Bis(1,10-phenanthroline-κ(2) N,N')(sulfato-κ(2) O,O')nickel(II) butane-2,3-diol monosolvate.

In the title compound, [Ni(SO4)(C12H8N2)2]·C4H10O2, the Ni(II) ion is six-coordinated by four N atoms from two chelating 1,10-phenanthroline ligands and two O atoms from an O,O'-bidentate sulfate anion, resulting in a distorted octa-hedral geometry for the metal ion. The dihedral angle between the two chelating N2C2 groups is 83.82 (12)°. The Ni(II) ion, the S atom and the mid-point of the central C-C bond of the butane-2,3-diol solvent mol-ecule lie on a twofold rotation axis. In the crystal, the complex mol-ecules and solvent mol-ecules are held together by pairs of symmetry-related Odiol-H⋯Osulfate hydrogen bonds involving the uncoordinating O atoms of the sulfate ions. The solvent mol-ecule is disordered over two sets of sites with site occupancies of 0.450 (9) and 0.550 (9).

Related literature

For the ethane-1,2-diol analog of the title complex, see: Zhong et al. (2009 ▶). For the propane-1,3-diol analog of the title complex, see: Ni et al. (2010 ▶). For an isotypic structure, see: Wang & Zhong (2011 ▶).

Experimental

Crystal data

[Ni(SO4)(C12H8N2)2]·C4H10O2

M = 605.29

Monoclinic,

a = 18.147 (4) Å

b = 13.051 (3) Å

c = 13.259 (3) Å

β = 122.43 (3)°

V = 2650.5 (14) Å3

Z = 4

Mo Kα radiation

μ = 0.86 mm−1

T = 223 K

0.35 × 0.30 × 0.20 mm

Data collection

Rigaku Mercury CCD diffractometer

Absorption correction: multi-scan (REQAB: Jacobson, 1998 ▶) T min = 0.736, T max = 1.000

6326 measured reflections

2325 independent reflections

1964 reflections with I > 2σ(I)

R int = 0.035

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.108

S = 1.14

2325 reflections

210 parameters

56 restraints

H-atom parameters constrained

Δρmax = 0.39 e Å−3

Δρmin = −0.39 e Å−3

Data collection: CrystalClear (Rigaku, 2007 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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.

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812047241/mw2096sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812047241/mw2096Isup2.hkl

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

[Ni(SO4)(C12H8N2)2]·C4H10O2	F(000) = 1256
Mr = 605.29	Dx = 1.517 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5284 reflections
a = 18.147 (4) Å	θ = 3.1–25.0°
b = 13.051 (3) Å	µ = 0.86 mm−1
c = 13.259 (3) Å	T = 223 K
β = 122.43 (3)°	Block, blue
V = 2650.5 (14) Å3	0.35 × 0.30 × 0.20 mm
Z = 4

Rigaku Mercury CCD diffractometer	2325 independent reflections
Radiation source: fine-focus sealed tube	1964 reflections with I > 2σ(I)
Graphite Monochromator monochromator	Rint = 0.035
Detector resolution: 28.5714 pixels mm-1	θmax = 25.0°, θmin = 3.2°
ω scans	h = −21→19
Absorption correction: multi-scan (REQAB: Jacobson, 1998)	k = −15→14
Tmin = 0.736, Tmax = 1.000	l = −13→15
6326 measured reflections

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.108	H-atom parameters constrained
S = 1.14	w = 1/[σ2(Fo2) + (0.0472P)2 + 2.5256P] where P = (Fo2 + 2Fc2)/3
2325 reflections	(Δ/σ)max = 0.006
210 parameters	Δρmax = 0.39 e Å−3
56 restraints	Δρmin = −0.39 e Å−3

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ni1	0.5000	0.32087 (4)	0.2500	0.0327 (2)
S1	0.5000	0.52556 (8)	0.2500	0.0338 (3)
O1	0.56037 (14)	0.45442 (17)	0.3492 (2)	0.0396 (6)
O2	0.45146 (16)	0.58892 (18)	0.2856 (2)	0.0478 (7)
O3	0.4425 (6)	0.7955 (5)	0.3087 (10)	0.108 (3)	0.550 (9)
H3A	0.4578	0.7392	0.2992	0.163*	0.550 (9)
O3'	0.4035 (5)	0.7861 (6)	0.1968 (10)	0.087 (3)	0.450 (9)
H3'A	0.4351	0.7392	0.2388	0.130*	0.450 (9)
N1	0.40659 (17)	0.21783 (19)	0.1282 (2)	0.0340 (7)
N2	0.42127 (17)	0.3083 (2)	0.3190 (2)	0.0349 (6)
C1	0.3964 (2)	0.1793 (3)	0.0285 (3)	0.0434 (9)
H1A	0.4366	0.1969	0.0082	0.052*
C2	0.3278 (3)	0.1135 (3)	−0.0468 (3)	0.0505 (10)
H2A	0.3229	0.0879	−0.1156	0.061*
C3	0.2678 (2)	0.0866 (3)	−0.0195 (3)	0.0459 (9)
H3B	0.2222	0.0426	−0.0691	0.055*
C4	0.2756 (2)	0.1262 (3)	0.0841 (3)	0.0377 (8)
C5	0.2166 (2)	0.1035 (3)	0.1210 (3)	0.0482 (9)
H5A	0.1709	0.0580	0.0761	0.058*
C6	0.2254 (2)	0.1464 (3)	0.2196 (3)	0.0497 (10)
H6A	0.1860	0.1297	0.2416	0.060*
C7	0.2946 (2)	0.2173 (3)	0.2906 (3)	0.0412 (9)
C8	0.3046 (3)	0.2696 (3)	0.3896 (3)	0.0524 (10)
H8A	0.2662	0.2572	0.4144	0.063*
C9	0.3709 (3)	0.3388 (3)	0.4497 (3)	0.0512 (10)
H9A	0.3776	0.3739	0.5152	0.061*
C10	0.4280 (2)	0.3563 (3)	0.4125 (3)	0.0435 (9)
H10A	0.4729	0.4033	0.4545	0.052*
C11	0.3548 (2)	0.2399 (2)	0.2583 (3)	0.0344 (8)
C12	0.3464 (2)	0.1929 (2)	0.1549 (3)	0.0321 (7)
C13	0.4921 (10)	0.8683 (7)	0.3028 (11)	0.093 (4)	0.550 (9)
H13A	0.5499	0.8622	0.3764	0.112*	0.550 (9)
C13'	0.4499 (5)	0.8753 (8)	0.2301 (12)	0.077 (4)	0.450 (9)
H13C	0.4167	0.9346	0.1816	0.092*	0.450 (9)
C14	0.4532 (8)	0.9682 (7)	0.3136 (10)	0.089 (3)	0.550 (9)
H14A	0.4484	0.9651	0.3822	0.134*	0.550 (9)
H14B	0.3963	0.9781	0.2430	0.134*	0.550 (9)
H14C	0.4903	1.0244	0.3222	0.134*	0.550 (9)
C14'	0.5030 (14)	0.8961 (18)	0.3636 (13)	0.142 (7)	0.450 (9)
H14G	0.4644	0.9039	0.3918	0.213*	0.450 (9)
H14H	0.5362	0.9578	0.3791	0.213*	0.450 (9)
H14I	0.5419	0.8398	0.4043	0.213*	0.450 (9)

	U11	U22	U33	U12	U13	U23
Ni1	0.0246 (3)	0.0300 (3)	0.0387 (4)	0.000	0.0139 (3)	0.000
S1	0.0230 (6)	0.0294 (6)	0.0429 (7)	0.000	0.0136 (5)	0.000
O1	0.0278 (12)	0.0351 (12)	0.0397 (13)	−0.0009 (10)	0.0073 (10)	−0.0017 (11)
O2	0.0398 (14)	0.0416 (14)	0.0680 (17)	0.0050 (11)	0.0329 (14)	−0.0031 (12)
O3	0.146 (6)	0.052 (4)	0.179 (8)	−0.003 (4)	0.122 (6)	−0.001 (4)
O3'	0.071 (5)	0.068 (5)	0.122 (7)	0.005 (4)	0.052 (5)	0.029 (5)
N1	0.0290 (15)	0.0309 (14)	0.0401 (16)	0.0016 (12)	0.0171 (13)	−0.0019 (13)
N2	0.0288 (14)	0.0331 (14)	0.0382 (15)	−0.0034 (12)	0.0149 (13)	−0.0050 (13)
C1	0.042 (2)	0.044 (2)	0.046 (2)	−0.0014 (17)	0.0244 (18)	−0.0082 (18)
C2	0.046 (2)	0.055 (2)	0.043 (2)	0.0032 (19)	0.0181 (18)	−0.0138 (19)
C3	0.0336 (19)	0.042 (2)	0.047 (2)	−0.0028 (16)	0.0113 (17)	−0.0106 (18)
C4	0.0285 (17)	0.0323 (18)	0.0418 (19)	−0.0010 (14)	0.0119 (15)	−0.0012 (16)
C5	0.0339 (19)	0.047 (2)	0.050 (2)	−0.0108 (17)	0.0139 (17)	−0.0034 (19)
C6	0.0329 (19)	0.060 (2)	0.055 (2)	−0.0110 (18)	0.0234 (18)	0.004 (2)
C7	0.0314 (19)	0.050 (2)	0.041 (2)	−0.0002 (16)	0.0182 (16)	0.0049 (17)
C8	0.046 (2)	0.074 (3)	0.046 (2)	−0.004 (2)	0.031 (2)	−0.001 (2)
C9	0.053 (2)	0.061 (2)	0.042 (2)	−0.001 (2)	0.0276 (19)	−0.0101 (19)
C10	0.040 (2)	0.043 (2)	0.042 (2)	−0.0033 (17)	0.0192 (17)	−0.0079 (17)
C11	0.0274 (17)	0.0331 (17)	0.0362 (18)	0.0022 (14)	0.0127 (15)	0.0017 (15)
C12	0.0252 (16)	0.0294 (16)	0.0351 (18)	0.0039 (13)	0.0117 (14)	0.0041 (14)
C13	0.118 (8)	0.075 (6)	0.114 (8)	−0.004 (6)	0.080 (7)	0.011 (6)
C13'	0.067 (7)	0.069 (7)	0.102 (8)	0.000 (5)	0.051 (6)	0.016 (6)
C14	0.107 (7)	0.090 (6)	0.110 (7)	0.020 (5)	0.084 (6)	0.018 (5)
C14'	0.153 (10)	0.180 (11)	0.130 (9)	−0.013 (8)	0.100 (8)	0.017 (8)

Ni1—N2i	2.075 (3)	C4—C5	1.427 (5)
Ni1—N2	2.075 (3)	C5—C6	1.350 (5)
Ni1—N1	2.086 (3)	C5—H5A	0.9300
Ni1—N1i	2.086 (3)	C6—C7	1.433 (5)
Ni1—O1	2.103 (2)	C6—H6A	0.9300
Ni1—O1i	2.103 (2)	C7—C11	1.402 (5)
Ni1—S1	2.6714 (14)	C7—C8	1.402 (5)
S1—O2i	1.459 (2)	C8—C9	1.368 (5)
S1—O2	1.459 (2)	C8—H8A	0.9300
S1—O1i	1.499 (2)	C9—C10	1.384 (5)
S1—O1	1.499 (2)	C9—H9A	0.9300
O3—C13	1.340 (9)	C10—H10A	0.9300
O3—H3A	0.8200	C11—C12	1.435 (5)
O3'—C13'	1.362 (9)	C13—C14	1.526 (10)
O3'—H3'A	0.8200	C13—C13i	1.572 (14)
N1—C1	1.332 (4)	C13—H13A	0.9800
N1—C12	1.355 (4)	C13'—C14'	1.519 (11)
N2—C10	1.335 (4)	C13'—C13'i	1.600 (14)
N2—C11	1.363 (4)	C13'—H13C	0.9800
C1—C2	1.398 (5)	C14—H14A	0.9600
C1—H1A	0.9300	C14—H14B	0.9600
C2—C3	1.365 (5)	C14—H14C	0.9600
C2—H2A	0.9300	C14'—H14G	0.9600
C3—C4	1.401 (5)	C14'—H14H	0.9600
C3—H3B	0.9300	C14'—H14I	0.9600
C4—C12	1.412 (5)
N2i—Ni1—N2	170.97 (15)	C3—C4—C5	124.0 (3)
N2i—Ni1—N1	94.23 (11)	C12—C4—C5	118.8 (3)
N2—Ni1—N1	79.90 (11)	C6—C5—C4	121.7 (3)
N2i—Ni1—N1i	79.90 (11)	C6—C5—H5A	119.1
N2—Ni1—N1i	94.23 (11)	C4—C5—H5A	119.1
N1—Ni1—N1i	99.75 (15)	C5—C6—C7	120.7 (3)
N2i—Ni1—O1	95.18 (10)	C5—C6—H6A	119.7
N2—Ni1—O1	92.30 (10)	C7—C6—H6A	119.7
N1—Ni1—O1	162.31 (9)	C11—C7—C8	116.9 (3)
N1i—Ni1—O1	96.63 (10)	C11—C7—C6	119.2 (3)
N2i—Ni1—O1i	92.30 (10)	C8—C7—C6	123.9 (3)
N2—Ni1—O1i	95.18 (10)	C9—C8—C7	119.9 (4)
N1—Ni1—O1i	96.63 (10)	C9—C8—H8A	120.1
N1i—Ni1—O1i	162.31 (9)	C7—C8—H8A	120.1
O1—Ni1—O1i	68.06 (12)	C8—C9—C10	119.6 (4)
N2i—Ni1—S1	94.52 (7)	C8—C9—H9A	120.2
N2—Ni1—S1	94.52 (7)	C10—C9—H9A	120.2
N1—Ni1—S1	130.13 (7)	N2—C10—C9	122.7 (3)
N1i—Ni1—S1	130.13 (7)	N2—C10—H10A	118.6
O1—Ni1—S1	34.03 (6)	C9—C10—H10A	118.6
O1i—Ni1—S1	34.03 (6)	N2—C11—C7	123.1 (3)
O2i—S1—O2	110.9 (2)	N2—C11—C12	116.8 (3)
O2i—S1—O1i	110.55 (14)	C7—C11—C12	120.1 (3)
O2—S1—O1i	110.56 (14)	N1—C12—C4	123.2 (3)
O2i—S1—O1	110.56 (14)	N1—C12—C11	117.3 (3)
O2—S1—O1	110.55 (14)	C4—C12—C11	119.4 (3)
O1i—S1—O1	103.47 (18)	O3—C13—C14	103.9 (8)
O2i—S1—Ni1	124.53 (11)	O3—C13—C13i	120.1 (10)
O2—S1—Ni1	124.53 (11)	C14—C13—C13i	113.5 (7)
O1i—S1—Ni1	51.74 (9)	O3—C13—H13A	106.1
O1—S1—Ni1	51.74 (9)	C14—C13—H13A	106.1
S1—O1—Ni1	94.23 (11)	C13i—C13—H13A	106.1
C13—O3—H3A	109.5	O3'—C13'—C14'	115.2 (14)
C13'—O3'—H3'A	109.5	O3'—C13'—C13'i	120.1 (5)
C1—N1—C12	117.8 (3)	C14'—C13'—C13'i	73.6 (11)
C1—N1—Ni1	129.3 (2)	O3'—C13'—H13C	114.0
C12—N1—Ni1	112.8 (2)	C14'—C13'—H13C	114.0
C10—N2—C11	117.8 (3)	C13'i—C13'—H13C	114.0
C10—N2—Ni1	129.1 (2)	C13—C14—H14A	109.5
C11—N2—Ni1	113.1 (2)	C13—C14—H14B	109.5
N1—C1—C2	122.4 (4)	H14A—C14—H14B	109.5
N1—C1—H1A	118.8	C13—C14—H14C	109.5
C2—C1—H1A	118.8	H14A—C14—H14C	109.5
C3—C2—C1	120.1 (4)	H14B—C14—H14C	109.5
C3—C2—H2A	120.0	C13'—C14'—H14G	109.5
C1—C2—H2A	120.0	C13'—C14'—H14H	109.5
C2—C3—C4	119.3 (3)	H14G—C14'—H14H	109.5
C2—C3—H3B	120.3	C13'—C14'—H14I	109.5
C4—C3—H3B	120.3	H14G—C14'—H14I	109.5
C3—C4—C12	117.2 (3)	H14H—C14'—H14I	109.5
N2i—Ni1—S1—O2i	−2.57 (14)	O1i—Ni1—N2—C10	−82.1 (3)
N2—Ni1—S1—O2i	177.43 (14)	S1—Ni1—N2—C10	−47.9 (3)
N1—Ni1—S1—O2i	−101.97 (16)	N1—Ni1—N2—C11	2.9 (2)
N1i—Ni1—S1—O2i	78.03 (16)	N1i—Ni1—N2—C11	−96.3 (2)
O1—Ni1—S1—O2i	90.01 (17)	O1—Ni1—N2—C11	166.9 (2)
O1i—Ni1—S1—O2i	−89.99 (17)	O1i—Ni1—N2—C11	98.7 (2)
N2i—Ni1—S1—O2	177.43 (14)	S1—Ni1—N2—C11	132.9 (2)
N2—Ni1—S1—O2	−2.57 (14)	C12—N1—C1—C2	−1.3 (5)
N1—Ni1—S1—O2	78.03 (16)	Ni1—N1—C1—C2	−177.4 (3)
N1i—Ni1—S1—O2	−101.97 (16)	N1—C1—C2—C3	0.2 (6)
O1—Ni1—S1—O2	−89.99 (17)	C1—C2—C3—C4	0.4 (5)
O1i—Ni1—S1—O2	90.01 (17)	C2—C3—C4—C12	0.2 (5)
N2i—Ni1—S1—O1i	87.43 (14)	C2—C3—C4—C5	179.8 (3)
N2—Ni1—S1—O1i	−92.57 (14)	C3—C4—C5—C6	−177.7 (4)
N1—Ni1—S1—O1i	−11.98 (16)	C12—C4—C5—C6	1.9 (5)
N1i—Ni1—S1—O1i	168.02 (16)	C4—C5—C6—C7	0.4 (6)
O1—Ni1—S1—O1i	180.0	C5—C6—C7—C11	−1.6 (6)
N2i—Ni1—S1—O1	−92.57 (14)	C5—C6—C7—C8	175.9 (4)
N2—Ni1—S1—O1	87.43 (14)	C11—C7—C8—C9	−0.1 (5)
N1—Ni1—S1—O1	168.02 (16)	C6—C7—C8—C9	−177.6 (4)
N1i—Ni1—S1—O1	−11.98 (16)	C7—C8—C9—C10	−0.3 (6)
O1i—Ni1—S1—O1	180.0	C11—N2—C10—C9	0.3 (5)
O2i—S1—O1—Ni1	−118.38 (13)	Ni1—N2—C10—C9	−178.9 (3)
O2—S1—O1—Ni1	118.39 (13)	C8—C9—C10—N2	0.2 (6)
O1i—S1—O1—Ni1	0.0	C10—N2—C11—C7	−0.8 (5)
N2i—Ni1—O1—S1	90.40 (12)	Ni1—N2—C11—C7	178.5 (3)
N2—Ni1—O1—S1	−94.66 (12)	C10—N2—C11—C12	177.2 (3)
N1—Ni1—O1—S1	−31.5 (4)	Ni1—N2—C11—C12	−3.5 (3)
N1i—Ni1—O1—S1	170.81 (12)	C8—C7—C11—N2	0.7 (5)
O1i—Ni1—O1—S1	0.0	C6—C7—C11—N2	178.3 (3)
N2i—Ni1—N1—C1	−12.5 (3)	C8—C7—C11—C12	−177.3 (3)
N2—Ni1—N1—C1	174.4 (3)	C6—C7—C11—C12	0.4 (5)
N1i—Ni1—N1—C1	−93.0 (3)	C1—N1—C12—C4	1.9 (4)
O1—Ni1—N1—C1	109.5 (4)	Ni1—N1—C12—C4	178.6 (2)
O1i—Ni1—N1—C1	80.3 (3)	C1—N1—C12—C11	−176.1 (3)
S1—Ni1—N1—C1	87.0 (3)	Ni1—N1—C12—C11	0.6 (3)
N2i—Ni1—N1—C12	171.2 (2)	C3—C4—C12—N1	−1.3 (5)
N2—Ni1—N1—C12	−1.9 (2)	C5—C4—C12—N1	179.0 (3)
N1i—Ni1—N1—C12	90.7 (2)	C3—C4—C12—C11	176.6 (3)
O1—Ni1—N1—C12	−66.8 (4)	C5—C4—C12—C11	−3.1 (5)
O1i—Ni1—N1—C12	−96.0 (2)	N2—C11—C12—N1	1.9 (4)
S1—Ni1—N1—C12	−89.3 (2)	C7—C11—C12—N1	180.0 (3)
N1—Ni1—N2—C10	−177.9 (3)	N2—C11—C12—C4	−176.1 (3)
N1i—Ni1—N2—C10	82.9 (3)	C7—C11—C12—C4	1.9 (5)
O1—Ni1—N2—C10	−13.9 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O2	0.82	1.97	2.729 (7)	154
O3′—H3′A···O2	0.82	2.03	2.769 (8)	150

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯O2	0.82	1.97	2.729 (7)	154
O3′—H3′A⋯O2	0.82	2.03	2.769 (8)	150