Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803018154/su6042sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803018154/su6042Isup2.hkl |
CCDC reference: 222817
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.007 Å
- R factor = 0.045
- wR factor = 0.145
- Data-to-parameter ratio = 14.8
checkCIF/PLATON results
No syntax errors found
Alert level A PLAT761_ALERT_1_A CIF Contains no X-H Bonds ...................... ? PLAT762_ALERT_1_A CIF Contains no X-Y-H or H-Y-H Angles .......... ?
Alert level C PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT242_ALERT_2_C Check Low U(eq) as Compared to Neighbors .... C11 PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 7
2 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 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion
N-cyclohexyl-1,3-diaminopropane and salicylaldehyde were available commercially and were used without further purification. N-cyclohexyl-1,3-diaminopropane (2.0 mmol, 312 mg) and salicylaldehyde (2.0 mmol, 244 mg) were dissoved in methanol (10 ml). The mixture was stirred for ca 30 min to obtain a clear yellow solution of L (2.0 mmol), where L is 2-[(3-cyclohexylaminopropylimino)methyl]phenol. To the solution of L was added a solution of Ni(NCS)2 (1.0 mmol, 175 mg) in pyridine, with stirring. After keeping the resulting solution in air for 5 d, petal-like green crystals were formed on slow evaporation of the solvents. The crystals were isolated, washed with methanol three times and dried in a vacuum desiccator using CaCl2 (yield 52%). Analysis found: C 59.06, H 6.76, N 12.10%; calculated for C34H46N6NiO2S2: C 58.88, H 6.68, N 12.12%.
The amino H atom was located from a difference Fourier synthesis and refined isotropically. All the C—H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.97 Å and Uiso(H) values equal to 1.2Ueq of the parent C atom.
Data collection: SMART (Siemens, 1996); cell refinement: SMART; data reduction: SHELXTL (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[Ni(C16H23N2O)2(NCS)2] | F(000) = 736 |
Mr = 693.60 | Dx = 1.318 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 10.906 (7) Å | Cell parameters from 1432 reflections |
b = 7.796 (5) Å | θ = 2.6–18.5° |
c = 20.721 (13) Å | µ = 0.71 mm−1 |
β = 97.131 (11)° | T = 298 K |
V = 1748.0 (18) Å3 | Petal-like, green |
Z = 2 | 0.24 × 0.22 × 0.17 mm |
Bruker SMART CCD area-detector diffractometer | 3085 independent reflections |
Radiation source: fine-focus sealed tube | 1857 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.050 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→12 |
Tmin = 0.847, Tmax = 0.888 | k = −9→9 |
8924 measured reflections | l = −14→24 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.145 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.94 | w = 1/[σ2(Fo2) + (0.0718P)2] where P = (Fo2 + 2Fc2)/3 |
3085 reflections | (Δ/σ)max < 0.001 |
209 parameters | Δρmax = 0.48 e Å−3 |
2 restraints | Δρmin = −0.50 e Å−3 |
[Ni(C16H23N2O)2(NCS)2] | V = 1748.0 (18) Å3 |
Mr = 693.60 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.906 (7) Å | µ = 0.71 mm−1 |
b = 7.796 (5) Å | T = 298 K |
c = 20.721 (13) Å | 0.24 × 0.22 × 0.17 mm |
β = 97.131 (11)° |
Bruker SMART CCD area-detector diffractometer | 3085 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1857 reflections with I > 2σ(I) |
Tmin = 0.847, Tmax = 0.888 | Rint = 0.050 |
8924 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 2 restraints |
wR(F2) = 0.145 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.94 | Δρmax = 0.48 e Å−3 |
3085 reflections | Δρmin = −0.50 e Å−3 |
209 parameters |
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 | ||
Ni1 | 0.5000 | 0.5000 | 0.0000 | 0.0447 (3) | |
N1 | 0.4030 (3) | 0.3537 (4) | −0.07313 (17) | 0.0460 (9) | |
N2 | 0.2117 (3) | 0.2458 (4) | 0.05256 (17) | 0.0461 (9) | |
N3 | 0.6557 (3) | 0.3439 (5) | −0.01038 (19) | 0.0588 (10) | |
O1 | 0.5526 (2) | 0.6577 (4) | −0.06953 (14) | 0.0509 (7) | |
S1 | 0.82244 (11) | 0.17350 (15) | −0.08026 (6) | 0.0614 (4) | |
C1 | 0.3780 (4) | 0.4052 (6) | −0.1316 (2) | 0.0530 (12) | |
H1 | 0.3403 | 0.3260 | −0.1612 | 0.064* | |
C2 | 0.4016 (4) | 0.5736 (6) | −0.1573 (2) | 0.0498 (11) | |
C3 | 0.4856 (4) | 0.6917 (6) | −0.1253 (2) | 0.0480 (11) | |
C4 | 0.4996 (4) | 0.8487 (6) | −0.1568 (2) | 0.0551 (12) | |
H4 | 0.5540 | 0.9297 | −0.1366 | 0.066* | |
C5 | 0.4361 (4) | 0.8863 (7) | −0.2160 (2) | 0.0622 (13) | |
H5 | 0.4464 | 0.9926 | −0.2350 | 0.075* | |
C6 | 0.3560 (5) | 0.7666 (8) | −0.2480 (2) | 0.0692 (14) | |
H6 | 0.3136 | 0.7908 | −0.2887 | 0.083* | |
C7 | 0.3408 (4) | 0.6137 (7) | −0.2187 (2) | 0.0595 (13) | |
H7 | 0.2881 | 0.5328 | −0.2403 | 0.071* | |
C8 | 0.3659 (4) | 0.1756 (6) | −0.0604 (2) | 0.0605 (13) | |
H8A | 0.4064 | 0.1396 | −0.0182 | 0.073* | |
H8B | 0.3933 | 0.1004 | −0.0930 | 0.073* | |
C9 | 0.2258 (4) | 0.1577 (6) | −0.0615 (2) | 0.0642 (13) | |
H9A | 0.1873 | 0.1765 | −0.1056 | 0.077* | |
H9B | 0.2078 | 0.0406 | −0.0498 | 0.077* | |
C10 | 0.1669 (4) | 0.2766 (6) | −0.0172 (2) | 0.0575 (12) | |
H10A | 0.1847 | 0.3943 | −0.0281 | 0.069* | |
H10B | 0.0779 | 0.2614 | −0.0243 | 0.069* | |
C11 | 0.1355 (4) | 0.3315 (5) | 0.0996 (2) | 0.0471 (11) | |
H11 | 0.1250 | 0.4525 | 0.0874 | 0.057* | |
C12 | 0.0090 (4) | 0.2500 (8) | 0.0962 (3) | 0.0839 (17) | |
H12A | 0.0178 | 0.1275 | 0.1038 | 0.101* | |
H12B | −0.0355 | 0.2669 | 0.0532 | 0.101* | |
C13 | −0.0644 (5) | 0.3289 (9) | 0.1471 (3) | 0.095 (2) | |
H13A | −0.0819 | 0.4480 | 0.1360 | 0.114* | |
H13B | −0.1427 | 0.2693 | 0.1460 | 0.114* | |
C14 | 0.0020 (5) | 0.3198 (7) | 0.2135 (3) | 0.0792 (16) | |
H14A | 0.0109 | 0.2007 | 0.2269 | 0.095* | |
H14B | −0.0455 | 0.3784 | 0.2434 | 0.095* | |
C15 | 0.1277 (5) | 0.4011 (8) | 0.2162 (3) | 0.0857 (17) | |
H15A | 0.1720 | 0.3861 | 0.2594 | 0.103* | |
H15B | 0.1184 | 0.5232 | 0.2080 | 0.103* | |
C16 | 0.2022 (4) | 0.3223 (7) | 0.1664 (2) | 0.0703 (14) | |
H16A | 0.2804 | 0.3823 | 0.1676 | 0.084* | |
H16B | 0.2197 | 0.2033 | 0.1776 | 0.084* | |
C17 | 0.7234 (4) | 0.2723 (5) | −0.0392 (2) | 0.0453 (10) | |
H2 | 0.211 (3) | 0.1303 (14) | 0.0621 (14) | 0.038 (11)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0365 (4) | 0.0509 (5) | 0.0478 (5) | −0.0032 (4) | 0.0103 (3) | −0.0042 (4) |
N1 | 0.0376 (19) | 0.053 (2) | 0.049 (2) | −0.0046 (16) | 0.0141 (18) | −0.0104 (19) |
N2 | 0.048 (2) | 0.038 (2) | 0.054 (2) | 0.0018 (17) | 0.0097 (18) | −0.0014 (18) |
N3 | 0.046 (2) | 0.062 (3) | 0.069 (3) | 0.0049 (19) | 0.012 (2) | −0.011 (2) |
O1 | 0.0401 (16) | 0.0641 (19) | 0.0484 (18) | −0.0103 (14) | 0.0050 (15) | 0.0011 (15) |
S1 | 0.0578 (7) | 0.0506 (7) | 0.0789 (9) | 0.0024 (6) | 0.0211 (7) | −0.0028 (6) |
C1 | 0.041 (3) | 0.067 (3) | 0.052 (3) | −0.007 (2) | 0.009 (2) | −0.020 (3) |
C2 | 0.038 (2) | 0.068 (3) | 0.044 (3) | −0.001 (2) | 0.011 (2) | −0.008 (2) |
C3 | 0.036 (2) | 0.064 (3) | 0.048 (3) | 0.004 (2) | 0.019 (2) | −0.004 (2) |
C4 | 0.041 (3) | 0.064 (3) | 0.061 (3) | 0.002 (2) | 0.011 (2) | 0.004 (3) |
C5 | 0.054 (3) | 0.073 (4) | 0.061 (3) | 0.012 (3) | 0.015 (3) | 0.013 (3) |
C6 | 0.063 (3) | 0.095 (4) | 0.048 (3) | 0.016 (3) | 0.005 (3) | 0.005 (3) |
C7 | 0.049 (3) | 0.077 (4) | 0.052 (3) | 0.003 (2) | 0.009 (2) | −0.008 (3) |
C8 | 0.068 (3) | 0.052 (3) | 0.064 (3) | −0.006 (2) | 0.019 (3) | −0.015 (2) |
C9 | 0.067 (3) | 0.070 (3) | 0.057 (3) | −0.025 (3) | 0.010 (3) | −0.006 (3) |
C10 | 0.041 (2) | 0.073 (3) | 0.059 (3) | −0.009 (2) | 0.004 (2) | 0.005 (3) |
C11 | 0.042 (2) | 0.041 (2) | 0.060 (3) | 0.0028 (19) | 0.015 (2) | 0.000 (2) |
C12 | 0.037 (3) | 0.128 (5) | 0.089 (4) | −0.010 (3) | 0.019 (3) | −0.026 (4) |
C13 | 0.048 (3) | 0.135 (5) | 0.109 (5) | −0.007 (3) | 0.034 (4) | −0.027 (4) |
C14 | 0.077 (4) | 0.078 (4) | 0.090 (4) | −0.002 (3) | 0.043 (4) | 0.000 (3) |
C15 | 0.066 (3) | 0.125 (5) | 0.069 (4) | 0.004 (3) | 0.019 (3) | −0.020 (4) |
C16 | 0.047 (3) | 0.098 (4) | 0.066 (3) | 0.005 (3) | 0.010 (3) | −0.016 (3) |
C17 | 0.040 (2) | 0.042 (2) | 0.053 (3) | −0.006 (2) | 0.000 (2) | 0.002 (2) |
Ni1—O1 | 2.030 (3) | C2—C7 | 1.395 (6) |
Ni1—O1i | 2.030 (3) | C2—C3 | 1.405 (6) |
Ni1—N1 | 2.078 (3) | C3—C4 | 1.403 (6) |
Ni1—N1i | 2.078 (3) | C4—C5 | 1.364 (6) |
Ni1—N3i | 2.121 (4) | C5—C6 | 1.389 (7) |
Ni1—N3 | 2.121 (4) | C6—C7 | 1.358 (6) |
N1—C1 | 1.273 (5) | C8—C9 | 1.531 (6) |
N1—C8 | 1.479 (5) | C9—C10 | 1.503 (6) |
N2—C10 | 1.488 (5) | C11—C16 | 1.482 (6) |
N2—C11 | 1.512 (5) | C11—C12 | 1.513 (6) |
N3—C17 | 1.150 (5) | C12—C13 | 1.529 (6) |
O1—C3 | 1.316 (5) | C13—C14 | 1.475 (7) |
S1—C17 | 1.648 (5) | C14—C15 | 1.505 (7) |
C1—C2 | 1.452 (7) | C15—C16 | 1.520 (6) |
O1—Ni1—O1i | 180.00 (11) | C7—C2—C3 | 119.4 (4) |
O1—Ni1—N1 | 88.74 (13) | C7—C2—C1 | 116.8 (4) |
O1i—Ni1—N1 | 91.26 (13) | C3—C2—C1 | 123.7 (4) |
O1—Ni1—N1i | 91.26 (13) | O1—C3—C4 | 120.2 (4) |
O1i—Ni1—N1i | 88.74 (13) | O1—C3—C2 | 122.7 (4) |
N1—Ni1—N1i | 180.00 (15) | C4—C3—C2 | 117.1 (4) |
O1—Ni1—N3i | 91.43 (13) | C5—C4—C3 | 122.2 (5) |
O1i—Ni1—N3i | 88.57 (13) | C4—C5—C6 | 120.3 (5) |
N1—Ni1—N3i | 92.73 (14) | C7—C6—C5 | 118.7 (5) |
N1i—Ni1—N3i | 87.27 (14) | C6—C7—C2 | 122.3 (5) |
O1—Ni1—N3 | 88.57 (13) | N1—C8—C9 | 112.2 (4) |
O1i—Ni1—N3 | 91.43 (13) | C10—C9—C8 | 115.9 (4) |
N1—Ni1—N3 | 87.27 (14) | N2—C10—C9 | 112.3 (4) |
N1i—Ni1—N3 | 92.73 (14) | C16—C11—N2 | 109.6 (3) |
N3i—Ni1—N3 | 180.0 (2) | C16—C11—C12 | 111.2 (4) |
C1—N1—C8 | 115.8 (4) | N2—C11—C12 | 110.8 (3) |
C1—N1—Ni1 | 123.4 (3) | C11—C12—C13 | 110.6 (4) |
C8—N1—Ni1 | 120.7 (3) | C14—C13—C12 | 112.7 (5) |
C10—N2—C11 | 114.5 (3) | C13—C14—C15 | 110.7 (4) |
C17—N3—Ni1 | 154.8 (4) | C14—C15—C16 | 111.4 (4) |
C3—O1—Ni1 | 124.8 (3) | C11—C16—C15 | 111.9 (4) |
N1—C1—C2 | 127.4 (4) | N3—C17—S1 | 178.7 (4) |
Symmetry code: (i) −x+1, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···S1ii | 0.92 (1) | 2.43 (1) | 3.348 (4) | 171 (3) |
Symmetry code: (ii) −x+1, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | [Ni(C16H23N2O)2(NCS)2] |
Mr | 693.60 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 10.906 (7), 7.796 (5), 20.721 (13) |
β (°) | 97.131 (11) |
V (Å3) | 1748.0 (18) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.71 |
Crystal size (mm) | 0.24 × 0.22 × 0.17 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.847, 0.888 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8924, 3085, 1857 |
Rint | 0.050 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.145, 0.94 |
No. of reflections | 3085 |
No. of parameters | 209 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.48, −0.50 |
Computer programs: SMART (Siemens, 1996), SMART, SHELXTL (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···S1i | 0.922 (10) | 2.433 (12) | 3.348 (4) | 171 (3) |
Symmetry code: (i) −x+1, −y, −z. |
The title compound, (I), is a discrete electronically neutral centrosymmetric mononuclear nickel(II) complex (Fig. 1). The central Ni atom is in an octahedral geometry and coordinates to two Schiff base ligands and two thiocyanate groups. The Schiff base acts as a bidentate ligand and ligates to atom Ni1 through the phenolate O and imine N atoms. The thiocyanate anion is a monodentate ligand and coordinates to the metal via the N atom. The three diagonal angles for the nickel(II) octahedron are all 180°, and all the other angles around atom Ni1 are close to 90°, varying from 87.27 (14) to 92.73 (14)°, which indicates a slightly distorted octahedral geometry around the Ni atom. The Ni1—O1 (phenolate O atom) bond length of 2.030 (3) Å is comparable to the value of 2.013 (5) Å observed in a salicylaldehyde nickel(II) complex (Stewart et al., 1961). The Ni1—N1 bond distance of 2.078 (3) Å (imine N atom) is close to the value of 2.068 (3) Å observed in the complex [Ni2(tp)(pren)4(Him)2](ClO4)2 (Zhu et al., 2001), [where tp is terephthalate, pren is 1,3-diaminopropane and Him is imidazole]. The NCS angle of 178.7 (4)° in the coordinated thiocyanate anions is comparable to that observed in other nickel(II) complexes with NCS− anions.
In the crystal structure, the molecules are connected by intermolecular N2—H2···S1i hydrogen bonds (see Fig. 2 and Table 1) to form columns parallel to the b axis (Fig. 3). As expected, the cyclohexyl groups in the complex adopt chair conformations to minimize steric effects.