Diaqua-bis-(propane-1,3-diamine)-nickel(II) bis-(propane-1,3-diamine)-disulfato-nickelate(II).

The ionic Ni(II) title complex, [Ni(C(3)H(10)N(2))(2)(H(2)O)(2)][Ni(SO(4))(2)(C(3)H(10)N(2))(2)], is built up of [Ni(dipr)(2)(H(2)O)(2)](2+) complex cations and [Ni(dipr)(2)(SO(4))(2)](2-) complex anions (dipr is propane-1,3-diamine). Both Ni(II) atoms display a slightly distorted octa-hedral coordination and are located on inversion centers. There are several types of hydrogen-bonding inter-actions, which connect complex cations and anions into a two-dimensional network parallel to (010). Hydrogen bonds formed by the axially coordinated water mol-ecule of the complex cation and one of the O atoms of the sulfate groups of the complex anion (first type) link them into chains along the c axis. These chains are linked to each other through hydrogen bonds formed by an O atom (second type) of the SO(4) groups and NH(2) groups of the ligand of the complex cations from neighboring chains, forming a two-dimensional hydrogen-bonded net perpendicular to the b axis. The third type of O atoms of the sulfate groups of the complex anion are also linked into chains by a combination of both previously described types of H-atom connections.

Related literature

For background to direct synthesis, see: Nesterov et al. (2004 ▶, 2006 ▶); Kovbasyuk et al. (1997 ▶, 1998 ▶); Vassilyeva et al. (1997 ▶). For the structures of related complexes, see: Clegg et al. (1992 ▶); Kim & Lee (2002 ▶); Fritsky et al. (2004 ▶); Nowicka et al. (2002 ▶); Stockner et al. (2007 ▶); Duesler & Raymond (1978 ▶); Jurnak & Raymond (1974 ▶); Solans et al. (1982 ▶).

Experimental

Crystal data

[Ni(C3H10N2)2(H2O)2][Ni(SO4)2(C3H10N2)2]

M = 642.1

Triclinic,

a = 6.7055 (1) Å

b = 8.9098 (2) Å

c = 11.9504 (4) Å

α = 103.016 (2)°

β = 103.795 (2)°

γ = 105.729 (1)°

V = 634.52 (3) Å3

Z = 1

Mo Kα radiation

μ = 1.71 mm−1

T = 296 K

0.49 × 0.15 × 0.12 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: numerical (SADABS; Sheldrick, 2009 ▶) T min = 0.488, T max = 0.703

10425 measured reflections

3078 independent reflections

2728 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.024

wR(F 2) = 0.063

S = 1.07

3078 reflections

197 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.41 e Å−3

Δρmin = −0.37 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812009750/br2192sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812009750/br2192Isup2.hkl

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

[Ni(C3H10N2)2(H2O)2][Ni(SO4)2(C3H10N2)2]	Z = 1
Mr = 642.1	F(000) = 340
Triclinic, P1	Dx = 1.680 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.7055 (1) Å	Cell parameters from 5917 reflections
b = 8.9098 (2) Å	θ = 2.5–28.2°
c = 11.9504 (4) Å	µ = 1.71 mm−1
α = 103.016 (2)°	T = 296 K
β = 103.795 (2)°	Prism, light blue
γ = 105.729 (1)°	0.49 × 0.15 × 0.12 mm
V = 634.52 (3) Å3

Bruker APEXII CCD area-detector diffractometer	3078 independent reflections
Radiation source: fine-focus sealed tube	2728 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
phi and ω scans	θmax = 28.2°, θmin = 2.5°
Absorption correction: numerical (SADABS; Sheldrick, 2009)	h = −8→7
Tmin = 0.488, Tmax = 0.703	k = −11→10
10425 measured reflections	l = −15→15

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.063	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ2(Fo2) + (0.0341P)2 + 0.0694P] where P = (Fo2 + 2Fc2)/3
3078 reflections	(Δ/σ)max = 0.006
197 parameters	Δρmax = 0.41 e Å−3
0 restraints	Δρmin = −0.37 e Å−3
12 constraints

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	0.5000	1.0000	0.0000	0.01064 (8)
Ni2	0.5000	1.0000	0.5000	0.01320 (8)
S1	0.89097 (6)	1.01326 (4)	0.23292 (3)	0.01404 (9)
O1	0.70097 (16)	1.06228 (13)	0.18226 (9)	0.0155 (2)
O2	1.05971 (18)	1.06347 (15)	0.17662 (11)	0.0263 (3)
O3	0.97660 (18)	1.09600 (14)	0.36389 (10)	0.0240 (3)
O4	0.8164 (2)	0.83460 (14)	0.20784 (11)	0.0287 (3)
O5	0.4535 (2)	1.07096 (17)	0.33786 (11)	0.0246 (3)
N1	0.2544 (2)	0.83826 (16)	0.03946 (12)	0.0175 (3)
N2	0.6059 (2)	0.80081 (15)	−0.05714 (12)	0.0155 (3)
N3	0.6379 (2)	0.82954 (16)	0.43334 (13)	0.0165 (3)
N4	0.1851 (2)	0.82026 (17)	0.43194 (13)	0.0180 (3)
C1	0.1280 (2)	0.67732 (18)	−0.05413 (15)	0.0203 (3)
H1A	0.0603	0.6943	−0.1294	0.024*
H1B	0.0126	0.6173	−0.0285	0.024*
C2	0.2734 (3)	0.57695 (18)	−0.07559 (15)	0.0222 (3)
H2A	0.1811	0.4660	−0.1253	0.027*
H2B	0.3524	0.5713	0.0018	0.027*
C3	0.4379 (3)	0.64240 (18)	−0.13651 (14)	0.0200 (3)
H3A	0.5084	0.5631	−0.1570	0.024*
H3B	0.3618	0.6566	−0.2112	0.024*
C4	0.5382 (3)	0.65484 (19)	0.42206 (15)	0.0226 (3)
H4A	0.5551	0.6437	0.5024	0.027*
H4B	0.6151	0.5921	0.3839	0.027*
C5	0.2966 (3)	0.5844 (2)	0.34818 (16)	0.0264 (4)
H5A	0.2774	0.6134	0.2738	0.032*
H5B	0.2489	0.4657	0.3263	0.032*
C6	0.1537 (3)	0.64477 (19)	0.41474 (16)	0.0246 (4)
H6A	0.0017	0.5803	0.3696	0.030*
H6B	0.1856	0.6275	0.4934	0.030*
H1	0.667 (3)	0.788 (2)	0.0068 (17)	0.018 (5)*
H2	0.707 (3)	0.830 (2)	−0.0962 (16)	0.018 (4)*
H3	0.319 (3)	0.826 (2)	0.1079 (18)	0.030 (5)*
H4	0.165 (3)	0.882 (2)	0.0580 (18)	0.031 (6)*
H5	0.765 (3)	0.868 (2)	0.4867 (18)	0.023 (5)*
H6	0.663 (3)	0.836 (2)	0.3633 (18)	0.029 (5)*
H7	0.127 (3)	0.852 (2)	0.490 (2)	0.037 (6)*
H8	0.122 (3)	0.828 (2)	0.3723 (18)	0.022 (5)*
H9	0.533 (4)	1.078 (3)	0.295 (2)	0.041 (6)*
H10	0.357 (4)	1.070 (3)	0.299 (2)	0.042 (7)*

	U11	U22	U33	U12	U13	U23
Ni1	0.00944 (13)	0.01273 (13)	0.01009 (13)	0.00461 (10)	0.00306 (10)	0.00329 (10)
Ni2	0.01046 (13)	0.01788 (14)	0.01234 (14)	0.00583 (10)	0.00410 (10)	0.00503 (10)
S1	0.01275 (17)	0.02077 (18)	0.01136 (17)	0.00832 (14)	0.00423 (14)	0.00661 (14)
O1	0.0124 (5)	0.0248 (5)	0.0122 (5)	0.0096 (4)	0.0042 (4)	0.0067 (4)
O2	0.0192 (6)	0.0456 (7)	0.0277 (6)	0.0188 (5)	0.0154 (5)	0.0192 (6)
O3	0.0206 (6)	0.0370 (6)	0.0124 (5)	0.0131 (5)	0.0019 (5)	0.0036 (5)
O4	0.0374 (7)	0.0228 (6)	0.0256 (6)	0.0128 (5)	0.0043 (6)	0.0099 (5)
O5	0.0158 (6)	0.0495 (8)	0.0182 (6)	0.0175 (6)	0.0084 (5)	0.0176 (5)
N1	0.0169 (6)	0.0183 (6)	0.0196 (7)	0.0065 (5)	0.0085 (6)	0.0067 (5)
N2	0.0158 (6)	0.0186 (6)	0.0140 (6)	0.0085 (5)	0.0051 (5)	0.0052 (5)
N3	0.0129 (6)	0.0215 (6)	0.0152 (7)	0.0070 (5)	0.0037 (6)	0.0052 (5)
N4	0.0143 (6)	0.0239 (7)	0.0164 (7)	0.0073 (5)	0.0040 (6)	0.0070 (5)
C1	0.0156 (7)	0.0162 (7)	0.0260 (8)	0.0015 (6)	0.0050 (7)	0.0071 (6)
C2	0.0254 (8)	0.0139 (7)	0.0264 (9)	0.0059 (6)	0.0076 (7)	0.0059 (6)
C3	0.0225 (8)	0.0172 (7)	0.0182 (8)	0.0082 (6)	0.0054 (7)	0.0012 (6)
C4	0.0214 (8)	0.0214 (8)	0.0251 (8)	0.0108 (6)	0.0052 (7)	0.0052 (6)
C5	0.0225 (8)	0.0209 (8)	0.0279 (9)	0.0056 (6)	0.0027 (7)	0.0005 (7)
C6	0.0181 (8)	0.0224 (8)	0.0299 (9)	0.0033 (6)	0.0062 (7)	0.0079 (7)

Ni1—N1i	2.0978 (13)	N2—H2	0.923 (19)
Ni1—N1	2.0978 (13)	N3—C4	1.479 (2)
Ni1—N2i	2.1187 (13)	N3—H5	0.86 (2)
Ni1—N2	2.1187 (13)	N3—H6	0.90 (2)
Ni1—O1i	2.1257 (10)	N4—C6	1.479 (2)
Ni1—O1	2.1257 (10)	N4—H7	0.91 (2)
Ni2—N3ii	2.0893 (13)	N4—H8	0.76 (2)
Ni2—N3	2.0893 (13)	C1—C2	1.518 (2)
Ni2—N4ii	2.1083 (13)	C1—H1A	0.9700
Ni2—N4	2.1083 (13)	C1—H1B	0.9700
Ni2—O5	2.1499 (12)	C2—C3	1.521 (2)
Ni2—O5ii	2.1499 (12)	C2—H2A	0.9700
S1—O3	1.4645 (11)	C2—H2B	0.9700
S1—O4	1.4682 (12)	C3—H3A	0.9700
S1—O2	1.4688 (11)	C3—H3B	0.9700
S1—O1	1.4945 (10)	C4—C5	1.521 (2)
O5—H9	0.82 (2)	C4—H4A	0.9700
O5—H10	0.70 (2)	C4—H4B	0.9700
N1—C1	1.4806 (19)	C5—C6	1.514 (2)
N1—H3	0.88 (2)	C5—H5A	0.9700
N1—H4	0.84 (2)	C5—H5B	0.9700
N2—C3	1.4785 (19)	C6—H6A	0.9700
N2—H1	0.823 (19)	C6—H6B	0.9700
N1i—Ni1—N1	180.0	Ni1—N2—H2	109.3 (11)
N1i—Ni1—N2i	87.81 (5)	H1—N2—H2	109.5 (16)
N1—Ni1—N2i	92.19 (5)	C4—N3—Ni2	120.00 (10)
N1i—Ni1—N2	92.19 (5)	C4—N3—H5	108.9 (13)
N1—Ni1—N2	87.81 (5)	Ni2—N3—H5	100.4 (12)
N2i—Ni1—N2	180.0	C4—N3—H6	108.8 (12)
N1i—Ni1—O1i	88.28 (5)	Ni2—N3—H6	112.6 (13)
N1—Ni1—O1i	91.72 (5)	H5—N3—H6	104.8 (17)
N2i—Ni1—O1i	92.13 (5)	C6—N4—Ni2	121.41 (10)
N2—Ni1—O1i	87.87 (5)	C6—N4—H7	106.6 (13)
N1i—Ni1—O1	91.72 (5)	Ni2—N4—H7	101.2 (13)
N1—Ni1—O1	88.28 (5)	C6—N4—H8	107.8 (14)
N2i—Ni1—O1	87.87 (5)	Ni2—N4—H8	109.4 (14)
N2—Ni1—O1	92.13 (5)	H7—N4—H8	110 (2)
O1i—Ni1—O1	180.00 (6)	N1—C1—C2	111.30 (13)
N3ii—Ni2—N3	180.000 (1)	N1—C1—H1A	109.4
N3ii—Ni2—N4ii	91.66 (5)	C2—C1—H1A	109.4
N3—Ni2—N4ii	88.34 (5)	N1—C1—H1B	109.4
N3ii—Ni2—N4	88.34 (5)	C2—C1—H1B	109.4
N3—Ni2—N4	91.66 (5)	H1A—C1—H1B	108.0
N4ii—Ni2—N4	180.00 (7)	C1—C2—C3	115.06 (13)
N3ii—Ni2—O5	87.79 (5)	C1—C2—H2A	108.5
N3—Ni2—O5	92.21 (5)	C3—C2—H2A	108.5
N4ii—Ni2—O5	87.84 (5)	C1—C2—H2B	108.5
N4—Ni2—O5	92.16 (5)	C3—C2—H2B	108.5
N3ii—Ni2—O5ii	92.21 (5)	H2A—C2—H2B	107.5
N3—Ni2—O5ii	87.79 (5)	N2—C3—C2	111.60 (13)
N4ii—Ni2—O5ii	92.16 (5)	N2—C3—H3A	109.3
N4—Ni2—O5ii	87.84 (5)	C2—C3—H3A	109.3
O5—Ni2—O5ii	180.000 (1)	N2—C3—H3B	109.3
O3—S1—O4	110.23 (7)	C2—C3—H3B	109.3
O3—S1—O2	110.28 (7)	H3A—C3—H3B	108.0
O4—S1—O2	109.99 (7)	N3—C4—C5	112.50 (13)
O3—S1—O1	107.70 (6)	N3—C4—H4A	109.1
O4—S1—O1	109.11 (7)	C5—C4—H4A	109.1
O2—S1—O1	109.48 (6)	N3—C4—H4B	109.1
S1—O1—Ni1	130.04 (6)	C5—C4—H4B	109.1
Ni2—O5—H9	127.9 (16)	H4A—C4—H4B	107.8
Ni2—O5—H10	128.6 (19)	C6—C5—C4	113.29 (14)
H9—O5—H10	101 (2)	C6—C5—H5A	108.9
C1—N1—Ni1	116.97 (10)	C4—C5—H5A	108.9
C1—N1—H3	110.9 (12)	C6—C5—H5B	108.9
Ni1—N1—H3	105.9 (13)	C4—C5—H5B	108.9
C1—N1—H4	108.0 (13)	H5A—C5—H5B	107.7
Ni1—N1—H4	111.9 (13)	N4—C6—C5	113.15 (13)
H3—N1—H4	102.2 (18)	N4—C6—H6A	108.9
C3—N2—Ni1	117.85 (10)	C5—C6—H6A	108.9
C3—N2—H1	108.5 (12)	N4—C6—H6B	108.9
Ni1—N2—H1	103.6 (12)	C5—C6—H6B	108.9
C3—N2—H2	107.8 (11)	H6A—C6—H6B	107.8

D—H···A	D—H	H···A	D···A	D—H···A
O5—H9···O1	0.82 (2)	1.96 (2)	2.7739 (16)	172 (2)
N2—H1···O4	0.823 (19)	2.265 (19)	3.0528 (18)	160.4 (16)
N1—H4···O2iii	0.84 (2)	2.28 (2)	3.0621 (18)	154.9 (18)
O5—H10···O2iii	0.70 (2)	2.15 (3)	2.8476 (18)	179 (3)
N3—H5···O3iv	0.86 (2)	2.06 (2)	2.8900 (17)	161.4 (17)
N2—H2···O2v	0.923 (19)	2.145 (19)	3.0600 (17)	171.2 (15)
N4—H7···O3ii	0.91 (2)	2.03 (2)	2.9269 (18)	170 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H9⋯O1	0.82 (2)	1.96 (2)	2.7739 (16)	172 (2)
N2—H1⋯O4	0.823 (19)	2.265 (19)	3.0528 (18)	160.4 (16)
N1—H4⋯O2i	0.84 (2)	2.28 (2)	3.0621 (18)	154.9 (18)
O5—H10⋯O2i	0.70 (2)	2.15 (3)	2.8476 (18)	179 (3)
N3—H5⋯O3ii	0.86 (2)	2.06 (2)	2.8900 (17)	161.4 (17)
N2—H2⋯O2iii	0.923 (19)	2.145 (19)	3.0600 (17)	171.2 (15)
N4—H7⋯O3iv	0.91 (2)	2.03 (2)	2.9269 (18)	170 (2)

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