Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807036938/hb2484sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807036938/hb2484Isup2.hkl |
CCDC reference: 660047
The title compound was prepared by direct reaction of Zn(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 colorless, 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 63% (O11A) and 37% (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).
As part of our ongoing studies of salts of 3-aminonaphthalene-1,5-sulfonate with divalent transition metals, we now report the structure of the title compound, (I), which is isostructural with its nickel(II) (Gunderman, Kabell et al., 1997) and cobalt(II) analogues (Genther et al., 2007). Compound (I) consists of centrosymmetic hexaaquazinc(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 the zinc naphthalene-1,5-disulfonate compound without the amine functionality (Huo et al., 2005).
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).
Compound (I) is isostructural with its nickel(II) (Gunderman, Kabell et al., 1997) and cobalt(II) (Genther et al., 2007) analogues. For background, see: Chen et al. (2002); Gunderman, Dubey & Squattrito (1997); Huo et al. (2005).
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.
[Zn(H2O)6](C10H8NO6S2)2·4H2O | Z = 1 |
Mr = 850.12 | F(000) = 440 |
Triclinic, P1 | Dx = 1.778 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 5.4294 (2) Å | Cell parameters from 6586 reflections |
b = 12.7411 (5) Å | θ = 3.0–34.4° |
c = 12.9537 (6) Å | µ = 1.13 mm−1 |
α = 114.497 (1)° | T = 273 K |
β = 101.563 (1)° | Pyramidal, colourless |
γ = 90.889 (1)° | 0.25 × 0.22 × 0.10 mm |
V = 793.97 (6) Å3 |
Bruker SMART 6000 CCD area-detector diffractometer | 6235 independent reflections |
Radiation source: fine-focus sealed tube | 5724 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
ω scans | θmax = 34.5°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −8→8 |
Tmin = 0.757, Tmax = 0.890 | k = −20→19 |
17231 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)] = 0.038 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.107 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.94 | w = 1/[σ2(Fo2) + (0.0664P)2 + 0.8611P] where P = (Fo2 + 2Fc2)/3 |
6235 reflections | (Δ/σ)max = 0.004 |
281 parameters | Δρmax = 1.21 e Å−3 |
8 restraints | Δρmin = −1.03 e Å−3 |
[Zn(H2O)6](C10H8NO6S2)2·4H2O | γ = 90.889 (1)° |
Mr = 850.12 | V = 793.97 (6) Å3 |
Triclinic, P1 | Z = 1 |
a = 5.4294 (2) Å | Mo Kα radiation |
b = 12.7411 (5) Å | µ = 1.13 mm−1 |
c = 12.9537 (6) Å | T = 273 K |
α = 114.497 (1)° | 0.25 × 0.22 × 0.10 mm |
β = 101.563 (1)° |
Bruker SMART 6000 CCD area-detector diffractometer | 6235 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 5724 reflections with I > 2σ(I) |
Tmin = 0.757, Tmax = 0.890 | Rint = 0.026 |
17231 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 8 restraints |
wR(F2) = 0.107 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.94 | Δρmax = 1.21 e Å−3 |
6235 reflections | Δρmin = −1.03 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) | |
Zn1 | 0.0000 | 0.0000 | 0.0000 | 0.01329 (6) | |
O7 | −0.2667 (2) | −0.12300 (10) | −0.00440 (10) | 0.01655 (19) | |
H9 | −0.347 (5) | −0.168 (2) | −0.0698 (16) | 0.025* | |
H10 | −0.227 (5) | −0.154 (2) | 0.037 (2) | 0.025* | |
O8 | −0.0542 (2) | 0.10549 (11) | 0.16894 (10) | 0.0191 (2) | |
H11 | −0.166 (4) | 0.148 (2) | 0.181 (2) | 0.029* | |
H12 | 0.062 (4) | 0.148 (2) | 0.220 (2) | 0.029* | |
O9 | 0.3033 (2) | −0.05209 (12) | 0.08378 (12) | 0.0214 (2) | |
H13 | 0.433 (4) | −0.066 (2) | 0.060 (2) | 0.032* | |
H14 | 0.275 (6) | −0.090 (2) | 0.119 (2) | 0.032* | |
S1 | 0.53398 (6) | 0.32440 (3) | 0.32236 (3) | 0.01257 (7) | |
O1 | 0.5772 (2) | 0.25319 (10) | 0.20550 (10) | 0.0174 (2) | |
O2 | 0.3014 (2) | 0.28147 (10) | 0.33812 (10) | 0.0182 (2) | |
O3 | 0.7536 (2) | 0.34056 (10) | 0.41396 (11) | 0.0197 (2) | |
S2 | 0.01825 (7) | 0.76440 (3) | 0.20463 (3) | 0.01679 (8) | |
O4 | 0.2443 (2) | 0.80350 (13) | 0.18042 (14) | 0.0272 (3) | |
O5 | −0.2114 (2) | 0.75525 (12) | 0.12018 (12) | 0.0237 (2) | |
O6 | 0.0005 (3) | 0.83525 (11) | 0.32527 (11) | 0.0236 (2) | |
N1 | 0.8696 (3) | 0.75553 (12) | 0.48044 (12) | 0.0181 (2) | |
H6 | 0.931 (5) | 0.779 (2) | 0.441 (2) | 0.022* | |
H7 | 0.975 (5) | 0.731 (2) | 0.523 (2) | 0.022* | |
H8 | 0.810 (5) | 0.811 (2) | 0.524 (2) | 0.022* | |
C1 | 0.4944 (3) | 0.46453 (12) | 0.32637 (12) | 0.0129 (2) | |
C2 | 0.6842 (3) | 0.55153 (12) | 0.39906 (12) | 0.0140 (2) | |
H1 | 0.823 (5) | 0.537 (2) | 0.442 (2) | 0.017* | |
C3 | 0.6666 (3) | 0.66315 (12) | 0.40379 (12) | 0.0143 (2) | |
C4 | 0.4673 (3) | 0.68879 (12) | 0.33900 (13) | 0.0150 (2) | |
H2 | 0.453 (5) | 0.762 (2) | 0.342 (2) | 0.018* | |
C5 | 0.0526 (3) | 0.62251 (13) | 0.19425 (13) | 0.0149 (2) | |
C6 | −0.1367 (3) | 0.53564 (14) | 0.12033 (14) | 0.0182 (3) | |
H3 | −0.266 (5) | 0.556 (2) | 0.080 (2) | 0.022* | |
C7 | −0.1215 (3) | 0.42251 (14) | 0.11220 (14) | 0.0185 (3) | |
H4 | −0.257 (5) | 0.358 (2) | 0.055 (2) | 0.022* | |
C8 | 0.0801 (3) | 0.39811 (13) | 0.17860 (13) | 0.0159 (2) | |
H5 | 0.083 (5) | 0.321 (2) | 0.171 (2) | 0.019* | |
C9 | 0.2798 (3) | 0.48562 (12) | 0.25578 (12) | 0.0129 (2) | |
C10 | 0.2676 (3) | 0.60071 (12) | 0.26362 (12) | 0.0133 (2) | |
O10 | −0.2280 (5) | 0.04341 (18) | 0.3472 (2) | 0.0540 (5) | |
H15 | −0.171 (8) | −0.028 (2) | 0.338 (4) | 0.081* | |
H16 | −0.233 (9) | 0.036 (4) | 0.273 (2) | 0.081* | |
O11A | 0.5941 (15) | 0.9487 (4) | 0.5787 (5) | 0.091 (3) | 0.628 (15) |
O11B | 0.687 (2) | 0.9475 (6) | 0.5944 (16) | 0.136 (7) | 0.372 (15) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.01269 (10) | 0.01336 (11) | 0.01533 (11) | 0.00281 (7) | 0.00337 (8) | 0.00746 (8) |
O7 | 0.0166 (5) | 0.0175 (5) | 0.0169 (5) | 0.0004 (4) | 0.0012 (4) | 0.0099 (4) |
O8 | 0.0162 (5) | 0.0202 (5) | 0.0175 (5) | 0.0044 (4) | 0.0030 (4) | 0.0050 (4) |
O9 | 0.0170 (5) | 0.0293 (6) | 0.0305 (6) | 0.0088 (4) | 0.0090 (4) | 0.0230 (5) |
S1 | 0.01214 (13) | 0.01096 (13) | 0.01408 (14) | 0.00084 (10) | 0.00037 (10) | 0.00599 (11) |
O1 | 0.0180 (5) | 0.0148 (5) | 0.0174 (5) | 0.0041 (4) | 0.0042 (4) | 0.0047 (4) |
O2 | 0.0168 (5) | 0.0185 (5) | 0.0206 (5) | −0.0025 (4) | 0.0037 (4) | 0.0100 (4) |
O3 | 0.0171 (5) | 0.0174 (5) | 0.0226 (5) | −0.0008 (4) | −0.0061 (4) | 0.0115 (4) |
S2 | 0.01698 (15) | 0.01829 (16) | 0.02169 (16) | 0.00366 (12) | 0.00445 (12) | 0.01480 (13) |
O4 | 0.0202 (5) | 0.0358 (7) | 0.0423 (7) | 0.0043 (5) | 0.0094 (5) | 0.0318 (6) |
O5 | 0.0200 (5) | 0.0283 (6) | 0.0302 (6) | 0.0056 (4) | 0.0014 (5) | 0.0215 (5) |
O6 | 0.0353 (7) | 0.0156 (5) | 0.0235 (5) | 0.0048 (5) | 0.0084 (5) | 0.0111 (4) |
N1 | 0.0224 (6) | 0.0141 (5) | 0.0156 (5) | −0.0039 (4) | −0.0032 (4) | 0.0079 (4) |
C1 | 0.0130 (5) | 0.0115 (5) | 0.0139 (5) | 0.0017 (4) | 0.0019 (4) | 0.0057 (4) |
C2 | 0.0143 (5) | 0.0123 (5) | 0.0145 (5) | −0.0003 (4) | 0.0000 (4) | 0.0065 (4) |
C3 | 0.0164 (6) | 0.0120 (5) | 0.0133 (5) | −0.0010 (4) | 0.0005 (4) | 0.0057 (4) |
C4 | 0.0175 (6) | 0.0120 (5) | 0.0158 (6) | 0.0008 (4) | 0.0019 (5) | 0.0072 (4) |
C5 | 0.0148 (6) | 0.0163 (6) | 0.0164 (6) | 0.0034 (4) | 0.0029 (5) | 0.0099 (5) |
C6 | 0.0156 (6) | 0.0206 (6) | 0.0197 (6) | 0.0019 (5) | 0.0002 (5) | 0.0116 (5) |
C7 | 0.0160 (6) | 0.0178 (6) | 0.0197 (6) | 0.0003 (5) | −0.0010 (5) | 0.0083 (5) |
C8 | 0.0139 (5) | 0.0143 (6) | 0.0184 (6) | 0.0010 (4) | 0.0008 (5) | 0.0072 (5) |
C9 | 0.0129 (5) | 0.0127 (5) | 0.0135 (5) | 0.0022 (4) | 0.0024 (4) | 0.0061 (4) |
C10 | 0.0141 (5) | 0.0133 (5) | 0.0138 (5) | 0.0021 (4) | 0.0025 (4) | 0.0074 (4) |
O10 | 0.0723 (15) | 0.0376 (10) | 0.0527 (12) | 0.0136 (9) | 0.0136 (11) | 0.0199 (9) |
O11A | 0.117 (5) | 0.042 (2) | 0.057 (3) | 0.039 (3) | −0.040 (3) | −0.0083 (18) |
O11B | 0.103 (7) | 0.018 (3) | 0.253 (15) | −0.019 (3) | 0.150 (9) | −0.023 (5) |
Zn1—O9 | 2.0605 (12) | N1—H7 | 0.86 (3) |
Zn1—O9i | 2.0605 (12) | N1—H8 | 0.82 (3) |
Zn1—O7 | 2.0925 (11) | C1—C2 | 1.3739 (19) |
Zn1—O7i | 2.0926 (11) | C1—C9 | 1.4328 (19) |
Zn1—O8 | 2.1244 (12) | C2—C3 | 1.404 (2) |
Zn1—O8i | 2.1244 (12) | C2—H1 | 0.91 (2) |
O7—H9 | 0.823 (17) | C3—C4 | 1.363 (2) |
O7—H10 | 0.794 (17) | C4—C10 | 1.420 (2) |
O8—H11 | 0.817 (17) | C4—H2 | 0.92 (2) |
O8—H12 | 0.811 (17) | C5—C6 | 1.375 (2) |
O9—H13 | 0.814 (17) | C5—C10 | 1.4297 (19) |
O9—H14 | 0.812 (17) | C6—C7 | 1.406 (2) |
S1—O3 | 1.4471 (11) | C6—H3 | 0.89 (3) |
S1—O2 | 1.4526 (12) | C7—C8 | 1.375 (2) |
S1—O1 | 1.4764 (12) | C7—H4 | 1.01 (3) |
S1—C1 | 1.7820 (14) | C8—C9 | 1.422 (2) |
S2—O5 | 1.4520 (13) | C8—H5 | 0.94 (2) |
S2—O4 | 1.4554 (13) | C9—C10 | 1.431 (2) |
S2—O6 | 1.4694 (14) | O10—H15 | 0.93 (4) |
S2—C5 | 1.7721 (15) | O10—H16 | 0.92 (3) |
N1—C3 | 1.4621 (19) | O11A—O11B | 0.510 (15) |
N1—H6 | 0.80 (3) | ||
O9—Zn1—O9i | 180.0 | C3—N1—H7 | 110.0 (17) |
O9—Zn1—O7 | 94.77 (5) | H6—N1—H7 | 115 (3) |
O9i—Zn1—O7 | 85.24 (5) | C3—N1—H8 | 109.7 (18) |
O9—Zn1—O7i | 85.24 (5) | H6—N1—H8 | 106 (3) |
O9i—Zn1—O7i | 94.76 (5) | H7—N1—H8 | 108 (2) |
O7—Zn1—O7i | 180.0 | C2—C1—C9 | 121.35 (13) |
O9—Zn1—O8i | 93.93 (5) | C2—C1—S1 | 116.45 (10) |
O9i—Zn1—O8i | 86.07 (5) | C9—C1—S1 | 122.18 (10) |
O7—Zn1—O8i | 93.91 (5) | C1—C2—C3 | 119.06 (13) |
O7i—Zn1—O8i | 86.09 (5) | C1—C2—H1 | 121.1 (15) |
O9—Zn1—O8 | 86.07 (5) | C3—C2—H1 | 119.8 (15) |
O9i—Zn1—O8 | 93.93 (5) | C4—C3—C2 | 122.40 (13) |
O7—Zn1—O8 | 86.08 (5) | C4—C3—N1 | 118.54 (13) |
O7i—Zn1—O8 | 93.92 (5) | C2—C3—N1 | 119.06 (13) |
O8i—Zn1—O8 | 180.0 | C3—C4—C10 | 119.75 (13) |
Zn1—O7—H9 | 115.4 (19) | C3—C4—H2 | 123.3 (15) |
Zn1—O7—H10 | 118 (2) | C10—C4—H2 | 116.9 (15) |
H9—O7—H10 | 113 (3) | C6—C5—C10 | 121.47 (13) |
Zn1—O8—H11 | 124 (2) | C6—C5—S2 | 117.93 (11) |
Zn1—O8—H12 | 121 (2) | C10—C5—S2 | 120.57 (11) |
H11—O8—H12 | 99 (3) | C5—C6—C7 | 119.90 (14) |
Zn1—O9—H13 | 122 (2) | C5—C6—H3 | 116.4 (17) |
Zn1—O9—H14 | 118 (2) | C7—C6—H3 | 123.7 (17) |
H13—O9—H14 | 113 (3) | C8—C7—C6 | 120.54 (14) |
O3—S1—O2 | 114.10 (7) | C8—C7—H4 | 119.9 (15) |
O3—S1—O1 | 112.15 (7) | C6—C7—H4 | 119.6 (15) |
O2—S1—O1 | 111.45 (7) | C7—C8—C9 | 121.15 (14) |
O3—S1—C1 | 105.83 (7) | C7—C8—H5 | 118.2 (15) |
O2—S1—C1 | 107.51 (7) | C9—C8—H5 | 120.7 (15) |
O1—S1—C1 | 105.11 (7) | C8—C9—C10 | 118.74 (13) |
O5—S2—O4 | 113.19 (8) | C8—C9—C1 | 123.30 (13) |
O5—S2—O6 | 112.69 (8) | C10—C9—C1 | 117.96 (12) |
O4—S2—O6 | 111.13 (9) | C4—C10—C5 | 122.34 (13) |
O5—S2—C5 | 106.45 (7) | C4—C10—C9 | 119.47 (13) |
O4—S2—C5 | 107.12 (8) | C5—C10—C9 | 118.19 (13) |
O6—S2—C5 | 105.70 (7) | H15—O10—H16 | 97 (4) |
C3—N1—H6 | 108.6 (19) | ||
O3—S1—C1—C2 | 7.97 (13) | S2—C5—C6—C7 | −177.90 (12) |
O2—S1—C1—C2 | 130.29 (12) | C5—C6—C7—C8 | 0.7 (2) |
O1—S1—C1—C2 | −110.88 (12) | C6—C7—C8—C9 | −0.9 (2) |
O3—S1—C1—C9 | −173.49 (12) | C7—C8—C9—C10 | 0.1 (2) |
O2—S1—C1—C9 | −51.18 (13) | C7—C8—C9—C1 | −179.69 (14) |
O1—S1—C1—C9 | 67.66 (13) | C2—C1—C9—C8 | 179.43 (14) |
C9—C1—C2—C3 | −0.1 (2) | S1—C1—C9—C8 | 1.0 (2) |
S1—C1—C2—C3 | 178.47 (11) | C2—C1—C9—C10 | −0.4 (2) |
C1—C2—C3—C4 | 0.2 (2) | S1—C1—C9—C10 | −178.83 (11) |
C1—C2—C3—N1 | −179.51 (13) | C3—C4—C10—C5 | 179.46 (14) |
C2—C3—C4—C10 | 0.2 (2) | C3—C4—C10—C9 | −0.7 (2) |
N1—C3—C4—C10 | 179.88 (14) | C6—C5—C10—C4 | 178.88 (15) |
O5—S2—C5—C6 | −4.21 (15) | S2—C5—C10—C4 | −3.0 (2) |
O4—S2—C5—C6 | −125.58 (13) | C6—C5—C10—C9 | −1.0 (2) |
O6—S2—C5—C6 | 115.84 (13) | S2—C5—C10—C9 | 177.09 (11) |
O5—S2—C5—C10 | 177.62 (12) | C8—C9—C10—C4 | −179.08 (13) |
O4—S2—C5—C10 | 56.25 (14) | C1—C9—C10—C4 | 0.7 (2) |
O6—S2—C5—C10 | −62.33 (13) | C8—C9—C10—C5 | 0.8 (2) |
C10—C5—C6—C7 | 0.3 (2) | C1—C9—C10—C5 | −179.38 (12) |
Symmetry code: (i) −x, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H9···O1i | 0.82 (2) | 1.82 (2) | 2.6360 (16) | 169 (3) |
O7—H10···O5ii | 0.79 (2) | 1.87 (2) | 2.6452 (16) | 166 (3) |
O8—H11···O1iii | 0.82 (2) | 1.93 (2) | 2.7439 (16) | 177 (3) |
O8—H12···O2 | 0.81 (2) | 1.97 (2) | 2.7662 (17) | 166 (3) |
O9—H13···O7iv | 0.81 (2) | 1.99 (2) | 2.8015 (17) | 172 (3) |
O9—H14···O4ii | 0.81 (2) | 1.87 (2) | 2.6660 (17) | 169 (3) |
N1—H6···O6iv | 0.80 (3) | 2.01 (3) | 2.7966 (19) | 166 (3) |
N1—H7···O3v | 0.86 (3) | 1.97 (3) | 2.8107 (18) | 166 (2) |
N1—H8···O11A | 0.82 (3) | 2.08 (3) | 2.863 (6) | 160 (3) |
O10—H15···O6ii | 0.93 (4) | 1.95 (2) | 2.876 (2) | 171 (4) |
O10—H16···O8 | 0.92 (3) | 2.24 (3) | 3.036 (3) | 144 (4) |
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 | [Zn(H2O)6](C10H8NO6S2)2·4H2O |
Mr | 850.12 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 273 |
a, b, c (Å) | 5.4294 (2), 12.7411 (5), 12.9537 (6) |
α, β, γ (°) | 114.497 (1), 101.563 (1), 90.889 (1) |
V (Å3) | 793.97 (6) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.13 |
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 | 0.757, 0.890 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17231, 6235, 5724 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.797 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.107, 0.94 |
No. of reflections | 6235 |
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) | 1.21, −1.03 |
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 | 0.823 (17) | 1.824 (17) | 2.6360 (16) | 169 (3) |
O7—H10···O5ii | 0.794 (17) | 1.868 (18) | 2.6452 (16) | 166 (3) |
O8—H11···O1iii | 0.816 (17) | 1.928 (17) | 2.7439 (16) | 177 (3) |
O8—H12···O2 | 0.811 (17) | 1.971 (18) | 2.7662 (17) | 166 (3) |
O9—H13···O7iv | 0.814 (17) | 1.994 (18) | 2.8015 (17) | 172 (3) |
O9—H14···O4ii | 0.812 (17) | 1.865 (18) | 2.6660 (17) | 169 (3) |
N1—H6···O6iv | 0.80 (3) | 2.01 (3) | 2.7966 (19) | 166 (3) |
N1—H7···O3v | 0.86 (3) | 1.97 (3) | 2.8107 (18) | 166 (2) |
N1—H8···O11A | 0.82 (3) | 2.08 (3) | 2.863 (6) | 160 (3) |
O10—H15···O6ii | 0.93 (4) | 1.95 (2) | 2.876 (2) | 171 (4) |
O10—H16···O8 | 0.92 (3) | 2.24 (3) | 3.036 (3) | 144 (4) |
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. |
As part of our ongoing studies of salts of 3-aminonaphthalene-1,5-sulfonate with divalent transition metals, we now report the structure of the title compound, (I), which is isostructural with its nickel(II) (Gunderman, Kabell et al., 1997) and cobalt(II) analogues (Genther et al., 2007). Compound (I) consists of centrosymmetic hexaaquazinc(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 the zinc naphthalene-1,5-disulfonate compound without the amine functionality (Huo et al., 2005).
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).