Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107052286/sk3173sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107052286/sk3173Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107052286/sk3173IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107052286/sk3173IIIsup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107052286/sk3173IVsup5.hkl |
CCDC references: 672425; 672426; 672427; 672428
The starting acid, (I), was crystallized inadvertently from a reaction of itself with Ni(NO3)2·6H2O. The Mn salt, (II), was prepared by direct reaction of Mn(NO3)2·6H2O and 5-aminonaphthalene-1-sulfonic acid (1:2 stoichiometry) in aqueous solution. A small amount of NaOH was added to the sulfonic acid to aid in deprotonation prior to introduction of the manganese nitrate. Following approximately 1 h of heating (Temperature?), during which most of the reactants dissolved, the resulting dark-purple solution was gravity filtered and set out in open air. Upon evaporation of the water, many purple plate-shaped crystals suitable for X-ray diffraction were recovered. The Ni salt, (III), was prepared by combining NiCO3 with 5-aminonaphthalene-1-sulfonic acid (1:2 stoichiometry) in aqueous solution. Following approximately 1 h of heating (Temperature?), during which the reactants dissolved, the resulting dark-purple solution was gravity filtered and set out in open air. Upon evaporation of the water, many purple clumps of needle-shaped crystals growing from a central point were obtained. The Co salt, (IV), was obtained from a reaction of Co(OH)2 and 5-aminonaphthalene-1-sulfonic acid (1:2 stoichiometry) in water. The reactants dissolved over about 30 min of heating (Temperature?) and the solution was then gravity filtered. Large (>5 mm) red plate-shaped crystals were left following complete evaporation of the solvent from the dark-red–purple solution.
For (I), (II) and (III), all H atoms were located in difference Fourier maps and refined isotropically. All crystals of (IV) under investigation were identified as non-merohedral twins using RLATT (Bruker, 2000). Two orientation matrices were assigned to the two different twin components [GEMINI (Bruker, 2000) and SMART (Bruker, 2003)]. Integration of the data using SAINT-Plus (Bruker, 2003) using both orientation matrices deconvoluted the data set into overlapped reflections and reflections originated by only one of the twin components. Correction for absorption, decay and inhomogeneity of the X-ray beam were applied using TWINABS (Sheldrick, 2007), where each component was scaled separately, followed by applying the resulting scale factors to the overlapping reflections. The twinning law is a 180° rotation around c* and the ratio of the two twin components was refined to 0.344 (4):0.656 (4). Equivalent reflections were merged if they originated from the same twin component, or if they originated simultaneously from both components. Thus, a total of 8586 reflections measured were merged to 5584 unique data that include reflections from each of the twin components. All non-H atoms were refined with anisotropic atomic displacement parameters, with the exception of water atom O14, which is disordered over two sites (80:20) and which was refined isotropically; no H atoms were included in the refinement for this water molecule. Other H atoms were located in difference Fourier syntheses and refined with distance restraints of O—H = 0.82 (5) Å, N—H = 0.86 (5) Å and C—H = 0.95 (5) Å, and with Uiso = 1.5Ueq(N,O) or 1.2Ueq(C).
For all compounds, data collection: SMART (Bruker, 2003); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus (Bruker, 2003); program(s) used to solve structure: SHELXTL (Sheldrick, 2000); program(s) used to refine structure: SHELXTL (Sheldrick, 2000); molecular graphics: SHELXTL (Sheldrick, 2000); software used to prepare material for publication: SHELXTL (Sheldrick, 2000) and local programs.
C10H9NO3S·H2O | Z = 4 |
Mr = 241.26 | F(000) = 504 |
Monoclinic, P21/c | Dx = 1.516 Mg m−3 |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 8.1157 (16) Å | µ = 0.30 mm−1 |
b = 7.8434 (16) Å | T = 150 K |
c = 16.723 (3) Å | Block, purple |
β = 96.90 (3)° | 0.30 × 0.06 × 0.03 mm |
V = 1056.8 (4) Å3 |
Bruker SMART 6000 CCD area-detector diffractometer | 1957 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.024 |
Graphite monochromator | θmax = 28.5°, θmin = 2.5° |
ω scans | h = −10→10 |
9016 measured reflections | k = −10→9 |
2475 independent reflections | l = −22→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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.120 | All H-atom parameters refined |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0634P)2 + 0.4287P] where P = (Fo2 + 2Fc2)/3 |
2475 reflections | (Δ/σ)max < 0.001 |
189 parameters | Δρmax = 0.29 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
C10H9NO3S·H2O | V = 1056.8 (4) Å3 |
Mr = 241.26 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.1157 (16) Å | µ = 0.30 mm−1 |
b = 7.8434 (16) Å | T = 150 K |
c = 16.723 (3) Å | 0.30 × 0.06 × 0.03 mm |
β = 96.90 (3)° |
Bruker SMART 6000 CCD area-detector diffractometer | 1957 reflections with I > 2σ(I) |
9016 measured reflections | Rint = 0.024 |
2475 independent reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.120 | All H-atom parameters refined |
S = 1.04 | Δρmax = 0.29 e Å−3 |
2475 reflections | Δρmin = −0.27 e Å−3 |
189 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 | ||
S1 | 0.29464 (6) | 0.78581 (7) | 0.16340 (3) | 0.03429 (17) | |
O1 | 0.4086 (2) | 0.90939 (19) | 0.20430 (9) | 0.0475 (4) | |
O2 | 0.3358 (3) | 0.6167 (2) | 0.19111 (9) | 0.0609 (5) | |
O3 | 0.1242 (2) | 0.8310 (4) | 0.16788 (11) | 0.0855 (8) | |
O4 | −0.0571 (3) | 0.8956 (3) | 0.29399 (14) | 0.0708 (6) | |
N1 | 0.6426 (3) | 0.7435 (2) | −0.16997 (11) | 0.0374 (4) | |
C1 | 0.3210 (2) | 0.7977 (2) | 0.05947 (11) | 0.0308 (4) | |
C2 | 0.1899 (3) | 0.8564 (3) | 0.00856 (13) | 0.0393 (5) | |
C3 | 0.2011 (3) | 0.8756 (3) | −0.07399 (13) | 0.0454 (5) | |
C4 | 0.3441 (3) | 0.8341 (3) | −0.10422 (12) | 0.0390 (5) | |
C5 | 0.6329 (2) | 0.7232 (3) | −0.08349 (12) | 0.0335 (4) | |
C6 | 0.7650 (3) | 0.6612 (3) | −0.03517 (13) | 0.0411 (5) | |
C7 | 0.7554 (3) | 0.6420 (3) | 0.04748 (14) | 0.0464 (5) | |
C8 | 0.6140 (3) | 0.6849 (3) | 0.07968 (13) | 0.0400 (5) | |
C9 | 0.4737 (2) | 0.7504 (2) | 0.03040 (11) | 0.0295 (4) | |
C10 | 0.4821 (2) | 0.7700 (2) | −0.05357 (11) | 0.0301 (4) | |
H2 | 0.091 (3) | 0.885 (3) | 0.0303 (15) | 0.052 (7)* | |
H3 | 0.102 (3) | 0.923 (3) | −0.1086 (17) | 0.063 (8)* | |
H4 | 0.349 (3) | 0.846 (3) | −0.1593 (15) | 0.039 (6)* | |
H6 | 0.866 (3) | 0.626 (3) | −0.0579 (14) | 0.046 (6)* | |
H7 | 0.848 (3) | 0.602 (3) | 0.0767 (15) | 0.054 (7)* | |
H8 | 0.613 (2) | 0.677 (3) | 0.1359 (13) | 0.029 (5)* | |
H1A | 0.617 (3) | 0.858 (4) | −0.1851 (15) | 0.050 (7)* | |
H1B | 0.565 (3) | 0.677 (3) | −0.2016 (16) | 0.052 (7)* | |
H1C | 0.748 (3) | 0.713 (3) | −0.1819 (16) | 0.052 (7)* | |
H4A | 0.003 (4) | 0.880 (5) | 0.255 (2) | 0.090 (11)* | |
H4B | −0.091 (5) | 1.001 (6) | 0.280 (3) | 0.120 (16)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0382 (3) | 0.0402 (3) | 0.0254 (2) | −0.0015 (2) | 0.00772 (18) | −0.00102 (19) |
O1 | 0.0719 (11) | 0.0367 (9) | 0.0321 (7) | −0.0088 (7) | −0.0010 (7) | −0.0015 (6) |
O2 | 0.1184 (15) | 0.0329 (9) | 0.0326 (8) | −0.0100 (9) | 0.0136 (9) | 0.0043 (7) |
O3 | 0.0455 (10) | 0.176 (2) | 0.0380 (9) | 0.0199 (12) | 0.0161 (8) | −0.0026 (12) |
O4 | 0.0667 (12) | 0.0761 (16) | 0.0775 (14) | 0.0163 (11) | 0.0416 (11) | 0.0153 (11) |
N1 | 0.0469 (10) | 0.0341 (10) | 0.0335 (9) | −0.0023 (8) | 0.0143 (8) | −0.0019 (7) |
C1 | 0.0340 (9) | 0.0306 (10) | 0.0281 (9) | −0.0024 (8) | 0.0051 (7) | −0.0012 (7) |
C2 | 0.0346 (10) | 0.0493 (13) | 0.0344 (10) | 0.0060 (9) | 0.0059 (8) | 0.0013 (9) |
C3 | 0.0395 (11) | 0.0632 (15) | 0.0325 (11) | 0.0105 (10) | 0.0000 (8) | 0.0057 (10) |
C4 | 0.0433 (11) | 0.0480 (13) | 0.0254 (10) | 0.0022 (9) | 0.0034 (8) | 0.0028 (9) |
C5 | 0.0389 (10) | 0.0320 (10) | 0.0307 (10) | −0.0032 (8) | 0.0087 (8) | −0.0029 (8) |
C6 | 0.0349 (10) | 0.0465 (13) | 0.0428 (12) | 0.0034 (9) | 0.0089 (9) | −0.0059 (10) |
C7 | 0.0375 (11) | 0.0584 (15) | 0.0419 (12) | 0.0117 (10) | −0.0004 (9) | −0.0008 (11) |
C8 | 0.0417 (11) | 0.0483 (13) | 0.0295 (10) | 0.0061 (9) | 0.0028 (8) | 0.0016 (9) |
C9 | 0.0320 (9) | 0.0284 (10) | 0.0281 (9) | −0.0007 (7) | 0.0033 (7) | −0.0006 (7) |
C10 | 0.0347 (9) | 0.0271 (10) | 0.0291 (9) | −0.0027 (7) | 0.0065 (7) | −0.0015 (7) |
S1—O2 | 1.4309 (18) | C3—C4 | 1.360 (3) |
S1—O3 | 1.4386 (18) | C3—H3 | 1.00 (3) |
S1—O1 | 1.4526 (16) | C4—C10 | 1.413 (3) |
S1—C1 | 1.7788 (19) | C4—H4 | 0.93 (2) |
O4—H4A | 0.87 (4) | C5—C6 | 1.353 (3) |
O4—H4B | 0.89 (5) | C5—C10 | 1.425 (3) |
N1—C5 | 1.466 (3) | C6—C7 | 1.402 (3) |
N1—H1A | 0.95 (3) | C6—H6 | 0.98 (2) |
N1—H1B | 0.93 (3) | C7—C8 | 1.366 (3) |
N1—H1C | 0.93 (3) | C7—H7 | 0.90 (2) |
C1—C2 | 1.360 (3) | C8—C9 | 1.419 (3) |
C1—C9 | 1.433 (3) | C8—H8 | 0.94 (2) |
C2—C3 | 1.402 (3) | C9—C10 | 1.422 (3) |
C2—H2 | 0.95 (3) | ||
O2—S1—O3 | 113.56 (15) | C3—C4—C10 | 120.85 (19) |
O2—S1—O1 | 110.82 (11) | C3—C4—H4 | 119.0 (14) |
O3—S1—O1 | 111.88 (13) | C10—C4—H4 | 120.1 (14) |
O2—S1—C1 | 108.33 (9) | C6—C5—C10 | 122.37 (18) |
O3—S1—C1 | 105.49 (10) | C6—C5—N1 | 119.68 (18) |
O1—S1—C1 | 106.29 (9) | C10—C5—N1 | 117.95 (18) |
H4A—O4—H4B | 97 (4) | C5—C6—C7 | 119.55 (19) |
C5—N1—H1A | 109.3 (15) | C5—C6—H6 | 120.5 (14) |
C5—N1—H1B | 112.7 (16) | C7—C6—H6 | 119.9 (14) |
H1A—N1—H1B | 105 (2) | C8—C7—C6 | 120.7 (2) |
C5—N1—H1C | 110.0 (17) | C8—C7—H7 | 123.7 (17) |
H1A—N1—H1C | 111 (2) | C6—C7—H7 | 115.5 (17) |
H1B—N1—H1C | 108 (2) | C7—C8—C9 | 120.9 (2) |
C2—C1—C9 | 121.22 (18) | C7—C8—H8 | 119.1 (12) |
C2—C1—S1 | 116.90 (15) | C9—C8—H8 | 119.9 (12) |
C9—C1—S1 | 121.87 (14) | C8—C9—C10 | 118.82 (18) |
C1—C2—C3 | 120.94 (19) | C8—C9—C1 | 124.26 (18) |
C1—C2—H2 | 118.3 (15) | C10—C9—C1 | 116.92 (17) |
C3—C2—H2 | 120.7 (15) | C4—C10—C9 | 120.10 (17) |
C4—C3—C2 | 119.95 (19) | C4—C10—C5 | 122.27 (18) |
C4—C3—H3 | 122.2 (16) | C9—C10—C5 | 117.64 (18) |
C2—C3—H3 | 117.8 (16) | ||
O2—S1—C1—C2 | 126.91 (19) | C7—C8—C9—C1 | 179.8 (2) |
O3—S1—C1—C2 | 5.0 (2) | C2—C1—C9—C8 | −178.6 (2) |
O1—S1—C1—C2 | −113.95 (18) | S1—C1—C9—C8 | 2.4 (3) |
O2—S1—C1—C9 | −54.02 (19) | C2—C1—C9—C10 | 0.9 (3) |
O3—S1—C1—C9 | −175.94 (18) | S1—C1—C9—C10 | −178.16 (14) |
O1—S1—C1—C9 | 65.12 (18) | C3—C4—C10—C9 | −0.9 (3) |
C9—C1—C2—C3 | −1.2 (3) | C3—C4—C10—C5 | 179.1 (2) |
S1—C1—C2—C3 | 177.85 (18) | C8—C9—C10—C4 | 179.68 (19) |
C1—C2—C3—C4 | 0.5 (4) | C1—C9—C10—C4 | 0.2 (3) |
C2—C3—C4—C10 | 0.6 (4) | C8—C9—C10—C5 | −0.4 (3) |
C10—C5—C6—C7 | −0.1 (3) | C1—C9—C10—C5 | −179.85 (16) |
N1—C5—C6—C7 | 180.0 (2) | C6—C5—C10—C4 | −179.8 (2) |
C5—C6—C7—C8 | 0.1 (4) | N1—C5—C10—C4 | 0.1 (3) |
C6—C7—C8—C9 | −0.2 (4) | C6—C5—C10—C9 | 0.3 (3) |
C7—C8—C9—C10 | 0.3 (3) | N1—C5—C10—C9 | −179.87 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1i | 0.95 (3) | 1.86 (3) | 2.803 (3) | 172 (2) |
N1—H1B···O1ii | 0.93 (3) | 2.01 (3) | 2.917 (3) | 162 (2) |
N1—H1C···O4iii | 0.93 (3) | 1.88 (3) | 2.801 (3) | 168 (2) |
O4—H4A···O3 | 0.87 (4) | 1.89 (4) | 2.759 (3) | 176 (4) |
O4—H4B···O2iv | 0.89 (5) | 2.29 (4) | 2.884 (3) | 124 (4) |
Symmetry codes: (i) −x+1, −y+2, −z; (ii) x, −y+3/2, z−1/2; (iii) x+1, −y+3/2, z−1/2; (iv) −x, y+1/2, −z+1/2. |
[Mn(H2O)6](C10H8NO3S)2·3H2O | F(000) = 690 |
Mr = 661.55 | Dx = 1.541 Mg m−3 |
Orthorhombic, P21212 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2 2ab | Cell parameters from 42059 reflections |
a = 8.3263 (3) Å | θ = 2.4–35.4° |
b = 22.8436 (7) Å | µ = 0.68 mm−1 |
c = 7.4940 (2) Å | T = 140 K |
V = 1425.38 (8) Å3 | Plate, purple |
Z = 2 | 0.35 × 0.20 × 0.08 mm |
Bruker SMART 6000 CCD area-detector diffractometer | 6245 independent reflections |
Radiation source: fine-focus sealed tube | 6115 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
ω scans | θmax = 35.4°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS and SAINT-Plus; Bruker, 2003) | h = −13→13 |
Tmin = 0.815, Tmax = 0.947 | k = −36→37 |
47963 measured reflections | l = −12→11 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.028 | All H-atom parameters refined |
wR(F2) = 0.074 | w = 1/[σ2(Fo2) + (0.0534P)2 + 0.065P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.002 |
6245 reflections | Δρmax = 0.55 e Å−3 |
250 parameters | Δρmin = −0.24 e Å−3 |
0 restraints | Absolute structure: Flack (1983), with 2571 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.103 (9) |
[Mn(H2O)6](C10H8NO3S)2·3H2O | V = 1425.38 (8) Å3 |
Mr = 661.55 | Z = 2 |
Orthorhombic, P21212 | Mo Kα radiation |
a = 8.3263 (3) Å | µ = 0.68 mm−1 |
b = 22.8436 (7) Å | T = 140 K |
c = 7.4940 (2) Å | 0.35 × 0.20 × 0.08 mm |
Bruker SMART 6000 CCD area-detector diffractometer | 6245 independent reflections |
Absorption correction: multi-scan (SADABS and SAINT-Plus; Bruker, 2003) | 6115 reflections with I > 2σ(I) |
Tmin = 0.815, Tmax = 0.947 | Rint = 0.023 |
47963 measured reflections |
R[F2 > 2σ(F2)] = 0.028 | All H-atom parameters refined |
wR(F2) = 0.074 | Δρmax = 0.55 e Å−3 |
S = 1.09 | Δρmin = −0.24 e Å−3 |
6245 reflections | Absolute structure: Flack (1983), with 2571 Friedel pairs |
250 parameters | Absolute structure parameter: 0.103 (9) |
0 restraints |
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 | ||
Mn1 | 0.5000 | 1.0000 | 0.84874 (2) | 0.01670 (5) | |
O4 | 0.48042 (9) | 0.93283 (3) | 0.64516 (10) | 0.02070 (12) | |
O5 | 0.42741 (11) | 0.93488 (4) | 1.04010 (11) | 0.02382 (14) | |
O6 | 0.75874 (10) | 0.97859 (4) | 0.82986 (12) | 0.02961 (17) | |
S1 | 0.38905 (3) | 0.611453 (9) | 0.55423 (3) | 0.01675 (5) | |
O1 | 0.50792 (10) | 0.59555 (3) | 0.69145 (10) | 0.02180 (12) | |
O2 | 0.23843 (10) | 0.57938 (3) | 0.58196 (12) | 0.02382 (14) | |
O3 | 0.45030 (11) | 0.60407 (3) | 0.37392 (10) | 0.02441 (14) | |
N1 | 0.16964 (12) | 0.85279 (4) | 0.95060 (14) | 0.02448 (16) | |
C1 | 0.34692 (11) | 0.68653 (4) | 0.58644 (12) | 0.01633 (14) | |
C2 | 0.38820 (12) | 0.72426 (4) | 0.45065 (13) | 0.02075 (15) | |
C3 | 0.36681 (15) | 0.78511 (4) | 0.47268 (15) | 0.02468 (18) | |
C4 | 0.30299 (13) | 0.80635 (4) | 0.62772 (15) | 0.02267 (17) | |
C5 | 0.19104 (11) | 0.79134 (4) | 0.93068 (13) | 0.01930 (15) | |
C6 | 0.15266 (13) | 0.75375 (5) | 1.06824 (14) | 0.02320 (17) | |
C7 | 0.17482 (14) | 0.69304 (5) | 1.04901 (15) | 0.02465 (18) | |
C8 | 0.23551 (13) | 0.66947 (4) | 0.89420 (13) | 0.02051 (16) | |
C9 | 0.27917 (11) | 0.70686 (4) | 0.75118 (12) | 0.01560 (13) | |
C10 | 0.25750 (11) | 0.76874 (4) | 0.76933 (12) | 0.01688 (14) | |
H2 | 0.433 (2) | 0.7098 (7) | 0.349 (2) | 0.022 (4)* | |
H3 | 0.405 (2) | 0.8128 (9) | 0.372 (3) | 0.035 (5)* | |
H4 | 0.275 (3) | 0.8490 (10) | 0.635 (3) | 0.050 (6)* | |
H6 | 0.107 (3) | 0.7697 (8) | 1.179 (3) | 0.035 (5)* | |
H7 | 0.146 (2) | 0.6658 (8) | 1.146 (3) | 0.028 (4)* | |
H8 | 0.261 (3) | 0.6305 (9) | 0.892 (3) | 0.044 (5)* | |
H1A | 0.129 (3) | 0.8692 (9) | 0.851 (3) | 0.033 (4)* | |
H1B | 0.111 (3) | 0.8604 (9) | 1.039 (3) | 0.037 (5)* | |
H4A | 0.422 (2) | 0.9410 (8) | 0.570 (3) | 0.029 (4)* | |
H4B | 0.559 (3) | 0.9240 (10) | 0.598 (3) | 0.045 (6)* | |
H5A | 0.392 (2) | 0.9428 (8) | 1.141 (3) | 0.030 (4)* | |
H5B | 0.369 (3) | 0.9087 (9) | 1.012 (3) | 0.037 (5)* | |
H6A | 0.818 (3) | 0.9839 (11) | 0.911 (4) | 0.060 (7)* | |
H6B | 0.808 (3) | 0.9543 (10) | 0.757 (3) | 0.039 (5)* | |
O7 | 0.5000 | 0.5000 | 0.92418 (13) | 0.02178 (17) | |
H7A | 0.490 (3) | 0.5272 (10) | 0.864 (3) | 0.050 (6)* | |
O8 | 0.79367 (9) | 0.53913 (4) | 0.63220 (11) | 0.02230 (14) | |
H8A | 0.772 (3) | 0.5061 (11) | 0.622 (3) | 0.049 (6)* | |
H8B | 0.711 (3) | 0.5546 (9) | 0.630 (3) | 0.036 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.01585 (8) | 0.01996 (8) | 0.01431 (8) | 0.00087 (6) | 0.000 | 0.000 |
O4 | 0.0210 (3) | 0.0216 (3) | 0.0195 (3) | −0.0009 (2) | −0.0014 (3) | −0.0015 (2) |
O5 | 0.0305 (4) | 0.0236 (3) | 0.0174 (3) | −0.0004 (3) | 0.0024 (3) | 0.0016 (2) |
O6 | 0.0170 (3) | 0.0428 (4) | 0.0290 (4) | 0.0063 (3) | −0.0050 (3) | −0.0176 (3) |
S1 | 0.01827 (9) | 0.01499 (8) | 0.01699 (9) | −0.00041 (7) | −0.00175 (7) | −0.00270 (6) |
O1 | 0.0216 (3) | 0.0208 (3) | 0.0230 (3) | 0.0040 (3) | −0.0058 (3) | −0.0015 (2) |
O2 | 0.0218 (3) | 0.0193 (3) | 0.0303 (4) | −0.0060 (2) | −0.0021 (3) | −0.0019 (3) |
O3 | 0.0317 (4) | 0.0230 (3) | 0.0185 (3) | −0.0004 (3) | 0.0032 (3) | −0.0057 (2) |
N1 | 0.0272 (4) | 0.0200 (3) | 0.0262 (4) | 0.0039 (3) | 0.0013 (3) | −0.0061 (3) |
C1 | 0.0170 (3) | 0.0161 (3) | 0.0159 (3) | −0.0008 (3) | −0.0001 (3) | −0.0016 (3) |
C2 | 0.0247 (4) | 0.0197 (3) | 0.0179 (3) | −0.0008 (3) | 0.0032 (3) | 0.0008 (3) |
C3 | 0.0314 (5) | 0.0191 (4) | 0.0235 (4) | −0.0014 (3) | 0.0059 (4) | 0.0033 (3) |
C4 | 0.0271 (4) | 0.0162 (3) | 0.0248 (4) | −0.0009 (3) | 0.0040 (3) | 0.0004 (3) |
C5 | 0.0179 (3) | 0.0198 (3) | 0.0202 (4) | 0.0011 (3) | 0.0006 (3) | −0.0043 (3) |
C6 | 0.0233 (4) | 0.0265 (4) | 0.0198 (4) | 0.0018 (3) | 0.0045 (3) | −0.0022 (3) |
C7 | 0.0288 (4) | 0.0252 (4) | 0.0200 (4) | 0.0003 (4) | 0.0057 (4) | 0.0021 (3) |
C8 | 0.0236 (4) | 0.0193 (4) | 0.0187 (3) | 0.0000 (3) | 0.0035 (3) | 0.0013 (3) |
C9 | 0.0159 (3) | 0.0157 (3) | 0.0152 (3) | −0.0007 (2) | 0.0001 (3) | −0.0011 (3) |
C10 | 0.0160 (3) | 0.0153 (3) | 0.0193 (3) | −0.0008 (3) | 0.0004 (3) | −0.0024 (3) |
O7 | 0.0214 (4) | 0.0272 (4) | 0.0168 (4) | −0.0004 (4) | 0.000 | 0.000 |
O8 | 0.0197 (3) | 0.0242 (3) | 0.0230 (3) | −0.0003 (3) | 0.0023 (3) | −0.0034 (3) |
Mn1—O5 | 2.1528 (8) | C1—C9 | 1.4346 (12) |
Mn1—O5i | 2.1529 (8) | C2—C3 | 1.4111 (14) |
Mn1—O4 | 2.1699 (7) | C2—H2 | 0.907 (17) |
Mn1—O4i | 2.1699 (8) | C3—C4 | 1.3667 (15) |
Mn1—O6 | 2.2137 (8) | C3—H3 | 1.03 (2) |
Mn1—O6i | 2.2137 (8) | C4—C10 | 1.4170 (13) |
O4—H4A | 0.77 (2) | C4—H4 | 1.00 (2) |
O4—H4B | 0.77 (3) | C5—C6 | 1.3792 (15) |
O5—H5A | 0.83 (2) | C5—C10 | 1.4265 (13) |
O5—H5B | 0.80 (2) | C6—C7 | 1.4066 (15) |
O6—H6A | 0.80 (3) | C6—H6 | 0.98 (2) |
O6—H6B | 0.88 (2) | C7—C8 | 1.3751 (14) |
S1—O3 | 1.4542 (8) | C7—H7 | 0.985 (19) |
S1—O2 | 1.4673 (8) | C8—C9 | 1.4178 (13) |
S1—O1 | 1.4728 (8) | C8—H8 | 0.92 (2) |
S1—C1 | 1.7670 (9) | C9—C10 | 1.4316 (12) |
N1—C5 | 1.4228 (13) | O7—H7A | 0.77 (2) |
N1—H1A | 0.90 (2) | O8—H8A | 0.78 (3) |
N1—H1B | 0.84 (2) | O8—H8B | 0.77 (2) |
C1—C2 | 1.3771 (13) | ||
O5—Mn1—O5i | 96.47 (5) | H1A—N1—H1B | 110.5 (18) |
O5—Mn1—O4 | 87.63 (3) | C2—C1—C9 | 122.11 (8) |
O5i—Mn1—O4 | 167.97 (3) | C2—C1—S1 | 117.19 (7) |
O5—Mn1—O4i | 167.97 (3) | C9—C1—S1 | 120.65 (7) |
O5i—Mn1—O4i | 87.63 (3) | C1—C2—C3 | 119.90 (9) |
O4—Mn1—O4i | 90.65 (4) | C1—C2—H2 | 119.5 (11) |
O5—Mn1—O6 | 99.39 (4) | C3—C2—H2 | 120.6 (11) |
O5i—Mn1—O6 | 85.53 (3) | C4—C3—C2 | 119.89 (9) |
O4—Mn1—O6 | 82.64 (3) | C4—C3—H3 | 121.3 (12) |
O4i—Mn1—O6 | 92.19 (4) | C2—C3—H3 | 118.7 (12) |
O5—Mn1—O6i | 85.53 (3) | C3—C4—C10 | 121.69 (9) |
O5i—Mn1—O6i | 99.39 (4) | C3—C4—H4 | 118.7 (14) |
O4—Mn1—O6i | 92.19 (4) | C10—C4—H4 | 119.1 (14) |
O4i—Mn1—O6i | 82.64 (3) | C6—C5—N1 | 120.45 (9) |
O6—Mn1—O6i | 172.67 (5) | C6—C5—C10 | 119.87 (9) |
Mn1—O4—H4A | 112.9 (15) | N1—C5—C10 | 119.65 (9) |
Mn1—O4—H4B | 116.5 (18) | C5—C6—C7 | 120.46 (9) |
H4A—O4—H4B | 105 (2) | C5—C6—H6 | 119.4 (11) |
Mn1—O5—H5A | 123.7 (13) | C7—C6—H6 | 120.1 (11) |
Mn1—O5—H5B | 121.1 (15) | C8—C7—C6 | 121.37 (10) |
H5A—O5—H5B | 100.7 (19) | C8—C7—H7 | 117.5 (10) |
Mn1—O6—H6A | 121.6 (19) | C6—C7—H7 | 121.1 (10) |
Mn1—O6—H6B | 128.9 (14) | C7—C8—C9 | 119.75 (9) |
H6A—O6—H6B | 107 (2) | C7—C8—H8 | 118.7 (15) |
O3—S1—O2 | 111.93 (5) | C9—C8—H8 | 120.9 (15) |
O3—S1—O1 | 112.61 (5) | C8—C9—C10 | 119.38 (8) |
O2—S1—O1 | 110.63 (5) | C8—C9—C1 | 123.81 (8) |
O3—S1—C1 | 108.01 (5) | C10—C9—C1 | 116.80 (8) |
O2—S1—C1 | 107.20 (4) | C4—C10—C5 | 121.26 (8) |
O1—S1—C1 | 106.11 (4) | C4—C10—C9 | 119.60 (8) |
C5—N1—H1A | 111.7 (13) | C5—C10—C9 | 119.13 (8) |
C5—N1—H1B | 111.0 (15) | H8A—O8—H8B | 103 (2) |
O3—S1—C1—C2 | −4.89 (9) | C7—C8—C9—C1 | 178.46 (10) |
O2—S1—C1—C2 | −125.66 (8) | C2—C1—C9—C8 | −179.84 (9) |
O1—S1—C1—C2 | 116.09 (8) | S1—C1—C9—C8 | −2.68 (13) |
O3—S1—C1—C9 | 177.82 (7) | C2—C1—C9—C10 | −0.60 (13) |
O2—S1—C1—C9 | 57.05 (9) | S1—C1—C9—C10 | 176.56 (7) |
O1—S1—C1—C9 | −61.20 (8) | C3—C4—C10—C5 | 179.98 (10) |
C9—C1—C2—C3 | 1.15 (15) | C3—C4—C10—C9 | 0.31 (16) |
S1—C1—C2—C3 | −176.10 (8) | C6—C5—C10—C4 | −177.96 (10) |
C1—C2—C3—C4 | −0.96 (17) | N1—C5—C10—C4 | 0.03 (15) |
C2—C3—C4—C10 | 0.23 (17) | C6—C5—C10—C9 | 1.71 (14) |
N1—C5—C6—C7 | −179.57 (10) | N1—C5—C10—C9 | 179.70 (9) |
C10—C5—C6—C7 | −1.60 (16) | C8—C9—C10—C4 | 179.14 (9) |
C5—C6—C7—C8 | 0.27 (17) | C1—C9—C10—C4 | −0.13 (13) |
C6—C7—C8—C9 | 0.92 (17) | C8—C9—C10—C5 | −0.54 (14) |
C7—C8—C9—C10 | −0.76 (15) | C1—C9—C10—C5 | −179.81 (8) |
Symmetry code: (i) −x+1, −y+2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O3ii | 0.90 (2) | 2.33 (2) | 3.1970 (13) | 161.2 (18) |
N1—H1B···O1iii | 0.84 (2) | 2.41 (2) | 3.2251 (12) | 161.9 (19) |
O4—H4A···O8ii | 0.77 (2) | 1.91 (2) | 2.6737 (11) | 174 (2) |
O4—H4B···O2iv | 0.77 (3) | 2.01 (3) | 2.7549 (11) | 162 (2) |
O5—H5A···O8iii | 0.83 (2) | 1.93 (2) | 2.7611 (12) | 175 (2) |
O5—H5B···N1 | 0.80 (2) | 2.14 (2) | 2.9279 (13) | 167 (2) |
O6—H6A···O7v | 0.80 (3) | 1.99 (3) | 2.7698 (11) | 168 (3) |
O6—H6B···O3iv | 0.88 (2) | 2.04 (2) | 2.9054 (11) | 169 (2) |
O7—H7A···O1 | 0.77 (2) | 2.04 (2) | 2.7947 (10) | 169 (3) |
O8—H8A···O2vi | 0.78 (3) | 1.98 (3) | 2.7462 (11) | 168 (2) |
O8—H8B···O1 | 0.77 (2) | 1.99 (2) | 2.7421 (11) | 165 (2) |
Symmetry codes: (ii) x−1/2, −y+3/2, −z+1; (iii) x−1/2, −y+3/2, −z+2; (iv) x+1/2, −y+3/2, −z+1; (v) −x+3/2, y+1/2, −z+2; (vi) −x+1, −y+1, z. |
[Ni(H2O)6](C10H8NO3S)2·3H2O | F(000) = 696 |
Mr = 665.32 | Dx = 1.593 Mg m−3 |
Orthorhombic, P21212 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2 2ab | Cell parameters from 5158 reflections |
a = 8.1031 (6) Å | θ = 2.7–28.3° |
b = 22.9375 (18) Å | µ = 0.93 mm−1 |
c = 7.4607 (6) Å | T = 140 K |
V = 1386.68 (19) Å3 | Needle, purple |
Z = 2 | 0.22 × 0.12 × 0.06 mm |
Bruker SMART 6000 CCD area-detector diffractometer | 3435 independent reflections |
Radiation source: fine-focus sealed tube | 3309 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
ω scans | θmax = 28.3°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS and SAINT-Plus; Bruker, 2003) | h = −10→10 |
Tmin = 0.844, Tmax = 0.950 | k = −30→28 |
14174 measured reflections | l = −9→9 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.025 | All H-atom parameters refined |
wR(F2) = 0.059 | w = 1/[σ2(Fo2) + (0.0269P)2 + 0.3548P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max = 0.001 |
3435 reflections | Δρmax = 0.35 e Å−3 |
250 parameters | Δρmin = −0.27 e Å−3 |
11 restraints | Absolute structure: Flack (1983), with 1433 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.072 (10) |
[Ni(H2O)6](C10H8NO3S)2·3H2O | V = 1386.68 (19) Å3 |
Mr = 665.32 | Z = 2 |
Orthorhombic, P21212 | Mo Kα radiation |
a = 8.1031 (6) Å | µ = 0.93 mm−1 |
b = 22.9375 (18) Å | T = 140 K |
c = 7.4607 (6) Å | 0.22 × 0.12 × 0.06 mm |
Bruker SMART 6000 CCD area-detector diffractometer | 3435 independent reflections |
Absorption correction: multi-scan (SADABS and SAINT-Plus; Bruker, 2003) | 3309 reflections with I > 2σ(I) |
Tmin = 0.844, Tmax = 0.950 | Rint = 0.023 |
14174 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | All H-atom parameters refined |
wR(F2) = 0.059 | Δρmax = 0.35 e Å−3 |
S = 1.10 | Δρmin = −0.27 e Å−3 |
3435 reflections | Absolute structure: Flack (1983), with 1433 Friedel pairs |
250 parameters | Absolute structure parameter: 0.072 (10) |
11 restraints |
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 | 0.0000 | 0.16459 (4) | 0.01453 (7) | |
O4 | 0.52792 (15) | 0.06370 (5) | 0.35328 (18) | 0.0183 (3) | |
O5 | 0.54423 (17) | 0.06237 (6) | −0.02426 (18) | 0.0210 (3) | |
O6 | 0.24743 (16) | 0.01656 (6) | 0.1793 (2) | 0.0249 (3) | |
H4A | 0.588 (3) | 0.0553 (10) | 0.436 (3) | 0.019 (6)* | |
H4B | 0.442 (2) | 0.0730 (11) | 0.406 (3) | 0.034 (7)* | |
H5A | 0.584 (3) | 0.0527 (11) | −0.121 (3) | 0.037 (7)* | |
H5B | 0.603 (3) | 0.0888 (10) | 0.008 (3) | 0.040 (8)* | |
H6A | 0.190 (3) | 0.0098 (12) | 0.095 (3) | 0.042 (7)* | |
H6B | 0.212 (4) | 0.0436 (10) | 0.241 (3) | 0.045 (8)* | |
S1 | 0.60765 (5) | 0.389280 (18) | 0.44610 (6) | 0.01671 (9) | |
O1 | 0.48764 (17) | 0.40606 (5) | 0.30697 (16) | 0.0212 (3) | |
O2 | 0.76543 (16) | 0.41907 (6) | 0.41785 (19) | 0.0237 (3) | |
O3 | 0.54535 (17) | 0.39794 (6) | 0.62683 (18) | 0.0255 (3) | |
N1 | 0.8111 (2) | 0.14556 (7) | 0.0538 (2) | 0.0236 (3) | |
C1 | 0.6438 (2) | 0.31376 (7) | 0.4158 (2) | 0.0160 (3) | |
C2 | 0.6004 (2) | 0.27733 (8) | 0.5532 (3) | 0.0196 (3) | |
C3 | 0.6174 (2) | 0.21633 (8) | 0.5327 (3) | 0.0227 (4) | |
C4 | 0.6795 (2) | 0.19426 (8) | 0.3774 (3) | 0.0216 (4) | |
C5 | 0.7934 (2) | 0.20710 (8) | 0.0713 (3) | 0.0186 (3) | |
C6 | 0.8337 (2) | 0.24341 (9) | −0.0676 (3) | 0.0225 (4) | |
C7 | 0.8163 (2) | 0.30410 (9) | −0.0498 (3) | 0.0234 (4) | |
C8 | 0.7572 (2) | 0.32862 (8) | 0.1046 (3) | 0.0203 (4) | |
C9 | 0.7104 (2) | 0.29261 (7) | 0.2501 (2) | 0.0159 (3) | |
C10 | 0.7281 (2) | 0.23058 (8) | 0.2336 (2) | 0.0174 (3) | |
H2 | 0.561 (2) | 0.2945 (8) | 0.656 (3) | 0.014 (5)* | |
H3 | 0.583 (3) | 0.1928 (9) | 0.626 (3) | 0.015 (5)* | |
H4 | 0.692 (3) | 0.1542 (10) | 0.369 (3) | 0.022 (6)* | |
H6 | 0.875 (3) | 0.2291 (10) | −0.184 (3) | 0.029 (6)* | |
H7 | 0.849 (3) | 0.3286 (10) | −0.143 (4) | 0.029 (6)* | |
H8 | 0.747 (3) | 0.3686 (10) | 0.110 (3) | 0.020 (5)* | |
H1A | 0.855 (3) | 0.1281 (9) | 0.148 (3) | 0.023 (6)* | |
H1B | 0.864 (3) | 0.1375 (11) | −0.042 (3) | 0.040 (7)* | |
O7 | 0.5000 | 0.5000 | 0.0704 (2) | 0.0220 (3) | |
H7A | 0.508 (4) | 0.4718 (9) | 0.132 (3) | 0.045 (8)* | |
O8 | 0.19375 (16) | 0.46432 (6) | 0.3492 (2) | 0.0208 (3) | |
H8A | 0.220 (3) | 0.4971 (8) | 0.362 (3) | 0.036 (6)* | |
H8B | 0.280 (2) | 0.4482 (10) | 0.350 (4) | 0.031 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.01453 (13) | 0.01568 (14) | 0.01337 (13) | 0.00068 (12) | 0.000 | 0.000 |
O4 | 0.0194 (7) | 0.0178 (6) | 0.0177 (6) | −0.0001 (4) | −0.0018 (5) | −0.0013 (5) |
O5 | 0.0257 (7) | 0.0192 (6) | 0.0180 (7) | −0.0001 (5) | 0.0006 (5) | 0.0001 (5) |
O6 | 0.0168 (6) | 0.0330 (8) | 0.0250 (7) | 0.0044 (5) | −0.0034 (5) | −0.0120 (6) |
S1 | 0.0188 (2) | 0.01335 (18) | 0.01800 (19) | −0.00040 (15) | −0.00160 (16) | −0.00255 (16) |
O1 | 0.0217 (6) | 0.0179 (6) | 0.0241 (6) | 0.0037 (5) | −0.0037 (6) | −0.0023 (4) |
O2 | 0.0227 (6) | 0.0183 (6) | 0.0301 (8) | −0.0055 (5) | −0.0031 (6) | −0.0015 (5) |
O3 | 0.0336 (7) | 0.0215 (6) | 0.0214 (6) | −0.0004 (5) | 0.0034 (5) | −0.0055 (5) |
N1 | 0.0272 (8) | 0.0202 (8) | 0.0234 (8) | 0.0026 (6) | 0.0015 (7) | −0.0069 (7) |
C1 | 0.0150 (7) | 0.0136 (7) | 0.0194 (8) | 0.0002 (6) | −0.0014 (6) | −0.0017 (6) |
C2 | 0.0200 (8) | 0.0204 (8) | 0.0182 (8) | 0.0003 (7) | 0.0013 (7) | −0.0031 (7) |
C3 | 0.0263 (9) | 0.0184 (8) | 0.0235 (9) | −0.0030 (7) | 0.0016 (8) | 0.0045 (7) |
C4 | 0.0224 (9) | 0.0140 (8) | 0.0283 (10) | −0.0014 (7) | −0.0004 (7) | 0.0000 (7) |
C5 | 0.0140 (7) | 0.0187 (8) | 0.0230 (9) | −0.0005 (6) | −0.0029 (7) | −0.0039 (7) |
C6 | 0.0204 (8) | 0.0280 (9) | 0.0190 (9) | 0.0015 (7) | 0.0017 (7) | −0.0040 (8) |
C7 | 0.0236 (9) | 0.0258 (9) | 0.0208 (8) | −0.0009 (7) | 0.0027 (8) | 0.0041 (8) |
C8 | 0.0212 (8) | 0.0169 (8) | 0.0227 (9) | −0.0010 (7) | 0.0006 (7) | 0.0010 (7) |
C9 | 0.0134 (7) | 0.0154 (8) | 0.0189 (8) | −0.0010 (6) | −0.0016 (6) | −0.0010 (7) |
C10 | 0.0140 (8) | 0.0171 (8) | 0.0210 (8) | 0.0001 (6) | −0.0010 (6) | −0.0023 (7) |
O7 | 0.0225 (8) | 0.0257 (9) | 0.0179 (8) | 0.0003 (9) | 0.000 | 0.000 |
O8 | 0.0189 (6) | 0.0206 (6) | 0.0231 (7) | −0.0001 (5) | 0.0020 (6) | −0.0028 (6) |
Ni1—O5 | 2.0396 (13) | C1—C9 | 1.433 (2) |
Ni1—O5i | 2.0397 (13) | C2—C3 | 1.414 (2) |
Ni1—O4 | 2.0414 (13) | C2—H2 | 0.92 (2) |
Ni1—O4i | 2.0415 (13) | C3—C4 | 1.361 (3) |
Ni1—O6 | 2.0844 (13) | C3—H3 | 0.93 (2) |
Ni1—O6i | 2.0845 (13) | C4—C10 | 1.414 (3) |
O4—H4A | 0.809 (16) | C4—H4 | 0.93 (2) |
O4—H4B | 0.826 (17) | C5—C6 | 1.369 (3) |
O5—H5A | 0.824 (17) | C5—C10 | 1.427 (2) |
O5—H5B | 0.811 (17) | C6—C7 | 1.405 (3) |
O6—H6A | 0.794 (17) | C6—H6 | 0.99 (2) |
O6—H6B | 0.823 (17) | C7—C8 | 1.368 (3) |
S1—O3 | 1.4534 (13) | C7—H7 | 0.93 (3) |
S1—O2 | 1.4649 (14) | C8—C9 | 1.416 (3) |
S1—O1 | 1.4735 (13) | C8—H8 | 0.92 (2) |
S1—C1 | 1.7714 (17) | C9—C10 | 1.435 (2) |
N1—C5 | 1.425 (2) | O7—H7A | 0.796 (16) |
N1—H1A | 0.884 (16) | O8—H8A | 0.788 (17) |
N1—H1B | 0.858 (17) | O8—H8B | 0.793 (16) |
C1—C2 | 1.368 (3) | ||
O5—Ni1—O5i | 92.62 (8) | H1A—N1—H1B | 111 (2) |
O5—Ni1—O4 | 87.42 (5) | C2—C1—C9 | 122.42 (16) |
O5i—Ni1—O4 | 176.19 (5) | C2—C1—S1 | 117.31 (13) |
O5—Ni1—O4i | 176.19 (5) | C9—C1—S1 | 120.23 (13) |
O5i—Ni1—O4i | 87.41 (5) | C1—C2—C3 | 119.89 (17) |
O4—Ni1—O4i | 92.81 (7) | C1—C2—H2 | 116.9 (13) |
O5—Ni1—O6 | 94.65 (6) | C3—C2—H2 | 123.2 (12) |
O5i—Ni1—O6 | 89.52 (5) | C4—C3—C2 | 119.71 (18) |
O4—Ni1—O6 | 86.68 (5) | C4—C3—H3 | 122.5 (13) |
O4i—Ni1—O6 | 89.16 (5) | C2—C3—H3 | 117.8 (13) |
O5—Ni1—O6i | 89.52 (5) | C3—C4—C10 | 122.00 (17) |
O5i—Ni1—O6i | 94.65 (6) | C3—C4—H4 | 117.8 (14) |
O4—Ni1—O6i | 89.16 (5) | C10—C4—H4 | 120.2 (14) |
O4i—Ni1—O6i | 86.68 (5) | C6—C5—N1 | 120.63 (17) |
O6—Ni1—O6i | 173.96 (8) | C6—C5—C10 | 120.09 (17) |
Ni1—O4—H4A | 115.0 (17) | N1—C5—C10 | 119.26 (17) |
Ni1—O4—H4B | 114.8 (18) | C5—C6—C7 | 120.45 (18) |
H4A—O4—H4B | 102 (2) | C5—C6—H6 | 123.0 (14) |
Ni1—O5—H5A | 119.2 (18) | C7—C6—H6 | 116.5 (14) |
Ni1—O5—H5B | 115.0 (19) | C8—C7—C6 | 121.47 (19) |
H5A—O5—H5B | 104 (3) | C8—C7—H7 | 118.8 (15) |
Ni1—O6—H6A | 120 (2) | C6—C7—H7 | 119.7 (15) |
Ni1—O6—H6B | 121 (2) | C7—C8—C9 | 119.96 (17) |
H6A—O6—H6B | 113 (3) | C7—C8—H8 | 118.4 (14) |
O3—S1—O2 | 111.89 (8) | C9—C8—H8 | 121.6 (14) |
O3—S1—O1 | 112.87 (8) | C8—C9—C1 | 124.38 (16) |
O2—S1—O1 | 110.65 (8) | C8—C9—C10 | 119.05 (16) |
O3—S1—C1 | 108.04 (8) | C1—C9—C10 | 116.56 (16) |
O2—S1—C1 | 107.06 (8) | C4—C10—C5 | 121.65 (16) |
O1—S1—C1 | 105.95 (7) | C4—C10—C9 | 119.41 (16) |
C5—N1—H1A | 114.6 (15) | C5—C10—C9 | 118.94 (16) |
C5—N1—H1B | 110.0 (18) | H8A—O8—H8B | 102 (2) |
O3—S1—C1—C2 | 3.93 (16) | C7—C8—C9—C10 | 0.8 (3) |
O2—S1—C1—C2 | 124.60 (14) | C2—C1—C9—C8 | −179.91 (17) |
O1—S1—C1—C2 | −117.28 (14) | S1—C1—C9—C8 | 2.4 (2) |
O3—S1—C1—C9 | −178.29 (13) | C2—C1—C9—C10 | 0.7 (2) |
O2—S1—C1—C9 | −57.62 (15) | S1—C1—C9—C10 | −176.98 (13) |
O1—S1—C1—C9 | 60.50 (15) | C3—C4—C10—C5 | 179.86 (17) |
C9—C1—C2—C3 | −1.4 (3) | C3—C4—C10—C9 | −0.6 (3) |
S1—C1—C2—C3 | 176.34 (14) | C6—C5—C10—C4 | 177.67 (17) |
C1—C2—C3—C4 | 1.1 (3) | N1—C5—C10—C4 | −0.4 (3) |
C2—C3—C4—C10 | −0.1 (3) | C6—C5—C10—C9 | −1.9 (2) |
N1—C5—C6—C7 | −179.89 (17) | N1—C5—C10—C9 | −179.91 (15) |
C10—C5—C6—C7 | 2.1 (3) | C8—C9—C10—C4 | −179.14 (16) |
C5—C6—C7—C8 | −0.9 (3) | C1—C9—C10—C4 | 0.3 (2) |
C6—C7—C8—C9 | −0.6 (3) | C8—C9—C10—C5 | 0.4 (2) |
C7—C8—C9—C1 | −178.59 (17) | C1—C9—C10—C5 | 179.87 (15) |
Symmetry code: (i) −x+1, −y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O3ii | 0.88 (2) | 2.36 (2) | 3.206 (2) | 161 (2) |
N1—H1B···O1iii | 0.86 (2) | 2.43 (2) | 3.270 (2) | 168 (2) |
O4—H4A···O8ii | 0.81 (2) | 1.87 (2) | 2.673 (2) | 171 (2) |
O4—H4B···O2iv | 0.83 (2) | 1.95 (2) | 2.7561 (18) | 164 (3) |
O5—H5A···O8iii | 0.82 (2) | 1.96 (2) | 2.778 (2) | 175 (3) |
O5—H5B···N1 | 0.81 (2) | 2.16 (2) | 2.942 (2) | 164 (3) |
O6—H6A···O7v | 0.79 (2) | 1.99 (2) | 2.7629 (18) | 165 (3) |
O6—H6B···O3iv | 0.82 (2) | 2.14 (2) | 2.9358 (19) | 161 (3) |
O7—H7A···O1 | 0.80 (2) | 2.00 (2) | 2.7872 (16) | 169 (3) |
O8—H8A···O2vi | 0.79 (2) | 1.97 (2) | 2.7435 (18) | 166 (3) |
O8—H8B···O1 | 0.79 (2) | 1.97 (2) | 2.7487 (18) | 170 (3) |
Symmetry codes: (ii) x+1/2, −y+1/2, −z+1; (iii) x+1/2, −y+1/2, −z; (iv) x−1/2, −y+1/2, −z+1; (v) −x+1/2, y−1/2, −z; (vi) −x+1, −y+1, z. |
[Co(H2O)6](C10H8NO3S)2·2H2O | Z = 2 |
Mr = 647.53 | F(000) = 674 |
Triclinic, P1 | Dx = 1.582 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.013 (2) Å | Cell parameters from 1152 reflections |
b = 8.710 (3) Å | θ = 3.1–24.6° |
c = 22.385 (7) Å | µ = 0.86 mm−1 |
α = 89.394 (8)° | T = 150 K |
β = 83.909 (8)° | Plate, red |
γ = 88.271 (8)° | 0.41 × 0.18 × 0.02 mm |
V = 1359.1 (7) Å3 |
Bruker SMART 6000 CCD area-detector diffractometer | 5584 independent reflections |
Radiation source: fine-focus sealed tube | 4971 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.052 |
ω scans | θmax = 27.8°, θmin = 1.8° |
Absorption correction: multi-scan (TWINABS; Sheldrick 2007) | h = −9→9 |
Tmin = 0.702, Tmax = 0.983 | k = −11→11 |
8586 measured reflections | l = 0→29 |
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)] = 0.058 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.157 | Only H-atom coordinates refined |
S = 1.12 | w = 1/[σ2(Fo2) + (0.1514P)2 + 50.7497P] where P = (Fo2 + 2Fc2)/3 |
5525 reflections | (Δ/σ)max < 0.001 |
445 parameters | Δρmax = 0.77 e Å−3 |
35 restraints | Δρmin = −0.79 e Å−3 |
[Co(H2O)6](C10H8NO3S)2·2H2O | γ = 88.271 (8)° |
Mr = 647.53 | V = 1359.1 (7) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.013 (2) Å | Mo Kα radiation |
b = 8.710 (3) Å | µ = 0.86 mm−1 |
c = 22.385 (7) Å | T = 150 K |
α = 89.394 (8)° | 0.41 × 0.18 × 0.02 mm |
β = 83.909 (8)° |
Bruker SMART 6000 CCD area-detector diffractometer | 5584 independent reflections |
Absorption correction: multi-scan (TWINABS; Sheldrick 2007) | 4971 reflections with I > 2σ(I) |
Tmin = 0.702, Tmax = 0.983 | Rint = 0.052 |
8586 measured reflections |
R[F2 > 2σ(F2)] = 0.058 | 35 restraints |
wR(F2) = 0.157 | Only H-atom coordinates refined |
S = 1.12 | w = 1/[σ2(Fo2) + (0.1514P)2 + 50.7497P] where P = (Fo2 + 2Fc2)/3 |
5525 reflections | Δρmax = 0.77 e Å−3 |
445 parameters | Δρmin = −0.79 e Å−3 |
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 | 0.5000 | 0.0200 (7) | |
Co2 | 0.0000 | 0.5000 | 0.0000 | 0.0244 (7) | |
S1 | 0.4555 (5) | 0.2457 (4) | 0.11300 (18) | 0.0246 (9) | |
S2 | 0.5592 (5) | 0.7446 (4) | 0.38705 (17) | 0.0199 (8) | |
N1 | 0.180 (2) | 0.3611 (17) | 0.3963 (7) | 0.033 (3) | |
H1A | 0.08 (2) | 0.40 (2) | 0.417 (8) | 0.050* | |
H1B | 0.284 (18) | 0.41 (2) | 0.399 (10) | 0.050* | |
N2 | 1.020 (2) | 0.8713 (17) | 0.1234 (7) | 0.030 (3) | |
H2A | 0.919 (18) | 0.89 (2) | 0.105 (8) | 0.044* | |
H2B | 1.11 (2) | 0.933 (18) | 0.119 (9) | 0.044* | |
O1 | 0.2885 (15) | 0.1628 (13) | 0.0991 (5) | 0.028 (3) | |
O2 | 0.4453 (16) | 0.4070 (13) | 0.0942 (6) | 0.031 (3) | |
O3 | 0.6342 (16) | 0.1693 (14) | 0.0881 (6) | 0.032 (3) | |
O4 | 0.5509 (15) | 0.9053 (12) | 0.4040 (5) | 0.027 (2) | |
O5 | 0.7139 (16) | 0.6596 (12) | 0.4130 (5) | 0.026 (2) | |
O6 | 0.3770 (15) | 0.6707 (12) | 0.4018 (5) | 0.025 (2) | |
O7 | −0.1795 (18) | 0.0913 (14) | 0.4407 (6) | 0.031 (3) | |
H7A | −0.22 (3) | 0.179 (10) | 0.440 (10) | 0.047* | |
H7B | −0.27 (2) | 0.04 (2) | 0.431 (9) | 0.047* | |
O8 | 0.0222 (15) | −0.2258 (13) | 0.4624 (5) | 0.028 (3) | |
H8A | −0.066 (15) | −0.24 (2) | 0.443 (7) | 0.041* | |
H8B | 0.120 (13) | −0.25 (2) | 0.442 (7) | 0.041* | |
O9 | 0.2256 (18) | 0.0738 (15) | 0.4455 (7) | 0.042 (4) | |
H9A | 0.23 (3) | 0.162 (10) | 0.434 (10) | 0.063* | |
H9B | 0.328 (17) | 0.03 (2) | 0.434 (10) | 0.063* | |
O10 | 0.2627 (17) | 0.4158 (15) | −0.0402 (6) | 0.036 (3) | |
H10A | 0.360 (17) | 0.467 (17) | −0.045 (10) | 0.054* | |
H10B | 0.30 (2) | 0.331 (11) | −0.053 (9) | 0.054* | |
O11 | −0.0215 (19) | 0.2932 (17) | 0.0470 (7) | 0.047 (4) | |
H11A | −0.126 (15) | 0.26 (3) | 0.057 (9) | 0.071* | |
H11B | 0.04 (2) | 0.28 (3) | 0.075 (7) | 0.071* | |
O12 | 0.146 (2) | 0.5974 (18) | 0.0641 (7) | 0.052 (4) | |
H12A | 0.23 (3) | 0.55 (2) | 0.079 (10) | 0.077* | |
H12B | 0.10 (3) | 0.66 (2) | 0.088 (8) | 0.077* | |
O13 | 0.369 (2) | 0.6311 (14) | 0.5393 (6) | 0.044 (3) | |
H13A | 0.30 (3) | 0.560 (19) | 0.551 (11) | 0.067* | |
H13B | 0.39 (3) | 0.62 (3) | 0.502 (3) | 0.067* | |
O14 | 0.673 (3) | 0.894 (2) | 0.0316 (9) | 0.056 (5)* | 0.80 |
O14B | 0.539 (16) | 0.862 (12) | 0.035 (5) | 0.09 (3)* | 0.20 |
C1 | 0.458 (2) | 0.2449 (17) | 0.1920 (7) | 0.021 (3) | |
C2 | 0.618 (2) | 0.1841 (19) | 0.2148 (8) | 0.029 (4) | |
H2 | 0.717 (18) | 0.143 (19) | 0.187 (6) | 0.034* | |
C3 | 0.631 (2) | 0.1841 (19) | 0.2762 (8) | 0.030 (4) | |
H3 | 0.747 (15) | 0.15 (2) | 0.291 (8) | 0.036* | |
C4 | 0.487 (3) | 0.2445 (19) | 0.3149 (8) | 0.030 (4) | |
H4 | 0.50 (3) | 0.24 (2) | 0.357 (3) | 0.036* | |
C5 | 0.162 (2) | 0.3683 (17) | 0.3338 (7) | 0.026 (3) | |
C6 | 0.002 (2) | 0.4263 (19) | 0.3112 (8) | 0.032 (4) | |
H6 | −0.099 (19) | 0.465 (19) | 0.339 (7) | 0.038* | |
C7 | −0.013 (2) | 0.4282 (19) | 0.2503 (8) | 0.030 (4) | |
H7 | −0.126 (16) | 0.46 (2) | 0.234 (8) | 0.036* | |
C8 | 0.130 (2) | 0.3698 (18) | 0.2092 (7) | 0.025 (3) | |
H8 | 0.12 (2) | 0.38 (2) | 0.168 (3) | 0.029* | |
C9 | 0.301 (2) | 0.3080 (16) | 0.2305 (7) | 0.020 (3) | |
C10 | 0.317 (2) | 0.3059 (16) | 0.2932 (7) | 0.023 (3) | |
C11 | 0.613 (2) | 0.7393 (17) | 0.3078 (7) | 0.020 (3) | |
C12 | 0.483 (2) | 0.6802 (17) | 0.2745 (8) | 0.024 (3) | |
H12 | 0.371 (15) | 0.646 (19) | 0.297 (7) | 0.029* | |
C13 | 0.516 (2) | 0.6775 (19) | 0.2115 (8) | 0.028 (4) | |
H13 | 0.413 (18) | 0.634 (19) | 0.194 (7) | 0.033* | |
C14 | 0.679 (2) | 0.7387 (18) | 0.1833 (7) | 0.026 (3) | |
H14 | 0.70 (2) | 0.73 (2) | 0.141 (3) | 0.031* | |
C15 | 0.985 (2) | 0.8724 (17) | 0.1869 (7) | 0.023 (3) | |
C16 | 1.117 (2) | 0.9292 (18) | 0.2200 (8) | 0.029 (4) | |
H16 | 1.226 (17) | 0.969 (19) | 0.196 (7) | 0.034* | |
C17 | 1.090 (2) | 0.9243 (17) | 0.2828 (8) | 0.025 (3) | |
H17 | 1.183 (19) | 0.969 (18) | 0.304 (7) | 0.030* | |
C18 | 0.930 (2) | 0.8646 (17) | 0.3131 (7) | 0.022 (3) | |
H18 | 0.92 (2) | 0.862 (19) | 0.355 (2) | 0.026* | |
C19 | 0.788 (2) | 0.8027 (16) | 0.2800 (6) | 0.018 (3) | |
C20 | 0.816 (2) | 0.8043 (17) | 0.2159 (7) | 0.023 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0173 (15) | 0.0191 (16) | 0.0231 (16) | 0.0013 (11) | −0.0002 (11) | −0.0021 (11) |
Co2 | 0.0245 (17) | 0.0258 (17) | 0.0228 (17) | −0.0045 (12) | −0.0019 (12) | 0.0007 (12) |
S1 | 0.022 (2) | 0.024 (2) | 0.027 (2) | −0.0019 (15) | −0.0005 (15) | 0.0002 (16) |
S2 | 0.0184 (18) | 0.0177 (19) | 0.023 (2) | −0.0004 (13) | 0.0004 (14) | −0.0037 (14) |
N1 | 0.041 (9) | 0.028 (8) | 0.029 (8) | −0.004 (6) | 0.005 (7) | −0.001 (6) |
N2 | 0.030 (8) | 0.033 (8) | 0.025 (7) | −0.007 (6) | 0.003 (6) | 0.003 (6) |
O1 | 0.025 (6) | 0.028 (6) | 0.034 (7) | −0.007 (5) | −0.004 (5) | −0.005 (5) |
O2 | 0.026 (6) | 0.026 (6) | 0.040 (7) | −0.005 (5) | −0.002 (5) | 0.009 (5) |
O3 | 0.027 (6) | 0.031 (7) | 0.036 (7) | −0.004 (5) | 0.004 (5) | −0.005 (5) |
O4 | 0.024 (6) | 0.023 (6) | 0.032 (6) | 0.002 (4) | 0.002 (5) | −0.007 (5) |
O5 | 0.031 (6) | 0.023 (6) | 0.025 (6) | −0.002 (5) | −0.003 (5) | 0.000 (5) |
O6 | 0.023 (6) | 0.025 (6) | 0.026 (6) | −0.003 (4) | 0.004 (5) | −0.002 (5) |
O7 | 0.034 (7) | 0.024 (6) | 0.037 (7) | 0.004 (5) | −0.013 (6) | −0.008 (5) |
O8 | 0.021 (6) | 0.028 (6) | 0.035 (7) | 0.004 (5) | −0.006 (5) | −0.009 (5) |
O9 | 0.031 (7) | 0.031 (7) | 0.056 (9) | 0.011 (5) | 0.022 (6) | 0.018 (6) |
O10 | 0.032 (7) | 0.030 (7) | 0.042 (8) | −0.004 (5) | 0.012 (6) | 0.000 (6) |
O11 | 0.029 (7) | 0.046 (8) | 0.066 (10) | −0.010 (6) | −0.004 (6) | 0.029 (7) |
O12 | 0.056 (10) | 0.043 (9) | 0.062 (10) | 0.015 (7) | −0.033 (8) | −0.021 (7) |
O13 | 0.071 (10) | 0.021 (7) | 0.038 (8) | 0.010 (6) | 0.005 (7) | 0.003 (6) |
C1 | 0.023 (8) | 0.018 (8) | 0.023 (8) | −0.005 (6) | −0.005 (6) | 0.000 (6) |
C2 | 0.023 (8) | 0.023 (8) | 0.039 (10) | 0.000 (6) | 0.001 (7) | −0.001 (7) |
C3 | 0.024 (8) | 0.025 (9) | 0.041 (10) | −0.005 (7) | −0.008 (7) | 0.003 (7) |
C4 | 0.033 (9) | 0.026 (9) | 0.033 (9) | −0.010 (7) | −0.010 (7) | 0.003 (7) |
C5 | 0.033 (9) | 0.010 (7) | 0.032 (9) | −0.008 (6) | 0.004 (7) | −0.001 (6) |
C6 | 0.028 (9) | 0.024 (9) | 0.040 (10) | 0.004 (7) | 0.012 (7) | −0.006 (7) |
C7 | 0.026 (8) | 0.022 (8) | 0.041 (10) | 0.002 (6) | −0.002 (7) | 0.002 (7) |
C8 | 0.027 (8) | 0.023 (8) | 0.025 (8) | −0.002 (6) | −0.006 (7) | 0.006 (6) |
C9 | 0.019 (7) | 0.012 (7) | 0.028 (8) | −0.004 (5) | −0.001 (6) | 0.002 (6) |
C10 | 0.025 (8) | 0.012 (7) | 0.030 (8) | −0.006 (6) | 0.001 (7) | 0.003 (6) |
C11 | 0.023 (7) | 0.017 (7) | 0.018 (7) | 0.006 (6) | −0.001 (6) | −0.001 (6) |
C12 | 0.016 (7) | 0.018 (8) | 0.038 (9) | −0.002 (6) | −0.002 (6) | −0.005 (6) |
C13 | 0.023 (8) | 0.029 (9) | 0.034 (9) | −0.006 (6) | −0.013 (7) | −0.002 (7) |
C14 | 0.031 (9) | 0.023 (8) | 0.023 (8) | −0.001 (6) | −0.003 (7) | −0.006 (6) |
C15 | 0.026 (8) | 0.015 (7) | 0.027 (8) | 0.003 (6) | 0.000 (6) | 0.000 (6) |
C16 | 0.021 (8) | 0.025 (8) | 0.037 (10) | −0.001 (6) | 0.006 (7) | 0.004 (7) |
C17 | 0.021 (8) | 0.018 (8) | 0.038 (9) | −0.005 (6) | −0.008 (7) | −0.002 (6) |
C18 | 0.028 (8) | 0.017 (7) | 0.020 (8) | 0.000 (6) | −0.004 (6) | −0.004 (6) |
C19 | 0.019 (7) | 0.015 (7) | 0.020 (7) | 0.004 (5) | −0.001 (6) | −0.001 (5) |
C20 | 0.021 (8) | 0.016 (7) | 0.031 (9) | 0.003 (6) | −0.003 (6) | 0.000 (6) |
Co1—O9 | 2.009 (11) | O12—H12B | 0.81 (5) |
Co1—O9i | 2.009 (11) | O13—H13A | 0.82 (5) |
Co1—O7 | 2.061 (12) | O13—H13B | 0.83 (5) |
Co1—O7i | 2.061 (12) | C1—C2 | 1.37 (2) |
Co1—O8i | 2.142 (11) | C1—C9 | 1.43 (2) |
Co1—O8 | 2.142 (11) | C2—C3 | 1.39 (3) |
Co2—O12 | 2.055 (14) | C2—H2 | 0.95 (5) |
Co2—O12ii | 2.055 (13) | C3—C4 | 1.36 (3) |
Co2—O11 | 2.078 (12) | C3—H3 | 0.94 (5) |
Co2—O11ii | 2.078 (12) | C4—C10 | 1.42 (2) |
Co2—O10ii | 2.079 (11) | C4—H4 | 0.94 (5) |
Co2—O10 | 2.079 (11) | C5—C6 | 1.36 (2) |
S1—O1 | 1.457 (11) | C5—C10 | 1.44 (2) |
S1—O3 | 1.460 (12) | C6—C7 | 1.38 (3) |
S1—O2 | 1.465 (12) | C6—H6 | 0.94 (5) |
S1—C1 | 1.771 (16) | C7—C8 | 1.38 (2) |
S2—O4 | 1.452 (11) | C7—H7 | 0.95 (5) |
S2—O6 | 1.453 (11) | C8—C9 | 1.42 (2) |
S2—O5 | 1.462 (12) | C8—H8 | 0.94 (5) |
S2—C11 | 1.776 (15) | C9—C10 | 1.42 (2) |
N1—C5 | 1.42 (2) | C11—C12 | 1.36 (2) |
N1—H1A | 0.86 (5) | C11—C19 | 1.43 (2) |
N1—H1B | 0.86 (5) | C12—C13 | 1.40 (2) |
N2—C15 | 1.42 (2) | C12—H12 | 0.94 (5) |
N2—H2A | 0.86 (5) | C13—C14 | 1.36 (2) |
N2—H2B | 0.86 (5) | C13—H13 | 0.95 (5) |
O7—H7A | 0.82 (5) | C14—C20 | 1.41 (2) |
O7—H7B | 0.82 (5) | C14—H14 | 0.95 (5) |
O8—H8A | 0.82 (5) | C15—C16 | 1.36 (2) |
O8—H8B | 0.82 (5) | C15—C20 | 1.43 (2) |
O9—H9A | 0.81 (5) | C16—C17 | 1.40 (2) |
O9—H9B | 0.81 (5) | C16—H16 | 0.95 (5) |
O10—H10A | 0.82 (5) | C17—C18 | 1.36 (2) |
O10—H10B | 0.81 (5) | C17—H17 | 0.95 (5) |
O11—H11A | 0.81 (5) | C18—C19 | 1.43 (2) |
O11—H11B | 0.82 (5) | C18—H18 | 0.94 (5) |
O12—H12A | 0.82 (5) | C19—C20 | 1.43 (2) |
O9—Co1—O9i | 179.998 (2) | Co2—O12—H12B | 126 (10) |
O9—Co1—O7 | 89.0 (6) | H12A—O12—H12B | 108 (9) |
O9i—Co1—O7 | 91.0 (6) | H13A—O13—H13B | 105 (10) |
O9—Co1—O7i | 91.0 (6) | C2—C1—C9 | 121.1 (15) |
O9i—Co1—O7i | 89.0 (6) | C2—C1—S1 | 117.8 (12) |
O7—Co1—O7i | 180.0 (6) | C9—C1—S1 | 121.1 (12) |
O9—Co1—O8i | 87.0 (5) | C1—C2—C3 | 120.6 (16) |
O9i—Co1—O8i | 93.0 (5) | C1—C2—H2 | 117 (10) |
O7—Co1—O8i | 84.1 (5) | C3—C2—H2 | 122 (10) |
O7i—Co1—O8i | 95.9 (5) | C4—C3—C2 | 120.8 (17) |
O9—Co1—O8 | 93.0 (5) | C4—C3—H3 | 119 (10) |
O9i—Co1—O8 | 87.0 (5) | C2—C3—H3 | 120 (10) |
O7—Co1—O8 | 95.9 (5) | C3—C4—C10 | 120.4 (17) |
O7i—Co1—O8 | 84.1 (5) | C3—C4—H4 | 119 (10) |
O8i—Co1—O8 | 179.999 (1) | C10—C4—H4 | 121 (10) |
O12—Co2—O12ii | 180.000 (2) | C6—C5—N1 | 122.5 (15) |
O12—Co2—O11 | 92.1 (7) | C6—C5—C10 | 119.1 (16) |
O12ii—Co2—O11 | 87.9 (7) | N1—C5—C10 | 118.3 (15) |
O12—Co2—O11ii | 87.9 (7) | C5—C6—C7 | 121.3 (15) |
O12ii—Co2—O11ii | 92.1 (7) | C5—C6—H6 | 118 (10) |
O11—Co2—O11ii | 179.999 (1) | C7—C6—H6 | 121 (10) |
O12—Co2—O10ii | 92.2 (6) | C6—C7—C8 | 122.1 (16) |
O12ii—Co2—O10ii | 87.8 (6) | C6—C7—H7 | 122 (10) |
O11—Co2—O10ii | 93.0 (5) | C8—C7—H7 | 116 (10) |
O11ii—Co2—O10ii | 87.0 (5) | C7—C8—C9 | 118.8 (16) |
O12—Co2—O10 | 87.8 (6) | C7—C8—H8 | 119 (10) |
O12ii—Co2—O10 | 92.2 (6) | C9—C8—H8 | 122 (10) |
O11—Co2—O10 | 87.0 (5) | C10—C9—C8 | 119.2 (14) |
O11ii—Co2—O10 | 93.0 (5) | C10—C9—C1 | 117.4 (14) |
O10ii—Co2—O10 | 179.999 (1) | C8—C9—C1 | 123.3 (15) |
O1—S1—O3 | 111.7 (7) | C9—C10—C4 | 119.6 (15) |
O1—S1—O2 | 111.8 (7) | C9—C10—C5 | 119.5 (15) |
O3—S1—O2 | 111.7 (7) | C4—C10—C5 | 120.9 (16) |
O1—S1—C1 | 108.1 (7) | C12—C11—C19 | 121.3 (14) |
O3—S1—C1 | 106.5 (7) | C12—C11—S2 | 118.4 (12) |
O2—S1—C1 | 106.6 (7) | C19—C11—S2 | 120.2 (11) |
O4—S2—O6 | 112.4 (6) | C11—C12—C13 | 120.7 (14) |
O4—S2—O5 | 111.7 (7) | C11—C12—H12 | 115 (10) |
O6—S2—O5 | 110.9 (7) | C13—C12—H12 | 125 (10) |
O4—S2—C11 | 106.8 (7) | C14—C13—C12 | 119.7 (15) |
O6—S2—C11 | 107.6 (7) | C14—C13—H13 | 129 (10) |
O5—S2—C11 | 107.1 (7) | C12—C13—H13 | 112 (10) |
C5—N1—H1A | 111 (10) | C13—C14—C20 | 121.6 (15) |
C5—N1—H1B | 102 (10) | C13—C14—H14 | 116 (10) |
H1A—N1—H1B | 112 (10) | C20—C14—H14 | 122 (10) |
C15—N2—H2A | 114 (10) | C16—C15—N2 | 119.7 (14) |
C15—N2—H2B | 99 (10) | C16—C15—C20 | 120.3 (15) |
H2A—N2—H2B | 121 (10) | N2—C15—C20 | 119.9 (14) |
Co1—O7—H7A | 126 (10) | C15—C16—C17 | 120.6 (14) |
Co1—O7—H7B | 122 (10) | C15—C16—H16 | 114 (10) |
H7A—O7—H7B | 104 (10) | C17—C16—H16 | 126 (10) |
Co1—O8—H8A | 113 (10) | C18—C17—C16 | 121.9 (15) |
Co1—O8—H8B | 119 (10) | C18—C17—H17 | 120 (10) |
H8A—O8—H8B | 106 (9) | C16—C17—H17 | 118 (10) |
Co1—O9—H9A | 121 (10) | C17—C18—C19 | 119.2 (14) |
Co1—O9—H9B | 132 (10) | C17—C18—H18 | 120 (10) |
H9A—O9—H9B | 107 (9) | C19—C18—H18 | 121 (10) |
Co2—O10—H10A | 124 (10) | C18—C19—C20 | 119.2 (13) |
Co2—O10—H10B | 131 (10) | C18—C19—C11 | 123.3 (13) |
H10A—O10—H10B | 105 (8) | C20—C19—C11 | 117.4 (14) |
Co2—O11—H11A | 120 (10) | C14—C20—C19 | 119.2 (14) |
Co2—O11—H11B | 120 (10) | C14—C20—C15 | 122.1 (15) |
H11A—O11—H11B | 107 (9) | C19—C20—C15 | 118.7 (14) |
Co2—O12—H12A | 123 (10) | ||
O1—S1—C1—C2 | 122.7 (12) | O4—S2—C11—C12 | −117.4 (13) |
O3—S1—C1—C2 | 2.6 (14) | O6—S2—C11—C12 | 3.6 (14) |
O2—S1—C1—C2 | −116.9 (12) | O5—S2—C11—C12 | 122.8 (12) |
O1—S1—C1—C9 | −58.3 (13) | O4—S2—C11—C19 | 59.9 (13) |
O3—S1—C1—C9 | −178.4 (11) | O6—S2—C11—C19 | −179.2 (11) |
O2—S1—C1—C9 | 62.1 (13) | O5—S2—C11—C19 | −60.0 (13) |
C9—C1—C2—C3 | −1 (2) | C19—C11—C12—C13 | 1 (2) |
S1—C1—C2—C3 | 178.1 (12) | S2—C11—C12—C13 | 178.1 (12) |
C1—C2—C3—C4 | 0 (3) | C11—C12—C13—C14 | −2 (3) |
C2—C3—C4—C10 | 2 (2) | C12—C13—C14—C20 | 0 (3) |
N1—C5—C6—C7 | −178.3 (15) | N2—C15—C16—C17 | −176.7 (15) |
C10—C5—C6—C7 | −1 (2) | C20—C15—C16—C17 | −1 (2) |
C5—C6—C7—C8 | 1 (3) | C15—C16—C17—C18 | −1 (3) |
C6—C7—C8—C9 | −1 (2) | C16—C17—C18—C19 | 1 (2) |
C7—C8—C9—C10 | 1 (2) | C17—C18—C19—C20 | 0 (2) |
C7—C8—C9—C1 | −179.9 (14) | C17—C18—C19—C11 | −179.2 (14) |
C2—C1—C9—C10 | 0 (2) | C12—C11—C19—C18 | −179.3 (15) |
S1—C1—C9—C10 | −178.6 (10) | S2—C11—C19—C18 | 4 (2) |
C2—C1—C9—C8 | −178.7 (14) | C12—C11—C19—C20 | 1 (2) |
S1—C1—C9—C8 | 2 (2) | S2—C11—C19—C20 | −175.8 (11) |
C8—C9—C10—C4 | −179.9 (14) | C13—C14—C20—C19 | 2 (2) |
C1—C9—C10—C4 | 1 (2) | C13—C14—C20—C15 | −178.3 (15) |
C8—C9—C10—C5 | −1 (2) | C18—C19—C20—C14 | 178.0 (14) |
C1—C9—C10—C5 | 179.9 (13) | C11—C19—C20—C14 | −3 (2) |
C3—C4—C10—C9 | −2 (2) | C18—C19—C20—C15 | −2 (2) |
C3—C4—C10—C5 | 179.2 (15) | C11—C19—C20—C15 | 177.5 (13) |
C6—C5—C10—C9 | 1 (2) | C16—C15—C20—C14 | −177.5 (15) |
N1—C5—C10—C9 | 178.4 (13) | N2—C15—C20—C14 | −2 (2) |
C6—C5—C10—C4 | 179.9 (15) | C16—C15—C20—C19 | 2 (2) |
N1—C5—C10—C4 | −3 (2) | N2—C15—C20—C19 | 178.0 (14) |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H7A···O13iii | 0.82 (5) | 1.95 (8) | 2.741 (18) | 163 (21) |
O8—H8A···O5iv | 0.82 (5) | 1.96 (8) | 2.750 (15) | 162 (19) |
O8—H8B···O6v | 0.82 (5) | 2.02 (6) | 2.832 (15) | 172 (17) |
O9—H9A···N1 | 0.81 (5) | 1.95 (7) | 2.748 (19) | 166 (23) |
O9—H9B···O4v | 0.81 (5) | 1.95 (6) | 2.757 (16) | 173 (21) |
O10—H10A···O2vi | 0.82 (5) | 2.01 (12) | 2.768 (15) | 153 (22) |
O10—H10B···O14vi | 0.81 (5) | 2.02 (13) | 2.73 (2) | 144 (21) |
O11—H11A···O3vii | 0.81 (5) | 1.93 (6) | 2.740 (16) | 174 (20) |
O11—H11B···O1 | 0.82 (5) | 2.08 (16) | 2.781 (18) | 141 (24) |
O12—H12A···O2 | 0.82 (5) | 1.98 (7) | 2.769 (18) | 165 (22) |
O12—H12B···N2vii | 0.81 (5) | 2.04 (10) | 2.82 (2) | 160 (25) |
O13—H13A···O5viii | 0.82 (5) | 2.07 (14) | 2.790 (16) | 147 (23) |
O13—H13B···O6 | 0.83 (5) | 2.29 (9) | 3.088 (18) | 163 (23) |
Symmetry codes: (iii) −x, −y+1, −z+1; (iv) x−1, y−1, z; (v) x, y−1, z; (vi) −x+1, −y+1, −z; (vii) x−1, y, z; (viii) −x+1, −y+1, −z+1. |
Experimental details
(I) | (II) | (III) | (IV) | |
Crystal data | ||||
Chemical formula | C10H9NO3S·H2O | [Mn(H2O)6](C10H8NO3S)2·3H2O | [Ni(H2O)6](C10H8NO3S)2·3H2O | [Co(H2O)6](C10H8NO3S)2·2H2O |
Mr | 241.26 | 661.55 | 665.32 | 647.53 |
Crystal system, space group | Monoclinic, P21/c | Orthorhombic, P21212 | Orthorhombic, P21212 | Triclinic, P1 |
Temperature (K) | 150 | 140 | 140 | 150 |
a, b, c (Å) | 8.1157 (16), 7.8434 (16), 16.723 (3) | 8.3263 (3), 22.8436 (7), 7.4940 (2) | 8.1031 (6), 22.9375 (18), 7.4607 (6) | 7.013 (2), 8.710 (3), 22.385 (7) |
α, β, γ (°) | 90, 96.90 (3), 90 | 90, 90, 90 | 90, 90, 90 | 89.394 (8), 83.909 (8), 88.271 (8) |
V (Å3) | 1056.8 (4) | 1425.38 (8) | 1386.68 (19) | 1359.1 (7) |
Z | 4 | 2 | 2 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.30 | 0.68 | 0.93 | 0.86 |
Crystal size (mm) | 0.30 × 0.06 × 0.03 | 0.35 × 0.20 × 0.08 | 0.22 × 0.12 × 0.06 | 0.41 × 0.18 × 0.02 |
Data collection | ||||
Diffractometer | Bruker SMART 6000 CCD area-detector diffractometer | Bruker SMART 6000 CCD area-detector diffractometer | Bruker SMART 6000 CCD area-detector diffractometer | Bruker SMART 6000 CCD area-detector diffractometer |
Absorption correction | – | Multi-scan (SADABS and SAINT-Plus; Bruker, 2003) | Multi-scan (SADABS and SAINT-Plus; Bruker, 2003) | Multi-scan (TWINABS; Sheldrick 2007) |
Tmin, Tmax | – | 0.815, 0.947 | 0.844, 0.950 | 0.702, 0.983 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9016, 2475, 1957 | 47963, 6245, 6115 | 14174, 3435, 3309 | 8586, 5584, 4971 |
Rint | 0.024 | 0.023 | 0.023 | 0.052 |
(sin θ/λ)max (Å−1) | 0.671 | 0.815 | 0.667 | 0.657 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.120, 1.04 | 0.028, 0.074, 1.09 | 0.025, 0.059, 1.10 | 0.058, 0.157, 1.12 |
No. of reflections | 2475 | 6245 | 3435 | 5525 |
No. of parameters | 189 | 250 | 250 | 445 |
No. of restraints | 0 | 0 | 11 | 35 |
H-atom treatment | All H-atom parameters refined | All H-atom parameters refined | All H-atom parameters refined | Only H-atom coordinates refined |
w = 1/[σ2(Fo2) + (0.0634P)2 + 0.4287P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.0534P)2 + 0.065P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.0269P)2 + 0.3548P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.1514P)2 + 50.7497P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.29, −0.27 | 0.55, −0.24 | 0.35, −0.27 | 0.77, −0.79 |
Absolute structure | ? | Flack (1983), with 2571 Friedel pairs | Flack (1983), with 1433 Friedel pairs | ? |
Absolute structure parameter | ? | 0.103 (9) | 0.072 (10) | ? |
Computer programs: SMART (Bruker, 2003), SAINT-Plus (Bruker, 2003), SHELXTL (Sheldrick, 2000) and local programs.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1i | 0.95 (3) | 1.86 (3) | 2.803 (3) | 172 (2) |
N1—H1B···O1ii | 0.93 (3) | 2.01 (3) | 2.917 (3) | 162 (2) |
N1—H1C···O4iii | 0.93 (3) | 1.88 (3) | 2.801 (3) | 168 (2) |
O4—H4A···O3 | 0.87 (4) | 1.89 (4) | 2.759 (3) | 176 (4) |
O4—H4B···O2iv | 0.89 (5) | 2.29 (4) | 2.884 (3) | 124 (4) |
Symmetry codes: (i) −x+1, −y+2, −z; (ii) x, −y+3/2, z−1/2; (iii) x+1, −y+3/2, z−1/2; (iv) −x, y+1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O3i | 0.90 (2) | 2.33 (2) | 3.1970 (13) | 161.2 (18) |
N1—H1B···O1ii | 0.84 (2) | 2.41 (2) | 3.2251 (12) | 161.9 (19) |
O4—H4A···O8i | 0.77 (2) | 1.91 (2) | 2.6737 (11) | 174 (2) |
O4—H4B···O2iii | 0.77 (3) | 2.01 (3) | 2.7549 (11) | 162 (2) |
O5—H5A···O8ii | 0.83 (2) | 1.93 (2) | 2.7611 (12) | 175 (2) |
O5—H5B···N1 | 0.80 (2) | 2.14 (2) | 2.9279 (13) | 167 (2) |
O6—H6A···O7iv | 0.80 (3) | 1.99 (3) | 2.7698 (11) | 168 (3) |
O6—H6B···O3iii | 0.88 (2) | 2.04 (2) | 2.9054 (11) | 169 (2) |
O7—H7A···O1 | 0.77 (2) | 2.04 (2) | 2.7947 (10) | 169 (3) |
O8—H8A···O2v | 0.78 (3) | 1.98 (3) | 2.7462 (11) | 168 (2) |
O8—H8B···O1 | 0.77 (2) | 1.99 (2) | 2.7421 (11) | 165 (2) |
Symmetry codes: (i) x−1/2, −y+3/2, −z+1; (ii) x−1/2, −y+3/2, −z+2; (iii) x+1/2, −y+3/2, −z+1; (iv) −x+3/2, y+1/2, −z+2; (v) −x+1, −y+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O3i | 0.884 (16) | 2.356 (17) | 3.206 (2) | 161 (2) |
N1—H1B···O1ii | 0.858 (17) | 2.427 (18) | 3.270 (2) | 168 (2) |
O4—H4A···O8i | 0.809 (16) | 1.872 (17) | 2.673 (2) | 171 (2) |
O4—H4B···O2iii | 0.826 (17) | 1.954 (18) | 2.7561 (18) | 164 (3) |
O5—H5A···O8ii | 0.824 (17) | 1.957 (17) | 2.778 (2) | 175 (3) |
O5—H5B···N1 | 0.811 (17) | 2.155 (18) | 2.942 (2) | 164 (3) |
O6—H6A···O7iv | 0.794 (17) | 1.989 (18) | 2.7629 (18) | 165 (3) |
O6—H6B···O3iii | 0.823 (17) | 2.144 (19) | 2.9358 (19) | 161 (3) |
O7—H7A···O1 | 0.796 (16) | 2.001 (17) | 2.7872 (16) | 169 (3) |
O8—H8A···O2v | 0.788 (17) | 1.971 (18) | 2.7435 (18) | 166 (3) |
O8—H8B···O1 | 0.793 (16) | 1.965 (17) | 2.7487 (18) | 170 (3) |
Symmetry codes: (i) x+1/2, −y+1/2, −z+1; (ii) x+1/2, −y+1/2, −z; (iii) x−1/2, −y+1/2, −z+1; (iv) −x+1/2, y−1/2, −z; (v) −x+1, −y+1, z. |
Co1—O9 | 2.009 (11) | Co2—O12 | 2.055 (14) |
Co1—O7 | 2.061 (12) | Co2—O11 | 2.078 (12) |
Co1—O8 | 2.142 (11) | Co2—O10 | 2.079 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H7A···O13i | 0.82 (5) | 1.95 (8) | 2.741 (18) | 163 (21) |
O8—H8A···O5ii | 0.82 (5) | 1.96 (8) | 2.750 (15) | 162 (19) |
O8—H8B···O6iii | 0.82 (5) | 2.02 (6) | 2.832 (15) | 172 (17) |
O9—H9A···N1 | 0.81 (5) | 1.95 (7) | 2.748 (19) | 166 (23) |
O9—H9B···O4iii | 0.81 (5) | 1.95 (6) | 2.757 (16) | 173 (21) |
O10—H10A···O2iv | 0.82 (5) | 2.01 (12) | 2.768 (15) | 153 (22) |
O10—H10B···O14iv | 0.81 (5) | 2.02 (13) | 2.73 (2) | 144 (21) |
O11—H11A···O3v | 0.81 (5) | 1.93 (6) | 2.740 (16) | 174 (20) |
O11—H11B···O1 | 0.82 (5) | 2.08 (16) | 2.781 (18) | 141 (24) |
O12—H12A···O2 | 0.82 (5) | 1.98 (7) | 2.769 (18) | 165 (22) |
O12—H12B···N2v | 0.81 (5) | 2.04 (10) | 2.82 (2) | 160 (25) |
O13—H13A···O5vi | 0.82 (5) | 2.07 (14) | 2.790 (16) | 147 (23) |
O13—H13B···O6 | 0.83 (5) | 2.29 (9) | 3.088 (18) | 163 (23) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x−1, y−1, z; (iii) x, y−1, z; (iv) −x+1, −y+1, −z; (v) x−1, y, z; (vi) −x+1, −y+1, −z+1. |
Mixed organic–inorganic structures have been of interest over the past three decades due to their potential as functional materials. One class of compounds that has received considerable attention is metal organophosphonate salts (Thompson, 1994; Clearfield, 1998). Metal organosulfonate salts have also been actively studied in recent years as part of the growing field of crystal engineering. Both similarities with and differences from the corresponding phosphonates have been found. Key results have been summarized in two recent reviews (Cote & Shimizu, 2003; Cai, 2004).
We have previously characterized a variety of amine-substituted naphthalenesulfonate salts of main group and transition metals with the goal of discerning structural trends as functions of metal cation and substitution of the sulfonate group. Having examined structures containing 6-aminonaphthalene-2-sulfonate (Gunderman & Squattrito, 1995), 4-aminonaphthalene-1-sulfonate (Morris et al., 2003) and 5-aminonaphthalene-2-sulfonate (Downer et al., 2006), we now report the structures of a series of salts of 5-aminonaphthalene-1-sulfonate, as well as the parent acid itself. These results are compared with those of the isomeric sulfonates.
The 5-aminonaphthalene-1-sulfonic acid, (I), crystallizes as a monohydrate. The unit cell and space group have been reported previously (Corbridge et al., 1966), but this is the first complete structure determination. As is typical for amine-substituted sulfonic acids (Gunderman & Squattrito, 1996; Leonard & Squattrito, 1997), the molecules exist in the zwitterionic ammoniosulfonate form, with the acidic H atom on the amine N atom (Fig. 1). The conformation of the sulfonate group has atom O3 essentially eclipsing the naphthalene ring system [O3—S1—C1—C2 torsion angle 5.0 (2)°]. The molecules are packed in layers that stack along the c axis, with the charged groups directed to the surfaces of the layer (Fig. 2). The anions are positioned so that all the rings are parallel, with contacts between adjacent rings of ca 3.7 Å. Within each layer, rows of molecules have the sulfonate and ammonio groups alternating in opposite orientations along b. The packing is directed both within and between layers by four nearly linear hydrogen bonds involving the three ammonio H atoms (two to sulfonate O atoms and one to the water O atom) and one of the water H atoms to a sulfonate O atom (Table 1). The other water H atom is involved in a slightly weaker non-linear interaction with a sulfonate O atom.
The manganese and nickel salts, (II) and (III), respectively, crystallize in the orthorhombic space group P21212 with the formula [M(H2O)6](H2NC10H6SO3)2·3H2O (M = Mn or Ni), consisting of hexaaquametal(II) cations, 5-aminonaphthalene-1-sulfonate anions and three water molecules of crystallization (Fig. 3). The two salts are isostructural and differ only in that the absolute structure refinements yield apparently opposite enantiomers. It is likely that we have both enantiomeric crystals in both products and that the selection was accidental. The presence of fully hydrated cations is typical of the behavior of divalent transition metals in these aminosulfonate systems, which are crystallized from aqueous solutions (Gunderman et al., 1997). Only a few examples have been observed where either the N or O atoms of the sulfonate coordinate directly to the metal under these conditions (Gunderman et al., 1996; Downer et al., 2006). The cations reside on twofold rotation axes and display a modestly distorted octahedral geometry. The maximum deviations from ideal bond angles are in the range of 10–12° for Mn [O5—Mn1—O4 167.97 (3)° and O5—Mn1—O6i 99.39 (4)°; symmetry code: (i) 1 - x, 2 - y, z], while for Ni, all angles are within 5° of ideal. The sulfonate group displays the same eclipsed conformation as in the parent acid [O3—S1—C1—C2 torsion angle -4.89 (9)° for (II) and 3.93 (16)° for (III)].
The crystal packing (Fig. 4) is typical for transition metal arene- and naphthalenesulfonates (Chen et al., 2002; Gunderman et al., 1997), consisting of alternating layers of hexaaquametal cations and sulfonate anions parallel to the ac plane, with the anions positioned so that the polar and charged groups (i.e. NH2 and SO3-) line the surface of the layer. Within each layer, alternating rows of molecules have the sulfonate and amino groups in opposite orientations and the rings canted in opposite directions (interplanar angle ca 43°) in a herringbone arrangement. 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 located on a twofold rotation axis. The layers are held together by a series of robust (H···A ca 2.0 Å) approximately linear O—H···O and O—H···N hydrogen bonds involving water donors and sulfonate, amine and water acceptors (Table 2). The amine H atoms participate in slightly longer hydrogen bonds (H···O ca 2.3–2.4 Å) with sulfonate O atoms. The packing is comparable with that found in the Mn salt of 4-aminonaphthalene-1-sulfonate (Morris et al., 2003), which has very similar cell dimensions and a herringbone arrangement of the anions. This is not surprising given that both isomers have the polar/ionic groups perpendicular to the long dimension of the naphthalene ring system (i.e. in ring positions 1, 4, 5 or 8), and so would be similarly positioned to maximize favorable interactions with the cation layers. This is borne out by the very comparable distances between the metal atom layers, ca 11.4 Å for (II) and ca 11.7 Å for the 4,1 isomer. The structures do differ in degree of hydration, crystal system and space group (the 4,1 isomer crystallizes with two solvent water molecules per formula unit in the monoclinic space group P21/c). By contrast, the Mn salt of 5-aminonaphthalene-2-sulfonate (Downer et al., 2006) has a very different packing, caused primarily by the positioning of the SO3- group on one of the terminal C atoms of the ring system (positions 2, 3, 6 and 7), which causes the anions to be situated in the layer with the long dimension of the ring system closer to perpendicular to the layer. This is reflected in the longer repeat distance between the layers (ca 14.2 Å). The spacing within the layers is also somewhat larger and the added voids between the metal complexes are occupied by water, as the 5,2 isomer has six solvent water molecules per formula unit. Although only alkali metal salts of 6-aminonaphthalene-2-sulfonate have been characterized to date (Gunderman & Squattrito, 1995), the anion packing follows the expected pattern. If fully hydrated transition metal salts of the 6,2 isomer were to be obtained, the interlayer repeat distance would be expected to be slightly larger than that of the 5,2 isomer.
Nickel shows somewhat greater variability in its behavior. The Ni salt of 4-aminonaphthalene-1-sulfonate (Morris et al., 2003) crystallizes as a trihydrate like (III), but in an orthorhombic cell with both the b and c axes doubled. This unprecedented layered sulfonate structure contains a quadruple layer repeat pattern with two different types of sulfonate layer. Nevertheless, the layer thicknesses are very similar [(ca 11.3 Å, versus ca 11.5 Å for (III)], as is the case for the Mn salts. The Ni salt of 5-aminonaphthalene-2-sulfonate (Downer et al., 2006) also has a completely different structure from the Mn (or Co) salt. In that compound, the Ni atom is coordinated by four water molecules and two sulfonate anions through the amine N atom, and it thus constitutes one of the rare examples of direct coordination involving the sulfonate anion with a transition metal ion. Due to the direct Ni—N bonding, the thickness of the layer (ca 11.5 Å) is less than the ca 14.2 Å dimension for the fully hydrated Mn salt.
The Co salt of 5-aminonaphthalene-1-sulfonate, (IV), is not isostructural with the Mn and Ni analogs. It crystallizes as a dihydrate, [Co(H2O)6](H2NC10H6SO3)2·2H2O, in the triclinic system. The unit cell has almost the same dimensions as the orthorhombic cell of (II) and (III) and the overall structure is quite similar. The asymmetric unit in (IV) (Fig. 5) contains two independent Co2+ cations on centers of inversion, six coordinated water molecules, two sulfonate anions and two solvent water molecules (one of which is disordered over two nearby positions). The coordination geometries of the cations are quite regular, with maximum angular deviations of only 1° for Co1 and just under 6° for Co2. The sulfonate groups adopt the same conformation as in (I)–(III), with one O atom eclipsing the naphthalene ring (O—S—C—C torsion angles <4° in both anions). The anions are packed in a similar herringbone arrangement with a slightly larger interplanar angle of ca 51°. Comparison of the stacking of the anionic and cationic layers in (III) (Fig. 4) with that in (IV) (Fig. 6) shows that they are almost the same. The main difference is that the water molecules at (0, 0, z) and (1/2, 1/2, z) in (III) are absent in (IV). The anions also appear to have a small extra tilt in (III) that is not present in (IV).
In our previous studies, there is precedence for both differences and a lack of difference in the sulfonate salts of these metals. The Mn, Co and Ni salts of 4-styrenesulfonate are isostructural, with no extra water beyond that coordinated to the metal cations (Leonard et al., 1999). For 4-aminonaphthalene-1-sulfonate, the Co and Ni salts are isostructural orthorhombic trihydrates, while the Mn salt is a monoclinic dihydrate (Morris et al., 2003). And for 5-aminonaphthalene-2-sulfonate, the Mn and Co salts are isostructural monoclinic hexahydrates, while the Ni salt is a triclinic dihydrate with direct Ni—N bonding to the amino group of the sulfonate (Downer et al., 2006). Taken together, these results demonstrate an unexpected structural diversity in these divalent aminonaphthalenesulfonate salts.