Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807024439/lh2390sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807024439/lh2390Isup2.hkl |
CCDC reference: 622513
Key indicators
- Single-crystal X-ray study
- T = 292 K
- Mean (C-C) = 0.003 Å
- R factor = 0.038
- wR factor = 0.086
- Data-to-parameter ratio = 14.2
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ? PLAT420_ALERT_2_C D-H Without Acceptor N3 - H3A ... ? PLAT480_ALERT_4_C Long H...A H-Bond Reported H3A .. O2 .. 2.67 Ang.
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn1 (2) 1.80 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 10
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
The isostructural NiII, CuII and CdII analogues have been reported previously (Li et al., 2005a,b, 2006).
For related literature, see: Gunderman et al. (1997); Işık et al. (2005); Kosnic et al. (1992); Shubnell et al. (1994).
Ethylenediamine (0.06 g, 1 mmol) was added to an aqueous solution (20 mL) of Zn(OAc)2˙2H2O(0.110 g, 0.5 mmol). After the mixture was stirred for 2 h at the room temperature, the solution was then treated with 4-aminonaphthalene-1-sulfonic acid sodium salt tetrahydrate (0.32 g, 1 mmol) in 10 ml e thanol. After filtration, the colorless solutions were allowed to stand at room temperature. The well shaped colorless block crystals of the title complex were obtained by slow evaporation of solvent about one week.
The water H atoms and amine H atoms were located in a difference Fourier map and refined with the restraints O—H = 0.75 (2)–0.87 (2) Å and N—H = 0.782 (19)–0.915 (2) Å, and Uiso(H) = 1.5Ueq(carrier). H atoms on C atoms were placed in geometrically idealized positions and refined in riding mode, with C—H = 0.93 or 0.97 Å and Uiso(H) = 1.2Ueq(C).
Due to the weak coordination strength of sulfonate anions with transition metals, the sulfonates usually act as the counterbalance of the charge (Kosnic et al., 1992; Shubnell et al., 1994; Gunderman et al., 1997). Herein, we report the crystal structure of such a novel compound, [Cu(en)2(H2O)2](ans)2 2H2O, (I), (en = diethylenediamine; ans = 4-aminonaphthalene-1-sulfonate). The molecular structure of (I) is shown in Fig.1. The Zn atom lies on an inversion center and has has a distorted octahedral geometry, coordinated by four N atoms from two diethylenediamine ligands, which lie in the equatorial plane, and by two water O atoms occupying the axial sites. The average Zn—N bond length of 2.1278 (16) Å, is longer than the Zn—N bond distances in [Zn(en)2(H2O)2](sap)23H2O (sap = 2-sulfanilamidopyrimidine; Zn—N 1.996 (2)–2.016 (2) Å) (Isik et al., 2005). The Zn—O bond distance of 2.2386 (17) Å, is significantly shorter than the Zn—O distances in [Zn(en)2(H2O)2](sap)2 (Zn—O 2.49 (2) Å and 2.68 (2) Å)(Isik et al., 2005). The naphthalene ring is essentially planar (r.m.s. deviation 0.002 Å), with the greatest deviation from planarity being 0.0258 (18)Å for C6. The S and N atoms deviate by 0.1632 (5) Å and 0.0035 (19) Å from the naphthalene plane, respectively. As shown in Fig.2, an organic cation layer is linked to an inorganic anionic layer through a series of N—H···O, O—H···O and O—H···N hydrogen bonds, and adjacent 4-aminonaphthalene-1-sulfonate anions are antiparallel, showing significant π-π interactions interactions. The plane-to-plane distances and displacement angles of Cg1···Cg2i are 3.378, 3.367 Å and 1.04, 16.37 °, respectively [Cg1 and Cg2 are C3—C7/C12 and C7—C12 ring centroids; symmetry code: (i) 1 - x, 2 - y, -z]). These interactions together with the hydrogen bonds stabilize the crystal structure.
The isostructural NiII, CuII and CdII analogues have been reported previously (Li et al., 2005a,b, 2006).
For related literature, see: Gunderman et al. (1997); Işık et al. (2005); Kosnic et al. (1992); Shubnell et al. (1994).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXS97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.
[Zn(C2H8N2)2(H2O)2](C10H8NO3S)2·2H2O | F(000) = 736 |
Mr = 702.11 | Dx = 1.575 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3865 reflections |
a = 12.425 (3) Å | θ = 2.7–28.1° |
b = 9.6851 (19) Å | µ = 1.04 mm−1 |
c = 12.305 (3) Å | T = 292 K |
β = 90.50 (3)° | Block, colourless |
V = 1480.7 (5) Å3 | 0.46 × 0.36 × 0.20 mm |
Z = 2 |
Bruker SMART CCD area-detector diffractometer | 3354 independent reflections |
Radiation source: fine-focus sealed tube | 2729 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.073 |
φ and ω scans | θmax = 27.5°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −12→16 |
Tmin = 0.647, Tmax = 0.820 | k = −12→12 |
9734 measured reflections | l = −10→15 |
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: inferred from neighbouring sites |
wR(F2) = 0.086 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.98 | w = 1/[σ2(Fo2) + (0.0458P)2] where P = (Fo2 + 2Fc2)/3 |
3354 reflections | (Δ/σ)max < 0.001 |
236 parameters | Δρmax = 0.47 e Å−3 |
10 restraints | Δρmin = −0.66 e Å−3 |
[Zn(C2H8N2)2(H2O)2](C10H8NO3S)2·2H2O | V = 1480.7 (5) Å3 |
Mr = 702.11 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.425 (3) Å | µ = 1.04 mm−1 |
b = 9.6851 (19) Å | T = 292 K |
c = 12.305 (3) Å | 0.46 × 0.36 × 0.20 mm |
β = 90.50 (3)° |
Bruker SMART CCD area-detector diffractometer | 3354 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 2729 reflections with I > 2σ(I) |
Tmin = 0.647, Tmax = 0.820 | Rint = 0.073 |
9734 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 10 restraints |
wR(F2) = 0.086 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.98 | Δρmax = 0.47 e Å−3 |
3354 reflections | Δρmin = −0.66 e Å−3 |
236 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 | ||
Zn1 | 0.0000 | 0.0000 | 0.5000 | 0.02820 (11) | |
N1 | 0.00131 (16) | 0.16231 (19) | 0.38096 (15) | 0.0372 (4) | |
N2 | −0.01612 (14) | 0.16750 (18) | 0.60803 (15) | 0.0338 (4) | |
O1 | 0.17965 (13) | 0.00886 (17) | 0.51362 (15) | 0.0394 (4) | |
C1 | 0.02957 (17) | 0.2888 (2) | 0.4403 (2) | 0.0461 (6) | |
H1C | 0.0134 | 0.3690 | 0.3959 | 0.055* | |
H1D | 0.1060 | 0.2894 | 0.4572 | 0.055* | |
C2 | −0.03471 (18) | 0.2943 (2) | 0.54452 (19) | 0.0466 (6) | |
H2C | −0.0131 | 0.3742 | 0.5870 | 0.056* | |
H2D | −0.1107 | 0.3032 | 0.5273 | 0.056* | |
C3 | 0.38445 (13) | 0.94913 (18) | 0.18557 (14) | 0.0241 (4) | |
C4 | 0.44306 (15) | 1.0471 (2) | 0.24009 (15) | 0.0296 (4) | |
H4 | 0.4095 | 1.1022 | 0.2916 | 0.036* | |
C5 | 0.55247 (15) | 1.06581 (19) | 0.21962 (16) | 0.0310 (4) | |
H5 | 0.5904 | 1.1337 | 0.2573 | 0.037* | |
C6 | 0.60475 (15) | 0.98605 (17) | 0.14515 (15) | 0.0266 (4) | |
C7 | 0.54778 (14) | 0.87878 (17) | 0.08887 (14) | 0.0235 (4) | |
C8 | 0.59937 (15) | 0.79072 (19) | 0.01412 (15) | 0.0303 (4) | |
H8 | 0.6727 | 0.8010 | 0.0020 | 0.036* | |
C9 | 0.54368 (16) | 0.6911 (2) | −0.04046 (16) | 0.0354 (5) | |
H9 | 0.5788 | 0.6347 | −0.0900 | 0.043* | |
C10 | 0.43368 (16) | 0.67369 (19) | −0.02191 (15) | 0.0337 (4) | |
H10 | 0.3962 | 0.6051 | −0.0591 | 0.040* | |
C11 | 0.38054 (14) | 0.75566 (17) | 0.04986 (14) | 0.0274 (4) | |
H11 | 0.3073 | 0.7426 | 0.0606 | 0.033* | |
C12 | 0.43560 (14) | 0.86090 (16) | 0.10847 (14) | 0.0228 (4) | |
N3 | 0.71563 (14) | 1.00495 (19) | 0.12848 (16) | 0.0339 (4) | |
O2 | 0.21294 (11) | 0.80591 (14) | 0.23913 (12) | 0.0429 (4) | |
O3 | 0.19412 (12) | 0.98569 (15) | 0.10337 (13) | 0.0431 (4) | |
O4 | 0.22193 (11) | 1.04667 (15) | 0.29095 (12) | 0.0408 (4) | |
O5 | 0.20692 (14) | 0.1749 (2) | 0.70145 (14) | 0.0477 (4) | |
S1 | 0.24345 (4) | 0.94473 (5) | 0.20564 (4) | 0.02944 (13) | |
H1E | 0.2027 (19) | 0.060 (2) | 0.558 (2) | 0.056 (9)* | |
H1F | 0.206 (2) | 0.023 (3) | 0.4602 (19) | 0.055 (9)* | |
H3A | 0.7328 (17) | 1.075 (2) | 0.1555 (19) | 0.045 (7)* | |
H3B | 0.7366 (17) | 0.9997 (19) | 0.0642 (16) | 0.030 (6)* | |
H5A | 0.215 (2) | 0.250 (2) | 0.720 (2) | 0.077 (11)* | |
H5B | 0.226 (2) | 0.124 (3) | 0.757 (2) | 0.067 (9)* | |
H2A | −0.0723 (18) | 0.151 (2) | 0.6477 (19) | 0.062 (8)* | |
H1A | −0.0590 (15) | 0.169 (2) | 0.3507 (18) | 0.048 (7)* | |
H1B | 0.0491 (19) | 0.146 (3) | 0.332 (2) | 0.072 (9)* | |
H2B | 0.0438 (16) | 0.175 (2) | 0.6514 (18) | 0.049 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.03346 (19) | 0.02544 (17) | 0.02576 (18) | 0.00102 (12) | 0.00379 (13) | 0.00048 (12) |
N1 | 0.0362 (11) | 0.0407 (10) | 0.0347 (10) | 0.0026 (8) | 0.0058 (9) | 0.0084 (8) |
N2 | 0.0300 (9) | 0.0361 (9) | 0.0354 (10) | 0.0002 (7) | 0.0058 (8) | −0.0064 (8) |
O1 | 0.0314 (8) | 0.0494 (10) | 0.0373 (9) | −0.0016 (7) | 0.0041 (7) | −0.0020 (8) |
C1 | 0.0479 (13) | 0.0299 (10) | 0.0605 (15) | −0.0024 (9) | 0.0058 (11) | 0.0109 (10) |
C2 | 0.0516 (13) | 0.0294 (10) | 0.0589 (15) | 0.0065 (10) | 0.0076 (12) | −0.0037 (10) |
C3 | 0.0252 (9) | 0.0256 (8) | 0.0215 (9) | −0.0002 (7) | 0.0032 (7) | 0.0040 (7) |
C4 | 0.0349 (10) | 0.0307 (9) | 0.0233 (9) | 0.0012 (8) | 0.0042 (8) | −0.0034 (8) |
C5 | 0.0355 (10) | 0.0289 (9) | 0.0284 (10) | −0.0056 (8) | −0.0025 (8) | −0.0042 (8) |
C6 | 0.0270 (9) | 0.0283 (9) | 0.0244 (9) | −0.0026 (7) | −0.0012 (8) | 0.0067 (7) |
C7 | 0.0272 (9) | 0.0231 (8) | 0.0203 (9) | 0.0014 (7) | 0.0011 (7) | 0.0045 (7) |
C8 | 0.0297 (10) | 0.0325 (10) | 0.0288 (10) | 0.0050 (8) | 0.0061 (8) | 0.0029 (8) |
C9 | 0.0432 (11) | 0.0315 (10) | 0.0317 (11) | 0.0056 (9) | 0.0081 (9) | −0.0054 (8) |
C10 | 0.0443 (12) | 0.0267 (9) | 0.0301 (11) | −0.0049 (8) | 0.0004 (9) | −0.0042 (8) |
C11 | 0.0284 (9) | 0.0273 (9) | 0.0267 (10) | −0.0034 (7) | 0.0010 (8) | 0.0013 (8) |
C12 | 0.0278 (9) | 0.0221 (8) | 0.0186 (8) | 0.0007 (7) | 0.0026 (7) | 0.0034 (7) |
N3 | 0.0279 (9) | 0.0405 (10) | 0.0332 (10) | −0.0067 (7) | 0.0001 (8) | 0.0006 (8) |
O2 | 0.0391 (8) | 0.0380 (8) | 0.0518 (10) | −0.0064 (6) | 0.0161 (7) | 0.0035 (7) |
O3 | 0.0302 (8) | 0.0623 (10) | 0.0370 (9) | 0.0054 (6) | 0.0007 (7) | 0.0058 (7) |
O4 | 0.0390 (8) | 0.0435 (8) | 0.0400 (9) | 0.0044 (7) | 0.0145 (7) | −0.0087 (7) |
O5 | 0.0522 (10) | 0.0440 (10) | 0.0466 (10) | −0.0010 (8) | −0.0133 (8) | 0.0002 (8) |
S1 | 0.0265 (2) | 0.0334 (3) | 0.0286 (3) | 0.00020 (19) | 0.00845 (19) | −0.0001 (2) |
Zn1—N2 | 2.1080 (17) | C4—H4 | 0.9300 |
Zn1—N2i | 2.1080 (17) | C5—C6 | 1.367 (3) |
Zn1—N1i | 2.1488 (18) | C5—H5 | 0.9300 |
Zn1—N1 | 2.1488 (18) | C6—N3 | 1.407 (3) |
Zn1—O1i | 2.2386 (17) | C6—C7 | 1.432 (2) |
Zn1—O1 | 2.2386 (17) | C7—C8 | 1.412 (2) |
N1—C1 | 1.468 (3) | C7—C12 | 1.427 (2) |
N1—H1A | 0.836 (18) | C8—C9 | 1.361 (3) |
N1—H1B | 0.86 (2) | C8—H8 | 0.9300 |
N2—C2 | 1.473 (3) | C9—C10 | 1.398 (3) |
N2—H2A | 0.87 (2) | C9—H9 | 0.9300 |
N2—H2B | 0.915 (18) | C10—C11 | 1.362 (2) |
O1—H1E | 0.79 (2) | C10—H10 | 0.9300 |
O1—H1F | 0.75 (2) | C11—C12 | 1.421 (2) |
C1—C2 | 1.517 (3) | C11—H11 | 0.9300 |
C1—H1C | 0.9700 | N3—H3A | 0.782 (19) |
C1—H1D | 0.9700 | N3—H3B | 0.836 (19) |
C2—H2C | 0.9700 | O2—S1 | 1.4573 (15) |
C2—H2D | 0.9700 | O3—S1 | 1.4504 (16) |
C3—C4 | 1.369 (3) | O4—S1 | 1.4674 (15) |
C3—C12 | 1.430 (2) | O5—H5A | 0.77 (2) |
C3—S1 | 1.7719 (17) | O5—H5B | 0.87 (2) |
C4—C5 | 1.397 (3) | ||
N2—Zn1—N2i | 180.0 | H2C—C2—H2D | 108.2 |
N2—Zn1—N1i | 97.57 (8) | C4—C3—C12 | 120.14 (16) |
N2i—Zn1—N1i | 82.43 (8) | C4—C3—S1 | 118.09 (14) |
N2—Zn1—N1 | 82.43 (8) | C12—C3—S1 | 121.59 (13) |
N2i—Zn1—N1 | 97.57 (8) | C3—C4—C5 | 121.07 (17) |
N1i—Zn1—N1 | 180.0 | C3—C4—H4 | 119.5 |
N2—Zn1—O1i | 88.66 (7) | C5—C4—H4 | 119.5 |
N2i—Zn1—O1i | 91.34 (7) | C6—C5—C4 | 121.12 (17) |
N1i—Zn1—O1i | 90.55 (7) | C6—C5—H5 | 119.4 |
N1—Zn1—O1i | 89.45 (7) | C4—C5—H5 | 119.4 |
N2—Zn1—O1 | 91.34 (7) | C5—C6—N3 | 119.74 (17) |
N2i—Zn1—O1 | 88.66 (7) | C5—C6—C7 | 119.88 (17) |
N1i—Zn1—O1 | 89.45 (7) | N3—C6—C7 | 120.29 (17) |
N1—Zn1—O1 | 90.55 (7) | C8—C7—C12 | 119.09 (16) |
O1i—Zn1—O1 | 180.0 | C8—C7—C6 | 121.85 (16) |
C1—N1—Zn1 | 105.95 (13) | C12—C7—C6 | 119.05 (16) |
C1—N1—H1A | 111.5 (16) | C9—C8—C7 | 121.18 (17) |
Zn1—N1—H1A | 110.4 (16) | C9—C8—H8 | 119.4 |
C1—N1—H1B | 109.7 (17) | C7—C8—H8 | 119.4 |
Zn1—N1—H1B | 110.5 (17) | C8—C9—C10 | 119.90 (17) |
H1A—N1—H1B | 109 (2) | C8—C9—H9 | 120.0 |
C2—N2—Zn1 | 108.81 (13) | C10—C9—H9 | 120.0 |
C2—N2—H2A | 109.1 (16) | C11—C10—C9 | 121.03 (17) |
Zn1—N2—H2A | 107.2 (16) | C11—C10—H10 | 119.5 |
C2—N2—H2B | 111.5 (15) | C9—C10—H10 | 119.5 |
Zn1—N2—H2B | 110.3 (15) | C10—C11—C12 | 120.88 (16) |
H2A—N2—H2B | 110 (2) | C10—C11—H11 | 119.6 |
Zn1—O1—H1E | 115.4 (18) | C12—C11—H11 | 119.6 |
Zn1—O1—H1F | 113 (2) | C11—C12—C7 | 117.90 (15) |
H1E—O1—H1F | 110 (3) | C11—C12—C3 | 123.41 (16) |
N1—C1—C2 | 108.92 (17) | C7—C12—C3 | 118.69 (15) |
N1—C1—H1C | 109.9 | C6—N3—H3A | 108.4 (17) |
C2—C1—H1C | 109.9 | C6—N3—H3B | 116.3 (15) |
N1—C1—H1D | 109.9 | H3A—N3—H3B | 112 (2) |
C2—C1—H1D | 109.9 | H5A—O5—H5B | 106 (3) |
H1C—C1—H1D | 108.3 | O3—S1—O2 | 112.87 (9) |
N2—C2—C1 | 109.75 (16) | O3—S1—O4 | 111.00 (9) |
N2—C2—H2C | 109.7 | O2—S1—O4 | 111.66 (9) |
C1—C2—H2C | 109.7 | O3—S1—C3 | 106.46 (9) |
N2—C2—H2D | 109.7 | O2—S1—C3 | 108.76 (8) |
C1—C2—H2D | 109.7 | O4—S1—C3 | 105.67 (9) |
N2—Zn1—N1—C1 | 19.84 (14) | C6—C7—C8—C9 | −178.60 (17) |
N2i—Zn1—N1—C1 | −160.16 (14) | C7—C8—C9—C10 | −0.7 (3) |
O1i—Zn1—N1—C1 | 108.55 (14) | C8—C9—C10—C11 | 0.4 (3) |
O1—Zn1—N1—C1 | −71.45 (14) | C9—C10—C11—C12 | −0.3 (3) |
N1i—Zn1—N2—C2 | −171.14 (14) | C10—C11—C12—C7 | 0.7 (3) |
N1—Zn1—N2—C2 | 8.86 (14) | C10—C11—C12—C3 | −179.36 (17) |
O1i—Zn1—N2—C2 | −80.76 (14) | C8—C7—C12—C11 | −1.0 (2) |
O1—Zn1—N2—C2 | 99.24 (14) | C6—C7—C12—C11 | 178.68 (15) |
Zn1—N1—C1—C2 | −44.7 (2) | C8—C7—C12—C3 | 179.03 (16) |
Zn1—N2—C2—C1 | −35.8 (2) | C6—C7—C12—C3 | −1.3 (2) |
N1—C1—C2—N2 | 55.4 (3) | C4—C3—C12—C11 | 179.11 (17) |
C12—C3—C4—C5 | 1.9 (3) | S1—C3—C12—C11 | −5.9 (2) |
S1—C3—C4—C5 | −173.30 (14) | C4—C3—C12—C7 | −0.9 (3) |
C3—C4—C5—C6 | −0.6 (3) | S1—C3—C12—C7 | 174.10 (12) |
C4—C5—C6—N3 | −178.31 (17) | C4—C3—S1—O3 | 112.32 (16) |
C4—C5—C6—C7 | −1.7 (3) | C12—C3—S1—O3 | −62.78 (16) |
C5—C6—C7—C8 | −177.73 (17) | C4—C3—S1—O2 | −125.78 (16) |
N3—C6—C7—C8 | −1.2 (3) | C12—C3—S1—O2 | 59.12 (16) |
C5—C6—C7—C12 | 2.6 (2) | C4—C3—S1—O4 | −5.78 (17) |
N3—C6—C7—C12 | 179.19 (16) | C12—C3—S1—O4 | 179.12 (14) |
C12—C7—C8—C9 | 1.1 (3) |
Symmetry code: (i) −x, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···O4ii | 0.86 (2) | 2.41 (2) | 3.170 (2) | 147 (2) |
N1—H1A···O2iii | 0.84 (2) | 2.57 (2) | 3.337 (3) | 153 (2) |
N2—H2A···O2iv | 0.87 (2) | 2.28 (2) | 3.109 (2) | 159 (2) |
N2—H2B···O5 | 0.92 (2) | 2.11 (2) | 2.992 (3) | 161 (2) |
N3—H3A···O2v | 0.78 (2) | 2.67 (2) | 3.451 (2) | 176 (2) |
N3—H3B···O3vi | 0.84 (2) | 2.25 (2) | 3.076 (3) | 172 (2) |
O1—H1E···O5 | 0.79 (2) | 2.08 (2) | 2.834 (3) | 158 (2) |
O5—H5B···N3vii | 0.87 (2) | 2.02 (2) | 2.882 (3) | 173 (3) |
O5—H5A···O4viii | 0.77 (2) | 2.15 (2) | 2.918 (3) | 172 (3) |
O1—H1F···O4ii | 0.75 (2) | 2.11 (2) | 2.818 (2) | 159 (3) |
Symmetry codes: (ii) x, y−1, z; (iii) −x, y−1/2, −z+1/2; (iv) −x, −y+1, −z+1; (v) −x+1, y+1/2, −z+1/2; (vi) −x+1, −y+2, −z; (vii) −x+1, −y+1, −z+1; (viii) x, −y+3/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C2H8N2)2(H2O)2](C10H8NO3S)2·2H2O |
Mr | 702.11 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 292 |
a, b, c (Å) | 12.425 (3), 9.6851 (19), 12.305 (3) |
β (°) | 90.50 (3) |
V (Å3) | 1480.7 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.04 |
Crystal size (mm) | 0.46 × 0.36 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.647, 0.820 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9734, 3354, 2729 |
Rint | 0.073 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.086, 0.98 |
No. of reflections | 3354 |
No. of parameters | 236 |
No. of restraints | 10 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.47, −0.66 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXS97 (Sheldrick, 1997), SHELXTL (Bruker, 2001), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···O4i | 0.86 (2) | 2.41 (2) | 3.170 (2) | 147 (2) |
N1—H1A···O2ii | 0.836 (18) | 2.570 (19) | 3.337 (3) | 153 (2) |
N2—H2A···O2iii | 0.87 (2) | 2.28 (2) | 3.109 (2) | 159 (2) |
N2—H2B···O5 | 0.915 (18) | 2.113 (19) | 2.992 (3) | 161 (2) |
N3—H3A···O2iv | 0.782 (19) | 2.67 (2) | 3.451 (2) | 176 (2) |
N3—H3B···O3v | 0.836 (19) | 2.246 (19) | 3.076 (3) | 171.6 (18) |
O1—H1E···O5 | 0.79 (2) | 2.08 (2) | 2.834 (3) | 158 (2) |
O5—H5B···N3vi | 0.87 (2) | 2.02 (2) | 2.882 (3) | 173 (3) |
O5—H5A···O4vii | 0.77 (2) | 2.15 (2) | 2.918 (3) | 172 (3) |
O1—H1F···O4i | 0.75 (2) | 2.11 (2) | 2.818 (2) | 159 (3) |
Symmetry codes: (i) x, y−1, z; (ii) −x, y−1/2, −z+1/2; (iii) −x, −y+1, −z+1; (iv) −x+1, y+1/2, −z+1/2; (v) −x+1, −y+2, −z; (vi) −x+1, −y+1, −z+1; (vii) x, −y+3/2, z+1/2. |
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Due to the weak coordination strength of sulfonate anions with transition metals, the sulfonates usually act as the counterbalance of the charge (Kosnic et al., 1992; Shubnell et al., 1994; Gunderman et al., 1997). Herein, we report the crystal structure of such a novel compound, [Cu(en)2(H2O)2](ans)2 2H2O, (I), (en = diethylenediamine; ans = 4-aminonaphthalene-1-sulfonate). The molecular structure of (I) is shown in Fig.1. The Zn atom lies on an inversion center and has has a distorted octahedral geometry, coordinated by four N atoms from two diethylenediamine ligands, which lie in the equatorial plane, and by two water O atoms occupying the axial sites. The average Zn—N bond length of 2.1278 (16) Å, is longer than the Zn—N bond distances in [Zn(en)2(H2O)2](sap)23H2O (sap = 2-sulfanilamidopyrimidine; Zn—N 1.996 (2)–2.016 (2) Å) (Isik et al., 2005). The Zn—O bond distance of 2.2386 (17) Å, is significantly shorter than the Zn—O distances in [Zn(en)2(H2O)2](sap)2 (Zn—O 2.49 (2) Å and 2.68 (2) Å)(Isik et al., 2005). The naphthalene ring is essentially planar (r.m.s. deviation 0.002 Å), with the greatest deviation from planarity being 0.0258 (18)Å for C6. The S and N atoms deviate by 0.1632 (5) Å and 0.0035 (19) Å from the naphthalene plane, respectively. As shown in Fig.2, an organic cation layer is linked to an inorganic anionic layer through a series of N—H···O, O—H···O and O—H···N hydrogen bonds, and adjacent 4-aminonaphthalene-1-sulfonate anions are antiparallel, showing significant π-π interactions interactions. The plane-to-plane distances and displacement angles of Cg1···Cg2i are 3.378, 3.367 Å and 1.04, 16.37 °, respectively [Cg1 and Cg2 are C3—C7/C12 and C7—C12 ring centroids; symmetry code: (i) 1 - x, 2 - y, -z]). These interactions together with the hydrogen bonds stabilize the crystal structure.