Diaquabis(1,3-propanediamine-κ²N,N′)nickel(II) bis(sulfanilate)

The title compound, [Ni(C₃H₁₀N₂)₂(H₂O)₂](C₆H₆NO₃S)₂, contains alternating layers of sulfanilate anions and di­aqua­bis(1,3-propane­di­amine)­nickel(II) cations. The Ni atom lies on an inversion centre and is hexacoordinated by the 1,3-propane­di­amine ligands, which function as N,N′-bidentate ligands, and the water mol­ecules, which are in a trans arrangement. The sulfanilate anions are arranged in layers, with the sulfonate and amine groups directed towards opposite sides of the layer. The structure is stabilized by a network of hydrogen bonding between the O and N atoms of the sulfanilate anions, the water mol­ecules, and the N atoms of the 1,3-propane­di­amine ligands.

S1. Comment

Layered compounds have been of great interest in both academic research and industrial applications because of their possible use as ion exchangers and intercalation materials (Clearfield, 1988). In particular, synthetic compounds such as the metal phosphates have been extensively studied as a new family of layered materials (Alberti, 1996). Most commonly, these layered compounds contain covalent metal-oxygen-nonmetal (Si or P) frameworks. In recent years, the metal organosulfonate compounds have been studied as a new family of layered materials by Squattrito et al. (Kosnic et al., 1992; Benedetto et al., 1997). In our group, research has focused on the development of new layered and porous materials, using weaker metal-sulfonate interactions and the chelating behaviour of diamine ligands, such as ethylenediamine or 1,2-propanediamine (Kim & Lee, 2001). In this paper, we report the preparation and crystal structure of the nickel(II) sulfanilate complex with the 1,3-propanediamine ligand, (I). \sch

As shown in Fig. 1, the Ni^II atom of cation of (I) rests on a crystallographic inversion centre, and is hexacoordinated by the O atoms of two water molecules in a trans arrangement and by the amine N atoms of two 1,3-propanediamine ligands at the equatorial positions. It is suggested that the trans geometry is favoured when the amine ligand is more bulky. Thus, the coordination environment of Ni in (I) shows a slightly distorted octahedron, similar to the previously reported nickel(II)-1,3-propanediamine-thiocyanate system (Moore & Squattrito, 1999).

The six-membered chelate rings of the 1,3-propanediamine ligands are in the stable chair conformation [Ni1—N10—C11—C12 - 55.7 (2) and Ni1—N20—C13—C12 51.9 (2)°]. As listed in Table 1, the Ni—N distances range from 2.100 (1) to 2.113 (1) Å and the Ni—O distance is 2.136 (1) Å. The intra-ligand N—Ni—N angle is 92.39 (6)°, while the inter-ligand N—Ni—N angle 87.61 (6)°. The N—Ni—O angles are in the range 88.80 (6)–91.20 (6)°. The bond distances and angles of the sulfanilate anion are consistent with those reported previously (Shakeri & Haussuhl, 1992).

As shown in Fig. 2, the packing diagram of (I) reveals a layered structure, with dicationic diaquabis(1,3-propanediamine)nickel(II) [Ni{NH₂(CH₂)₃NH₂}₂(H₂O)₂]²⁺ layers and anionic sulfanilate NH₂C₆H₄SO₃^- layers that stack along the a axis. Neighbouring sulfanilate anions within a layer have the amine and sulfonate groups oriented towards opposite sides of the layer. In addition, they are slightly slanted towards the c axis.

It is evident that there may be a π–π interaction between the sulfanilate anions (Janiak, 2000). Such π–π interactions provide important non-covalent intermolecular forces similar to hydrogen bonding, because they can contribute to the formation of the crystal structure of a metal complex from building blocks with aromatic moieties. This anion packing arrangement is also observed in another metal sulfanilate complex (Bats, 1977). However, there is no direct bonding between the Ni^II atom and the sulfonate O or amine N atoms of the anion. On the other hand, the Cu^II cation of [Cu(NH₂C₆H₄SO₃)₂(H₂O)₂]·2H₂O and the Mn^II cation of [Mn(NH₂C₆H₄SO₃)₂(H₂O)₂] are coordinated to the sulfonate O and amine N atoms of the sulfanilate anions (Gunderman et al., 1996). The Nd^III cation of [Nd(NH₂C₆H₄SO₃)₂(H₂O)₇](NH₂C₆H₄SO₃)·H₂O is directly coordinated to the sulfonate O atoms of two sulfanilate anions and uncoordinated to one sulfanilate anion (Starynowicz, 1992). Therefore, the title Ni^II sulfanilate compound, (I), is quite different in structure from the previously reported Cu^II, Mn^II and Nd^III sulfanilate complexes.

As listed in Table 2, the coordinated water molecules in the Ni^II cations and the sulfonate O and N atoms of the sulfanilate anions are linked together by hydrogen bonds (O1W—H1WB···O2, O1W—H1WA···N1, N1—H1A···O1 and N1—H1B···O2) along the [010] axis. These hydrogen-bond chains are cross-linked in the (110) plane by the N_diamine—H···O_sulfonate (N10—H10A···O1, N10—H10B···O2 and N20—H20B···O3) hydrogen-bonding interactions formed between the amine H atoms of the 1,3-propanediamine ligands and the sulfonate O atoms of the sulfanilate anions. Therefore, all the hydrogen bonds are formed by contacts between cations and anions, and the crystal structure is reinforced by further hydrogen bonds Involving which atoms?. This layer structure, with extended hydrogen-bonding interactions between metal-ligated cations and unligated anions, is also observed in calcium naphthionate octahydrate (Brown et al., 1984) and diamino-bipyridine metal complexes (Janiak et al., 1999).

S2. Experimental

NiCl₂·6H₂O (2.38 g) was mixed with sulfanilic acid (1.90 g) in water (50 ml). To this solution, 1,3-propanediamine (1.5 ml) was added dropwise. The resulting solution was filtered and the filtrate was kept in a refrigerator at 278 K. Blue block crystals of (I) suitable for X-ray analysis were obtained after a few weeks (yield 70%). Analysis calculated for C₁₈H₃₆N₆O₈S₂Ni: C 36.81, H 6.18, N 14.31, O 21.79, S 10.92, Ni 9.99%; found: C 36.77, H 6.22, N 14.32, O 21.03, S 10.85, Ni 10.18%.

S3. Refinement

Water H atoms were refined freely. All other H atoms were treated as riding, with N—H = 0.86–0.90 Å and C—H = 0.93–0.97 Å. Is this added text correct?

Computing details

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: SHELXTL (Siemens, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976) and SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. A view of the molecule of (I) with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A perspective view of the unit cell of (I) along the b axis; hydrogen bonds are shown by broken lines.

Diaquabis(1,3-propanediamine-κ²N,N')nickel(II) bis(sulfanilate)

Crystal data

[Ni(C3H10N2)2(H2O)2](C6H6NO3S)2	F(000) = 620
Mr = 587.36	Dx = 1.524 Mg m^−3 Dm = 1.52 Mg m^−3 Dm measured by flotation in mesitylene-bromoform
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.6079 (12) Å	Cell parameters from 54 reflections
b = 8.9177 (11) Å	θ = 3.5–12.5°
c = 16.717 (3) Å	µ = 0.98 mm^−1
β = 93.841 (13)°	T = 293 K
V = 1280.3 (3) Å^3	Block, blue
Z = 2	0.50 × 0.41 × 0.32 mm

Data collection

Siemens P4 diffractometer	2766 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.027
Graphite monochromator	θmax = 27.5°, θmin = 2.4°
ω/2θ scans	h = −1→11
Absorption correction: empirical (using intensity measurements) (North et al., 1968)	k = −1→11
Tmin = 0.604, Tmax = 0.732	l = −21→21
3949 measured reflections	3 standard reflections every 97 reflections
2932 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.084	w = 1/[σ^2(Fo^2) + (0.0411P)^2 + 0.5564P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
2932 reflections	Δρmax = 0.41 e Å^−3
169 parameters	Δρmin = −0.44 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.080 (3)

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
Ni1	0.5000	0.5000	0.0000	0.02678 (12)
O1W	0.64728 (17)	0.44675 (16)	0.10403 (8)	0.0401 (3)
H1WA	0.646 (4)	0.495 (3)	0.146 (2)	0.067 (9)*
H1WB	0.639 (3)	0.363 (4)	0.1222 (16)	0.069 (9)*
N10	0.35586 (17)	0.31640 (16)	0.02160 (9)	0.0358 (3)
H10A	0.3649	0.2498	−0.0183	0.043*
H10B	0.3933	0.2721	0.0673	0.043*
C11	0.1889 (2)	0.3451 (2)	0.02847 (13)	0.0432 (4)
H11A	0.1379	0.2519	0.0412	0.052*
H11B	0.1433	0.3799	−0.0228	0.052*
C12	0.1589 (3)	0.4599 (3)	0.09195 (14)	0.0489 (5)
H12A	0.2205	0.4341	0.1407	0.059*
H12B	0.0501	0.4550	0.1034	0.059*
C13	0.1971 (2)	0.6197 (2)	0.06876 (12)	0.0431 (4)
H13A	0.1473	0.6412	0.0162	0.052*
H13B	0.1546	0.6882	0.1068	0.052*
N20	0.36613 (17)	0.64655 (17)	0.06699 (9)	0.0367 (3)
H20A	0.4070	0.6453	0.1180	0.044*
H20B	0.3791	0.7399	0.0481	0.044*
S1	0.69591 (5)	0.03898 (5)	0.10808 (2)	0.03117 (13)
O1	0.65184 (17)	−0.11253 (15)	0.12870 (9)	0.0459 (3)
O2	0.59833 (15)	0.15130 (15)	0.14451 (8)	0.0415 (3)
O3	0.70337 (17)	0.05997 (18)	0.02269 (8)	0.0468 (3)
C1	0.88643 (19)	0.06886 (18)	0.15185 (9)	0.0304 (3)
C2	0.9124 (2)	0.1606 (2)	0.21812 (11)	0.0391 (4)
H2A	0.8288	0.2081	0.2399	0.047*
C3	1.0614 (2)	0.1822 (2)	0.25222 (11)	0.0399 (4)
H3A	1.0770	0.2434	0.2971	0.048*
C4	1.1881 (2)	0.11358 (18)	0.22019 (9)	0.0315 (3)
C5	1.1618 (2)	0.02138 (19)	0.15309 (11)	0.0345 (4)
H5A	1.2452	−0.0258	0.1310	0.041*
C6	1.0128 (2)	−0.00019 (18)	0.11942 (10)	0.0335 (4)
H6A	0.9967	−0.0615	0.0746	0.040*
N1	1.33816 (17)	0.13562 (18)	0.25594 (9)	0.0380 (3)
H1A	1.3518	0.1916	0.2977	0.046*
H1B	1.4167	0.0932	0.2361	0.046*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.02931 (17)	0.01929 (17)	0.03119 (17)	0.00093 (9)	−0.00198 (11)	−0.00145 (9)
O1W	0.0525 (8)	0.0293 (7)	0.0367 (7)	0.0032 (6)	−0.0102 (6)	−0.0003 (5)
N10	0.0367 (7)	0.0240 (7)	0.0460 (8)	−0.0013 (5)	−0.0025 (6)	0.0006 (6)
C11	0.0364 (9)	0.0325 (9)	0.0605 (11)	−0.0045 (7)	0.0016 (8)	0.0076 (8)
C12	0.0462 (11)	0.0439 (11)	0.0584 (12)	0.0016 (9)	0.0174 (9)	0.0107 (9)
C13	0.0406 (9)	0.0354 (9)	0.0543 (11)	0.0069 (7)	0.0114 (8)	0.0028 (8)
N20	0.0399 (8)	0.0290 (7)	0.0411 (7)	0.0042 (6)	0.0008 (6)	−0.0051 (6)
S1	0.0361 (2)	0.0233 (2)	0.0339 (2)	0.00114 (15)	0.00062 (15)	0.00176 (14)
O1	0.0535 (8)	0.0268 (7)	0.0557 (8)	−0.0072 (6)	−0.0075 (6)	0.0068 (6)
O2	0.0374 (6)	0.0341 (7)	0.0535 (7)	0.0054 (5)	0.0056 (5)	−0.0025 (6)
O3	0.0532 (8)	0.0524 (9)	0.0341 (6)	0.0025 (7)	−0.0021 (6)	0.0041 (6)
C1	0.0358 (8)	0.0241 (7)	0.0314 (7)	0.0009 (6)	0.0035 (6)	0.0006 (6)
C2	0.0394 (9)	0.0395 (10)	0.0389 (8)	0.0048 (7)	0.0078 (7)	−0.0101 (7)
C3	0.0433 (9)	0.0403 (9)	0.0362 (8)	0.0007 (8)	0.0037 (7)	−0.0135 (7)
C4	0.0382 (8)	0.0264 (8)	0.0300 (7)	−0.0009 (6)	0.0034 (6)	0.0034 (6)
C5	0.0388 (9)	0.0307 (8)	0.0346 (8)	0.0051 (7)	0.0079 (7)	−0.0032 (6)
C6	0.0431 (9)	0.0268 (8)	0.0309 (8)	0.0024 (6)	0.0040 (7)	−0.0051 (6)
N1	0.0373 (7)	0.0381 (8)	0.0385 (7)	0.0001 (6)	0.0018 (6)	−0.0025 (6)

Geometric parameters (Å, º)

Ni1—N10^i	2.1002 (14)	N20—H20A	0.9000
Ni1—N10	2.1002 (14)	N20—H20B	0.9000
Ni1—N20^i	2.1125 (14)	S1—O3	1.4454 (13)
Ni1—N20	2.1125 (14)	S1—O1	1.4512 (13)
Ni1—O1W^i	2.1358 (13)	S1—O2	1.4656 (13)
Ni1—O1W	2.1358 (13)	S1—C1	1.7706 (17)
O1W—H1WA	0.83 (3)	C1—C2	1.383 (2)
O1W—H1WB	0.81 (3)	C1—C6	1.391 (2)
N10—C11	1.472 (2)	C2—C3	1.382 (3)
N10—H10A	0.9000	C2—H2A	0.9300
N10—H10B	0.9000	C3—C4	1.389 (2)
C11—C12	1.509 (3)	C3—H3A	0.9300
C11—H11A	0.9700	C4—C5	1.397 (2)
C11—H11B	0.9700	C4—N1	1.400 (2)
C12—C13	1.519 (3)	C5—C6	1.379 (3)
C12—H12A	0.9700	C5—H5A	0.9300
C12—H12B	0.9700	C6—H6A	0.9300
C13—N20	1.477 (2)	N1—H1A	0.8600
C13—H13A	0.9700	N1—H1B	0.8600
C13—H13B	0.9700
N10^i—Ni1—N10	180.0	C12—C13—H13A	109.0
N10^i—Ni1—N20^i	92.39 (6)	N20—C13—H13B	109.0
N10—Ni1—N20^i	87.61 (6)	C12—C13—H13B	109.0
N10^i—Ni1—N20	87.61 (6)	H13A—C13—H13B	107.8
N10—Ni1—N20	92.39 (6)	C13—N20—Ni1	118.91 (12)
N20^i—Ni1—N20	180.00 (7)	C13—N20—H20A	107.6
N10^i—Ni1—O1W^i	90.69 (6)	Ni1—N20—H20A	107.6
N10—Ni1—O1W^i	89.31 (6)	C13—N20—H20B	107.6
N20^i—Ni1—O1W^i	91.20 (6)	Ni1—N20—H20B	107.6
N20—Ni1—O1W^i	88.80 (6)	H20A—N20—H20B	107.0
N10^i—Ni1—O1W	89.31 (6)	O3—S1—O1	112.63 (9)
N10—Ni1—O1W	90.69 (6)	O3—S1—O2	112.73 (9)
N20^i—Ni1—O1W	88.80 (6)	O1—S1—O2	111.80 (9)
N20—Ni1—O1W	91.20 (6)	O3—S1—C1	106.70 (8)
O1W^i—Ni1—O1W	180.00 (9)	O1—S1—C1	106.95 (8)
Ni1—O1W—H1WA	123 (2)	O2—S1—C1	105.44 (8)
Ni1—O1W—H1WB	117 (2)	C2—C1—C6	119.04 (16)
H1WA—O1W—H1WB	99 (3)	C2—C1—S1	121.01 (13)
C11—N10—Ni1	117.98 (11)	C6—C1—S1	119.95 (13)
C11—N10—H10A	107.8	C3—C2—C1	120.56 (16)
Ni1—N10—H10A	107.8	C3—C2—H2A	119.7
C11—N10—H10B	107.8	C1—C2—H2A	119.7
Ni1—N10—H10B	107.8	C2—C3—C4	120.72 (16)
H10A—N10—H10B	107.1	C2—C3—H3A	119.6
N10—C11—C12	112.73 (17)	C4—C3—H3A	119.6
N10—C11—H11A	109.0	C3—C4—C5	118.63 (16)
C12—C11—H11A	109.0	C3—C4—N1	119.96 (15)
N10—C11—H11B	109.0	C5—C4—N1	121.40 (15)
C12—C11—H11B	109.0	C6—C5—C4	120.44 (16)
H11A—C11—H11B	107.8	C6—C5—H5A	119.8
C11—C12—C13	114.02 (17)	C4—C5—H5A	119.8
C11—C12—H12A	108.7	C5—C6—C1	120.61 (15)
C13—C12—H12A	108.7	C5—C6—H6A	119.7
C11—C12—H12B	108.7	C1—C6—H6A	119.7
C13—C12—H12B	108.7	C4—N1—H1A	120.0
H12A—C12—H12B	107.6	C4—N1—H1B	120.0
N20—C13—C12	112.79 (16)	H1A—N1—H1B	120.0
N20—C13—H13A	109.0
N20^i—Ni1—N10—C11	−146.82 (14)	O2—S1—C1—C2	12.05 (17)
N20—Ni1—N10—C11	33.18 (14)	O3—S1—C1—C6	−47.69 (16)
O1W^i—Ni1—N10—C11	−55.59 (14)	O1—S1—C1—C6	73.07 (15)
O1W—Ni1—N10—C11	124.41 (14)	O2—S1—C1—C6	−167.79 (13)
Ni1—N10—C11—C12	−55.74 (19)	C6—C1—C2—C3	−0.7 (3)
N10—C11—C12—C13	73.2 (2)	S1—C1—C2—C3	179.47 (15)
C11—C12—C13—N20	−70.8 (2)	C1—C2—C3—C4	0.7 (3)
C12—C13—N20—Ni1	51.9 (2)	C2—C3—C4—C5	−0.4 (3)
N10^i—Ni1—N20—C13	148.30 (13)	C2—C3—C4—N1	−179.42 (17)
N10—Ni1—N20—C13	−31.70 (13)	C3—C4—C5—C6	0.2 (3)
O1W^i—Ni1—N20—C13	57.56 (13)	N1—C4—C5—C6	179.22 (16)
O1W—Ni1—N20—C13	−122.44 (13)	C4—C5—C6—C1	−0.3 (3)
O3—S1—C1—C2	132.15 (15)	C2—C1—C6—C5	0.5 (3)
O1—S1—C1—C2	−107.09 (16)	S1—C1—C6—C5	−179.66 (13)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···N1^ii	0.83 (3)	2.06 (3)	2.880 (2)	172 (3)
O1W—H1WB···O2	0.81 (3)	1.96 (3)	2.760 (2)	168 (3)
N10—H10A···O1^iii	0.90	2.21	3.098 (2)	168
N10—H10B···O2	0.90	2.37	3.189 (2)	151
N20—H20B···O3^i	0.90	2.23	3.055 (2)	152
N1—H1A···O1^ii	0.86	2.14	2.958 (2)	159
N1—H1B···O2^iv	0.86	2.32	3.011 (2)	138

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