Bis(1,10-phenanthroline-κ² N,N′)(sulfato-κ² O,O′)nickel(II) ethane-1,2-diol solvate

Abstract

In the title compound, [Ni(SO₄)(C₁₂H₈N₂)₂]·C₂H₆O₂, the coordination polyhedron around the Ni²⁺ ion is a distorted octahedron, with four N atoms from two phenanthroline groups and two O atoms from a bidentate sulfate ligand. The Ni²⁺ ion lies on a special position of site symmetry 2. Inter­molecular O—H⋯O hydrogen bonds help to stabilize the structure. The OH group of the ethane-1,2-diol solvent is disordered over two positions with equal occupancy.

Related literature

For Ni–phen complexes with chloride anions and water mol­ecules as a second ligand, see: Chen et al. (2005 ▶); Su & Xu (2005 ▶); Tang et al. (2007 ▶). For isostructural compounds, see: Zhong et al. (2006 ▶); Lu et al. (2006 ▶); Zhu et al. (2006a ▶,b ▶).

Experimental

Crystal data

• [Ni(SO₄)(C₁₂H₈N₂)₂]·C₂H₆O₂

• M _r = 577.25

• Monoclinic,

• a = 18.4551 (9) Å

• b = 11.8839 (5) Å

• c = 12.7526 (6) Å

• β = 118.991 (6)°

• V = 2446.4 (2) ų

• Z = 4

• Mo Kα radiation

• μ = 0.93 mm⁻¹

• T = 295 K

• 0.36 × 0.33 × 0.28 mm

Data collection

• Oxford Diffraction Gemini S Ultra diffractometer

• Absorption correction: multi-scan (ABSPACK; Oxford Diffraction, 2009 ▶) T _min = 0.731, T _max = 0.781

• 11586 measured reflections

• 3010 independent reflections

• 2467 reflections with I > 2σ(I)

• R _int = 0.029

Refinement

• R[F ² > 2σ(F ²)] = 0.036

• wR(F ²) = 0.106

• S = 1.08

• 3010 reflections

• 183 parameters

• 17 restraints

• H-atom parameters constrained

• Δρ_max = 0.35 e Å⁻³

• Δρ_min = −0.52 e Å⁻³

Data collection: CrysAlisPro (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlisPro; data reduction: CrysAlisPro; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯O1	0.82	2.15	2.659 (7)	121
O3′—H3′⋯O1	0.82	2.47	2.763 (5)	102

supplementary crystallographic information

Comment

Ni-phen (phen = phenanthroline) complexes with chloride-anion and water-molecule ligands have been synthesized and characterized by X-ray diffraction (Chen et al., 2005; Su & Xu, 2005; Tang et al., 2007). The title nickel complex [NiSO₄(phen)₂].C₂H₆O₂, Fig. 1, is isostructural to the recently reported cobalt(II) and cadmium(II) analogs (Zhong et al., 2006; Lu et al., 2006). A twofold rotation axis passes through the Ni and S atoms, and also through the mid-point of the C—C bond of the solvent molcule. The Ni^II center has an octahedral geometry, with four N atoms from two phen groups and two O atoms from a bidentate sulfate ligand. The geometry of the phen and sulfate ligands are in good agreement with those reported in the two isomorphous complexes [ZnSO₄(phen)₂].C₂H₆O₂ and [MnSO₄(phen)₂].C₂H₆O₂ (Zhu et al., 2006a,b).

The ethane-1,2-diol solvent is disordered over two positions, and is hydrogen bonded to the sulfate ligand (Table 1).

Experimental

Green block-shaped crystals of the title compound were obtained by a procedure similar to that described previously (Zhong et al., 2006), but with NiSO₄.7H₂O in place of CoSO₄.7H₂O.

Refinement

The H atoms of phen were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C). The O atom of the ethane-1,2-diol solvent is disordered over two positions with site-occupancy factors of 1/2, sharing a common atom C13. The C13—C13 ⁱ (i = -x, y, -z+3/2), C13—O3 and C13—O3' distances were restrained to 1.501 (4), 1.304 (5) and 1.339 (5) Å, respectively. The H atoms of the ethane-1,2-diol were located in a difference map and then allowed to ride on their parent atoms, with C—H = 0.97 Å and O—H = 0.82 Å; U_iso(H) = 1.2U_eq(C) and 1.5U_eq(O).

Figures

Fig. 1.

The molecular structure showing the atom-numbering scheme and with displacement ellipsoids drawn at the 50% probability level. The dashed lines represent O—H···O interactions. Unlabeled atoms are related to the labelled atoms by the symmetry operator (-x, y, -z +3/2). Only one disorder component is shown.

Crystal data

[Ni(SO4)(C12H8N2)2]·C2H6O2	F(000) = 1192
Mr = 577.25	Dx = 1.567 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6902 reflections
a = 18.4551 (9) Å	θ = 3.2–30.6°
b = 11.8839 (5) Å	µ = 0.93 mm−1
c = 12.7526 (6) Å	T = 295 K
β = 118.991 (6)°	Block, green
V = 2446.4 (2) Å3	0.36 × 0.33 × 0.28 mm
Z = 4

Data collection

Oxford Diffraction Gemini S Ultra diffractometer	3010 independent reflections
Radiation source: fine-focus sealed tube	2467 reflections with I > 2σ(I)
graphite	Rint = 0.029
Detector resolution: 8.1241 pixels mm-1	θmax = 28.3°, θmin = 3.2°
φ and ω scans	h = −24→24
Absorption correction: multi-scan (ABSPACK; Oxford Diffraction, 2009)	k = −15→15
Tmin = 0.731, Tmax = 0.781	l = −17→16
11586 measured reflections

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036	H-atom parameters constrained
wR(F2) = 0.106	w = 1/[σ2(Fo2) + (0.0643P)2 + 0.296P] where P = (Fo2 + 2Fc2)/3
S = 1.08	(Δ/σ)max < 0.001
3010 reflections	Δρmax = 0.35 e Å−3
183 parameters	Δρmin = −0.52 e Å−3
17 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0055 (6)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ni1	0.0000	0.19859 (3)	0.7500	0.02868 (15)
S1	0.0000	−0.02657 (6)	0.7500	0.02857 (19)
O2	−0.05633 (9)	0.05119 (13)	0.65249 (13)	0.0379 (4)
O1	0.04687 (11)	−0.09628 (15)	0.71006 (17)	0.0479 (5)
N1	0.07956 (11)	0.21105 (15)	0.67829 (16)	0.0314 (4)
N2	0.08892 (12)	0.30656 (14)	0.87419 (16)	0.0331 (4)
C5	0.14702 (13)	0.27545 (18)	0.74544 (17)	0.0291 (4)
C7	0.28779 (15)	0.4016 (2)	0.8974 (2)	0.0438 (6)
H7	0.3347	0.4428	0.9481	0.053*
C9	0.22836 (17)	0.4292 (2)	1.0353 (2)	0.0458 (6)
H9	0.2743	0.4702	1.0893	0.055*
C4	0.21016 (14)	0.2934 (2)	0.7163 (2)	0.0368 (5)
C8	0.22400 (15)	0.38596 (19)	0.92872 (19)	0.0368 (5)
C12	0.15344 (13)	0.32477 (17)	0.85260 (18)	0.0303 (5)
C6	0.28132 (15)	0.3577 (2)	0.7956 (2)	0.0454 (6)
H6	0.3236	0.3694	0.7769	0.055*
C1	0.07228 (15)	0.1648 (2)	0.5783 (2)	0.0391 (5)
H1	0.0260	0.1209	0.5310	0.047*
C2	0.13218 (17)	0.1802 (2)	0.5424 (2)	0.0474 (6)
H2	0.1250	0.1481	0.4715	0.057*
C3	0.20060 (16)	0.2421 (2)	0.6110 (2)	0.0475 (6)
H3	0.2413	0.2506	0.5885	0.057*
C10	0.16452 (19)	0.4099 (2)	1.0571 (2)	0.0507 (7)
H10	0.1667	0.4375	1.1268	0.061*
C11	0.09572 (16)	0.3488 (2)	0.9757 (2)	0.0428 (6)
H11	0.0527	0.3369	0.9927	0.051*
C13	0.0291 (3)	−0.4047 (3)	0.7245 (4)	0.0978 (14)
H13A	0.0809	−0.4351	0.7869	0.117*
H13B	0.0073	−0.4600	0.6606	0.117*
O3	0.0492 (5)	−0.3177 (5)	0.6817 (6)	0.098 (2)	0.50
H3A	0.0752	−0.2727	0.7359	0.147*	0.50
O3'	0.0850 (3)	−0.3224 (4)	0.7512 (6)	0.0726 (17)	0.50
H3'	0.0792	−0.2939	0.6891	0.109*	0.50

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Ni1	0.0250 (2)	0.0289 (2)	0.0293 (2)	0.000	0.01088 (16)	0.000
S1	0.0222 (3)	0.0282 (4)	0.0318 (4)	0.000	0.0103 (3)	0.000
O2	0.0302 (8)	0.0346 (9)	0.0318 (8)	−0.0013 (7)	0.0014 (6)	−0.0005 (6)
O1	0.0430 (10)	0.0455 (11)	0.0622 (11)	0.0066 (8)	0.0310 (9)	−0.0055 (8)
N1	0.0282 (9)	0.0318 (10)	0.0304 (9)	−0.0019 (8)	0.0111 (7)	−0.0032 (7)
N2	0.0377 (10)	0.0293 (10)	0.0325 (9)	−0.0029 (8)	0.0172 (8)	−0.0026 (7)
C5	0.0266 (10)	0.0280 (11)	0.0282 (9)	0.0013 (8)	0.0097 (8)	0.0015 (8)
C7	0.0300 (12)	0.0428 (15)	0.0448 (13)	−0.0097 (10)	0.0072 (10)	−0.0017 (10)
C9	0.0495 (15)	0.0406 (14)	0.0351 (12)	−0.0087 (12)	0.0109 (11)	−0.0088 (10)
C4	0.0307 (11)	0.0397 (13)	0.0387 (12)	−0.0003 (10)	0.0157 (9)	0.0034 (9)
C8	0.0375 (12)	0.0297 (12)	0.0326 (11)	−0.0042 (10)	0.0088 (9)	−0.0003 (9)
C12	0.0300 (11)	0.0267 (11)	0.0278 (10)	−0.0001 (8)	0.0091 (8)	0.0013 (8)
C6	0.0295 (11)	0.0544 (17)	0.0491 (14)	−0.0070 (12)	0.0164 (10)	0.0007 (12)
C1	0.0381 (12)	0.0429 (13)	0.0336 (11)	−0.0037 (11)	0.0154 (10)	−0.0085 (9)
C2	0.0504 (15)	0.0572 (17)	0.0388 (13)	−0.0021 (13)	0.0248 (12)	−0.0087 (11)
C3	0.0428 (14)	0.0621 (18)	0.0453 (13)	−0.0046 (13)	0.0275 (12)	−0.0026 (12)
C10	0.0664 (18)	0.0476 (16)	0.0360 (12)	−0.0080 (13)	0.0231 (12)	−0.0121 (11)
C11	0.0522 (15)	0.0417 (14)	0.0386 (12)	−0.0074 (12)	0.0252 (11)	−0.0086 (10)
C13	0.111 (3)	0.066 (2)	0.141 (3)	0.002 (2)	0.081 (3)	−0.002 (2)
O3	0.130 (5)	0.087 (4)	0.115 (4)	0.009 (3)	0.090 (4)	0.017 (3)
O3'	0.061 (3)	0.042 (3)	0.129 (5)	0.017 (2)	0.056 (3)	0.028 (3)

Geometric parameters (Å, °)

Ni1—N1i	2.0774 (18)	C9—C8	1.418 (3)
Ni1—N1	2.0774 (18)	C9—H9	0.9300
Ni1—N2	2.0805 (19)	C4—C3	1.406 (3)
Ni1—N2i	2.0805 (18)	C4—C6	1.430 (3)
Ni1—O2	2.1077 (16)	C8—C12	1.393 (3)
Ni1—O2i	2.1077 (16)	C6—H6	0.9300
Ni1—S1	2.6757 (8)	C1—C2	1.398 (3)
S1—O1i	1.4563 (17)	C1—H1	0.9300
S1—O1	1.4563 (17)	C2—C3	1.352 (4)
S1—O2i	1.4926 (16)	C2—H2	0.9300
S1—O2	1.4926 (16)	C3—H3	0.9300
N1—C1	1.334 (3)	C10—C11	1.392 (4)
N1—C5	1.355 (3)	C10—H10	0.9300
N2—C11	1.337 (3)	C11—H11	0.9300
N2—C12	1.363 (3)	C13—O3	1.304 (5)
C5—C4	1.401 (3)	C13—O3'	1.339 (5)
C5—C12	1.438 (3)	C13—C13i	1.501 (4)
C7—C6	1.349 (4)	C13—H13A	0.9700
C7—C8	1.427 (4)	C13—H13B	0.9700
C7—H7	0.9300	O3—H3A	0.8200
C9—C10	1.355 (4)	O3'—H3'	0.8200
N1i—Ni1—N1	171.82 (10)	C8—C7—H7	119.4
N1i—Ni1—N2	94.93 (7)	C10—C9—C8	119.0 (2)
N1—Ni1—N2	79.99 (7)	C10—C9—H9	120.5
N1i—Ni1—N2i	79.99 (7)	C8—C9—H9	120.5
N1—Ni1—N2i	94.93 (7)	C5—C4—C3	116.9 (2)
N2—Ni1—N2i	103.84 (10)	C5—C4—C6	119.4 (2)
N1i—Ni1—O2	93.85 (7)	C3—C4—C6	123.7 (2)
N1—Ni1—O2	92.94 (7)	C12—C8—C9	117.2 (2)
N2—Ni1—O2	160.60 (7)	C12—C8—C7	119.5 (2)
N2i—Ni1—O2	94.70 (6)	C9—C8—C7	123.3 (2)
N1i—Ni1—O2i	92.94 (7)	N2—C12—C8	123.7 (2)
N1—Ni1—O2i	93.85 (7)	N2—C12—C5	116.71 (19)
N2—Ni1—O2i	94.70 (6)	C8—C12—C5	119.6 (2)
N2i—Ni1—O2i	160.60 (7)	C7—C6—C4	120.7 (2)
O2—Ni1—O2i	67.58 (8)	C7—C6—H6	119.7
N1i—Ni1—S1	94.09 (5)	C4—C6—H6	119.7
N1—Ni1—S1	94.09 (5)	N1—C1—C2	122.0 (2)
N2—Ni1—S1	128.08 (5)	N1—C1—H1	119.0
N2i—Ni1—S1	128.08 (5)	C2—C1—H1	119.0
O2—Ni1—S1	33.79 (4)	C3—C2—C1	119.9 (2)
O2i—Ni1—S1	33.79 (4)	C3—C2—H2	120.1
O1i—S1—O1	110.66 (15)	C1—C2—H2	120.1
O1i—S1—O2i	110.65 (10)	C2—C3—C4	119.9 (2)
O1—S1—O2i	110.59 (10)	C2—C3—H3	120.0
O1i—S1—O2	110.59 (10)	C4—C3—H3	120.0
O1—S1—O2	110.65 (10)	C9—C10—C11	120.3 (2)
O2i—S1—O2	103.50 (13)	C9—C10—H10	119.9
O1i—S1—Ni1	124.67 (8)	C11—C10—H10	119.9
O1—S1—Ni1	124.67 (8)	N2—C11—C10	122.8 (2)
O2i—S1—Ni1	51.75 (6)	N2—C11—H11	118.6
O2—S1—Ni1	51.75 (6)	C10—C11—H11	118.6
S1—O2—Ni1	94.46 (7)	O3—C13—O3'	35.7 (4)
C1—N1—C5	118.22 (19)	O3—C13—C13i	126.2 (4)
C1—N1—Ni1	128.76 (16)	O3'—C13—C13i	121.0 (4)
C5—N1—Ni1	113.02 (13)	O3—C13—H13A	105.8
C11—N2—C12	117.1 (2)	O3'—C13—H13A	74.5
C11—N2—Ni1	129.66 (16)	C13i—C13—H13A	105.8
C12—N2—Ni1	112.83 (14)	O3—C13—H13B	105.8
N1—C5—C4	123.10 (19)	O3'—C13—H13B	131.5
N1—C5—C12	117.27 (18)	C13i—C13—H13B	105.8
C4—C5—C12	119.6 (2)	H13A—C13—H13B	106.2
C6—C7—C8	121.2 (2)	C13—O3—H3A	109.5
C6—C7—H7	119.4	C13—O3'—H3'	109.5
N1i—Ni1—S1—O1i	0.87 (10)	O2i—Ni1—N2—C11	−82.5 (2)
N1—Ni1—S1—O1i	−179.13 (10)	S1—Ni1—N2—C11	−88.3 (2)
N2—Ni1—S1—O1i	100.39 (11)	N1i—Ni1—N2—C12	−177.26 (15)
N2i—Ni1—S1—O1i	−79.61 (11)	N1—Ni1—N2—C12	−3.72 (14)
O2—Ni1—S1—O1i	−89.95 (12)	N2i—Ni1—N2—C12	−96.38 (15)
O2i—Ni1—S1—O1i	90.05 (12)	O2—Ni1—N2—C12	66.1 (3)
N1i—Ni1—S1—O1	−179.13 (10)	O2i—Ni1—N2—C12	89.37 (15)
N1—Ni1—S1—O1	0.87 (10)	S1—Ni1—N2—C12	83.62 (15)
N2—Ni1—S1—O1	−79.61 (11)	C1—N1—C5—C4	−1.6 (3)
N2i—Ni1—S1—O1	100.39 (11)	Ni1—N1—C5—C4	178.30 (17)
O2—Ni1—S1—O1	90.05 (12)	C1—N1—C5—C12	179.8 (2)
O2i—Ni1—S1—O1	−89.95 (12)	Ni1—N1—C5—C12	−0.3 (2)
N1i—Ni1—S1—O2i	−89.18 (9)	N1—C5—C4—C3	0.8 (3)
N1—Ni1—S1—O2i	90.82 (9)	C12—C5—C4—C3	179.4 (2)
N2—Ni1—S1—O2i	10.34 (10)	N1—C5—C4—C6	−176.7 (2)
N2i—Ni1—S1—O2i	−169.66 (10)	C12—C5—C4—C6	1.9 (3)
O2—Ni1—S1—O2i	180.0	C10—C9—C8—C12	−0.4 (4)
N1i—Ni1—S1—O2	90.82 (9)	C10—C9—C8—C7	−180.0 (2)
N1—Ni1—S1—O2	−89.18 (9)	C6—C7—C8—C12	−0.3 (4)
N2—Ni1—S1—O2	−169.66 (10)	C6—C7—C8—C9	179.2 (3)
N2i—Ni1—S1—O2	10.34 (10)	C11—N2—C12—C8	−1.3 (3)
O2i—Ni1—S1—O2	180.0	Ni1—N2—C12—C8	−174.28 (17)
O1i—S1—O2—Ni1	118.53 (10)	C11—N2—C12—C5	177.7 (2)
O1—S1—O2—Ni1	−118.49 (9)	Ni1—N2—C12—C5	4.7 (2)
O2i—S1—O2—Ni1	0.0	C9—C8—C12—N2	1.2 (3)
N1i—Ni1—O2—S1	−91.59 (8)	C7—C8—C12—N2	−179.2 (2)
N1—Ni1—O2—S1	92.96 (8)	C9—C8—C12—C5	−177.8 (2)
N2—Ni1—O2—S1	25.2 (2)	C7—C8—C12—C5	1.8 (3)
N2i—Ni1—O2—S1	−171.85 (8)	N1—C5—C12—N2	−3.0 (3)
O2i—Ni1—O2—S1	0.0	C4—C5—C12—N2	178.32 (19)
N1i—Ni1—N1—C1	−126.0 (2)	N1—C5—C12—C8	176.05 (19)
N2—Ni1—N1—C1	−178.0 (2)	C4—C5—C12—C8	−2.6 (3)
N2i—Ni1—N1—C1	−74.8 (2)	C8—C7—C6—C4	−0.4 (4)
O2—Ni1—N1—C1	20.2 (2)	C5—C4—C6—C7	−0.4 (4)
O2i—Ni1—N1—C1	87.9 (2)	C3—C4—C6—C7	−177.7 (3)
S1—Ni1—N1—C1	54.0 (2)	C5—N1—C1—C2	0.6 (4)
N1i—Ni1—N1—C5	54.20 (14)	Ni1—N1—C1—C2	−179.27 (19)
N2—Ni1—N1—C5	2.17 (14)	N1—C1—C2—C3	1.2 (4)
N2i—Ni1—N1—C5	105.39 (15)	C1—C2—C3—C4	−1.9 (4)
O2—Ni1—N1—C5	−159.64 (15)	C5—C4—C3—C2	1.0 (4)
O2i—Ni1—N1—C5	−91.93 (15)	C6—C4—C3—C2	178.3 (3)
S1—Ni1—N1—C5	−125.80 (14)	C8—C9—C10—C11	−0.3 (4)
N1i—Ni1—N2—C11	10.8 (2)	C12—N2—C11—C10	0.5 (4)
N1—Ni1—N2—C11	−175.6 (2)	Ni1—N2—C11—C10	172.17 (19)
N2i—Ni1—N2—C11	91.7 (2)	C9—C10—C11—N2	0.2 (4)
O2—Ni1—N2—C11	−105.8 (3)

Symmetry codes: (i) −x, y, −z+3/2.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O1	0.82	2.15	2.659 (7)	121
O3'—H3'···O1	0.82	2.47	2.763 (5)	102