Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100007289/bm1413sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100007289/bm1413Isup2.hkl |
CCDC reference: 150318
Solid KSCN (1.94 g, 20 mmol) was added slowly and with continuous stirring to a solution of NiSO4·6H2O (2.63 g, 10 mmol) in distilled water (15 ml). Diethanolamine (2.10 g, 20 mmol) was dissolved in distilled water (20 ml) and the two solutions mixed and stirred for 2 h. A pale green polycrystalline precipitate was filtered off and blue crystals suitable for X-ray diffraction analysis were obtained by slow evaporation from the resulting solution at room temperature.
Hydrogen atoms bonded to O and N were identified from difference syntheses and refined freely. Other H were included using a riding model (Sheldrick, 1997). The crystal is a non-merohedral twin. The twin-matrix was determined as (100/010/3/401) and the refined value of −0.7592 rather than −0.75 was derived from XPREP using the equation c(new) = (2c cos β)/a − c(old) to obtain the exact cell parameters. Reflections with h = 4 and 8 show partial overlapping and are therefore omitted. Reflections with h = 0 are split into two components with a refined BASF value of 0.216 (4). The resulting data set was read using HKLF 5 (Sheldrick, 1997).
Data collection: XSCANS (Fait, 1991); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994b); software used to prepare material for publication: SHELXL97.
[Ni(SCN)2(C4H11NO2)2] | Dx = 1.550 Mg m−3 |
Mr = 385.15 | Melting point: 476 K |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 6.8157 (8) Å | Cell parameters from 62 reflections |
b = 8.3508 (10) Å | θ = 4–12.5° |
c = 14.725 (2) Å | µ = 1.45 mm−1 |
β = 100.119 (10)° | T = 173 K |
V = 825.08 (18) Å3 | Square prism, blue |
Z = 2 | 0.30 × 0.16 × 0.14 mm |
F(000) = 404 |
Siemens P4 diffractometer | 1072 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.000 |
Graphite monochromator | θmax = 27.5°, θmin = 3.1° |
ω–scans | h = −7→7 |
Absorption correction: psi-scan (XEMP; Siemens 1994a) | k = −10→10 |
Tmin = 0.773, Tmax = 0.798 | l = −18→18 |
1568 measured reflections | 3 standard reflections every 247 reflections |
1568 independent reflections | intensity decay: none |
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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.071 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.93 | w = 1/[σ2(Fo2) + (0.0316P)2] where P = (Fo2 + 2Fc2)/3 |
1568 reflections | (Δ/σ)max < 0.001 |
110 parameters | Δρmax = 0.35 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
[Ni(SCN)2(C4H11NO2)2] | V = 825.08 (18) Å3 |
Mr = 385.15 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.8157 (8) Å | µ = 1.45 mm−1 |
b = 8.3508 (10) Å | T = 173 K |
c = 14.725 (2) Å | 0.30 × 0.16 × 0.14 mm |
β = 100.119 (10)° |
Siemens P4 diffractometer | 1072 reflections with I > 2σ(I) |
Absorption correction: psi-scan (XEMP; Siemens 1994a) | Rint = 0.000 |
Tmin = 0.773, Tmax = 0.798 | 3 standard reflections every 247 reflections |
1568 measured reflections | intensity decay: none |
1568 independent reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.071 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.93 | Δρmax = 0.35 e Å−3 |
1568 reflections | Δρmin = −0.36 e Å−3 |
110 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. The crystal is a non-merohedral twin. The twin-matrix was determined as 1 0 0 0 − 1 0 − 0.75 0 − 1 and the refined value of −0.7592 was derived from XPREP using the equation c(new) = (2c cos β)/a − c(old) to obtain the exact cell parameters. Reflections with h = 4 and 8 show partial overlapping and are therefore omitted. Reflections with h = 0 are split into two components with a refined BASF value of 0.21564 (416). The complete refinement was performed using HKLF 5. |
x | y | z | Uiso*/Ueq | ||
Ni1 | 0.0000 | 0.5000 | 0.5000 | 0.01420 (14) | |
S1 | 0.22997 (14) | 0.15137 (11) | 0.27554 (6) | 0.0283 (2) | |
O1 | 0.2858 (3) | 0.5809 (3) | 0.55181 (15) | 0.0193 (5) | |
H1 | 0.294 (6) | 0.606 (4) | 0.599 (3) | 0.033 (12)* | |
N2 | −0.0050 (4) | 0.6987 (3) | 0.41268 (16) | 0.0170 (6) | |
H2 | 0.036 (5) | 0.661 (3) | 0.364 (2) | 0.018 (8)* | |
N1 | 0.1135 (4) | 0.3647 (3) | 0.40347 (16) | 0.0201 (6) | |
C1 | 0.1627 (5) | 0.2782 (4) | 0.35009 (19) | 0.0170 (7) | |
C21 | −0.2004 (5) | 0.7761 (4) | 0.3828 (2) | 0.0208 (7) | |
H21A | −0.2393 | 0.8307 | 0.4366 | 0.025* | |
H21B | −0.3007 | 0.6917 | 0.3626 | 0.025* | |
C12 | 0.1540 (5) | 0.8078 (4) | 0.4576 (2) | 0.0225 (7) | |
H12A | 0.1085 | 0.8666 | 0.5085 | 0.027* | |
H12B | 0.1862 | 0.8870 | 0.4124 | 0.027* | |
C22 | −0.2075 (5) | 0.8970 (4) | 0.3053 (2) | 0.0246 (8) | |
H22A | −0.3434 | 0.9423 | 0.2894 | 0.030* | |
H22B | −0.1138 | 0.9858 | 0.3257 | 0.030* | |
C11 | 0.3379 (5) | 0.7089 (4) | 0.4952 (2) | 0.0239 (7) | |
H11A | 0.3951 | 0.6640 | 0.4434 | 0.029* | |
H11B | 0.4398 | 0.7781 | 0.5322 | 0.029* | |
O2 | −0.1544 (4) | 0.8212 (3) | 0.22578 (15) | 0.0344 (7) | |
H3 | −0.033 (6) | 0.805 (5) | 0.233 (3) | 0.044 (12)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0146 (3) | 0.0177 (3) | 0.0105 (2) | −0.0007 (3) | 0.00266 (19) | −0.0007 (3) |
S1 | 0.0324 (5) | 0.0274 (5) | 0.0295 (4) | −0.0063 (4) | 0.0179 (4) | −0.0111 (4) |
O1 | 0.0195 (12) | 0.0240 (13) | 0.0140 (10) | −0.0031 (11) | 0.0019 (10) | 0.0011 (9) |
N2 | 0.0171 (14) | 0.0220 (15) | 0.0126 (11) | 0.0002 (13) | 0.0046 (11) | 0.0013 (10) |
N1 | 0.0219 (15) | 0.0232 (15) | 0.0163 (12) | −0.0016 (13) | 0.0065 (11) | 0.0013 (11) |
C1 | 0.0151 (15) | 0.0206 (17) | 0.0155 (13) | −0.0012 (14) | 0.0027 (12) | 0.0022 (13) |
C21 | 0.0199 (16) | 0.0221 (18) | 0.0201 (14) | 0.0027 (15) | 0.0026 (13) | 0.0015 (13) |
C12 | 0.0240 (18) | 0.0218 (18) | 0.0205 (14) | −0.0059 (16) | 0.0005 (14) | 0.0050 (13) |
C22 | 0.0208 (18) | 0.0294 (19) | 0.0231 (15) | 0.0010 (16) | 0.0022 (14) | 0.0070 (14) |
C11 | 0.0177 (16) | 0.0298 (19) | 0.0231 (15) | −0.0081 (16) | 0.0008 (13) | 0.0058 (14) |
O2 | 0.0238 (14) | 0.0579 (19) | 0.0205 (11) | 0.0124 (14) | 0.0015 (11) | 0.0128 (11) |
Ni1—N1 | 2.069 (3) | O1—C11 | 1.438 (4) |
Ni1—N1i | 2.069 (3) | N2—C21 | 1.476 (4) |
Ni1—N2 | 2.096 (2) | N2—C12 | 1.480 (4) |
Ni1—O1i | 2.076 (2) | N1—C1 | 1.159 (4) |
Ni1—O1 | 2.076 (2) | C21—C22 | 1.518 (4) |
Ni1—N2i | 2.096 (2) | C12—C11 | 1.522 (4) |
S1—C1 | 1.647 (3) | C22—O2 | 1.432 (4) |
N1—Ni1—N1i | 180.00 (9) | O1—Ni1—N2i | 96.84 (9) |
N1—Ni1—N2 | 88.78 (10) | N2—Ni1—N2i | 180.000 (1) |
N1—Ni1—O1i | 90.56 (10) | Ni1—O1—C11 | 109.89 (18) |
N1i—Ni1—O1i | 89.44 (10) | C21—N2—C12 | 114.5 (3) |
N1—Ni1—O1 | 89.44 (10) | Ni1—N2—C21 | 116.5 (2) |
N1i—Ni1—O1 | 90.56 (10) | Ni1—N2—C12 | 106.34 (18) |
O1i—Ni1—O1 | 180.0 | Ni1—N1—C1 | 173.4 (3) |
N1i—Ni1—N2 | 91.22 (10) | N1—C1—S1 | 178.5 (3) |
O1i—Ni1—N2 | 96.84 (9) | N2—C21—C22 | 115.0 (3) |
N2—Ni1—O1 | 83.16 (9) | N2—C12—C11 | 108.7 (3) |
N1—Ni1—N2i | 91.22 (10) | O2—C22—C21 | 110.0 (3) |
N1i—Ni1—N2i | 88.78 (10) | O1—C11—C12 | 110.0 (3) |
O1i—Ni1—N2i | 83.16 (9) | ||
N1—Ni1—O1—C11 | 80.9 (2) | N2i—Ni1—N2—C12 | 6 (100) |
N1i—Ni1—O1—C11 | −99.1 (2) | N1i—Ni1—N1—C1 | 117 (100) |
O1i—Ni1—O1—C11 | 104 (100) | O1i—Ni1—N1—C1 | −33 (2) |
N2—Ni1—O1—C11 | −8.0 (2) | O1—Ni1—N1—C1 | 147 (2) |
N2i—Ni1—O1—C11 | 172.0 (2) | N2—Ni1—N1—C1 | −130 (2) |
N1—Ni1—N2—C21 | 121.7 (2) | N2i—Ni1—N1—C1 | 50 (2) |
N1i—Ni1—N2—C21 | −58.3 (2) | Ni1—N1—C1—S1 | −26 (13) |
O1i—Ni1—N2—C21 | 31.3 (2) | C12—N2—C21—C22 | 66.8 (3) |
O1—Ni1—N2—C21 | −148.7 (2) | Ni1—N2—C21—C22 | −168.2 (2) |
N2i—Ni1—N2—C21 | −123 (100) | C21—N2—C12—C11 | 173.0 (2) |
N1—Ni1—N2—C12 | −109.3 (2) | Ni1—N2—C12—C11 | 42.9 (3) |
N1i—Ni1—N2—C12 | 70.7 (2) | N2—C21—C22—O2 | 59.0 (4) |
O1i—Ni1—N2—C12 | 160.3 (2) | Ni1—O1—C11—C12 | 33.9 (3) |
O1—Ni1—N2—C12 | −19.7 (2) | N2—C12—C11—O1 | −52.3 (3) |
Symmetry code: (i) −x, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2ii | 0.72 (4) | 1.93 (4) | 2.651 (3) | 174 (5) |
N2—H2···S1iii | 0.88 (3) | 2.81 (3) | 3.630 (3) | 156 (3) |
O2—H3···S1iii | 0.83 (4) | 2.45 (4) | 3.225 (3) | 156 (4) |
Symmetry codes: (ii) x+1/2, −y+3/2, z+1/2; (iii) −x+1/2, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Ni(SCN)2(C4H11NO2)2] |
Mr | 385.15 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 173 |
a, b, c (Å) | 6.8157 (8), 8.3508 (10), 14.725 (2) |
β (°) | 100.119 (10) |
V (Å3) | 825.08 (18) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.45 |
Crystal size (mm) | 0.30 × 0.16 × 0.14 |
Data collection | |
Diffractometer | Siemens P4 diffractometer |
Absorption correction | Psi-scan (XEMP; Siemens 1994a) |
Tmin, Tmax | 0.773, 0.798 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1568, 1568, 1072 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.071, 0.93 |
No. of reflections | 1568 |
No. of parameters | 110 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.35, −0.36 |
Computer programs: XSCANS (Fait, 1991), XSCANS, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1994b), SHELXL97.
Ni1—N1 | 2.069 (3) | N2—C12 | 1.480 (4) |
Ni1—N2 | 2.096 (2) | N1—C1 | 1.159 (4) |
Ni1—O1 | 2.076 (2) | C21—C22 | 1.518 (4) |
S1—C1 | 1.647 (3) | C12—C11 | 1.522 (4) |
O1—C11 | 1.438 (4) | C22—O2 | 1.432 (4) |
N2—C21 | 1.476 (4) | ||
N1—Ni1—N2 | 88.78 (10) | Ni1—N2—C12 | 106.34 (18) |
N1—Ni1—O1 | 89.44 (10) | Ni1—N1—C1 | 173.4 (3) |
N2—Ni1—O1 | 83.16 (9) | N1—C1—S1 | 178.5 (3) |
Ni1—O1—C11 | 109.89 (18) | O2—C22—C21 | 110.0 (3) |
C21—N2—C12 | 114.5 (3) | O1—C11—C12 | 110.0 (3) |
Ni1—N2—C21 | 116.5 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2i | 0.72 (4) | 1.93 (4) | 2.651 (3) | 174 (5) |
N2—H2···S1ii | 0.88 (3) | 2.81 (3) | 3.630 (3) | 156 (3) |
O2—H3···S1ii | 0.83 (4) | 2.45 (4) | 3.225 (3) | 156 (4) |
Symmetry codes: (i) x+1/2, −y+3/2, z+1/2; (ii) −x+1/2, y+1/2, −z+1/2. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- Purchase subscription
- Reduced-price subscriptions
- If you have already subscribed, you may need to register
As part of our study on the synthesis and spectral and thermal analysis of transition metal complexes of ethanolamines (İçbudak et al., 1995; Karada\-g & Yilmaz, 2000), we describe here the structure of the title complex, (I), resulting from the reaction of diethanolamine with KSCN and NiSO4.6 H2O. \sch
The NiII ion is octahedrally coordinated by the two mutually trans diethanolamine molecules and the two mutually trans isocyanate ions. Each diethanolamine acts as bidentate donor, through one N atom and one O atom (O1); the other ethanolic group containing O2 does not participate in coordination. The coordinating N and O atoms of diethanolamine are positioned in the equatorial plane of the octahedron, while the monodentate isothiocyanate ions occupy the axial positions (Fig. 1). The Ni—Namine bonds [2.096 (3) Å] are somewhat longer than the Ni—N isothiocyanate bonds [2.069 (3) Å] and these Ni—N bond distances are comparable with the those found in the monoethanolamine analogous to the NiII complex [2.085 (5) and 2.065 (5) Å, respectively (Hursthouse et al., 1990)]. The Ni—O distances in the title complex are 2.076 (2) Å and also comparable with those in related di- and triethanolamine complexes of NiII reported by Hursthouse et al.(1990) and İçbudak et al. (1995) of 2.094 (4) and 2.068 (1) Å, respectively.
The Nisothiocyanate—Ni—Namine, Nisothiocyanate—Ni—O and N amine—Ni—O bond angles of 91.22 (10), 89.44 (10) and 83.16 (9)°, respectively, indicate significant distortion from ideally octahedral of the coordination geometry around NiII.
The NCS groups are almost linear, but significant bending is observed in the Ni—N—C(—S) linkage [Ni—N1—C1, 173.4 (3)]. The NCS, NH and free OH groups are involved in intermolecular hydrogen bonding. The H atoms of the NH and uncoordinated OH groups form hydrogen bonds with the S atom of adjacent molecules and the H atoms of coordinated OH groups also participate in hydrogen bonding with the H atom of the free OH groups of other molecules. The individual molecules are thus linked by hydrogen bonds to form a three-dimensional infinite network, part of which is shown in Fig. 2. Similar hydrogen bonding has been reported for other ethanolamine compounds (Yilmaz et al., 1996; Yilmaz et al., 1997).