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Acta Cryst. (2007). E63, m2628    [ doi:10.1107/S1600536807046648 ]

Aqua(hexamethylenetetramine-[kappa]N)bis(methanol)bis(thiocyanato-[kappa]N)nickel(II)

Y. Bai, W.-L. Shang, F.-L. Zhang, X.-J. Pan and X.-F. Niu

Abstract top

The Ni atom in the title complex, [Ni(SCN)2(C6H14N4)(CH4O)2(H2O)], is six-coordinate in a slightly distorted octahedral environment. The hexamethylenetetramine ligand binds to the Ni atom through only one of its N atoms, trans to the coordinated water molecule. The thiocyanate and methanol ligands are also mutually trans. In the crystal structure, complex molecules are linked by four different kinds of hydrogen bonds (O-H...S, O-H...N, C-H...N and C-H...O) to form a three-dimensional network structure.

Comment top

During the past decade, the self-assembly of transition metal ions and organic molecules has become a powerful methodology for the construction of different supramolecular architectures with unusual and interesting properties either by strong metal-ligand bonding or by weaker bonding forces such as hydrogen bonding and π—π interactions (Guo, et al., 2002; Kumar, Das et al., 2007; Venkateswaran et al., 2007). Among the ligands, hexamethylenetetramine (hmt) as a potential tetradentate ligand or hydrogen bond acceptor seems quite suitable in self-assembly systems. Several groups have reported that Co(II), Mn(II) or Ni(II) complexes with hmt and SCN− as ligands form two- or three-dimensional networks (Liu et al., 2006; Zhang et al., 1999; Meng et al., 2001; Li et al., 2002). Herein, we present a new hmt complex, (I), of nickel(II) with SCN−, Fig 1. The title complex, which contains one nickel center, one hmt, two NCS−, two coordinated methanol molecules and one coordinated water molecule, forms a mononuclear complex (Fig.1). The Ni2+ atom has a distorted octahedral coordination geometry. The N atom of hmt and the O atom of the water molecule, the N atoms of the two isothiocyanates and the O atoms of both methanol molecules are each mutually trans to each other. Intramolecular C—H···N and C—H···O hydrogen bonds (Table 2) are important factors in the stabilization of the molecule.

In the crystal structure, molecules interact with each other, forming a three-dimensional supramolecular network through multiform intermolecular hydrogen bonds (Fig. 2 and Table 1). The O1, O2 and O1w atoms form three O—H···N hydrogen bonds with the N6, N4 and N5 atoms of the adjacent hmt ligand, respectively. In addition, an O1w—H···S2 hydrogen bond is also found in the solid state.

Related literature top

For information on the self-assembly of transition-metal complexes see Guo et al. (2002); Kumar et al. (2007); Venkateswaran et al. (2007). For complexes of the hexamethylenetetramine (hmt) ligand see Liu et al. (2006); Zhang et al. (1999); Meng et al. (2001); Li et al. (2002).

Experimental top

All chemicals were of reagent grade quality obtained from commercial sources and used without further purification. The hexamethylenetetramine (0.50 mmol, 0.07 g), KSCN (2 mmol, 0.19 g) and NiCl2·6H2O (0.50 mmol, 0.12 g) were mixed in methanol (25 ml). The green solution was left for several weeks at room temperature to afford green crystals (yield 68%).

Refinement top

All H-atoms were positioned geometrically and refined using a riding model with d(C—H) = 0.97 Å, Uiso = 1.2Ueq (C) for CH2, 0.96 Å, Uiso = 1.5Ueq (C) for CH3 atoms and 0.85 Å, Uiso = 1.2Ueq (O) for the OH groups.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL (Bruker, 2000); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title complex, with displacement ellipsoids drawn at the 50% probability level. The hydrogen atoms are omitted for clarity.
[Figure 2] Fig. 2. Perspective view of the three-dimensional showing the intermolecular hydrogen bonds as dashed lines.
Aqua(hexamethylenetetramine-κN)bis(methanol)bis(thiocyanato-κN)nickel(II) top
Crystal data top
[Ni(SCN)2(C6H14N4)(CH4O)2(H2O)]F000 = 1664
Mr = 397.17Dx = 1.527 Mg m−3
Orthorhombic, PbcaMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 5794 reflections
a = 14.069 (3) Åθ = 2.3–27.0º
b = 15.312 (3) ŵ = 1.38 mm−1
c = 16.036 (3) ÅT = 293 (2) K
V = 3454.6 (12) Å3Block, green
Z = 80.25 × 0.20 × 0.20 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		3102 reflections with I > 2σ(I)
Radiation source: sealed tubeRint = 0.037
Monochromator: graphiteθmax = 27.5º
T = 293(2) Kθmin = 2.3º
φ and ω scansh = −17→18
Absorption correction: nonek = −19→19
20196 measured reflectionsl = −15→20
3954 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.031H-atom parameters constrained
wR(F2) = 0.077  w = 1/[σ2(Fo2) + (0.0346P)2 + 1.4403P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.002
3954 reflectionsΔρmax = 0.63 e Å−3
201 parametersΔρmin = −0.53 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Ni(SCN)2(C6H14N4)(CH4O)2(H2O)]V = 3454.6 (12) Å3
Mr = 397.17Z = 8
Orthorhombic, PbcaMo Kα
a = 14.069 (3) ŵ = 1.38 mm−1
b = 15.312 (3) ÅT = 293 (2) K
c = 16.036 (3) Å0.25 × 0.20 × 0.20 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		3954 independent reflections
Absorption correction: none3102 reflections with I > 2σ(I)
20196 measured reflectionsRint = 0.037
Refinement top
R[F2 > 2σ(F2)] = 0.031201 parameters
wR(F2) = 0.077H-atom parameters constrained
S = 1.02Δρmax = 0.63 e Å−3
3954 reflectionsΔρmin = −0.53 e Å−3
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ni11.051115 (17)1.037270 (16)0.284126 (16)0.02737 (9)
N11.15174 (12)0.97450 (11)0.35135 (12)0.0348 (4)
C11.21094 (14)0.94091 (13)0.38983 (13)0.0298 (4)
S11.29502 (5)0.89385 (4)0.44312 (5)0.0560 (2)
N20.95730 (13)1.10636 (13)0.21696 (12)0.0379 (4)
C20.90475 (15)1.14612 (13)0.17719 (13)0.0308 (4)
S20.83037 (4)1.20509 (4)0.12261 (4)0.04665 (16)
N30.94070 (11)0.94372 (10)0.32743 (10)0.0248 (3)
N40.88319 (12)0.86786 (11)0.45339 (11)0.0319 (4)
N50.88039 (12)0.79295 (11)0.31899 (10)0.0307 (4)
N60.77062 (11)0.91318 (11)0.34617 (11)0.0294 (4)
C30.95225 (14)0.93031 (14)0.41893 (12)0.0301 (4)
H3A1.01600.90920.42990.036*
H3B0.94500.98600.44710.036*
C40.89509 (16)0.78346 (14)0.40984 (13)0.0353 (5)
H4A0.95850.76110.42020.042*
H4B0.84980.74160.43180.042*
C50.78700 (15)0.90098 (15)0.43675 (13)0.0346 (5)
H5A0.77840.95630.46520.042*
H5B0.74060.86010.45860.042*
C60.78424 (15)0.82792 (14)0.30448 (14)0.0338 (5)
H6A0.73760.78670.32530.041*
H6B0.77400.83470.24500.041*
C70.94994 (14)0.85635 (13)0.28606 (13)0.0290 (4)
H7A0.94040.86300.22650.035*
H7B1.01370.83410.29480.035*
C80.84141 (13)0.97490 (13)0.31293 (13)0.0284 (4)
H8A0.83301.03130.33950.034*
H8B0.83110.98240.25350.034*
O11.08313 (10)0.95834 (10)0.18127 (9)0.0344 (3)
H1A1.14300.95110.17960.041*
C91.05023 (17)0.9745 (2)0.09820 (15)0.0551 (7)
H9A1.07260.92910.06190.083*
H9B1.07401.02980.07930.083*
H9C0.98200.97540.09770.083*
O21.02424 (11)1.12126 (9)0.38967 (9)0.0396 (4)
H2A1.07081.12180.42340.048*
C100.9735 (3)1.20139 (19)0.39099 (19)0.0753 (10)
H10A0.92961.20130.43690.113*
H10B0.93901.20810.33970.113*
H10C1.01731.24890.39730.113*
O1W1.15882 (11)1.12462 (9)0.24620 (10)0.0408 (4)
H1WB1.19521.13610.28710.049*
H1WD1.13431.17210.22920.049*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.02452 (14)0.02876 (15)0.02882 (15)0.00163 (10)−0.00440 (10)0.00596 (10)
N10.0296 (10)0.0369 (10)0.0378 (10)0.0010 (8)−0.0052 (8)0.0060 (8)
C10.0302 (11)0.0277 (10)0.0315 (11)−0.0021 (8)−0.0029 (9)−0.0016 (8)
S10.0549 (4)0.0463 (4)0.0668 (5)0.0131 (3)−0.0356 (3)−0.0032 (3)
N20.0335 (10)0.0405 (10)0.0398 (11)0.0044 (8)−0.0047 (8)0.0108 (8)
C20.0303 (11)0.0308 (11)0.0313 (11)0.0006 (9)−0.0006 (9)0.0019 (9)
S20.0430 (3)0.0513 (4)0.0457 (4)0.0130 (3)−0.0128 (3)0.0088 (3)
N30.0241 (8)0.0275 (8)0.0228 (8)0.0004 (6)−0.0025 (6)0.0015 (6)
N40.0333 (10)0.0356 (10)0.0269 (9)−0.0019 (7)0.0003 (7)0.0042 (7)
N50.0342 (10)0.0263 (9)0.0318 (9)−0.0009 (7)0.0025 (7)−0.0004 (7)
N60.0247 (9)0.0318 (9)0.0318 (9)−0.0007 (7)0.0004 (7)−0.0013 (7)
C30.0296 (11)0.0368 (11)0.0239 (10)−0.0031 (9)−0.0032 (8)0.0019 (8)
C40.0357 (12)0.0318 (11)0.0385 (12)0.0014 (9)0.0007 (9)0.0079 (9)
C50.0303 (11)0.0443 (13)0.0294 (11)0.0001 (9)0.0062 (9)−0.0017 (9)
C60.0310 (11)0.0348 (11)0.0356 (12)−0.0055 (9)−0.0019 (9)−0.0024 (9)
C70.0296 (10)0.0289 (10)0.0285 (10)0.0022 (8)0.0041 (8)−0.0016 (8)
C80.0250 (10)0.0297 (10)0.0307 (10)0.0021 (8)−0.0025 (8)0.0006 (8)
O10.0246 (7)0.0492 (9)0.0292 (8)−0.0004 (6)−0.0002 (6)0.0020 (7)
C90.0417 (15)0.091 (2)0.0326 (13)0.0067 (14)−0.0027 (10)−0.0001 (13)
O20.0487 (9)0.0349 (8)0.0352 (9)0.0078 (7)−0.0121 (7)−0.0017 (7)
C100.115 (3)0.0549 (18)0.0561 (18)0.0408 (18)−0.0207 (18)−0.0111 (14)
O1W0.0380 (9)0.0340 (8)0.0504 (10)−0.0035 (7)−0.0073 (7)0.0114 (7)
Geometric parameters (Å, °) top
Ni1—N22.005 (2)C3—H3B0.9700
Ni1—N12.022 (2)C4—H4A0.9700
Ni1—O12.094 (2)C4—H4B0.9700
Ni1—O1W2.111 (2)C5—H5A0.9700
Ni1—O22.159 (2)C5—H5B0.9700
Ni1—N32.224 (2)C6—H6A0.9700
N1—C11.157 (3)C6—H6B0.9700
C1—S11.627 (2)C7—H7A0.9700
N2—C21.151 (3)C7—H7B0.9700
C2—S21.636 (2)C8—H8A0.9700
N3—C31.490 (2)C8—H8B0.9700
N3—C81.494 (2)O1—C91.432 (3)
N3—C71.499 (2)O1—H1A0.8500
N4—C51.470 (3)C9—H9A0.9600
N4—C31.471 (3)C9—H9B0.9600
N4—C41.479 (3)C9—H9C0.9600
N5—C61.473 (3)O2—C101.420 (3)
N5—C71.476 (3)O2—H2A0.8500
N5—C41.479 (3)C10—H10A0.9600
N6—C81.473 (2)C10—H10B0.9600
N6—C61.479 (3)C10—H10C0.9600
N6—C51.482 (3)O1W—H1WB0.8500
C3—H3A0.9700O1W—H1WD0.8500
N2—Ni1—N1176.16 (7)N4—C5—N6111.39 (16)
N2—Ni1—O191.32 (7)N4—C5—H5A109.4
N1—Ni1—O189.71 (7)N6—C5—H5A109.4
N2—Ni1—O1W89.05 (7)N4—C5—H5B109.4
N1—Ni1—O1W87.26 (7)N6—C5—H5B109.4
O1—Ni1—O1W89.10 (6)H5A—C5—H5B108.0
N2—Ni1—O289.51 (7)N5—C6—N6111.62 (16)
N1—Ni1—O289.31 (7)N5—C6—H6A109.3
O1—Ni1—O2177.47 (6)N6—C6—H6A109.3
O1W—Ni1—O288.52 (6)N5—C6—H6B109.3
N2—Ni1—N392.74 (7)N6—C6—H6B109.3
N1—Ni1—N390.94 (7)H6A—C6—H6B108.0
O1—Ni1—N391.40 (6)N5—C7—N3111.79 (15)
O1W—Ni1—N3178.13 (6)N5—C7—H7A109.3
O2—Ni1—N390.95 (6)N3—C7—H7A109.3
C1—N1—Ni1177.90 (17)N5—C7—H7B109.3
N1—C1—S1179.4 (2)N3—C7—H7B109.3
C2—N2—Ni1178.66 (19)H7A—C7—H7B107.9
N2—C2—S2178.3 (2)N6—C8—N3111.76 (15)
C3—N3—C8107.41 (15)N6—C8—H8A109.3
C3—N3—C7107.66 (15)N3—C8—H8A109.3
C8—N3—C7107.29 (15)N6—C8—H8B109.3
C3—N3—Ni1108.66 (11)N3—C8—H8B109.3
C8—N3—Ni1113.48 (11)H8A—C8—H8B107.9
C7—N3—Ni1112.09 (11)C9—O1—Ni1124.31 (15)
C5—N4—C3108.40 (16)C9—O1—H1A108.3
C5—N4—C4108.67 (17)Ni1—O1—H1A108.3
C3—N4—C4108.42 (16)O1—C9—H9A109.5
C6—N5—C7108.24 (16)O1—C9—H9B109.5
C6—N5—C4108.65 (16)H9A—C9—H9B109.5
C7—N5—C4108.93 (16)O1—C9—H9C109.5
C8—N6—C6108.37 (16)H9A—C9—H9C109.5
C8—N6—C5109.29 (16)H9B—C9—H9C109.5
C6—N6—C5108.14 (16)C10—O2—Ni1127.92 (15)
N4—C3—N3112.79 (16)C10—O2—H2A111.7
N4—C3—H3A109.0Ni1—O2—H2A111.7
N3—C3—H3A109.0O2—C10—H10A109.5
N4—C3—H3B109.0O2—C10—H10B109.5
N3—C3—H3B109.0H10A—C10—H10B109.5
H3A—C3—H3B107.8O2—C10—H10C109.5
N5—C4—N4111.32 (16)H10A—C10—H10C109.5
N5—C4—H4A109.4H10B—C10—H10C109.5
N4—C4—H4A109.4Ni1—O1W—H1WB109.9
N5—C4—H4B109.4Ni1—O1W—H1WD110.0
N4—C4—H4B109.4H1WB—O1W—H1WD108.3
H4A—C4—H4B108.0
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WB···S2i0.852.613.431 (2)162
O1—H1A···N6i0.851.932.762 (2)165
O1W—H1WD···N5ii0.852.022.836 (2)162
O2—H2A···N4iii0.852.092.839 (2)148
C3—H3A···N10.972.503.084 (3)119
C3—H3B···O20.972.533.130 (3)120
C7—H7A···O10.972.592.962 (3)103
C10—H10B···N20.962.523.156 (4)123
Symmetry codes: (i) x+1/2, y, −z+1/2; (ii) −x+2, y+1/2, −z+1/2; (iii) −x+2, −y+2, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WB···S2i0.852.613.431 (2)162
O1—H1A···N6i0.851.932.762 (2)165
O1W—H1WD···N5ii0.852.022.836 (2)162
O2—H2A···N4iii0.852.092.839 (2)148
C3—H3A···N10.972.503.084 (3)119
C3—H3B···O20.972.533.130 (3)120
C7—H7A···O10.972.592.962 (3)103
C10—H10B···N20.962.523.156 (4)123
Symmetry codes: (i) x+1/2, y, −z+1/2; (ii) −x+2, y+1/2, −z+1/2; (iii) −x+2, −y+2, −z+1.
Acknowledgements top

We are grateful for financial support from the Natural Science Foundation of Henan Province and the Education Department of Henan Province.

references
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