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In the neutral title complex, trans-bis(2,2'-imino­di­ethanol-N,O)­bis­(iso­thio­cyanato)­nickel(II), [Ni(NCS)2(C4H11NO2)2], the iso­thio­cyanate ions and the di­ethanol­amine mol­ecules act as mono­dentate and bi­dentate ligands, respectively. The NiII ion exhibits a distorted octahedral configuration with crystallographically imposed inversion symmetry and NNCS-Ni-Namine and NNCS-Ni-Oamine bond angles of 88.78 (10) and 89.44 (10)°, respectively. The Ni-N bond distances are in the range 2.069 (3)-2.096 (2) Å. The mol­ecules are linked by hydrogen bonds to form a three-dimensional infinite lattice.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100007289/bm1413sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100007289/bm1413Isup2.hkl
Contains datablock I

CCDC reference: 150318

Comment top

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).

Experimental top

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.

Refinement top

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).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The structure of the title complex with the atom-numbering scheme. Displacement ellipsoids are shown at the 50% probability level. H atoms are omitted for clarity. Symmetry code: (i) −x, 1 − y, 1 − z.
[Figure 2] Fig. 2. A view along the b direction showing hydrogen bonding. H atoms not involved in hydrogen bonding are omitted.
Bis(2,2\'-iminodiethanol)bis(isothiocyanato)nickel(II) top
Crystal data top
[Ni(SCN)2(C4H11NO2)2]Dx = 1.550 Mg m3
Mr = 385.15Melting point: 476 K
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 6.8157 (8) ÅCell parameters from 62 reflections
b = 8.3508 (10) Åθ = 4–12.5°
c = 14.725 (2) ŵ = 1.45 mm1
β = 100.119 (10)°T = 173 K
V = 825.08 (18) Å3Square prism, blue
Z = 20.30 × 0.16 × 0.14 mm
F(000) = 404
Data collection top
Siemens P4
diffractometer
1072 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.000
Graphite monochromatorθmax = 27.5°, θmin = 3.1°
ω–scansh = 77
Absorption correction: psi-scan
(XEMP; Siemens 1994a)
k = 1010
Tmin = 0.773, Tmax = 0.798l = 1818
1568 measured reflections3 standard reflections every 247 reflections
1568 independent reflections intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.071H 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 parametersΔρmax = 0.35 e Å3
0 restraintsΔρmin = 0.36 e Å3
Crystal data top
[Ni(SCN)2(C4H11NO2)2]V = 825.08 (18) Å3
Mr = 385.15Z = 2
Monoclinic, P21/nMo Kα radiation
a = 6.8157 (8) ŵ = 1.45 mm1
b = 8.3508 (10) ÅT = 173 K
c = 14.725 (2) Å0.30 × 0.16 × 0.14 mm
β = 100.119 (10)°
Data collection top
Siemens P4
diffractometer
1072 reflections with I > 2σ(I)
Absorption correction: psi-scan
(XEMP; Siemens 1994a)
Rint = 0.000
Tmin = 0.773, Tmax = 0.7983 standard reflections every 247 reflections
1568 measured reflections intensity decay: none
1568 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.071H atoms treated by a mixture of independent and constrained refinement
S = 0.93Δρmax = 0.35 e Å3
1568 reflectionsΔρmin = 0.36 e Å3
110 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.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ni10.00000.50000.50000.01420 (14)
S10.22997 (14)0.15137 (11)0.27554 (6)0.0283 (2)
O10.2858 (3)0.5809 (3)0.55181 (15)0.0193 (5)
H10.294 (6)0.606 (4)0.599 (3)0.033 (12)*
N20.0050 (4)0.6987 (3)0.41268 (16)0.0170 (6)
H20.036 (5)0.661 (3)0.364 (2)0.018 (8)*
N10.1135 (4)0.3647 (3)0.40347 (16)0.0201 (6)
C10.1627 (5)0.2782 (4)0.35009 (19)0.0170 (7)
C210.2004 (5)0.7761 (4)0.3828 (2)0.0208 (7)
H21A0.23930.83070.43660.025*
H21B0.30070.69170.36260.025*
C120.1540 (5)0.8078 (4)0.4576 (2)0.0225 (7)
H12A0.10850.86660.50850.027*
H12B0.18620.88700.41240.027*
C220.2075 (5)0.8970 (4)0.3053 (2)0.0246 (8)
H22A0.34340.94230.28940.030*
H22B0.11380.98580.32570.030*
C110.3379 (5)0.7089 (4)0.4952 (2)0.0239 (7)
H11A0.39510.66400.44340.029*
H11B0.43980.77810.53220.029*
O20.1544 (4)0.8212 (3)0.22578 (15)0.0344 (7)
H30.033 (6)0.805 (5)0.233 (3)0.044 (12)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0146 (3)0.0177 (3)0.0105 (2)0.0007 (3)0.00266 (19)0.0007 (3)
S10.0324 (5)0.0274 (5)0.0295 (4)0.0063 (4)0.0179 (4)0.0111 (4)
O10.0195 (12)0.0240 (13)0.0140 (10)0.0031 (11)0.0019 (10)0.0011 (9)
N20.0171 (14)0.0220 (15)0.0126 (11)0.0002 (13)0.0046 (11)0.0013 (10)
N10.0219 (15)0.0232 (15)0.0163 (12)0.0016 (13)0.0065 (11)0.0013 (11)
C10.0151 (15)0.0206 (17)0.0155 (13)0.0012 (14)0.0027 (12)0.0022 (13)
C210.0199 (16)0.0221 (18)0.0201 (14)0.0027 (15)0.0026 (13)0.0015 (13)
C120.0240 (18)0.0218 (18)0.0205 (14)0.0059 (16)0.0005 (14)0.0050 (13)
C220.0208 (18)0.0294 (19)0.0231 (15)0.0010 (16)0.0022 (14)0.0070 (14)
C110.0177 (16)0.0298 (19)0.0231 (15)0.0081 (16)0.0008 (13)0.0058 (14)
O20.0238 (14)0.0579 (19)0.0205 (11)0.0124 (14)0.0015 (11)0.0128 (11)
Geometric parameters (Å, º) top
Ni1—N12.069 (3)O1—C111.438 (4)
Ni1—N1i2.069 (3)N2—C211.476 (4)
Ni1—N22.096 (2)N2—C121.480 (4)
Ni1—O1i2.076 (2)N1—C11.159 (4)
Ni1—O12.076 (2)C21—C221.518 (4)
Ni1—N2i2.096 (2)C12—C111.522 (4)
S1—C11.647 (3)C22—O21.432 (4)
N1—Ni1—N1i180.00 (9)O1—Ni1—N2i96.84 (9)
N1—Ni1—N288.78 (10)N2—Ni1—N2i180.000 (1)
N1—Ni1—O1i90.56 (10)Ni1—O1—C11109.89 (18)
N1i—Ni1—O1i89.44 (10)C21—N2—C12114.5 (3)
N1—Ni1—O189.44 (10)Ni1—N2—C21116.5 (2)
N1i—Ni1—O190.56 (10)Ni1—N2—C12106.34 (18)
O1i—Ni1—O1180.0Ni1—N1—C1173.4 (3)
N1i—Ni1—N291.22 (10)N1—C1—S1178.5 (3)
O1i—Ni1—N296.84 (9)N2—C21—C22115.0 (3)
N2—Ni1—O183.16 (9)N2—C12—C11108.7 (3)
N1—Ni1—N2i91.22 (10)O2—C22—C21110.0 (3)
N1i—Ni1—N2i88.78 (10)O1—C11—C12110.0 (3)
O1i—Ni1—N2i83.16 (9)
N1—Ni1—O1—C1180.9 (2)N2i—Ni1—N2—C126 (100)
N1i—Ni1—O1—C1199.1 (2)N1i—Ni1—N1—C1117 (100)
O1i—Ni1—O1—C11104 (100)O1i—Ni1—N1—C133 (2)
N2—Ni1—O1—C118.0 (2)O1—Ni1—N1—C1147 (2)
N2i—Ni1—O1—C11172.0 (2)N2—Ni1—N1—C1130 (2)
N1—Ni1—N2—C21121.7 (2)N2i—Ni1—N1—C150 (2)
N1i—Ni1—N2—C2158.3 (2)Ni1—N1—C1—S126 (13)
O1i—Ni1—N2—C2131.3 (2)C12—N2—C21—C2266.8 (3)
O1—Ni1—N2—C21148.7 (2)Ni1—N2—C21—C22168.2 (2)
N2i—Ni1—N2—C21123 (100)C21—N2—C12—C11173.0 (2)
N1—Ni1—N2—C12109.3 (2)Ni1—N2—C12—C1142.9 (3)
N1i—Ni1—N2—C1270.7 (2)N2—C21—C22—O259.0 (4)
O1i—Ni1—N2—C12160.3 (2)Ni1—O1—C11—C1233.9 (3)
O1—Ni1—N2—C1219.7 (2)N2—C12—C11—O152.3 (3)
Symmetry code: (i) x, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O2ii0.72 (4)1.93 (4)2.651 (3)174 (5)
N2—H2···S1iii0.88 (3)2.81 (3)3.630 (3)156 (3)
O2—H3···S1iii0.83 (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]
Mr385.15
Crystal system, space groupMonoclinic, P21/n
Temperature (K)173
a, b, c (Å)6.8157 (8), 8.3508 (10), 14.725 (2)
β (°) 100.119 (10)
V3)825.08 (18)
Z2
Radiation typeMo Kα
µ (mm1)1.45
Crystal size (mm)0.30 × 0.16 × 0.14
Data collection
DiffractometerSiemens P4
diffractometer
Absorption correctionPsi-scan
(XEMP; Siemens 1994a)
Tmin, Tmax0.773, 0.798
No. of measured, independent and
observed [I > 2σ(I)] reflections
1568, 1568, 1072
Rint0.000
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.071, 0.93
No. of reflections1568
No. of parameters110
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.35, 0.36

Computer programs: XSCANS (Fait, 1991), XSCANS, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1994b), SHELXL97.

Selected geometric parameters (Å, º) top
Ni1—N12.069 (3)N2—C121.480 (4)
Ni1—N22.096 (2)N1—C11.159 (4)
Ni1—O12.076 (2)C21—C221.518 (4)
S1—C11.647 (3)C12—C111.522 (4)
O1—C111.438 (4)C22—O21.432 (4)
N2—C211.476 (4)
N1—Ni1—N288.78 (10)Ni1—N2—C12106.34 (18)
N1—Ni1—O189.44 (10)Ni1—N1—C1173.4 (3)
N2—Ni1—O183.16 (9)N1—C1—S1178.5 (3)
Ni1—O1—C11109.89 (18)O2—C22—C21110.0 (3)
C21—N2—C12114.5 (3)O1—C11—C12110.0 (3)
Ni1—N2—C21116.5 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O2i0.72 (4)1.93 (4)2.651 (3)174 (5)
N2—H2···S1ii0.88 (3)2.81 (3)3.630 (3)156 (3)
O2—H3···S1ii0.83 (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.
 

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