mer-(4-Amino­benzene­sulfonato-κN)tri­aqua(1,10-phenanthroline-κ²N,N′)cobalt(II) chloride

Both coordination and hydrogen bonds contribute to networking in the supramolecular title compound, [Co(C₆H₆­NO₃S)(C₁₂H₈N₂)(H₂O)₃]Cl, which contains a discrete [Co(C₆H₆NO₃S)(C₁₂H₈N₂)(H₂O)₃]⁺ complex cation, formed by one 4-amino­benzene­sulfonate ligand, one 1,10-phenanthroline ligand and three coordinated water mol­ecules, together with one uncoordinated chloride anion. These discrete cations and chloride anions are connected by hydrogen-bonding interactions into a two-dimensional supramolecular motif. Further hydrogen-bonding interactions consolidate the structural architecture and extend the two-dimensional supramol­ecular structure into a three-dimensional network.

S1. Comment

Supramolecular frameworks based on metal and organic building blocks that contain diverse topologies with desired features are increasing receiving attention, because of their promising potential properties in catalysis (Fujita et al., 1994), gas storage (Kitaura et al., 2003) and magnetism (Inoue et al., 1996). However, there have been few reports of metal-based organosulfonate anions containing supramolecular compounds to date (Cai et al., 2001a; Cai et al., 2001b; Wang et al., 2002). We present here a novel compound, [Co(H₂O)₃(C₆H₆NO₃S)(C₁₂H₈N₂)]⁺Cl⁻ (1), built from discrete [Co(H₂O)₃(C₆H₆NO₃S)(C₁₂H₈N₂)]⁺ cations, each formed by one 4-aminobenzenesulfonate (4-ABS) ligand, one 1,10-phenanthroline (1,10-phen) ligand and three coordinated water molecules, and one uncoordinated chlorine anion.

As depicted by Fig. 1, the Co^II center exhibits slightly distorted octahedral coordination geometry, defined by three aqua O atoms [Co—OW1 = 2.065 (2) Å, Co—OW2 = 2.083 (2) Å and Co—OW3 = 2.0912 (18) Å], and two N atoms from a 1,10-phen ligand [Co—N1 = 2.119 (2) Å and Co—N2 = 2.116 (2) Å], and an N atom donor from a 4-ABS ligand [Co—N3 = 2.270 (2) Å]. The coordination environment and mode of 4-ABS differ from that in [Co(H₂O)₄(4-ABS)₂(4,4'-bipy)]·H₂O (Wang et al., 2002), in which the 4-ABS ligands are not coordinated to Co^II and form one-dimensional head-to-tail zigzag chains via hydrogen-bonding interactions. The two different rings from the 4-ABS and 1,10-phen groups are not completely parallel to one another, the dihedral angles between their planes being 12.6° and their average ring separation being 3.324 Å.

As shown in Fig. 2, these discrete [Co(H₂O)₃(C₆H₆NO₃S)(C₁₂H₈N₂)]⁺ cations and chloride anions are connected into a two-dimensional supramolecular motif. The rings of two 4-ABS and two 1,10-phen ligands from two different discrete cations lie parallel to one another. In the supramolecular architecture, unusual hydrogen-bonding interactions play a crucial role. The coordinated water molecules (OW2 and OW1) from one [Co(H₂O)₃(4-ABS)(1,10-phen)]⁺ cation interact with the SO₃⁻ group of the 4-ABS ligand from another, thus forming hydrogen-bonding interactions. ##AUTHOR: Supply s.u.'s for all the following O···O and Cl···O distances: [OW2A···O1 = 2.875 (2) and OW2A···O1(2) = 2.664(?) Å]. Furthermore, the coordinated water molecules (OW2 and OW1) from two adjacent cations are bridged via hydrogen-bonding interactions with a chloride anion [Cl···OW1 = 3.072(?) Å and Cl···OW2 = 3.018(?) Å]. In addition, there are hydrogen-bonding interactions between the OW3 coordinated water molecules and the SO₃⁻ groups of 4-ABS anions from two adjacent building blocks [O1···OW3 = 2.824(?)Å and O2···OW3 = 2.748(?) Å]. Therefore, such hydrogen-bonding interactions consolidate the structural architecture and further extend the two-dimensional supramolecular structure into a three-dimensional network containing many nanocavities formed by hydrogen bonds (see Fig. 3). ##AUTHOR: Are these "nanocavities" still present when (a) H atoms are considered and (b) van der Waals radii are used? Please check. If they are present I would expect to find voids in the structure.

S2. Experimental

To a solution of CoCl₂·6H₂O (0.2379 g, 1.00 mmol) was added 4-aminobenzenesulfonic acid (0.074 g, 0.54 mmol) with stirring. ##AUTHOR: Give temperature used for the above reaction. After the solution pH had been adjusted to ca 5.5 with dilute NaOH, 1,10-phen (0.078 g, 0.50 mmol) was added slowly and the mixture was stirred for 30 min at 333 K. After filtration, a clear orange solution was obtained, which was allowed to stand at room temperatur. Orange crystals were obtained after two weeks.

S3. Refinement

An 8% decay correction was applied to the data during processing. Water H atoms were located from difference maps and their positions were fixed during refinement. Other H atoms were placed in geometric positions using a riding model, with C—H distances of 0.93 Å and N—H distances of 0.90 Å [U_iso(H) = 1.2 U_eq(C)].

Computing details

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: SHELXTL (Siemens, 1994); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecular structure of the title compound, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The two-dimensional network of [Co(H2O)3(4-ABS)(1,10-phen)]^+ cations and chloride anions formed via hydrogen-bonding interactions.
	Fig. 3. A packing diagram, showing the three-dimensional structure viewed along the a axis.

mer-(4-Aminobenzenesulfonate-κN)triaqua(1,10-phenanthroline- κ²N,N')cobalt(II) chloride

Crystal data

[Co(C6H6NO3S)(C12H8N2)(H2O)3]Cl	F(000) = 1028
Mr = 500.81	Dx = 1.616 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.0148 (10) Å	Cell parameters from 24 reflections
b = 15.896 (4) Å	θ = 5.2–10.2°
c = 18.587 (5) Å	µ = 1.11 mm^−1
β = 96.548 (18)°	T = 293 K
V = 2059.0 (8) Å^3	Block, orange
Z = 4	0.50 × 0.38 × 0.32 mm

Data collection

Siemens P4 diffractometer	2959 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.026
Graphite monochromator	θmax = 26.0°, θmin = 1.7°
ω scans	h = −1→8
Absorption correction: ψ scan (SHELXTL; Siemens, 1994)	k = −1→19
Tmin = 0.561, Tmax = 0.687	l = −22→22
5562 measured reflections	3 standard reflections every 97 reflections
4060 independent reflections	intensity decay: 8.0%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.073	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.02P)^2] where P = (Fo^2 + 2Fc^2)/3
4060 reflections	(Δ/σ)max = 0.001
271 parameters	Δρmax = 0.31 e Å^−3
0 restraints	Δρmin = −0.37 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Co	0.18360 (6)	0.18776 (2)	0.42688 (2)	0.0273 (1)
S	−0.16070 (10)	0.48381 (4)	0.14583 (3)	0.0277 (2)
O1	−0.0033 (3)	0.46813 (11)	0.10247 (10)	0.0387 (7)
OW1	0.0349 (3)	0.15217 (13)	0.51162 (11)	0.0521 (8)
O2	−0.3478 (3)	0.47139 (11)	0.10292 (9)	0.0350 (6)
OW2	0.4412 (3)	0.14893 (11)	0.48404 (10)	0.0437 (7)
O3	−0.1511 (3)	0.56343 (10)	0.18319 (9)	0.0398 (6)
OW3	0.1668 (3)	0.06711 (11)	0.38174 (10)	0.0366 (6)
N1	0.3058 (3)	0.24285 (13)	0.33898 (11)	0.0283 (7)
N2	0.2252 (3)	0.31366 (13)	0.46217 (11)	0.0292 (7)
N3	−0.1159 (3)	0.21745 (13)	0.37323 (11)	0.0311 (7)
C1	0.3422 (4)	0.20688 (17)	0.27748 (14)	0.0359 (9)
C2	0.3801 (5)	0.2534 (2)	0.21722 (15)	0.0443 (10)
C3	0.3821 (4)	0.33875 (19)	0.22010 (15)	0.0423 (10)
C4	0.3509 (4)	0.37970 (18)	0.28475 (15)	0.0356 (9)
C5	0.3116 (4)	0.32830 (15)	0.34274 (14)	0.0276 (8)
C6	0.2756 (4)	0.36596 (15)	0.40964 (14)	0.0290 (8)
C7	0.2905 (4)	0.45374 (16)	0.41875 (16)	0.0371 (9)
C8	0.2583 (5)	0.48595 (18)	0.48658 (17)	0.0475 (11)
C9	0.2159 (5)	0.43275 (19)	0.53929 (16)	0.0468 (10)
C10	0.1983 (4)	0.34738 (17)	0.52587 (14)	0.0372 (9)
C11	0.3577 (5)	0.46915 (18)	0.29430 (17)	0.0460 (11)
C12	0.3299 (5)	0.50389 (17)	0.35808 (18)	0.0473 (11)
C13	−0.1362 (4)	0.28042 (16)	0.31810 (13)	0.0282 (8)
C14	−0.1596 (4)	0.36385 (16)	0.33630 (13)	0.0314 (9)
C15	−0.1645 (4)	0.42566 (15)	0.28423 (13)	0.0307 (9)
C16	−0.1458 (4)	0.40461 (14)	0.21292 (13)	0.0262 (8)
C17	−0.1216 (4)	0.32105 (15)	0.19419 (13)	0.0306 (8)
C18	−0.1182 (4)	0.25938 (15)	0.24649 (14)	0.0315 (8)
Cl	0.22774 (12)	0.21391 (4)	0.02904 (4)	0.0433 (2)
H1	0.34230	0.14850	0.27450	0.0430*
HW1	0.07190	0.11440	0.54180	0.0630*
H2	0.40410	0.22600	0.17500	0.0530*
HW2	−0.07260	0.18240	0.52550	0.0630*
H3	0.40400	0.36990	0.17950	0.0510*
HW3	0.52740	0.19310	0.50390	0.0520*
H3A	−0.16690	0.16950	0.35390	0.0370*
H3B	−0.18750	0.23320	0.40820	0.0370*
HW4	0.45280	0.10360	0.51280	0.0520*
HW5	0.05590	0.03880	0.38600	0.0440*
HW6	0.28190	0.03790	0.39200	0.0440*
H8	0.26600	0.54350	0.49530	0.0570*
H9	0.19850	0.45370	0.58480	0.0560*
H10	0.16660	0.31220	0.56270	0.0450*
H11	0.38150	0.50350	0.25580	0.0550*
H12	0.33650	0.56210	0.36310	0.0570*
H14	−0.17210	0.37830	0.38400	0.0380*
H15	−0.18040	0.48160	0.29690	0.0370*
H17	−0.10770	0.30670	0.14660	0.0370*
H18	−0.10370	0.20330	0.23380	0.0380*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co	0.0355 (2)	0.0203 (2)	0.0257 (2)	−0.0001 (2)	0.0020 (2)	0.0024 (2)
S	0.0342 (4)	0.0189 (3)	0.0289 (3)	−0.0003 (3)	−0.0005 (3)	−0.0001 (3)
O1	0.0407 (13)	0.0335 (10)	0.0438 (11)	−0.0029 (10)	0.0131 (10)	0.0023 (9)
OW1	0.0613 (16)	0.0519 (12)	0.0468 (12)	0.0231 (12)	0.0222 (12)	0.0273 (10)
O2	0.0380 (12)	0.0289 (9)	0.0354 (10)	0.0036 (9)	−0.0075 (9)	−0.0033 (8)
OW2	0.0471 (13)	0.0306 (10)	0.0485 (12)	−0.0048 (10)	−0.0153 (11)	0.0074 (9)
O3	0.0587 (14)	0.0206 (9)	0.0378 (10)	−0.0025 (10)	−0.0039 (10)	−0.0031 (8)
OW3	0.0347 (11)	0.0249 (9)	0.0501 (11)	0.0001 (9)	0.0047 (10)	−0.0039 (8)
N1	0.0293 (13)	0.0274 (11)	0.0282 (11)	0.0020 (10)	0.0036 (10)	0.0008 (9)
N2	0.0342 (13)	0.0252 (10)	0.0276 (11)	−0.0015 (11)	0.0011 (10)	−0.0022 (9)
N3	0.0385 (14)	0.0255 (10)	0.0282 (11)	−0.0013 (11)	−0.0003 (11)	0.0035 (9)
C1	0.0365 (17)	0.0368 (15)	0.0348 (15)	0.0055 (14)	0.0061 (14)	−0.0023 (12)
C2	0.0434 (19)	0.0610 (19)	0.0302 (15)	0.0042 (17)	0.0115 (14)	−0.0019 (14)
C3	0.0396 (19)	0.0548 (18)	0.0337 (15)	−0.0008 (16)	0.0088 (14)	0.0159 (14)
C4	0.0274 (16)	0.0388 (15)	0.0392 (16)	−0.0007 (13)	−0.0019 (13)	0.0109 (13)
C5	0.0253 (15)	0.0239 (13)	0.0333 (14)	−0.0008 (11)	0.0021 (12)	0.0044 (10)
C6	0.0262 (15)	0.0241 (12)	0.0355 (14)	−0.0010 (12)	−0.0021 (12)	0.0025 (11)
C7	0.0359 (17)	0.0244 (13)	0.0492 (17)	−0.0008 (13)	−0.0026 (14)	−0.0005 (12)
C8	0.050 (2)	0.0282 (14)	0.062 (2)	0.0002 (15)	−0.0038 (18)	−0.0155 (15)
C9	0.055 (2)	0.0427 (17)	0.0423 (16)	−0.0009 (17)	0.0041 (16)	−0.0181 (14)
C10	0.0420 (18)	0.0389 (15)	0.0300 (14)	−0.0016 (14)	0.0017 (14)	−0.0031 (12)
C11	0.047 (2)	0.0369 (16)	0.0535 (19)	−0.0075 (15)	0.0037 (17)	0.0214 (15)
C12	0.045 (2)	0.0240 (14)	0.071 (2)	−0.0044 (14)	−0.0014 (18)	0.0084 (14)
C13	0.0269 (15)	0.0266 (12)	0.0298 (13)	−0.0026 (12)	−0.0018 (12)	0.0033 (11)
C14	0.0372 (17)	0.0310 (14)	0.0255 (13)	0.0047 (13)	0.0017 (13)	−0.0025 (11)
C15	0.0375 (17)	0.0230 (13)	0.0312 (14)	0.0039 (13)	0.0017 (13)	−0.0046 (11)
C16	0.0292 (15)	0.0207 (11)	0.0278 (13)	−0.0005 (11)	−0.0004 (12)	0.0003 (10)
C17	0.0398 (17)	0.0268 (13)	0.0243 (12)	0.0012 (13)	−0.0006 (12)	−0.0022 (11)
C18	0.0398 (17)	0.0192 (12)	0.0340 (14)	0.0013 (12)	−0.0017 (13)	−0.0033 (11)
Cl	0.0453 (5)	0.0342 (3)	0.0498 (4)	0.0008 (3)	0.0025 (4)	0.0056 (3)

Geometric parameters (Å, º)

Co—OW1	2.065 (2)	C4—C11	1.433 (4)
Co—OW2	2.083 (2)	C5—C6	1.428 (4)
Co—OW3	2.091 (2)	C6—C7	1.408 (4)
Co—N1	2.119 (2)	C7—C8	1.403 (4)
Co—N2	2.116 (2)	C7—C12	1.433 (4)
Co—N3	2.270 (2)	C8—C9	1.353 (4)
S—O1	1.461 (2)	C9—C10	1.383 (4)
S—O2	1.469 (2)	C11—C12	1.342 (5)
S—O3	1.4415 (18)	C13—C18	1.392 (4)
S—C16	1.767 (2)	C13—C14	1.383 (4)
OW1—HW1	0.8422	C14—C15	1.377 (3)
OW1—HW2	0.9542	C15—C16	1.388 (3)
OW2—HW3	0.9716	C16—C17	1.389 (3)
OW2—HW4	0.8954	C17—C18	1.379 (3)
OW3—HW6	0.9321	C1—H1	0.93
OW3—HW5	0.9100	C2—H2	0.93
N1—C1	1.329 (3)	C3—H3	0.93
N1—C5	1.361 (3)	C8—H8	0.93
N2—C10	1.333 (3)	C9—H9	0.93
N2—C6	1.360 (3)	C10—H10	0.93
N3—C13	1.428 (3)	C11—H11	0.93
N3—H3A	0.90	C12—H12	0.93
N3—H3B	0.90	C14—H14	0.93
C1—C2	1.393 (4)	C15—H15	0.93
C2—C3	1.358 (4)	C17—H17	0.93
C3—C4	1.406 (4)	C18—H18	0.93
C4—C5	1.405 (4)
OW1—Co—OW2	90.81 (8)	N1—C5—C6	117.1 (2)
OW1—Co—OW3	92.55 (8)	C4—C5—C6	119.6 (2)
OW1—Co—N1	170.16 (8)	N1—C5—C4	123.3 (2)
OW1—Co—N2	94.96 (8)	C5—C6—C7	120.1 (2)
OW1—Co—N3	82.49 (8)	N2—C6—C5	117.1 (2)
OW2—Co—OW3	86.49 (8)	N2—C6—C7	122.8 (2)
OW2—Co—N1	96.43 (8)	C8—C7—C12	124.7 (2)
OW2—Co—N2	92.36 (8)	C6—C7—C12	118.4 (3)
OW2—Co—N3	172.50 (8)	C6—C7—C8	116.9 (3)
OW3—Co—N1	94.52 (8)	C7—C8—C9	119.6 (3)
OW3—Co—N2	172.41 (8)	C8—C9—C10	120.4 (3)
OW3—Co—N3	90.43 (8)	N2—C10—C9	122.4 (2)
N1—Co—N2	78.14 (8)	C4—C11—C12	120.8 (3)
N1—Co—N3	90.62 (8)	C7—C12—C11	121.8 (3)
N2—Co—N3	91.58 (8)	N3—C13—C18	120.4 (2)
O1—S—O2	111.23 (11)	N3—C13—C14	120.1 (2)
O1—S—O3	114.76 (12)	C14—C13—C18	119.4 (2)
O1—S—C16	106.28 (12)	C13—C14—C15	120.4 (2)
O2—S—O3	111.67 (12)	C14—C15—C16	120.1 (2)
O2—S—C16	105.35 (12)	C15—C16—C17	119.9 (2)
O3—S—C16	106.85 (11)	S—C16—C15	119.86 (18)
Co—OW1—HW2	123.49	S—C16—C17	120.25 (19)
HW1—OW1—HW2	111.84	C16—C17—C18	119.8 (2)
Co—OW1—HW1	124.00	C13—C18—C17	120.5 (2)
Co—OW2—HW3	116.48	N1—C1—H1	118.84
HW3—OW2—HW4	110.15	C2—C1—H1	118.72
Co—OW2—HW4	123.89	C1—C2—H2	119.98
Co—OW3—HW5	115.36	C3—C2—H2	119.96
HW5—OW3—HW6	117.71	C2—C3—H3	120.13
Co—OW3—HW6	111.52	C4—C3—H3	120.23
Co—N1—C5	112.67 (16)	C7—C8—H8	120.25
C1—N1—C5	117.8 (2)	C9—C8—H8	120.14
Co—N1—C1	128.30 (18)	C8—C9—H9	119.83
C6—N2—C10	117.8 (2)	C10—C9—H9	119.82
Co—N2—C6	113.19 (16)	N2—C10—H10	118.81
Co—N2—C10	128.86 (18)	C9—C10—H10	118.76
Co—N3—C13	118.20 (17)	C4—C11—H11	119.57
Co—N3—H3B	107.76	C12—C11—H11	119.66
C13—N3—H3A	107.75	C7—C12—H12	119.07
C13—N3—H3B	107.74	C11—C12—H12	119.15
H3A—N3—H3B	107.14	C13—C14—H14	119.80
Co—N3—H3A	107.78	C15—C14—H14	119.77
N1—C1—C2	122.4 (3)	C14—C15—H15	119.90
C1—C2—C3	120.1 (3)	C16—C15—H15	119.98
C2—C3—C4	119.6 (3)	C16—C17—H17	120.17
C3—C4—C11	124.0 (3)	C18—C17—H17	120.08
C5—C4—C11	119.3 (3)	C13—C18—H18	119.80
C3—C4—C5	116.7 (3)	C17—C18—H18	119.73

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
OW1—HW1···O2^i	0.84	1.82	2.664 (3)	177
OW1—HW2···Cl^ii	0.95	2.17	3.072 (2)	158
OW2—HW3···Cl^i	0.97	2.06	3.018 (2)	170
N3—H3A···O3^iii	0.90	2.18	3.062 (3)	167
N3—H3B···Cl^ii	0.90	2.53	3.392 (2)	160
OW2—HW4···O1^i	0.90	2.01	2.875 (3)	161
OW3—HW5···O2^iii	0.91	1.84	2.748 (3)	174
OW3—HW6···O1^iv	0.93	1.90	2.824 (3)	170

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