Bis(2-dimethylamino-1,10-phenanthroline-κ2N,N′)bis­(thio­cyanato-κN)nickel(II) methanol disolvate

Zhang, S.G.; Hu, T.Q.; Li, H.

doi:10.1107/S1600536808011811

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page m769

doi:10.1107/S1600536808011811

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Bis(2-dimethylamino-1,10-phenanthroline-κ²N,N′)bis(thiocyanato-κN)nickel(II) methanol disolvate

Shi Guo Zhang,^a ^* Tai Qiu Hu ^b and Hong Li ^a

^aDepartment of Chemistry and Chemical Engineering, Institute of Materials Chemistry, Binzhou University, Binzhou 256603, People's Republic of China, and ^bDepartment of Chemistry, Shandong Normal University, Jinan 250014, People's Republic of China
^*Correspondence e-mail: zhangshiguo1970@yahoo.com.cn

(Received 7 April 2008; accepted 24 April 2008; online 3 May 2008)

In the title complex, [Ni(NCS)₂(C₁₄H₁₃N₃)₂]·2CH₃OH, the Ni^II atom lies on a crystallographic twofold rotation axis and is in a slightly distorted octahedral NiN₆ coordination environment. The crystal structure is stabilized by a combination of weak π–π stacking interactions between symmetry-related 1,10-phenanthroline ligands [centroi–centroid distance between benzene rings = 3.5936 (18) Å] and weak O—H⋯S, C—H⋯O and C—H⋯S hydrogen bonds between methanol and complex molecules.

Related literature

For related literature, see: Zhang et al. (2006 ); Liu et al. (2008 ).

Experimental

Crystal data

[Ni(NCS)₂(C₁₄H₁₃N₃)₂]·2CH₄O
M_r = 685.50
Monoclinic, C 2/c
a = 19.573 (3) Å
b = 11.452 (3) Å
c = 16.338 (3) Å
β = 117.693 (4)°
V = 3242.6 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.77 mm⁻¹
T = 298 (2) K
0.31 × 0.24 × 0.21 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.796, T_max = 0.855
8459 measured reflections
3064 independent reflections
2668 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.100
S = 1.05
3064 reflections
210 parameters
H-atom parameters constrained
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

N1—Ni1	2.0569 (19)
N2—Ni1	2.2556 (18)
N3—Ni1	2.047 (2)

N3ⁱ—Ni1—N3	90.27 (11)
N3—Ni1—N1ⁱ	93.08 (7)
N3—Ni1—N1	88.63 (7)
N1ⁱ—Ni1—N1	177.57 (10)
N3—Ni1—N2	96.75 (7)
N1—Ni1—N2	77.31 (7)
N3—Ni1—N2ⁱ	167.90 (7)
N1—Ni1—N2ⁱ	100.76 (7)
N2—Ni1—N2ⁱ	78.13 (9)
Symmetry code: (i) $[-x+1, y, -z+{\script{1\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14C⋯S1ⁱⁱ	0.96	2.86	3.784 (3)	163
O1—H4⋯S1ⁱⁱⁱ	0.82	2.65	3.331 (2)	142
C15—H15B⋯O1^iv	0.96	2.51	3.427 (4)	161
Symmetry codes: (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) x, y+1, z; (iv) $[-x+{\script{3\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); 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/S1600536808011811/lh2613sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808011811/lh2613Isup2.hkl

checkCIF report

Comment top

The derivatives of 1,10-phenanthroline play a pivotal role in the area of modern coordination chemistry (Zhang et al. 2006) and a number of complexes have been reported with derivatives as ligands (Liu et al. 2008). Here we report the crystal structure of the title complex, (I), formed using 2-(dimethyl)amine-1,10-phenanthroline as a ligand.

The molecular structure of (I) is shown in Fig. 1. In the mononuclear complex, atom Ni1 is in a slightly distorted octahedral geometry (Table 1). There is a single π-π stacking interaction involving symmetry related 1,10-phenanthroline ligands, with the the relevant distances being Cg1···Cg1ⁱ = 3.5936 (18) Å and Cg1···Cg1ⁱ_perp = 3.449 Å; α = 0.00° [symmetry code: (i) 1-x,-y,-z; Cg1 is the centroid of the C4—C9 ring; Cg1···Cg1_perp is the perpendicular distance from ring Cg1 to ring Cg1ⁱ; α is the dihedral between the two ring planes]. In addition, the crystal structure contains weak O—H···S, C—H···O and C—H···S hydrogen bonds between methanol molecules and complex molecules [Fig. 2 and Table 2]. In addition to the π-π stacking interactions and the hydrogen bonds there is relatively close contact between the H atom of the hydroxyl and symmetry-related pyridine ring [H···Cg2 = 2.82, where Cg2 is the centroid of N1/C1—C5 ring]. The combination of the above interactions help stabilize the crystal structure.

Related literature top

For related literature, see: Zhang et al. (2006); Liu et al. (2008).

Experimental top

15 ml me thanol solution of Ni(ClO₄).6H₂O (0.2503 g, 0.684 mmol) was added into a 10 ml me thanol solution containing 2-(dimethl)amine-1,10-phenanthroline (0.1531 g, 0.686 mmol), and the mixed solution was stirred for a few minutes. Then 10 ml me thanol solution of NaSCN (0.1112 g, 1.37 mmol) was added into the mixed solution above. The green single crystals were obtained after the solution had been allowed to stand at room temperature for two weeks.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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. View of the molecular structure of complex (I), showing the the atom numbering scheme with thermal ellipsoids drawn at the 30% probability level (methanol molecules are not shown). Primed atoms are related by the symmetry operator (-x+1, y, -z+1/2).
	Fig. 2. Part of the crystal structure showing hydrogen bonds between methanol molecules and complex molecules (dashed lines).

Bis(2-dimethylamino-1,10-phenanthroline-κ²N,N')bis(thiocyanato- κN)nickel(II) methanol disolvate top

Crystal data top

[Ni(NCS)₂(C₁₄H₁₃N₃)₂]·2CH₄O	F(000) = 1432
M_r = 685.50	D_x = 1.404 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3100 reflections
a = 19.573 (3) Å	θ = 2.4–27.8°
b = 11.452 (3) Å	µ = 0.77 mm⁻¹
c = 16.338 (3) Å	T = 298 K
β = 117.693 (4)°	Block, green
V = 3242.6 (10) Å³	0.31 × 0.24 × 0.21 mm
Z = 4

Data collection top

Bruker SMART APEX CCD diffractometer	3064 independent reflections
Radiation source: fine-focus sealed tube	2668 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ϕ and ω scans	θ_max = 25.7°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −18→23
T_min = 0.796, T_max = 0.855	k = −12→13
8459 measured reflections	l = −19→19

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) = 0.100	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0522P)² + 2.7575P] where P = (F_o² + 2F_c²)/3
3064 reflections	(Δ/σ)_max < 0.001
210 parameters	Δρ_max = 0.52 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

[Ni(NCS)₂(C₁₄H₁₃N₃)₂]·2CH₄O	V = 3242.6 (10) Å³
M_r = 685.50	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 19.573 (3) Å	µ = 0.77 mm⁻¹
b = 11.452 (3) Å	T = 298 K
c = 16.338 (3) Å	0.31 × 0.24 × 0.21 mm
β = 117.693 (4)°

Data collection top

Bruker SMART APEX CCD diffractometer	3064 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2668 reflections with I > 2σ(I)
T_min = 0.796, T_max = 0.855	R_int = 0.030
8459 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.100	H-atom parameters constrained
S = 1.05	Δρ_max = 0.52 e Å⁻³
3064 reflections	Δρ_min = −0.27 e Å⁻³
210 parameters

Special details top

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
C1	0.38579 (14)	−0.2002 (2)	0.05726 (16)	0.0324 (6)
H1	0.3846	−0.2706	0.0850	0.039*
C2	0.33596 (15)	−0.1849 (2)	−0.03666 (17)	0.0385 (6)
H2	0.3033	−0.2451	−0.0711	0.046*
C3	0.33558 (15)	−0.0809 (3)	−0.07755 (17)	0.0371 (6)
H3	0.3013	−0.0688	−0.1396	0.045*
C4	0.38688 (14)	0.0075 (2)	−0.02593 (16)	0.0310 (5)
C5	0.43824 (13)	−0.01749 (19)	0.06749 (15)	0.0248 (5)
C6	0.49639 (13)	0.06546 (19)	0.12309 (15)	0.0234 (5)
C7	0.38961 (16)	0.1199 (2)	−0.06162 (17)	0.0358 (6)
H7	0.3562	0.1372	−0.1231	0.043*
C8	0.43990 (15)	0.2013 (2)	−0.00747 (17)	0.0359 (6)
H8	0.4391	0.2752	−0.0314	0.043*
C9	0.49437 (14)	0.1764 (2)	0.08600 (16)	0.0296 (5)
C10	0.54844 (15)	0.2582 (2)	0.14486 (18)	0.0351 (6)
H10	0.5475	0.3344	0.1248	0.042*
C11	0.60188 (15)	0.2262 (2)	0.23065 (17)	0.0336 (6)
H11	0.6366	0.2811	0.2701	0.040*
C12	0.60511 (14)	0.10882 (19)	0.26076 (16)	0.0269 (5)
C14	0.69963 (14)	−0.0403 (2)	0.34968 (18)	0.0340 (6)
H14A	0.6624	−0.0934	0.3064	0.051*
H14B	0.7179	−0.0700	0.4113	0.051*
H14C	0.7422	−0.0324	0.3362	0.051*
C15	0.71573 (17)	0.1587 (2)	0.40742 (18)	0.0445 (7)
H15A	0.7498	0.1885	0.3851	0.067*
H15B	0.7455	0.1225	0.4666	0.067*
H15C	0.6860	0.2216	0.4135	0.067*
C16	0.5917 (2)	0.4773 (3)	0.3971 (3)	0.0682 (10)
H6	0.5532	0.5318	0.3577	0.096 (14)*
H9	0.5911	0.4728	0.4554	0.14 (2)*
H5	0.5809	0.4016	0.3685	0.129 (19)*
C17	0.59639 (13)	−0.3261 (2)	0.21965 (15)	0.0258 (5)
N1	0.43477 (11)	−0.11804 (16)	0.10854 (12)	0.0257 (4)
N2	0.55031 (11)	0.03107 (15)	0.20930 (12)	0.0231 (4)
N3	0.56731 (12)	−0.24797 (17)	0.23466 (13)	0.0290 (4)
N4	0.66394 (12)	0.07266 (17)	0.34233 (13)	0.0305 (5)
Ni1	0.5000	−0.12186 (3)	0.2500	0.02153 (14)
O1	0.66464 (13)	0.5147 (2)	0.41138 (16)	0.0681 (7)
H4	0.6688	0.4940	0.3658	0.102*
S1	0.63832 (4)	−0.43760 (6)	0.19758 (5)	0.0419 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0360 (14)	0.0320 (13)	0.0322 (12)	−0.0045 (11)	0.0184 (11)	−0.0052 (10)
C2	0.0362 (15)	0.0467 (15)	0.0341 (13)	−0.0091 (12)	0.0177 (12)	−0.0138 (12)
C3	0.0300 (14)	0.0549 (16)	0.0236 (12)	0.0040 (12)	0.0102 (11)	−0.0049 (11)
C4	0.0321 (14)	0.0406 (14)	0.0246 (12)	0.0092 (11)	0.0167 (11)	0.0005 (10)
C5	0.0283 (12)	0.0275 (12)	0.0239 (11)	0.0060 (10)	0.0166 (10)	0.0002 (9)
C6	0.0283 (12)	0.0245 (11)	0.0247 (11)	0.0056 (9)	0.0186 (10)	0.0020 (9)
C7	0.0413 (15)	0.0440 (15)	0.0242 (12)	0.0139 (12)	0.0170 (11)	0.0085 (11)
C8	0.0494 (17)	0.0318 (13)	0.0339 (13)	0.0151 (12)	0.0256 (13)	0.0133 (11)
C9	0.0392 (14)	0.0246 (12)	0.0341 (12)	0.0067 (10)	0.0247 (12)	0.0048 (10)
C10	0.0466 (16)	0.0217 (12)	0.0459 (15)	0.0021 (11)	0.0291 (13)	0.0050 (11)
C11	0.0412 (15)	0.0265 (13)	0.0379 (14)	−0.0066 (11)	0.0225 (12)	−0.0033 (10)
C12	0.0316 (13)	0.0272 (12)	0.0286 (12)	−0.0013 (10)	0.0195 (10)	−0.0027 (9)
C14	0.0272 (13)	0.0349 (13)	0.0392 (14)	0.0001 (10)	0.0148 (11)	0.0060 (11)
C15	0.0419 (16)	0.0427 (16)	0.0365 (14)	−0.0094 (13)	0.0078 (13)	−0.0080 (12)
C16	0.060 (2)	0.059 (2)	0.093 (3)	−0.0081 (18)	0.041 (2)	0.012 (2)
C17	0.0264 (12)	0.0272 (12)	0.0234 (11)	0.0000 (10)	0.0112 (10)	0.0046 (9)
N1	0.0286 (11)	0.0259 (10)	0.0239 (9)	0.0002 (8)	0.0134 (8)	−0.0030 (8)
N2	0.0269 (10)	0.0217 (9)	0.0255 (9)	0.0008 (8)	0.0162 (8)	−0.0003 (7)
N3	0.0375 (12)	0.0237 (10)	0.0282 (10)	0.0038 (9)	0.0174 (9)	0.0018 (8)
N4	0.0307 (11)	0.0285 (10)	0.0285 (10)	−0.0030 (9)	0.0105 (9)	−0.0001 (8)
Ni1	0.0277 (2)	0.0178 (2)	0.0207 (2)	0.000	0.01265 (18)	0.000
O1	0.0449 (13)	0.0956 (18)	0.0573 (14)	0.0003 (12)	0.0182 (11)	0.0297 (13)
S1	0.0482 (4)	0.0367 (4)	0.0449 (4)	0.0161 (3)	0.0250 (3)	0.0006 (3)

Geometric parameters (Å, º) top

C1—N1	1.326 (3)	C12—N4	1.359 (3)
C1—C2	1.395 (3)	C14—N4	1.449 (3)
C1—H1	0.9300	C14—H14A	0.9600
C2—C3	1.364 (4)	C14—H14B	0.9600
C2—H2	0.9300	C14—H14C	0.9600
C3—C4	1.399 (4)	C15—N4	1.458 (3)
C3—H3	0.9300	C15—H15A	0.9600
C4—C5	1.413 (3)	C15—H15B	0.9600
C4—C7	1.424 (4)	C15—H15C	0.9600
C5—N1	1.350 (3)	C16—O1	1.402 (4)
C5—C6	1.436 (3)	C16—H6	0.9600
C6—N2	1.368 (3)	C16—H9	0.9600
C6—C9	1.400 (3)	C16—H5	0.9600
C7—C8	1.346 (4)	C17—N3	1.146 (3)
C7—H7	0.9300	C17—S1	1.646 (2)
C8—C9	1.427 (3)	N1—Ni1	2.0569 (19)
C8—H8	0.9300	N2—Ni1	2.2556 (18)
C9—C10	1.406 (3)	N3—Ni1	2.047 (2)
C10—C11	1.353 (4)	Ni1—N3ⁱ	2.047 (2)
C10—H10	0.9300	Ni1—N1ⁱ	2.0569 (19)
C11—C12	1.422 (3)	Ni1—N2ⁱ	2.2556 (18)
C11—H11	0.9300	O1—H4	0.8217
C12—N2	1.346 (3)

N1—C1—C2	122.5 (2)	H14B—C14—H14C	109.5
N1—C1—H1	118.8	N4—C15—H15A	109.5
C2—C1—H1	118.8	N4—C15—H15B	109.5
C3—C2—C1	119.3 (2)	H15A—C15—H15B	109.5
C3—C2—H2	120.3	N4—C15—H15C	109.5
C1—C2—H2	120.3	H15A—C15—H15C	109.5
C2—C3—C4	119.9 (2)	H15B—C15—H15C	109.5
C2—C3—H3	120.1	O1—C16—H6	109.5
C4—C3—H3	120.1	O1—C16—H9	109.5
C3—C4—C5	117.1 (2)	H6—C16—H9	109.5
C3—C4—C7	124.1 (2)	O1—C16—H5	109.5
C5—C4—C7	118.8 (2)	H6—C16—H5	109.5
N1—C5—C4	122.3 (2)	H9—C16—H5	109.5
N1—C5—C6	117.26 (19)	N3—C17—S1	179.6 (2)
C4—C5—C6	120.4 (2)	C1—N1—C5	118.7 (2)
N2—C6—C9	124.0 (2)	C1—N1—Ni1	125.71 (16)
N2—C6—C5	117.80 (19)	C5—N1—Ni1	115.34 (14)
C9—C6—C5	118.2 (2)	C12—N2—C6	117.53 (19)
C8—C7—C4	120.8 (2)	C12—N2—Ni1	131.28 (15)
C8—C7—H7	119.6	C6—N2—Ni1	107.06 (14)
C4—C7—H7	119.6	C17—N3—Ni1	171.3 (2)
C7—C8—C9	121.3 (2)	C12—N4—C14	120.6 (2)
C7—C8—H8	119.4	C12—N4—C15	119.6 (2)
C9—C8—H8	119.4	C14—N4—C15	113.4 (2)
C6—C9—C10	116.6 (2)	N3ⁱ—Ni1—N3	90.27 (11)
C6—C9—C8	120.1 (2)	N3ⁱ—Ni1—N1ⁱ	88.63 (7)
C10—C9—C8	123.3 (2)	N3—Ni1—N1ⁱ	93.08 (7)
C11—C10—C9	120.1 (2)	N3ⁱ—Ni1—N1	93.08 (7)
C11—C10—H10	119.9	N3—Ni1—N1	88.63 (7)
C9—C10—H10	119.9	N1ⁱ—Ni1—N1	177.57 (10)
C10—C11—C12	120.2 (2)	N3ⁱ—Ni1—N2	167.90 (7)
C10—C11—H11	119.9	N3—Ni1—N2	96.75 (7)
C12—C11—H11	119.9	N1ⁱ—Ni1—N2	100.76 (7)
N2—C12—N4	118.5 (2)	N1—Ni1—N2	77.31 (7)
N2—C12—C11	121.0 (2)	N3ⁱ—Ni1—N2ⁱ	96.75 (7)
N4—C12—C11	120.5 (2)	N3—Ni1—N2ⁱ	167.90 (7)
N4—C14—H14A	109.5	N1ⁱ—Ni1—N2ⁱ	77.31 (7)
N4—C14—H14B	109.5	N1—Ni1—N2ⁱ	100.76 (7)
H14A—C14—H14B	109.5	N2—Ni1—N2ⁱ	78.13 (9)
N4—C14—H14C	109.5	C16—O1—H4	106.5
H14A—C14—H14C	109.5

N1—C1—C2—C3	−1.8 (4)	C6—C5—N1—Ni1	11.1 (2)
C1—C2—C3—C4	2.3 (4)	N4—C12—N2—C6	−173.0 (2)
C2—C3—C4—C5	1.1 (4)	C11—C12—N2—C6	6.8 (3)
C2—C3—C4—C7	−178.3 (2)	N4—C12—N2—Ni1	33.1 (3)
C3—C4—C5—N1	−5.3 (3)	C11—C12—N2—Ni1	−147.06 (18)
C7—C4—C5—N1	174.2 (2)	C9—C6—N2—C12	−0.8 (3)
C3—C4—C5—C6	175.4 (2)	C5—C6—N2—C12	179.39 (19)
C7—C4—C5—C6	−5.2 (3)	C9—C6—N2—Ni1	158.98 (18)
N1—C5—C6—N2	8.4 (3)	C5—C6—N2—Ni1	−20.8 (2)
C4—C5—C6—N2	−172.2 (2)	N2—C12—N4—C14	41.2 (3)
N1—C5—C6—C9	−171.4 (2)	C11—C12—N4—C14	−138.6 (2)
C4—C5—C6—C9	8.0 (3)	N2—C12—N4—C15	−168.5 (2)
C3—C4—C7—C8	179.1 (2)	C11—C12—N4—C15	11.7 (3)
C5—C4—C7—C8	−0.3 (4)	C1—N1—Ni1—N3ⁱ	−17.9 (2)
C4—C7—C8—C9	2.8 (4)	C5—N1—Ni1—N3ⁱ	155.82 (16)
N2—C6—C9—C10	−4.6 (3)	C1—N1—Ni1—N3	72.3 (2)
C5—C6—C9—C10	175.2 (2)	C5—N1—Ni1—N3	−113.98 (16)
N2—C6—C9—C8	174.7 (2)	C1—N1—Ni1—N2	169.6 (2)
C5—C6—C9—C8	−5.5 (3)	C5—N1—Ni1—N2	−16.74 (15)
C7—C8—C9—C6	0.1 (4)	C1—N1—Ni1—N2ⁱ	−115.3 (2)
C7—C8—C9—C10	179.4 (2)	C5—N1—Ni1—N2ⁱ	58.34 (17)
C6—C9—C10—C11	3.9 (4)	C12—N2—Ni1—N3ⁱ	137.6 (3)
C8—C9—C10—C11	−175.4 (2)	C6—N2—Ni1—N3ⁱ	−18.3 (4)
C9—C10—C11—C12	1.8 (4)	C12—N2—Ni1—N3	−97.3 (2)
C10—C11—C12—N2	−7.5 (4)	C6—N2—Ni1—N3	106.84 (14)
C10—C11—C12—N4	172.3 (2)	C12—N2—Ni1—N1ⁱ	−2.8 (2)
C2—C1—N1—C5	−2.3 (4)	C6—N2—Ni1—N1ⁱ	−158.71 (14)
C2—C1—N1—Ni1	171.22 (18)	C12—N2—Ni1—N1	175.7 (2)
C4—C5—N1—C1	5.9 (3)	C6—N2—Ni1—N1	19.77 (14)
C6—C5—N1—C1	−174.8 (2)	C12—N2—Ni1—N2ⁱ	71.63 (19)
C4—C5—N1—Ni1	−168.28 (17)	C6—N2—Ni1—N2ⁱ	−84.28 (14)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14C···S1ⁱⁱ	0.96	2.86	3.784 (3)	163
O1—H4···S1ⁱⁱⁱ	0.82	2.65	3.331 (2)	142
C15—H15B···O1^iv	0.96	2.51	3.427 (4)	161

Symmetry codes: (ii) −x+3/2, y+1/2, −z+1/2; (iii) x, y+1, z; (iv) −x+3/2, −y+1/2, −z+1.

Experimental details

Crystal data
Chemical formula	[Ni(NCS)₂(C₁₄H₁₃N₃)₂]·2CH₄O
M_r	685.50
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	19.573 (3), 11.452 (3), 16.338 (3)
β (°)	117.693 (4)
V (Å³)	3242.6 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.77
Crystal size (mm)	0.31 × 0.24 × 0.21

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.796, 0.855
No. of measured, independent and observed [I > 2σ(I)] reflections	8459, 3064, 2668
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.610

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.100, 1.05
No. of reflections	3064
No. of parameters	210
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.52, −0.27

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

N1—Ni1	2.0569 (19)	N3—Ni1	2.047 (2)
N2—Ni1	2.2556 (18)

N3ⁱ—Ni1—N3	90.27 (11)	N1—Ni1—N2	77.31 (7)
N3—Ni1—N1ⁱ	93.08 (7)	N3—Ni1—N2ⁱ	167.90 (7)
N3—Ni1—N1	88.63 (7)	N1—Ni1—N2ⁱ	100.76 (7)
N1ⁱ—Ni1—N1	177.57 (10)	N2—Ni1—N2ⁱ	78.13 (9)
N3—Ni1—N2	96.75 (7)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14C···S1ⁱⁱ	0.96	2.86	3.784 (3)	163.0
O1—H4···S1ⁱⁱⁱ	0.82	2.65	3.331 (2)	141.9
C15—H15B···O1^iv	0.96	2.51	3.427 (4)	160.9

Symmetry codes: (ii) −x+3/2, y+1/2, −z+1/2; (iii) x, y+1, z; (iv) −x+3/2, −y+1/2, −z+1.

Acknowledgements

The authors thank the Natural Science Foundation of Shandong Province of China for support (grant No. Y2007B26).

References

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Liu, Q. S., Liu, L. D. & Shi, J. M. (2008). Acta Cryst. C64, m58–m60. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhang, J.-P., Lin, Y.-Y., Huang, X.-C. & Chen, X.-M. (2006). Eur. J. Inorg. Chem. pp. 3407–3412. Web of Science CSD CrossRef Google Scholar

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