2—C4	47.2 (2)	N2—C7—C8—N3	−49.6 (4)
N3—Ni1—N2—C4	−138.3 (2)	C8—N3—C10—C11	176.2 (3)
N4—Ni1—N2—C4	−52 (2)	Ni1—N3—C10—C11	−12.0 (5)
S1—Ni1—N2—C4	140.2 (2)	C8—N3—C10—C9	−4.5 (5)
N1—Ni1—N3—C10	−93.8 (12)	Ni1—N3—C10—C9	167.3 (3)
N2—Ni1—N3—C10	169.6 (3)	N3—C10—C11—C12	−8.1 (5)
N4—Ni1—N3—C10	−7.2 (3)	C9—C10—C11—C12	172.5 (3)
S1—Ni1—N3—C10	−97.2 (3)	C15—N4—C12—C13	−78.0 (3)
N1—Ni1—N3—C8	78.7 (12)	Ni1—N4—C12—C13	48.0 (3)
N2—Ni1—N3—C8	−17.9 (2)	C15—N4—C12—C11	161.5 (3)
N4—Ni1—N3—C8	165.3 (2)	Ni1—N4—C12—C11	−72.5 (3)
S1—Ni1—N3—C8	75.3 (2)	C15—N4—C12—C14	43.8 (4)
N1—Ni1—N4—C15	−7.0 (2)	Ni1—N4—C12—C14	169.8 (2)
N3—Ni1—N4—C15	178.5 (2)	C10—C11—C12—N4	50.3 (4)
N2—Ni1—N4—C15	92.6 (19)	C10—C11—C12—C13	−69.3 (4)
S1—Ni1—N4—C15	−99.9 (2)	C10—C11—C12—C14	169.9 (3)
N1—Ni1—N4—C12	−136.2 (2)	C12—N4—C15—C16	160.1 (3)
N3—Ni1—N4—C12	49.2 (2)	Ni1—N4—C15—C16	32.1 (3)
N2—Ni1—N4—C12	−37 (2)	C2—N1—C16—C15	−140.5 (3)
S1—Ni1—N4—C12	130.90 (19)	Ni1—N1—C16—C15	42.3 (3)
C16—N1—C2—C1	2.4 (5)	N4—C15—C16—N1	−48.1 (4)
Ni1—N1—C2—C1	178.8 (2)	Ni1—S1—C17—N5	31 (8)
C16—N1—C2—C3	−176.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2	0.91	2.28	3.16 (3)	162
N4—H4···N5	0.91	2.33	3.241 (5)	175
O5—H5F···N5	0.85	2.09	2.942 (6)	178
O5—H5G···N5ⁱ	0.85	2.15	2.997 (6)	178
C3—H3A···O4ⁱⁱ	0.97	2.49	3.450 (16)	172
C3—H3B···O2	0.97	2.48	3.26 (3)	137
C15—H15A···O1ⁱⁱⁱ	0.97	2.37	3.155 (6)	138

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

Experimental details

Crystal data
Chemical formula	[Ni(NCS)(C₁₆H₃₂N₄)]ClO₄·H₂O
M_r	514.71
Crystal system, space group	Triclinic, P1
Temperature (K)	291
a, b, c (Å)	7.2678 (11), 8.9998 (13), 19.513 (2)
α, β, γ (°)	84.143 (1), 87.005 (2), 67.348 (1)
V (Å³)	1171.6 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.07
Crystal size (mm)	0.49 × 0.40 × 0.39

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.623, 0.681
No. of measured, independent and observed [I > 2σ(I)] reflections	6103, 4062, 3247
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.109, 1.03
No. of reflections	4062
No. of parameters	299
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.90

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2	0.91	2.28	3.16 (3)	162.0
N4—H4···N5	0.91	2.33	3.241 (5)	175.0
O5—H5F···N5	0.85	2.09	2.942 (6)	178.0
O5—H5G···N5ⁱ	0.85	2.15	2.997 (6)	178.0
C3—H3A···O4ⁱⁱ	0.97	2.49	3.450 (16)	172.0
C3—H3B···O2	0.97	2.48	3.26 (3)	137.0
C15—H15A···O1ⁱⁱⁱ	0.97	2.37	3.155 (6)	138.0

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

Acknowledgements

The author is indebted to the National Natural Science Foundation of China for financial support (grant No. 20871039).

References

Bienko, A., Klak, J., Mrozinski, J., Boca, R., Brudgam, I. & Hartl, H. (2007). Dalton Trans. pp. 2681–2688. Web of Science PubMed Google Scholar
Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shen, H. Y., Liao, D. Z., Jiang, Z. H. & Yan, S. P. (1999). Transition Met. Chem. 24, 581–583. Web of Science CSD CrossRef CAS Google Scholar
Szalda, D. J. & Fujita, E. (1992). Acta Cryst. C48, 1767–1771. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.