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

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.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.041
• wR factor = 0.100
• Data-to-parameter ratio = 14.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT153_ALERT_1_C The su's on the Cell Axes   are Equal (x 100000)        300 Ang.
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S1     -   C17     ..       6.93 su

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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

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

S2. Experimental

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.

S3. Refinement

H atom of hydroxyl was located in a difference Fourier map and refined as riding in its as found position with U_iso(H) = 1.5 U_eq(O). Other H atoms were placed in calculated positions (C—H = 0.96 Å for methyl group and C—H = 0.93 Å for other H atoms) and refined as riding with U_iso = 1.5 U_eq(C) for methyl H and U_iso = 1.2 U_eq(C) for other H atoms.

Computing details

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

	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

Crystal data

[Ni(NCS)2(C14H13N3)2]·2CH4O	F(000) = 1432
Mr = 685.50	Dx = 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) Å^3	0.31 × 0.24 × 0.21 mm
Z = 4

Data collection

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

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.100	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0522P)^2 + 2.7575P] where P = (Fo^2 + 2Fc^2)/3
3064 reflections	(Δ/σ)max < 0.001
210 parameters	Δρmax = 0.52 e Å^−3
0 restraints	Δρmin = −0.27 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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—N3^i	2.047 (2)
C10—H10	0.9300	Ni1—N1^i	2.0569 (19)
C11—C12	1.422 (3)	Ni1—N2^i	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)	N3^i—Ni1—N3	90.27 (11)
C6—C9—C8	120.1 (2)	N3^i—Ni1—N1^i	88.63 (7)
C10—C9—C8	123.3 (2)	N3—Ni1—N1^i	93.08 (7)
C11—C10—C9	120.1 (2)	N3^i—Ni1—N1	93.08 (7)
C11—C10—H10	119.9	N3—Ni1—N1	88.63 (7)
C9—C10—H10	119.9	N1^i—Ni1—N1	177.57 (10)
C10—C11—C12	120.2 (2)	N3^i—Ni1—N2	167.90 (7)
C10—C11—H11	119.9	N3—Ni1—N2	96.75 (7)
C12—C11—H11	119.9	N1^i—Ni1—N2	100.76 (7)
N2—C12—N4	118.5 (2)	N1—Ni1—N2	77.31 (7)
N2—C12—C11	121.0 (2)	N3^i—Ni1—N2^i	96.75 (7)
N4—C12—C11	120.5 (2)	N3—Ni1—N2^i	167.90 (7)
N4—C14—H14A	109.5	N1^i—Ni1—N2^i	77.31 (7)
N4—C14—H14B	109.5	N1—Ni1—N2^i	100.76 (7)
H14A—C14—H14B	109.5	N2—Ni1—N2^i	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—N3^i	−17.9 (2)
C4—C7—C8—C9	2.8 (4)	C5—N1—Ni1—N3^i	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—N2^i	−115.3 (2)
C7—C8—C9—C10	179.4 (2)	C5—N1—Ni1—N2^i	58.34 (17)
C6—C9—C10—C11	3.9 (4)	C12—N2—Ni1—N3^i	137.6 (3)
C8—C9—C10—C11	−175.4 (2)	C6—N2—Ni1—N3^i	−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—N1^i	−2.8 (2)
C2—C1—N1—C5	−2.3 (4)	C6—N2—Ni1—N1^i	−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—N2^i	71.63 (19)
C4—C5—N1—Ni1	−168.28 (17)	C6—N2—Ni1—N2^i	−84.28 (14)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14C···S1^ii	0.96	2.86	3.784 (3)	163
O1—H4···S1^iii	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.