Di-μ-sulfato-bis-[diaqua-(1H-imidazo[4,5-f][1,10]phenanthroline)nickel(II)] dihydrate.

In the title compound, [Ni(2)(SO(4))(2)(C(13)H(8)N(4))(2)(H(2)O)(4)]·2H(2)O, the complete dimeric complex is generated by an inversion center. The Ni(II) atoms are octa-hedrally coordinated by two N atoms from one 1H-imidazo[4,5-f][1,10]phenanthroline (IP) ligand and two O atoms from two adjacent sulfate ions forming the equatorial plane, with two coordinated water mol-ecules in the axial sites. Both of the sulfate ions act as bidentate-bridging ligands connecting the two Ni(II) ions, thus generating a binuclear complex. In the crystal structure, O-H⋯O and O-H⋯N hydrogen bonds involving the coordinated and uncoordinated water mol-ecules and N-H⋯O links lead to the formation of a two-dimensional sheet structure developing parallel to (010). Weak π-π stacking inter-actions [centroid-centroid separation = 3.613 (2) Å] between the IP ligands also occur.

Related literature

For related structures, see: An et al. (2007 ▶); Gu et al. (2004 ▶). For general background, see: Ross et al. (1999 ▶); Xu et al. (2003 ▶); Xiong et al. (1999 ▶). For details of graph-set theory, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

[Ni2(SO4)2(C13H8N4)2(H2O)4]·2H2O

M = 858.10

Monoclinic,

a = 10.296 (2) Å

b = 9.0560 (18) Å

c = 16.836 (3) Å

β = 99.108 (3)°

V = 1550.0 (5) Å3

Z = 2

Mo Kα radiation

μ = 1.44 mm−1

T = 298 (2) K

0.28 × 0.20 × 0.13 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.689, T max = 0.835

7756 measured reflections

2887 independent reflections

2085 reflections with I > 2σ(I)

R int = 0.040

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.146

S = 0.81

2887 reflections

236 parameters

H-atom parameters constrained

Δρmax = 0.47 e Å−3

Δρmin = −0.41 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808040634/hb2874sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808040634/hb2874Isup2.hkl

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

[Ni2(SO4)2(C13H8N4)2(H2O)4]·2H2O	F(000) = 880
Mr = 858.10	Dx = 1.839 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2887 reflections
a = 10.296 (2) Å	θ = 2.5–25.5°
b = 9.0560 (18) Å	µ = 1.44 mm−1
c = 16.836 (3) Å	T = 298 K
β = 99.108 (3)°	Block, green
V = 1550.0 (5) Å3	0.28 × 0.20 × 0.13 mm
Z = 2

Bruker APEXII CCD diffractometer	2887 independent reflections
Radiation source: fine-focus sealed tube	2085 reflections with I > 2σ(I)
graphite	Rint = 0.040
φ and ω scans	θmax = 25.5°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −12→11
Tmin = 0.689, Tmax = 0.835	k = −8→10
7756 measured reflections	l = −20→20

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.146	H-atom parameters constrained
S = 0.81	w = 1/[σ2(Fo2) + (0.127P)2] where P = (Fo2 + 2Fc2)/3
2887 reflections	(Δ/σ)max < 0.001
236 parameters	Δρmax = 0.47 e Å−3
0 restraints	Δρmin = −0.40 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
Ni1	0.18902 (5)	0.68064 (6)	0.04131 (3)	0.0299 (2)
S1	−0.03201 (9)	0.60119 (10)	−0.11230 (5)	0.0263 (3)
N1	0.2570 (3)	0.9021 (4)	0.03289 (18)	0.0266 (7)
N2	0.3746 (3)	0.6769 (3)	0.11665 (19)	0.0275 (7)
N3	0.6436 (3)	1.2065 (4)	0.1392 (2)	0.0338 (8)
N4	0.7470 (3)	1.0131 (4)	0.20327 (19)	0.0340 (8)
H4A	0.8077	0.9627	0.2321	0.034 (12)*
O1W	0.0747 (3)	0.7638 (4)	0.12140 (18)	0.0487 (9)
H1WA	0.0783	0.8400	0.1457	0.058*
H1WB	0.0340	0.6894	0.1248	0.058*
O2W	0.2961 (3)	0.5649 (3)	−0.03940 (15)	0.0342 (7)
H2WA	0.3137	0.6304	−0.0678	0.041*
H2WB	0.2281	0.5421	−0.0666	0.041*
O2	−0.0906 (3)	0.6771 (3)	−0.18632 (17)	0.0401 (8)
O4	0.0613 (3)	0.4873 (3)	−0.13353 (15)	0.0311 (6)
O1	0.0382 (2)	0.7092 (3)	−0.05661 (16)	0.0300 (6)
O3W	0.0861 (4)	0.0146 (4)	0.20094 (19)	0.0661 (11)
H3WB	0.0873	0.1025	0.1963	0.079*
H3WA	0.0790	0.0137	0.2476	0.079*
C1	0.1913 (4)	1.0142 (5)	−0.0056 (2)	0.0314 (9)
H1A	0.1083	0.9961	−0.0347	0.038*
C2	0.2408 (4)	1.1571 (5)	−0.0042 (2)	0.0339 (10)
H2A	0.1915	1.2325	−0.0318	0.041*
C3	0.3637 (4)	1.1857 (4)	0.0385 (2)	0.0308 (9)
H3A	0.3989	1.2804	0.0395	0.037*
C4	0.4353 (3)	1.0702 (4)	0.0806 (2)	0.0263 (9)
C5	0.3759 (3)	0.9290 (4)	0.0770 (2)	0.0231 (8)
C6	0.4416 (4)	0.8062 (4)	0.1208 (2)	0.0250 (8)
C7	0.4319 (4)	0.5593 (5)	0.1541 (2)	0.0337 (9)
H7A	0.3860	0.4705	0.1505	0.040*
C8	0.5586 (4)	0.5636 (5)	0.1988 (2)	0.0358 (10)
H8A	0.5960	0.4790	0.2241	0.043*
C9	0.6267 (4)	0.6942 (4)	0.2048 (2)	0.0323 (10)
H9A	0.7107	0.6993	0.2347	0.039*
C10	0.5692 (4)	0.8195 (4)	0.1657 (2)	0.0250 (8)
C11	0.6261 (4)	0.9622 (5)	0.1659 (2)	0.0300 (9)
C12	0.5625 (4)	1.0813 (4)	0.1265 (2)	0.0291 (9)
C13	0.7502 (4)	1.1573 (5)	0.1853 (3)	0.0378 (10)
H13A	0.8218	1.2175	0.2039	0.045*
O3	−0.1354 (3)	0.5305 (3)	−0.07522 (17)	0.0352 (7)

	U11	U22	U33	U12	U13	U23
Ni1	0.0279 (3)	0.0279 (4)	0.0327 (3)	−0.0050 (2)	0.0010 (2)	−0.0018 (2)
S1	0.0263 (5)	0.0234 (6)	0.0273 (5)	−0.0047 (4)	−0.0016 (4)	0.0013 (4)
N1	0.0259 (17)	0.0269 (19)	0.0260 (16)	−0.0023 (14)	0.0013 (13)	0.0010 (14)
N2	0.0265 (17)	0.0267 (19)	0.0294 (17)	−0.0031 (14)	0.0046 (14)	−0.0015 (14)
N3	0.033 (2)	0.033 (2)	0.0345 (19)	−0.0099 (15)	0.0029 (16)	−0.0019 (15)
N4	0.0277 (18)	0.040 (2)	0.0310 (17)	−0.0034 (16)	−0.0053 (15)	0.0003 (16)
O1W	0.061 (2)	0.0305 (18)	0.061 (2)	−0.0183 (16)	0.0311 (18)	−0.0190 (16)
O2W	0.0315 (15)	0.0345 (17)	0.0370 (15)	−0.0029 (13)	0.0061 (13)	−0.0004 (12)
O2	0.0454 (19)	0.0349 (18)	0.0342 (16)	−0.0055 (13)	−0.0118 (14)	0.0063 (13)
O4	0.0293 (15)	0.0253 (15)	0.0375 (15)	−0.0050 (12)	0.0021 (12)	−0.0043 (12)
O1	0.0253 (14)	0.0252 (15)	0.0348 (15)	−0.0025 (11)	−0.0096 (12)	−0.0042 (11)
O3W	0.126 (4)	0.0292 (19)	0.0479 (19)	−0.015 (2)	0.028 (2)	−0.0107 (16)
C1	0.023 (2)	0.033 (2)	0.036 (2)	−0.0010 (17)	−0.0009 (16)	0.0032 (18)
C2	0.034 (2)	0.031 (2)	0.034 (2)	0.0067 (18)	−0.0012 (18)	0.0047 (18)
C3	0.036 (2)	0.019 (2)	0.036 (2)	−0.0032 (17)	0.0020 (18)	−0.0029 (17)
C4	0.025 (2)	0.028 (2)	0.0251 (18)	−0.0012 (16)	0.0022 (16)	−0.0029 (16)
C5	0.0232 (19)	0.021 (2)	0.0240 (18)	−0.0031 (15)	0.0006 (15)	0.0002 (15)
C6	0.026 (2)	0.025 (2)	0.0239 (19)	−0.0050 (16)	0.0027 (16)	−0.0018 (15)
C7	0.038 (2)	0.027 (2)	0.035 (2)	−0.0067 (18)	0.0029 (18)	0.0014 (18)
C8	0.039 (2)	0.029 (2)	0.038 (2)	0.0085 (19)	0.0021 (19)	0.0065 (18)
C9	0.024 (2)	0.038 (3)	0.032 (2)	−0.0001 (18)	−0.0031 (17)	−0.0009 (18)
C10	0.027 (2)	0.025 (2)	0.0236 (18)	−0.0011 (16)	0.0045 (16)	−0.0009 (15)
C11	0.024 (2)	0.039 (2)	0.0252 (19)	−0.0072 (18)	−0.0023 (16)	−0.0030 (18)
C12	0.031 (2)	0.030 (2)	0.0265 (19)	−0.0052 (17)	0.0061 (16)	−0.0013 (17)
C13	0.038 (3)	0.035 (3)	0.038 (2)	−0.019 (2)	−0.001 (2)	−0.0038 (19)
O3	0.0311 (15)	0.0242 (15)	0.0521 (17)	−0.0034 (12)	0.0116 (13)	0.0031 (13)

Ni1—O1W	2.067 (3)	O3W—H3WB	0.8000
Ni1—O3i	2.095 (3)	O3W—H3WA	0.8000
Ni1—O1	2.094 (3)	C1—C2	1.390 (6)
Ni1—N2	2.120 (3)	C1—H1A	0.9300
Ni1—N1	2.136 (3)	C2—C3	1.378 (6)
Ni1—O2W	2.152 (3)	C2—H2A	0.9300
S1—O1	1.464 (3)	C3—C4	1.405 (5)
S1—O3	1.464 (3)	C3—H3A	0.9300
S1—O2	1.467 (3)	C4—C5	1.414 (5)
S1—O4	1.491 (3)	C4—C12	1.415 (5)
N1—C1	1.330 (5)	C5—C6	1.442 (5)
N1—C5	1.349 (5)	C6—C10	1.413 (5)
N2—C7	1.327 (5)	C7—C8	1.400 (6)
N2—C6	1.355 (5)	C7—H7A	0.9300
N3—C13	1.317 (5)	C8—C9	1.371 (6)
N3—C12	1.405 (5)	C8—H8A	0.9300
N4—C13	1.341 (5)	C9—C10	1.396 (5)
N4—C11	1.382 (5)	C9—H9A	0.9300
N4—H4A	0.8600	C10—C11	1.419 (5)
O1W—H1WA	0.8000	C11—C12	1.376 (6)
O1W—H1WB	0.8000	C13—H13A	0.9300
O2W—H2WA	0.8000	O3—Ni1i	2.095 (3)
O2W—H2WB	0.8000
O1W—Ni1—O3i	87.30 (12)	N1—C1—H1A	118.5
O1W—Ni1—O1	92.33 (12)	C2—C1—H1A	118.5
O3i—Ni1—O1	97.62 (11)	C3—C2—C1	119.2 (4)
O1W—Ni1—N2	99.67 (13)	C3—C2—H2A	120.4
O3i—Ni1—N2	94.22 (11)	C1—C2—H2A	120.4
O1—Ni1—N2	163.51 (11)	C2—C3—C4	119.2 (4)
O1W—Ni1—N1	85.86 (12)	C2—C3—H3A	120.4
O3i—Ni1—N1	168.08 (11)	C4—C3—H3A	120.4
O1—Ni1—N1	92.40 (11)	C3—C4—C5	117.6 (3)
N2—Ni1—N1	77.35 (12)	C3—C4—C12	126.1 (4)
O1W—Ni1—O2W	172.06 (12)	C5—C4—C12	116.4 (3)
O3i—Ni1—O2W	84.89 (10)	N1—C5—C4	122.4 (3)
O1—Ni1—O2W	87.31 (11)	N1—C5—C6	117.0 (3)
N2—Ni1—O2W	82.35 (11)	C4—C5—C6	120.7 (3)
N1—Ni1—O2W	102.08 (11)	N2—C6—C10	121.6 (3)
O1—S1—O3	109.72 (16)	N2—C6—C5	116.5 (3)
O1—S1—O2	109.01 (16)	C10—C6—C5	121.9 (3)
O3—S1—O2	109.77 (17)	N2—C7—C8	122.7 (4)
O1—S1—O4	110.14 (15)	N2—C7—H7A	118.7
O3—S1—O4	109.85 (16)	C8—C7—H7A	118.7
O2—S1—O4	108.32 (17)	C9—C8—C7	119.1 (4)
C1—N1—C5	118.5 (3)	C9—C8—H8A	120.5
C1—N1—Ni1	127.0 (3)	C7—C8—H8A	120.5
C5—N1—Ni1	114.3 (2)	C8—C9—C10	119.5 (4)
C7—N2—C6	119.0 (3)	C8—C9—H9A	120.2
C7—N2—Ni1	126.0 (3)	C10—C9—H9A	120.2
C6—N2—Ni1	114.9 (3)	C9—C10—C11	126.5 (4)
C13—N3—C12	103.7 (3)	C9—C10—C6	118.2 (3)
C13—N4—C11	106.0 (3)	C11—C10—C6	115.3 (3)
C13—N4—H4A	127.0	N4—C11—C12	106.5 (4)
C11—N4—H4A	127.0	N4—C11—C10	130.3 (4)
Ni1—O1W—H1WA	131.4	C12—C11—C10	123.2 (3)
Ni1—O1W—H1WB	95.7	C11—C12—N3	109.4 (3)
H1WA—O1W—H1WB	132.3	C11—C12—C4	122.4 (4)
Ni1—O2W—H2WA	101.7	N3—C12—C4	128.1 (4)
Ni1—O2W—H2WB	89.9	N3—C13—N4	114.4 (4)
H2WA—O2W—H2WB	96.3	N3—C13—H13A	122.8
S1—O1—Ni1	130.62 (17)	N4—C13—H13A	122.8
H3WB—O3W—H3WA	96.4	S1—O3—Ni1i	139.12 (17)
N1—C1—C2	123.1 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···O2ii	0.86	2.03	2.870 (5)	165
O1W—H1WA···O3Wiii	0.80	1.83	2.630 (4)	180
O1W—H1WB···O4i	0.80	1.89	2.695 (4)	180
O1W—H1WB···O3i	0.80	2.46	2.873 (4)	114
O2W—H2WA···N3iv	0.80	2.00	2.797 (4)	179
O3W—H3WB···O2i	0.80	2.00	2.803 (4)	179
O3W—H3WA···O4v	0.80	2.04	2.839 (4)	180
O2W—H2WB···O4	0.80	1.96	2.764 (4)	180
O2W—H2WB···O1	0.80	2.50	2.932 (4)	115

Table 1

Selected bond lengths (Å)

Ni1—O1W	2.067 (3)
Ni1—O3i	2.095 (3)
Ni1—O1	2.094 (3)
Ni1—N2	2.120 (3)
Ni1—N1	2.136 (3)
Ni1—O2W	2.152 (3)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4A⋯O2ii	0.86	2.03	2.870 (5)	165
O1W—H1WA⋯O3Wiii	0.80	1.83	2.630 (4)	180
O1W—H1WB⋯O4i	0.80	1.89	2.695 (4)	180
O1W—H1WB⋯O3i	0.80	2.46	2.873 (4)	114
O2W—H2WA⋯N3iv	0.80	2.00	2.797 (4)	179
O3W—H3WB⋯O2i	0.80	2.00	2.803 (4)	179
O3W—H3WA⋯O4v	0.80	2.04	2.839 (4)	180
O2W—H2WB⋯O4	0.80	1.96	2.764 (4)	180
O2W—H2WB⋯O1	0.80	2.50	2.932 (4)	115

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .