Diaqua­bis(ethyl­enediamine-κ²N,N′)zinc(II) bis­(4-aminona­phthalene-1-sulfonate) dihydrate

In the title compound, [Zn(C₂H₈N₂)₂(H₂O)₂](C₁₀H₈NO₃S)₂·2H₂O, the Zn^II cation lies on an inversion centre and has a distorted octa­hedral coordination geometry, defined by four N atoms from two ethyl­enediamine ligands and two water O atoms. In the crystal structure, pairs of 4-aminona­phthalene-1-sulfonate anions are connected via N—H...O hydrogen bonds to form centrosymmetric R₂²(16) rings. Cations, anions and water mol­ecules are further connected by N—H...O, O—H...O and O—H...N hydrogen bonds and π–π stacking inter­actions [with a centroid-to-centroid distance of 3.5099 (13) Å] to form a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 292 K
• Mean [sigma](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

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S1. Comment

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.

Related literature

The isostructural Ni^II, Cu^II and Cd^II 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).

S2. Experimental

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.

S3. Refinement

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 U_iso(H) = 1.5U_eq(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 U_iso(H) = 1.2U_eq(C).

Computing details

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.

Figures

	Fig. 1. The molecular structure of (I), showing ellipsoids at the 50% probability level [symmetry code: -x, -y, 1 - z].
	Fig. 2. Part of the crystal structure of (I), with hydrogen bonds shown as dashed lines.

[Diaquabis(ethylenediamine-κ²N,N')zinc(II)] [bis(4-aminonaphthalene-1-sulfonate)] dihydrate

Crystal data

[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) Å^3	0.46 × 0.36 × 0.20 mm
Z = 2

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.086	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	w = 1/[σ^2(Fo^2) + (0.0458P)^2] where P = (Fo^2 + 2Fc^2)/3
3354 reflections	(Δ/σ)max < 0.001
236 parameters	Δρmax = 0.47 e Å^−3
10 restraints	Δρmin = −0.66 e Å^−3

Special details

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.

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

	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)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

Zn1—N2	2.1080 (17)	C4—H4	0.9300
Zn1—N2^i	2.1080 (17)	C5—C6	1.367 (3)
Zn1—N1^i	2.1488 (18)	C5—H5	0.9300
Zn1—N1	2.1488 (18)	C6—N3	1.407 (3)
Zn1—O1^i	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—N2^i	180.0	H2C—C2—H2D	108.2
N2—Zn1—N1^i	97.57 (8)	C4—C3—C12	120.14 (16)
N2^i—Zn1—N1^i	82.43 (8)	C4—C3—S1	118.09 (14)
N2—Zn1—N1	82.43 (8)	C12—C3—S1	121.59 (13)
N2^i—Zn1—N1	97.57 (8)	C3—C4—C5	121.07 (17)
N1^i—Zn1—N1	180.0	C3—C4—H4	119.5
N2—Zn1—O1^i	88.66 (7)	C5—C4—H4	119.5
N2^i—Zn1—O1^i	91.34 (7)	C6—C5—C4	121.12 (17)
N1^i—Zn1—O1^i	90.55 (7)	C6—C5—H5	119.4
N1—Zn1—O1^i	89.45 (7)	C4—C5—H5	119.4
N2—Zn1—O1	91.34 (7)	C5—C6—N3	119.74 (17)
N2^i—Zn1—O1	88.66 (7)	C5—C6—C7	119.88 (17)
N1^i—Zn1—O1	89.45 (7)	N3—C6—C7	120.29 (17)
N1—Zn1—O1	90.55 (7)	C8—C7—C12	119.09 (16)
O1^i—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)
N2^i—Zn1—N1—C1	−160.16 (14)	C7—C8—C9—C10	−0.7 (3)
O1^i—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)
N1^i—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)
O1^i—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.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O4^ii	0.86 (2)	2.41 (2)	3.170 (2)	147 (2)
N1—H1A···O2^iii	0.84 (2)	2.57 (2)	3.337 (3)	153 (2)
N2—H2A···O2^iv	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···O2^v	0.78 (2)	2.67 (2)	3.451 (2)	176 (2)
N3—H3B···O3^vi	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···N3^vii	0.87 (2)	2.02 (2)	2.882 (3)	173 (3)
O5—H5A···O4^viii	0.77 (2)	2.15 (2)	2.918 (3)	172 (3)
O1—H1F···O4^ii	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.