Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680703694X/hb2483sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680703694X/hb2483Isup2.hkl |
CCDC reference: 660046
Key indicators
- Single-crystal X-ray study
- T = 140 K
- Mean (C-C) = 0.002 Å
- H-atom completeness 89%
- Disorder in solvent or counterion
- R factor = 0.035
- wR factor = 0.098
- Data-to-parameter ratio = 23.4
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ? PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)... ? PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 100 Deg. PLAT164_ALERT_4_C Nr. of Refined C-H H-Atoms in Heavy-At Struct... 5 PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 = 4 PLAT214_ALERT_2_C Atom O11B (Anion/Solvent) ADP max/min Ratio 4.40 prola PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 10.00 Perc. PLAT311_ALERT_2_C Isolated Disordered Oxygen Atom (No H's ?) ..... >O11A PLAT311_ALERT_2_C Isolated Disordered Oxygen Atom (No H's ?) ..... <O11B PLAT430_ALERT_2_C Short Inter D...A Contact O11A .. O11A .. 2.88 Ang. PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 3 H2 O
Alert level G FORMU01_ALERT_1_G There is a discrepancy between the atom counts in the _chemical_formula_sum and _chemical_formula_moiety. This is usually due to the moiety formula being in the wrong format. Atom count from _chemical_formula_sum: C20 H36 Co1 N2 O22 S4 Atom count from _chemical_formula_moiety:C20 H36 Co1 N2 O22 S42 FORMU01_ALERT_2_G There is a discrepancy between the atom counts in the _chemical_formula_sum and the formula from the _atom_site* data. Atom count from _chemical_formula_sum:C20 H36 Co1 N2 O22 S4 Atom count from the _atom_site data: C20 H32 Co1 N2 O22 S4 CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected. CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional? From the CIF: _cell_formula_units_Z 1 From the CIF: _chemical_formula_sum C20 H36 Co N2 O22 S4 TEST: Compare cell contents of formula and atom_site data atom Z*formula cif sites diff C 20.00 20.00 0.00 H 36.00 32.00 4.00 Co 1.00 1.00 0.00 N 2.00 2.00 0.00 O 22.00 22.00 0.00 S 4.00 4.00 0.00 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 8
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 12 ALERT level C = Check and explain 5 ALERT level G = General alerts; check 7 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 5 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
The title compound was prepared by direct reaction of Co(NO3)2·6H2O and disodium 3-aminonaphthalene-1,5-disulfonate (1:2 stoichiometry) in aqueous solution. Following approximately one hour of heating, during which most of the reactants dissolved, the resulting solution was gravity filtered and set out in open air. Upon evaporation of the water, many small reddish, needles of (I) were recovered.
The O11 atom, corresponding to one water of crystallization, was found to be disordered and was refined on split positions ca 0.5 Å apart with occupancy factors constrained to sum to 1. Final occupancies were roughly 53% (O11A) and 47% (O11B). The B site has a significantly prolate displacement ellipsoid, but further splitting of the position could not be successfully modeled. The H atoms attached to the disordered water molecule could not be located. All other H atoms were located in difference maps and positionally refined either freely or with distance restraints of O—H = 0.82 (2) Å, and with Uiso(H) = 1.2Ueq(N,C) or Uiso(H) = 1.5Ueq(O).
Metal sulfonate salts have been actively studied in recent years as part of the growing field of mixed inorganic-organic structures of interest in crystal engineering. Key results have been summarized in two recent reviews (Cote & Shimizu, 2003; Cai, 2004).
We have characterized a variety of naphthalenesulfonate salts of main group and transition metals (Gunderman & Squattrito, 1995; Gunderman, Kabell et al., 1997; Morris et al., 2003; Downer et al., 2006) with the goal of discerning structural trends as functions of metal cation and substitution of the sulfonate group. As part of our continuing interest in this chemistry, we have synthesized a series of salts of 3-aminonaphthalene-1,5-sulfonate with divalent transition metals.
The result is a family of isostructural salts of formula [M(H2O)6](H3NC10H5(SO3)2)2·4H2O where M = Co, Ni & Zn. The title cobalt compound consists of hexaaquacobalt(II) cations, 3-ammonionaphthalene-1,5-disulfonate anions, and water molecules of crystallization (Fig. 1). Owing to the protonation of the amine group, each anion carries a single negative charge and the salt has the same 1:2 stoichiometry as would be observed with a monosulfonate anion. The cations reside on centers of inversion and display very regular octahedral geometry with maximum deviation from ideal 90° bond angles of just under 5°. This feature is very similar to what is found in other cobalt sulfonates (Gunderman, Dubey & Squattrito, 1997; Leonard et al., 1999).
The crystal packing (Fig. 2) is typical for transition metal arene- and naphthalenesulfonates (Chen et al., 2002; Gunderman, Dubey & Squattrito, 1997), consisting of alternating layers of hexaaquametal cations and sulfonate anions parallel to the ac plane, with the anions positioned so that the charged groups (i.e., NH3+ and SO3_) line the surface of the layer. The anions are positioned so that all the rings are parallel with contacts between adjacent rings of ca 3.7 Å. Neighboring rows of anions running along the a axis have the ammonio groups inverted. The water molecules of crystallization are located in between the cations in close association with the charged groups and coordinated water molecules so as to participate in hydrogen bonding interactions. One of the two crystallographically independent water molecules is disordered over at least two positions.
The layers are held together by a series of strong O—H···O and N—H···O hydrogen bonds involving water and ammonio donors and sulfonate and water acceptors (Table 2).
The title compound is isostructural with its nickel(II) (Gunderman, Kabell et al., 1997) and zinc(II) (Genther et al., 2007) analogues. For background, see: Cote & Shimizu (2003); Cai (2004); Gunderman & Squattrito (1995); Morris et al. (2003); Downer et al. (2006); Gunderman, Dubey & Squattrito (1997); Leonard et al. (1999). For related literature, see: Chen et al. (2002).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.
[Co(H2O)6](C10H8NO6S2)2·4H2O | Z = 1 |
Mr = 843.68 | F(000) = 437 |
Triclinic, P1 | Dx = 1.758 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 5.4549 (1) Å | Cell parameters from 6586 reflections |
b = 12.7528 (3) Å | θ = 3.0–34.4° |
c = 12.9382 (3) Å | µ = 0.90 mm−1 |
α = 114.646 (1)° | T = 140 K |
β = 101.477 (1)° | Triangular prism, red |
γ = 90.919 (1)° | 0.25 × 0.22 × 0.10 mm |
V = 796.73 (3) Å3 |
Bruker SMART 6000 CCD area-detector diffractometer | 6574 independent reflections |
Radiation source: fine-focus sealed tube | 6288 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.016 |
ω scans | θmax = 35.6°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −8→8 |
Tmin = 0.765, Tmax = 0.910 | k = −20→20 |
11827 measured reflections | l = −20→21 |
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)] = 0.035 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.098 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0405P)2 + 0.5867P] where P = (Fo2 + 2Fc2)/3 |
6574 reflections | (Δ/σ)max = 0.001 |
281 parameters | Δρmax = 1.10 e Å−3 |
8 restraints | Δρmin = −0.83 e Å−3 |
[Co(H2O)6](C10H8NO6S2)2·4H2O | γ = 90.919 (1)° |
Mr = 843.68 | V = 796.73 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 5.4549 (1) Å | Mo Kα radiation |
b = 12.7528 (3) Å | µ = 0.90 mm−1 |
c = 12.9382 (3) Å | T = 140 K |
α = 114.646 (1)° | 0.25 × 0.22 × 0.10 mm |
β = 101.477 (1)° |
Bruker SMART 6000 CCD area-detector diffractometer | 6574 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 6288 reflections with I > 2σ(I) |
Tmin = 0.765, Tmax = 0.910 | Rint = 0.016 |
11827 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 8 restraints |
wR(F2) = 0.098 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 1.10 e Å−3 |
6574 reflections | Δρmin = −0.83 e Å−3 |
281 parameters |
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) | |
Co1 | 0.0000 | 0.0000 | 0.0000 | 0.01194 (5) | |
O7 | −0.26578 (18) | −0.12241 (8) | −0.00331 (8) | 0.01604 (16) | |
H9 | −0.347 (4) | −0.1672 (18) | −0.0681 (15) | 0.024* | |
H10 | −0.224 (4) | −0.1529 (19) | 0.0394 (18) | 0.024* | |
O8 | −0.05274 (19) | 0.10605 (9) | 0.16887 (9) | 0.01862 (17) | |
H11 | −0.168 (4) | 0.1482 (18) | 0.178 (2) | 0.028* | |
H12 | 0.070 (4) | 0.1440 (19) | 0.2203 (18) | 0.028* | |
O9 | 0.30321 (19) | −0.05179 (10) | 0.08400 (10) | 0.02177 (19) | |
H13 | 0.435 (4) | −0.064 (2) | 0.061 (2) | 0.033* | |
H14 | 0.283 (5) | −0.088 (2) | 0.121 (2) | 0.033* | |
S1 | 0.53450 (5) | 0.32370 (2) | 0.32171 (2) | 0.01216 (6) | |
O1 | 0.57766 (18) | 0.25223 (8) | 0.20469 (8) | 0.01694 (16) | |
O2 | 0.30255 (18) | 0.28088 (8) | 0.33761 (9) | 0.01758 (16) | |
O3 | 0.75299 (19) | 0.33977 (8) | 0.41332 (9) | 0.01965 (18) | |
S2 | 0.02330 (6) | 0.76432 (3) | 0.20505 (3) | 0.01597 (6) | |
O4 | 0.2482 (2) | 0.80285 (11) | 0.18029 (11) | 0.0254 (2) | |
O5 | −0.2059 (2) | 0.75551 (10) | 0.12117 (10) | 0.0231 (2) | |
O6 | 0.0067 (2) | 0.83554 (9) | 0.32609 (9) | 0.02269 (19) | |
N1 | 0.8711 (2) | 0.75479 (10) | 0.47987 (10) | 0.01682 (18) | |
H6 | 0.947 (4) | 0.7786 (19) | 0.4385 (19) | 0.020* | |
H7 | 0.971 (4) | 0.7319 (19) | 0.5194 (19) | 0.020* | |
H8 | 0.816 (4) | 0.808 (2) | 0.523 (2) | 0.020* | |
C1 | 0.4958 (2) | 0.46391 (9) | 0.32593 (10) | 0.01224 (17) | |
C2 | 0.6852 (2) | 0.55077 (10) | 0.39846 (10) | 0.01341 (18) | |
H1 | 0.825 (4) | 0.5357 (18) | 0.4432 (18) | 0.016* | |
C3 | 0.6687 (2) | 0.66256 (10) | 0.40344 (10) | 0.01317 (18) | |
C4 | 0.4698 (2) | 0.68835 (10) | 0.33892 (10) | 0.01455 (19) | |
H2 | 0.455 (4) | 0.7608 (18) | 0.3429 (18) | 0.017* | |
C5 | 0.0561 (2) | 0.62243 (10) | 0.19476 (10) | 0.01454 (19) | |
C6 | −0.1328 (2) | 0.53561 (11) | 0.12103 (11) | 0.0175 (2) | |
H3 | −0.262 (4) | 0.5579 (19) | 0.0848 (19) | 0.021* | |
C7 | −0.1188 (2) | 0.42229 (11) | 0.11258 (12) | 0.0181 (2) | |
H4 | −0.263 (4) | 0.3552 (19) | 0.0557 (19) | 0.022* | |
C8 | 0.0825 (2) | 0.39777 (10) | 0.17861 (11) | 0.01547 (19) | |
H5 | 0.086 (4) | 0.3219 (19) | 0.1696 (19) | 0.019* | |
C9 | 0.2820 (2) | 0.48519 (10) | 0.25561 (10) | 0.01230 (17) | |
C10 | 0.2705 (2) | 0.60020 (10) | 0.26370 (10) | 0.01281 (17) | |
O10 | −0.2264 (4) | 0.04228 (14) | 0.34619 (16) | 0.0478 (4) | |
H15 | −0.173 (7) | −0.028 (2) | 0.342 (3) | 0.072* | |
H16 | −0.244 (7) | 0.043 (3) | 0.274 (2) | 0.072* | |
O11A | 0.5969 (16) | 0.9484 (5) | 0.5775 (6) | 0.087 (3) | 0.526 (16) |
O11B | 0.6756 (17) | 0.9458 (5) | 0.5908 (11) | 0.109 (4) | 0.474 (16) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.01256 (9) | 0.01138 (9) | 0.01237 (10) | 0.00226 (7) | 0.00272 (7) | 0.00557 (8) |
O7 | 0.0172 (4) | 0.0157 (4) | 0.0156 (4) | −0.0004 (3) | 0.0007 (3) | 0.0084 (3) |
O8 | 0.0165 (4) | 0.0186 (4) | 0.0162 (4) | 0.0040 (3) | 0.0024 (3) | 0.0036 (3) |
O9 | 0.0180 (4) | 0.0309 (5) | 0.0297 (5) | 0.0095 (4) | 0.0095 (4) | 0.0236 (4) |
S1 | 0.01264 (11) | 0.00967 (11) | 0.01284 (12) | 0.00055 (8) | 0.00019 (8) | 0.00475 (9) |
O1 | 0.0182 (4) | 0.0134 (4) | 0.0163 (4) | 0.0037 (3) | 0.0043 (3) | 0.0034 (3) |
O2 | 0.0171 (4) | 0.0168 (4) | 0.0192 (4) | −0.0025 (3) | 0.0030 (3) | 0.0087 (3) |
O3 | 0.0184 (4) | 0.0162 (4) | 0.0214 (4) | −0.0005 (3) | −0.0059 (3) | 0.0100 (4) |
S2 | 0.01772 (13) | 0.01645 (13) | 0.01914 (13) | 0.00369 (9) | 0.00455 (10) | 0.01259 (11) |
O4 | 0.0209 (4) | 0.0322 (5) | 0.0375 (6) | 0.0037 (4) | 0.0091 (4) | 0.0275 (5) |
O5 | 0.0209 (4) | 0.0261 (5) | 0.0286 (5) | 0.0057 (4) | 0.0015 (4) | 0.0194 (4) |
O6 | 0.0349 (5) | 0.0148 (4) | 0.0217 (5) | 0.0050 (4) | 0.0090 (4) | 0.0098 (4) |
N1 | 0.0210 (5) | 0.0127 (4) | 0.0141 (4) | −0.0036 (3) | −0.0023 (3) | 0.0061 (4) |
C1 | 0.0135 (4) | 0.0102 (4) | 0.0121 (4) | 0.0010 (3) | 0.0017 (3) | 0.0045 (4) |
C2 | 0.0147 (4) | 0.0112 (4) | 0.0128 (4) | −0.0004 (3) | −0.0001 (3) | 0.0053 (4) |
C3 | 0.0157 (4) | 0.0106 (4) | 0.0113 (4) | −0.0016 (3) | 0.0002 (3) | 0.0041 (4) |
C4 | 0.0178 (5) | 0.0117 (4) | 0.0141 (5) | 0.0005 (3) | 0.0014 (4) | 0.0064 (4) |
C5 | 0.0154 (4) | 0.0146 (5) | 0.0150 (5) | 0.0030 (4) | 0.0023 (4) | 0.0082 (4) |
C6 | 0.0161 (5) | 0.0184 (5) | 0.0180 (5) | 0.0017 (4) | −0.0003 (4) | 0.0097 (4) |
C7 | 0.0158 (5) | 0.0168 (5) | 0.0190 (5) | −0.0006 (4) | −0.0015 (4) | 0.0075 (4) |
C8 | 0.0153 (5) | 0.0124 (4) | 0.0164 (5) | 0.0005 (3) | −0.0001 (4) | 0.0057 (4) |
C9 | 0.0128 (4) | 0.0110 (4) | 0.0122 (4) | 0.0013 (3) | 0.0015 (3) | 0.0047 (4) |
C10 | 0.0146 (4) | 0.0118 (4) | 0.0120 (4) | 0.0015 (3) | 0.0016 (3) | 0.0057 (4) |
O10 | 0.0634 (11) | 0.0327 (7) | 0.0484 (9) | 0.0123 (7) | 0.0125 (8) | 0.0185 (7) |
O11A | 0.098 (4) | 0.043 (2) | 0.062 (3) | 0.033 (3) | −0.037 (3) | −0.010 (2) |
O11B | 0.079 (4) | 0.0177 (17) | 0.199 (9) | −0.010 (2) | 0.106 (5) | −0.015 (3) |
Co1—O9i | 2.0667 (10) | N1—H6 | 0.88 (2) |
Co1—O9 | 2.0667 (10) | N1—H7 | 0.82 (2) |
Co1—O7i | 2.0946 (9) | N1—H8 | 0.79 (2) |
Co1—O7 | 2.0946 (9) | C1—C2 | 1.3735 (16) |
Co1—O8i | 2.1175 (10) | C1—C9 | 1.4334 (16) |
Co1—O8 | 2.1175 (10) | C2—C3 | 1.4052 (16) |
O7—H9 | 0.818 (16) | C2—H1 | 0.94 (2) |
O7—H10 | 0.800 (15) | C3—C4 | 1.3644 (16) |
O8—H11 | 0.830 (16) | C4—C10 | 1.4214 (16) |
O8—H12 | 0.819 (16) | C4—H2 | 0.91 (2) |
O9—H13 | 0.826 (16) | C5—C6 | 1.3747 (18) |
O9—H14 | 0.818 (16) | C5—C10 | 1.4317 (16) |
S1—O3 | 1.4474 (10) | C6—C7 | 1.4076 (18) |
S1—O2 | 1.4548 (10) | C6—H3 | 0.88 (2) |
S1—O1 | 1.4752 (10) | C7—C8 | 1.3762 (17) |
S1—C1 | 1.7833 (11) | C7—H4 | 1.06 (2) |
S2—O5 | 1.4515 (11) | C8—C9 | 1.4224 (16) |
S2—O4 | 1.4553 (11) | C8—H5 | 0.93 (2) |
S2—O6 | 1.4691 (11) | C9—C10 | 1.4296 (16) |
S2—C5 | 1.7730 (12) | O10—H15 | 0.925 (18) |
N1—C3 | 1.4610 (16) | O10—H16 | 0.924 (18) |
O9i—Co1—O9 | 180.0 | C3—N1—H7 | 110.2 (15) |
O9i—Co1—O7i | 94.83 (4) | H6—N1—H7 | 111 (2) |
O9—Co1—O7i | 85.17 (4) | C3—N1—H8 | 110.2 (16) |
O9i—Co1—O7 | 85.17 (4) | H6—N1—H8 | 108 (2) |
O9—Co1—O7 | 94.83 (4) | H7—N1—H8 | 108 (2) |
O7i—Co1—O7 | 180.0 | C2—C1—C9 | 121.31 (10) |
O9i—Co1—O8i | 86.09 (4) | C2—C1—S1 | 116.45 (8) |
O9—Co1—O8i | 93.91 (4) | C9—C1—S1 | 122.22 (8) |
O7i—Co1—O8i | 85.98 (4) | C1—C2—C3 | 119.16 (10) |
O7—Co1—O8i | 94.02 (4) | C1—C2—H1 | 120.6 (13) |
O9i—Co1—O8 | 93.91 (4) | C3—C2—H1 | 120.2 (13) |
O9—Co1—O8 | 86.09 (4) | C4—C3—C2 | 122.30 (10) |
O7i—Co1—O8 | 94.02 (4) | C4—C3—N1 | 118.50 (10) |
O7—Co1—O8 | 85.98 (4) | C2—C3—N1 | 119.20 (10) |
O8i—Co1—O8 | 180.0 | C3—C4—C10 | 119.66 (10) |
Co1—O7—H9 | 115.7 (16) | C3—C4—H2 | 123.1 (13) |
Co1—O7—H10 | 117.1 (16) | C10—C4—H2 | 117.2 (13) |
H9—O7—H10 | 113 (2) | C6—C5—C10 | 121.30 (11) |
Co1—O8—H11 | 121.2 (17) | C6—C5—S2 | 118.00 (9) |
Co1—O8—H12 | 118.7 (17) | C10—C5—S2 | 120.67 (9) |
H11—O8—H12 | 106 (2) | C5—C6—C7 | 120.07 (11) |
Co1—O9—H13 | 122.3 (17) | C5—C6—H3 | 115.2 (14) |
Co1—O9—H14 | 120.9 (18) | C7—C6—H3 | 124.6 (14) |
H13—O9—H14 | 112 (2) | C8—C7—C6 | 120.39 (11) |
O3—S1—O2 | 114.09 (6) | C8—C7—H4 | 119.2 (12) |
O3—S1—O1 | 112.03 (6) | C6—C7—H4 | 120.4 (12) |
O2—S1—O1 | 111.47 (6) | C7—C8—C9 | 121.18 (11) |
O3—S1—C1 | 105.87 (5) | C7—C8—H5 | 117.7 (13) |
O2—S1—C1 | 107.54 (6) | C9—C8—H5 | 121.1 (13) |
O1—S1—C1 | 105.17 (5) | C8—C9—C10 | 118.76 (10) |
O5—S2—O4 | 113.34 (6) | C8—C9—C1 | 123.26 (10) |
O5—S2—O6 | 112.50 (7) | C10—C9—C1 | 117.97 (10) |
O4—S2—O6 | 111.14 (7) | C4—C10—C9 | 119.59 (10) |
O5—S2—C5 | 106.52 (6) | C4—C10—C5 | 122.13 (10) |
O4—S2—C5 | 107.20 (6) | C9—C10—C5 | 118.29 (10) |
O6—S2—C5 | 105.57 (6) | H15—O10—H16 | 109 (3) |
C3—N1—H6 | 110.3 (14) | ||
O3—S1—C1—C2 | 8.14 (11) | S2—C5—C6—C7 | −178.09 (10) |
O2—S1—C1—C2 | 130.48 (9) | C5—C6—C7—C8 | 0.6 (2) |
O1—S1—C1—C2 | −110.61 (10) | C6—C7—C8—C9 | −0.8 (2) |
O3—S1—C1—C9 | −173.34 (10) | C7—C8—C9—C10 | 0.05 (18) |
O2—S1—C1—C9 | −51.01 (11) | C7—C8—C9—C1 | −179.85 (12) |
O1—S1—C1—C9 | 67.90 (10) | C2—C1—C9—C8 | 179.47 (12) |
C9—C1—C2—C3 | −0.10 (17) | S1—C1—C9—C8 | 1.02 (16) |
S1—C1—C2—C3 | 178.43 (9) | C2—C1—C9—C10 | −0.43 (17) |
C1—C2—C3—C4 | 0.27 (18) | S1—C1—C9—C10 | −178.88 (9) |
C1—C2—C3—N1 | −179.52 (11) | C3—C4—C10—C9 | −0.65 (18) |
C2—C3—C4—C10 | 0.11 (18) | C3—C4—C10—C5 | 179.42 (11) |
N1—C3—C4—C10 | 179.90 (11) | C8—C9—C10—C4 | −179.11 (11) |
O5—S2—C5—C6 | −3.92 (12) | C1—C9—C10—C4 | 0.80 (17) |
O4—S2—C5—C6 | −125.54 (11) | C8—C9—C10—C5 | 0.82 (17) |
O6—S2—C5—C6 | 115.89 (11) | C1—C9—C10—C5 | −179.27 (10) |
O5—S2—C5—C10 | 177.64 (10) | C6—C5—C10—C4 | 178.90 (12) |
O4—S2—C5—C10 | 56.02 (11) | S2—C5—C10—C4 | −2.71 (16) |
O6—S2—C5—C10 | −62.55 (11) | C6—C5—C10—C9 | −1.03 (18) |
C10—C5—C6—C7 | 0.34 (19) | S2—C5—C10—C9 | 177.36 (9) |
Symmetry code: (i) −x, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H9···O1i | 0.82 (2) | 1.83 (2) | 2.6404 (13) | 169 (2) |
O7—H10···O5ii | 0.80 (2) | 1.87 (2) | 2.6501 (13) | 166 (2) |
O8—H11···O1iii | 0.83 (2) | 1.92 (2) | 2.7435 (13) | 177 (2) |
O8—H12···O2 | 0.82 (2) | 1.98 (2) | 2.7589 (14) | 159 (2) |
O9—H13···O7iv | 0.83 (2) | 1.99 (2) | 2.8092 (14) | 170 (2) |
O9—H14···O4ii | 0.82 (2) | 1.87 (2) | 2.6713 (14) | 168 (3) |
N1—H6···O6iv | 0.88 (2) | 1.95 (2) | 2.7993 (15) | 162 (2) |
N1—H7···O3v | 0.82 (2) | 2.01 (2) | 2.8124 (15) | 168 (2) |
N1—H8···O11A | 0.79 (2) | 2.12 (2) | 2.863 (7) | 159 (2) |
O10—H15···O6ii | 0.93 (2) | 1.97 (2) | 2.8816 (19) | 167 (3) |
O10—H16···O8 | 0.92 (2) | 2.25 (3) | 3.036 (2) | 143 (3) |
Symmetry codes: (i) −x, −y, −z; (ii) x, y−1, z; (iii) x−1, y, z; (iv) x+1, y, z; (v) −x+2, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Co(H2O)6](C10H8NO6S2)2·4H2O |
Mr | 843.68 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 140 |
a, b, c (Å) | 5.4549 (1), 12.7528 (3), 12.9382 (3) |
α, β, γ (°) | 114.646 (1), 101.477 (1), 90.919 (1) |
V (Å3) | 796.73 (3) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.90 |
Crystal size (mm) | 0.25 × 0.22 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART 6000 CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) |
Tmin, Tmax | 0.765, 0.910 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11827, 6574, 6288 |
Rint | 0.016 |
(sin θ/λ)max (Å−1) | 0.819 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.098, 1.07 |
No. of reflections | 6574 |
No. of parameters | 281 |
No. of restraints | 8 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.10, −0.83 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXTL (Sheldrick, 2001), SHELXTL and local programs.
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H9···O1i | 0.818 (16) | 1.832 (16) | 2.6404 (13) | 169 (2) |
O7—H10···O5ii | 0.800 (15) | 1.867 (16) | 2.6501 (13) | 166 (2) |
O8—H11···O1iii | 0.830 (16) | 1.915 (16) | 2.7435 (13) | 177 (2) |
O8—H12···O2 | 0.819 (16) | 1.977 (17) | 2.7589 (14) | 159 (2) |
O9—H13···O7iv | 0.826 (16) | 1.993 (17) | 2.8092 (14) | 170 (2) |
O9—H14···O4ii | 0.818 (16) | 1.865 (17) | 2.6713 (14) | 168 (3) |
N1—H6···O6iv | 0.88 (2) | 1.95 (2) | 2.7993 (15) | 162 (2) |
N1—H7···O3v | 0.82 (2) | 2.01 (2) | 2.8124 (15) | 168 (2) |
N1—H8···O11A | 0.79 (2) | 2.12 (2) | 2.863 (7) | 159 (2) |
O10—H15···O6ii | 0.925 (18) | 1.97 (2) | 2.8816 (19) | 167 (3) |
O10—H16···O8 | 0.924 (18) | 2.25 (3) | 3.036 (2) | 143 (3) |
Symmetry codes: (i) −x, −y, −z; (ii) x, y−1, z; (iii) x−1, y, z; (iv) x+1, y, z; (v) −x+2, −y+1, −z+1. |
Metal sulfonate salts have been actively studied in recent years as part of the growing field of mixed inorganic-organic structures of interest in crystal engineering. Key results have been summarized in two recent reviews (Cote & Shimizu, 2003; Cai, 2004).
We have characterized a variety of naphthalenesulfonate salts of main group and transition metals (Gunderman & Squattrito, 1995; Gunderman, Kabell et al., 1997; Morris et al., 2003; Downer et al., 2006) with the goal of discerning structural trends as functions of metal cation and substitution of the sulfonate group. As part of our continuing interest in this chemistry, we have synthesized a series of salts of 3-aminonaphthalene-1,5-sulfonate with divalent transition metals.
The result is a family of isostructural salts of formula [M(H2O)6](H3NC10H5(SO3)2)2·4H2O where M = Co, Ni & Zn. The title cobalt compound consists of hexaaquacobalt(II) cations, 3-ammonionaphthalene-1,5-disulfonate anions, and water molecules of crystallization (Fig. 1). Owing to the protonation of the amine group, each anion carries a single negative charge and the salt has the same 1:2 stoichiometry as would be observed with a monosulfonate anion. The cations reside on centers of inversion and display very regular octahedral geometry with maximum deviation from ideal 90° bond angles of just under 5°. This feature is very similar to what is found in other cobalt sulfonates (Gunderman, Dubey & Squattrito, 1997; Leonard et al., 1999).
The crystal packing (Fig. 2) is typical for transition metal arene- and naphthalenesulfonates (Chen et al., 2002; Gunderman, Dubey & Squattrito, 1997), consisting of alternating layers of hexaaquametal cations and sulfonate anions parallel to the ac plane, with the anions positioned so that the charged groups (i.e., NH3+ and SO3_) line the surface of the layer. The anions are positioned so that all the rings are parallel with contacts between adjacent rings of ca 3.7 Å. Neighboring rows of anions running along the a axis have the ammonio groups inverted. The water molecules of crystallization are located in between the cations in close association with the charged groups and coordinated water molecules so as to participate in hydrogen bonding interactions. One of the two crystallographically independent water molecules is disordered over at least two positions.
The layers are held together by a series of strong O—H···O and N—H···O hydrogen bonds involving water and ammonio donors and sulfonate and water acceptors (Table 2).