(IUCr) Crystallography Journals Online

Abstract top

The title compound, [Ni(C₆H₁₅NO₃)₂]SO₄, contains two triethanolamine (TEA) ligands bound to an Ni²⁺ metal centre, which lies on a crystallographic inversion centre, and one sulfate anion located on a twofold rotation axis such that the asymmetric unit contains one-half molecule of the cation and of the anion. The triethanolamine ligands coordinate via each axial N atom and two of the three O atoms, while the third arm of the ligand has the hydroxyl group pointing away from the metal centre. The sulfate anions are hydrogen bonded to the coordinated hydroxyl groups and also to the free arm, forming a two-dimensional supramolecular hydrogen-bonded network expanding parallel to (010).

Comment top

Many workers from a variety of scientific disciplines are interested in the crystal design and engineering of multidimensional arrays and networks containing metal ions as nodes. Metal-ion containing supramolecular structures can be used as zeolite-like materials (Venkataraman et al., 1995; Kepert & Rosseinsky, 1999), catalysts (Fujita et al., 1994) or magnetic materials (Kahn, 1993). Triethanolamine (TEA) is a good potential ligand to the incorporation of metals into metal-ion containing supramolecular framework, and many compounds constructed from TEA have been reported in the last decade (Krabbes et al., 2000; Topcu et al., 2001; Ucar et al., 2004; Haukka et al., 2005). In this work we employed TEA and NiSO₄ to produce a novel complex, [Ni(C₆H₁₅NO₃)₂]SO₄(I).

A view of the title compound and its numbering scheme are shown in Fig. 1. The crystal structure consists of a complex cation and one sulfate anion. In the cation, the Ni^II ion lies on a centre of symmetry, sandwiched by two bulky TEA ligands. Each TEA acts as a tridentate ligand through two of the three hydroxyl O atoms and the amine N atom, resulting in a six-coordinate Ni^II ion similar to those observed for the Ni complex of TEA with chloride (İçbudak et al., 1995), saccharine (Topcu et al., 2001), acetate (Krabbes et al., 2000) and squarate (Yeşilel et al., 2004).

The coordination geometry around the Ni^II ion is that of a distorted octahedron. The hydroxyl O atoms of two TEA ligands form the equatorial plane of the octahedral geometry, while atoms N1 and N1ⁱ are placed in axial positions (symmetry code as in Fig. 1). In the complex, Ni—O distances are in the range 2.0762 (13)–2.0768 (12)Å and the Ni—N distance is 2.1072 (16) Å, while the bond angles at Ni range from 82.30 (5)° to 97.70 (6)°.

In the crystal structure, classical intermolecular O—H···O hydrogen bonds are observed (Table 1), which link the cations and one sulfate anion into a two-dimensional hydrogen-bonded network and stabilize the crystal packing (Fig. 2). Each cation is bonded to four SO₄^2- anions, which in turn link four cations through O—H···O hydrogen bonding interactions to form a 2-D hydrogen bonding network. In addition, there is extensive hydrogen bonding between the –CH₂ and the uncoordinated hydroxyl O atoms, with C···O interatomic distances of 3.055 (3) Å.

Bis(triethanolamine)nickel(II) sulfate top

Crystal data top

[Ni(C₆H₁₅NO₃)₂]SO₄	F(000) = 960
M_r = 453.15	D_x = 1.676 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 8633 reflections
a = 10.316 (2) Å	θ = 3.6–27.5°
b = 11.234 (2) Å	µ = 1.25 mm⁻¹
c = 15.498 (3) Å	T = 293 K
β = 90.04 (3)°	Block, blue
V = 1796.0 (6) Å³	0.41 × 0.21 × 0.11 mm
Z = 4

Data collection top

Siemens SMART CCD area-detector diffractometer	2042 independent reflections
Radiation source: fine-focus sealed tube	1905 reflections with I > 2σ(I)
graphite	R_int = 0.029
ω scans	θ_max = 27.5°, θ_min = 3.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
T_min = 0.741, T_max = 0.879	k = −14→14
8633 measured reflections	l = −20→18

Refinement top

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.085	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.053P)² + 2.3273P] where P = (F_o² + 2F_c²)/3
2042 reflections	(Δ/σ)_max < 0.001
120 parameters	Δρ_max = 0.66 e Å⁻³
3 restraints	Δρ_min = −0.65 e Å⁻³

Crystal data top

[Ni(C₆H₁₅NO₃)₂]SO₄	V = 1796.0 (6) Å³
M_r = 453.15	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 10.316 (2) Å	µ = 1.25 mm⁻¹
b = 11.234 (2) Å	T = 293 K
c = 15.498 (3) Å	0.41 × 0.21 × 0.11 mm
β = 90.04 (3)°

Data collection top

Siemens SMART CCD area-detector diffractometer	2042 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1905 reflections with I > 2σ(I)
T_min = 0.741, T_max = 0.879	R_int = 0.029
8633 measured reflections	θ_max = 27.5°

Refinement top

R[F² > 2σ(F²)] = 0.030	H-atom parameters constrained
wR(F²) = 0.085	Δρ_max = 0.66 e Å⁻³
S = 1.02	Δρ_min = −0.65 e Å⁻³
2042 reflections	Absolute structure: ?
120 parameters	Flack parameter: ?
3 restraints	Rogers parameter: ?

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.

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 (Å²) top

	x	y	z	U_iso*/U_eq
Ni1	0.2500	0.7500	1.0000	0.01765 (12)
N1	0.40821 (14)	0.71956 (14)	0.91696 (9)	0.0218 (3)
O1	0.15355 (12)	0.64708 (12)	0.90906 (8)	0.0255 (3)
H1C	0.0790	0.6254	0.8997	0.038*
O2	0.22752 (12)	0.90445 (11)	0.92788 (8)	0.0242 (3)
H2C	0.1762	0.9553	0.9113	0.036*
O3	0.70194 (16)	0.79446 (17)	0.87607 (13)	0.0512 (5)
H3C	0.7766	0.7847	0.8594	0.077*
O4	0.89097 (13)	0.89514 (14)	0.72175 (9)	0.0351 (3)
O5	0.95708 (14)	0.74424 (13)	0.82252 (10)	0.0337 (3)
C1	0.37671 (18)	0.60337 (18)	0.87593 (13)	0.0303 (4)
H1A	0.3897	0.5400	0.9176	0.036*
H1B	0.4354	0.5898	0.8281	0.036*
C2	0.23847 (19)	0.59917 (19)	0.84339 (12)	0.0317 (4)
H2A	0.2307	0.6456	0.7909	0.038*
H2B	0.2143	0.5176	0.8305	0.038*
C3	0.40912 (18)	0.81992 (18)	0.85289 (12)	0.0293 (4)
H3A	0.3573	0.7986	0.8030	0.035*
H3B	0.4971	0.8347	0.8337	0.035*
C4	0.35485 (18)	0.93041 (17)	0.89416 (12)	0.0288 (4)
H4A	0.4114	0.9565	0.9405	0.035*
H4B	0.3493	0.9938	0.8518	0.035*
C5	0.53313 (17)	0.71242 (18)	0.96482 (12)	0.0265 (4)
H5A	0.5251	0.6503	1.0080	0.032*
H5B	0.5454	0.7870	0.9953	0.032*
C6	0.65530 (18)	0.68791 (18)	0.91236 (14)	0.0321 (4)
H6A	0.7212	0.6534	0.9493	0.039*
H6B	0.6360	0.6314	0.8668	0.039*
S1	1.0000	0.82070 (6)	0.7500	0.02289 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.01652 (17)	0.02186 (18)	0.01456 (17)	0.00161 (10)	0.00033 (11)	0.00006 (10)
N1	0.0191 (7)	0.0284 (7)	0.0179 (7)	0.0031 (6)	0.0008 (5)	0.0003 (6)
O1	0.0212 (6)	0.0335 (7)	0.0218 (6)	−0.0002 (5)	−0.0017 (5)	−0.0050 (5)
O2	0.0245 (6)	0.0257 (6)	0.0225 (6)	0.0044 (5)	−0.0008 (5)	0.0038 (5)
O3	0.0272 (8)	0.0572 (10)	0.0693 (12)	0.0037 (7)	0.0176 (8)	0.0185 (9)
O4	0.0287 (7)	0.0462 (8)	0.0303 (7)	0.0102 (6)	−0.0100 (6)	−0.0027 (6)
O5	0.0230 (7)	0.0524 (9)	0.0258 (7)	−0.0012 (5)	0.0023 (6)	0.0106 (6)
C1	0.0275 (9)	0.0335 (10)	0.0299 (9)	0.0064 (7)	0.0008 (7)	−0.0095 (8)
C2	0.0300 (10)	0.0393 (10)	0.0259 (9)	0.0030 (8)	−0.0013 (7)	−0.0127 (8)
C3	0.0249 (9)	0.0428 (11)	0.0201 (8)	0.0031 (7)	0.0028 (7)	0.0069 (7)
C4	0.0265 (9)	0.0304 (9)	0.0294 (9)	−0.0040 (7)	−0.0016 (7)	0.0081 (7)
C5	0.0208 (8)	0.0364 (9)	0.0223 (8)	0.0031 (7)	−0.0005 (7)	0.0024 (7)
C6	0.0221 (9)	0.0359 (10)	0.0383 (10)	0.0063 (7)	0.0015 (7)	−0.0019 (8)
S1	0.0172 (3)	0.0350 (3)	0.0165 (3)	0.000	−0.0021 (2)	0.000

Geometric parameters (Å, °) top

Ni1—O1ⁱ	2.0762 (13)	C1—C2	1.513 (3)
Ni1—O1	2.0762 (13)	C1—H1A	0.9700
Ni1—O2ⁱ	2.0768 (12)	C1—H1B	0.9700
Ni1—O2	2.0768 (12)	C2—H2A	0.9700
Ni1—N1	2.1072 (16)	C2—H2B	0.9700
Ni1—N1ⁱ	2.1072 (16)	C3—C4	1.505 (3)
N1—C1	1.488 (2)	C3—H3A	0.9700
N1—C5	1.489 (2)	C3—H3B	0.9700
N1—C3	1.502 (2)	C4—H4A	0.9700
O1—C2	1.447 (2)	C4—H4B	0.9700
O1—H1C	0.8200	C5—C6	1.525 (3)
O2—C4	1.444 (2)	C5—H5A	0.9700
O2—H2C	0.8200	C5—H5B	0.9700
O3—C6	1.407 (3)	C6—H6A	0.9700
O3—H3C	0.8200	C6—H6B	0.9700
O4—S1	1.4681 (14)	S1—O4ⁱⁱ	1.4681 (14)
O5—S1	1.4825 (14)	S1—O5ⁱⁱ	1.4825 (14)

O1ⁱ—Ni1—O1	180.0	O1—C2—H2A	109.9
O1ⁱ—Ni1—O2ⁱ	92.68 (5)	C1—C2—H2A	109.9
O1—Ni1—O2ⁱ	87.32 (5)	O1—C2—H2B	109.9
O1ⁱ—Ni1—O2	87.32 (5)	C1—C2—H2B	109.9
O1—Ni1—O2	92.68 (5)	H2A—C2—H2B	108.3
O2ⁱ—Ni1—O2	180.0	N1—C3—C4	109.61 (14)
O1ⁱ—Ni1—N1	97.70 (6)	N1—C3—H3A	109.7
O1—Ni1—N1	82.30 (5)	C4—C3—H3A	109.7
O2ⁱ—Ni1—N1	96.14 (5)	N1—C3—H3B	109.7
O2—Ni1—N1	83.86 (6)	C4—C3—H3B	109.7
O1ⁱ—Ni1—N1ⁱ	82.30 (5)	H3A—C3—H3B	108.2
O1—Ni1—N1ⁱ	97.70 (6)	O2—C4—C3	109.04 (15)
O2ⁱ—Ni1—N1ⁱ	83.86 (6)	O2—C4—H4A	109.9
O2—Ni1—N1ⁱ	96.14 (5)	C3—C4—H4A	109.9
N1—Ni1—N1ⁱ	180.0	O2—C4—H4B	109.9
C1—N1—C5	110.76 (15)	C3—C4—H4B	109.9
C1—N1—C3	112.18 (14)	H4A—C4—H4B	108.3
C5—N1—C3	111.34 (15)	N1—C5—C6	117.35 (15)
C1—N1—Ni1	103.56 (11)	N1—C5—H5A	108.0
C5—N1—Ni1	112.02 (11)	C6—C5—H5A	108.0
C3—N1—Ni1	106.69 (11)	N1—C5—H5B	108.0
C2—O1—Ni1	113.23 (10)	C6—C5—H5B	108.0
C2—O1—H1C	109.5	H5A—C5—H5B	107.2
Ni1—O1—H1C	137.3	O3—C6—C5	110.01 (16)
C4—O2—Ni1	105.21 (10)	O3—C6—H6A	109.7
C4—O2—H2C	109.5	C5—C6—H6A	109.7
Ni1—O2—H2C	145.3	O3—C6—H6B	109.7
C6—O3—H3C	109.5	C5—C6—H6B	109.7
N1—C1—C2	112.04 (15)	H6A—C6—H6B	108.2
N1—C1—H1A	109.2	O4ⁱⁱ—S1—O4	110.56 (13)
C2—C1—H1A	109.2	O4ⁱⁱ—S1—O5	109.46 (8)
N1—C1—H1B	109.2	O4—S1—O5	109.09 (9)
C2—C1—H1B	109.2	O4ⁱⁱ—S1—O5ⁱⁱ	109.09 (9)
H1A—C1—H1B	107.9	O4—S1—O5ⁱⁱ	109.46 (8)
O1—C2—C1	108.96 (15)	O5—S1—O5ⁱⁱ	109.18 (13)

O1ⁱ—Ni1—N1—C1	152.13 (11)	O1ⁱ—Ni1—O2—C4	72.48 (11)
O1—Ni1—N1—C1	−27.87 (11)	O1—Ni1—O2—C4	−107.52 (11)
O2ⁱ—Ni1—N1—C1	58.58 (11)	O2ⁱ—Ni1—O2—C4	−86 (100)
O2—Ni1—N1—C1	−121.42 (11)	N1—Ni1—O2—C4	−25.56 (11)
N1ⁱ—Ni1—N1—C1	−20 (100)	N1ⁱ—Ni1—O2—C4	154.44 (11)
O1ⁱ—Ni1—N1—C5	32.74 (13)	C5—N1—C1—C2	167.69 (16)
O1—Ni1—N1—C5	−147.26 (13)	C3—N1—C1—C2	−67.2 (2)
O2ⁱ—Ni1—N1—C5	−60.81 (13)	Ni1—N1—C1—C2	47.43 (17)
O2—Ni1—N1—C5	119.19 (13)	Ni1—O1—C2—C1	18.77 (19)
N1ⁱ—Ni1—N1—C5	−139 (100)	N1—C1—C2—O1	−45.3 (2)
O1ⁱ—Ni1—N1—C3	−89.34 (12)	C1—N1—C3—C4	143.10 (16)
O1—Ni1—N1—C3	90.66 (12)	C5—N1—C3—C4	−92.14 (18)
O2ⁱ—Ni1—N1—C3	177.11 (11)	Ni1—N1—C3—C4	30.37 (17)
O2—Ni1—N1—C3	−2.89 (11)	Ni1—O2—C4—C3	49.91 (15)
N1ⁱ—Ni1—N1—C3	98 (100)	N1—C3—C4—O2	−55.33 (19)
O1ⁱ—Ni1—O1—C2	29 (100)	C1—N1—C5—C6	63.6 (2)
O2ⁱ—Ni1—O1—C2	−91.17 (12)	C3—N1—C5—C6	−61.9 (2)
O2—Ni1—O1—C2	88.83 (12)	Ni1—N1—C5—C6	178.71 (13)
N1—Ni1—O1—C2	5.39 (12)	N1—C5—C6—O3	82.7 (2)
N1ⁱ—Ni1—O1—C2	−174.61 (12)

Symmetry codes: (i) −x+1/2, −y+3/2, −z+2; (ii) −x+2, y, −z+3/2.

Hydrogen-bond geometry (Å, °) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1C···O5ⁱⁱⁱ	0.82	2.19	2.663 (2)	117
O2—H2C···O4^iv	0.82	2.28	2.6227 (19)	106
O3—H3C···O5	0.82	2.00	2.818 (2)	174
C3—H3B···O3	0.97	2.26	3.055 (3)	139

Symmetry codes: (iii) x−1, y, z; (iv) −x+1, y, −z+3/2.

Table 1
Hydrogen-bond geometry (Å, °) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1C···O5ⁱ	0.82	2.19	2.663 (2)	117
O2—H2C···O4ⁱⁱ	0.82	2.28	2.6227 (19)	106
O3—H3C···O5	0.82	2.00	2.818 (2)	174
C3—H3B···O3	0.97	2.26	3.055 (3)	139

Symmetry codes: (i) x−1, y, z; (ii) −x+1, y, −z+3/2.

supplementary materials

Bis(triethanolamine)nickel(II) sulfate

H.-X. Guo, Z.-X. Du and X.-Z. Li

	Fig. 1. View of the structure showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 35% probability level; H-atoms are shown as small spheres of arbitrary radius. (Symmetry codes: i: -x+1/2, -y+3/2,-z+2; ii: -x+2, y, -z+3/2)
	Fig. 2. View of the 2-D hydrogen-bonded network in the packing of the title compound. The packing is viewed along the b axis; O-H···O and C—H···O interactions are shown as dashed lines.