Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807045849/pk2046sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807045849/pk2046Isup2.hkl |
CCDC reference: 663637
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.005 Å
- R factor = 0.053
- wR factor = 0.136
- Data-to-parameter ratio = 16.0
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.68 Ratio PLAT420_ALERT_2_C D-H Without Acceptor N4 - H4A ... ? PLAT731_ALERT_1_C Bond Calc 0.83(6), Rep 0.83(2) ...... 3.00 su-Ra O3 -H5 1.555 1.555
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn (2) 2.09 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 5
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 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 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
Preparation of H2DSNT.4H2O: A solution of diethylamine (3.66 g 0.05 mol) in 20 mL acetone was added dropwise to a solution of cynanuic chloride (4.61 g, 0.025 mol) in 100 mL acetone at 0°, under stirring over a period of 45 min. The resulting white deposit N(C2H5)2.HCl was filtered. To the filtrate was added dropwise a solution of 4-aminobenzenesulfonic sodium (9.81 g. 0.05 mol) in 200 mL water at 0°, under stirring over a period of 45 min, and then the mixture was heated to 45° and reacted with stirring for 12 h. After cooling to room temperature, acetone was evaporated in vacuo from the reaction solution. The white product H2DSNT.4H2O recrystallized in water and oven-dried at 60° in 70% yield.
Preparation of [Zn(2,2'-bipy)(H2O)4]DSNT: A solution of ZnCl2 (0.04 g, 0.3 mmol), 2,2'-bipy (0.07 g, 0.45 mmol), H2DSNT.4H2O (0.17 g, 0.3 mmol) and H2O (27.0 g, 1.5 mol) in the mole ratio of 1:1.5:1:5000 was heated in an autoclave at 160° for 2 days and then cooled to room temperature for 3 days. The colorless crystals were collected in 62% yield.
Anisotropic thermal parameters were applied to all non-hydrogen atoms. All H atoms were found in difference Fourier maps and all except water H atoms were subsequently placed in idealized positions with constrained distances of 0.96 Å (RCH3), 0.97 Å (R2CH2), 0.95 Å (R2CarH) and 0.86 Å (NH). Uiso(H) values were set to either 1.5Ueq (RCH3) or 1.2Ueq of the attached atom. Water molecule hydrogen atoms were refined using restraints on bond lengths and angles.
It is well known that chlorine atoms in cyanuric chloride are easily replaced by other organic groups (Thurston et al., 1951). Using cyanuric chloride as reactant and controlling stoichiometry and reaction temperature, we have synthesized a new triazine derivative, 2,4-bis(4-sulfophenylamino) -6-diethylamino-1,3,5-triazine (H2DSNT). Reaction of H2DSNT and 2,2-bipy with ZnCl2 in water yields a supramolecular compound [Zn(2,2'-bipy)(H2O)4]DSNT.
In the title compound, as shown in Fig. 1, the coordination geometry of ZnII is octahedral, with two nitrogen atoms from 2,2-bipy and four oxygen atoms from coordinated water. The Zn—N distance is 2.122 (2)Å and Zn—O distances are in the range of 2.059 (3)Å to 2.135 (3) Å. DSNT2- does not coordinate directly to ZnII but balances the charge of the ZnII cation. Previous studies revealed that the first row, divalent, transition metal ions have no tendency to coordinate to arenesulfonate (Kosnic et al., 1992; Shubnell et al., 1994; Gunderman et al., 1997). The crystal of the title compound is stablized not only by electrostatic interactions but also by abundant hydrogen-bonding interactions between the cation [Zn(2,2'-bipy)(H2O)4]2+ and the anion DSNT2- (Fig. 2). All of the four coordinated waters build up an intricate hydrogen-bonding network with sulfonic oxygen (O5 and O6) and triazine nitrogen (N2) in the anion DSNT2-.
For related literature, see: Gunderman et al. (1997); Kosnic et al. (1992); Shubnell et al. (1994); Thurston et al. (1951).
Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2000); cell refinement: CrystalClear (Molecular Structure Corporation & Rigaku, 2000); data reduction: CrystalClear (Molecular Structure Corporation & Rigaku, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: CrystalStructure (Molecular Structure Corporation & Rigaku, 2000); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
[Zn(C10H8N2)(H2O)4](C19H20N6O6S2) | F(000) = 1632 |
Mr = 786.19 | Dx = 1.518 Mg m−3 |
Orthorhombic, Pnma | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2n | Cell parameters from 7071 reflections |
a = 12.758 (3) Å | θ = 2.3–27.5° |
b = 21.015 (6) Å | µ = 0.90 mm−1 |
c = 12.828 (4) Å | T = 293 K |
V = 3439.3 (17) Å3 | Prism, colorless |
Z = 4 | 0.30 × 0.10 × 0.08 mm |
Rigaku Mercury CCD diffractometer | 4045 independent reflections |
Radiation source: Rotating Anode | 3553 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.045 |
ω scans | θmax = 27.5°, θmin = 2.3° |
Absorption correction: multi-scan (SPHERE in CrystalStructure; Molecular Structure Corporation & Rigaku, 2000)' | h = −15→16 |
Tmin = 0.886, Tmax = 0.930 | k = −27→27 |
25765 measured reflections | l = −14→16 |
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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.136 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0654P)2 + 2.7737P] where P = (Fo2 + 2Fc2)/3 |
4045 reflections | (Δ/σ)max < 0.001 |
253 parameters | Δρmax = 0.34 e Å−3 |
5 restraints | Δρmin = −0.28 e Å−3 |
[Zn(C10H8N2)(H2O)4](C19H20N6O6S2) | V = 3439.3 (17) Å3 |
Mr = 786.19 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 12.758 (3) Å | µ = 0.90 mm−1 |
b = 21.015 (6) Å | T = 293 K |
c = 12.828 (4) Å | 0.30 × 0.10 × 0.08 mm |
Rigaku Mercury CCD diffractometer | 4045 independent reflections |
Absorption correction: multi-scan (SPHERE in CrystalStructure; Molecular Structure Corporation & Rigaku, 2000)' | 3553 reflections with I > 2σ(I) |
Tmin = 0.886, Tmax = 0.930 | Rint = 0.045 |
25765 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 5 restraints |
wR(F2) = 0.136 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.34 e Å−3 |
4045 reflections | Δρmin = −0.28 e Å−3 |
253 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 > 2σ(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 | ||
Zn | 0.43110 (4) | 0.7500 | 0.85366 (3) | 0.03891 (16) | |
S1 | 0.19593 (6) | 0.59726 (3) | 0.70886 (6) | 0.0424 (2) | |
O1 | 0.4501 (2) | 0.67945 (15) | 0.7439 (2) | 0.0709 (8) | |
H1 | 0.400 (2) | 0.6628 (18) | 0.713 (3) | 0.072 (13)* | |
H2 | 0.507 (2) | 0.661 (2) | 0.735 (4) | 0.091 (16)* | |
O2 | 0.2694 (3) | 0.7500 | 0.8186 (3) | 0.0562 (8) | |
H3 | 0.234 (3) | 0.7166 (12) | 0.814 (3) | 0.065 (11)* | |
O3 | 0.5969 (3) | 0.7500 | 0.8764 (2) | 0.0452 (7) | |
H4 | 0.618 (4) | 0.7500 | 0.939 (2) | 0.061 (15)* | |
H5 | 0.649 (4) | 0.7500 | 0.838 (5) | 0.12 (3)* | |
O4 | 0.1134 (2) | 0.57237 (12) | 0.6439 (2) | 0.0667 (7) | |
O5 | 0.15724 (18) | 0.64062 (9) | 0.78904 (18) | 0.0525 (5) | |
O6 | 0.27985 (19) | 0.62531 (10) | 0.64805 (16) | 0.0514 (5) | |
N1 | 0.40742 (19) | 0.68676 (11) | 0.98049 (19) | 0.0421 (5) | |
N2 | 0.3459 (3) | 0.2500 | 0.9167 (3) | 0.0407 (8) | |
N3 | 0.3690 (2) | 0.30689 (11) | 0.75770 (19) | 0.0435 (6) | |
N4 | 0.3375 (2) | 0.35895 (11) | 0.91325 (19) | 0.0488 (6) | |
H4A | 0.3432 | 0.3574 | 0.9800 | 0.059* | |
N5 | 0.3937 (3) | 0.2500 | 0.6057 (3) | 0.0537 (9) | |
C1 | 0.4098 (3) | 0.62307 (15) | 0.9743 (3) | 0.0557 (8) | |
H1B | 0.4235 | 0.6040 | 0.9103 | 0.067* | |
C2 | 0.3923 (3) | 0.58491 (18) | 1.0608 (4) | 0.0706 (11) | |
H2C | 0.3931 | 0.5408 | 1.0548 | 0.085* | |
C3 | 0.3740 (3) | 0.6129 (2) | 1.1541 (4) | 0.0737 (12) | |
H3C | 0.3624 | 0.5880 | 1.2128 | 0.088* | |
C4 | 0.3726 (3) | 0.6784 (2) | 1.1621 (3) | 0.0625 (10) | |
H4C | 0.3607 | 0.6980 | 1.2261 | 0.075* | |
C5 | 0.3892 (2) | 0.71461 (15) | 1.0731 (2) | 0.0429 (6) | |
C6 | 0.3526 (2) | 0.30361 (13) | 0.8596 (2) | 0.0391 (6) | |
C7 | 0.5088 (4) | 0.3373 (3) | 0.5446 (4) | 0.1052 (18) | |
H7A | 0.5078 | 0.3766 | 0.5064 | 0.158* | |
H7B | 0.5549 | 0.3078 | 0.5106 | 0.158* | |
H7C | 0.5332 | 0.3451 | 0.6142 | 0.158* | |
C8 | 0.3780 (3) | 0.2500 | 0.7101 (3) | 0.0417 (9) | |
C9 | 0.4006 (3) | 0.31016 (19) | 0.5486 (3) | 0.0679 (10) | |
H9A | 0.3543 | 0.3409 | 0.5812 | 0.082* | |
H9B | 0.3760 | 0.3034 | 0.4778 | 0.082* | |
C10 | 0.2344 (3) | 0.45445 (14) | 0.9133 (2) | 0.0494 (7) | |
H10A | 0.2026 | 0.4406 | 0.9745 | 0.059* | |
C11 | 0.3135 (3) | 0.41848 (13) | 0.8685 (2) | 0.0431 (7) | |
C12 | 0.3653 (3) | 0.44191 (14) | 0.7808 (3) | 0.0510 (8) | |
H12A | 0.4218 | 0.4197 | 0.7530 | 0.061* | |
C13 | 0.3325 (2) | 0.49819 (14) | 0.7351 (3) | 0.0480 (7) | |
H13A | 0.3667 | 0.5134 | 0.6761 | 0.058* | |
C14 | 0.2496 (2) | 0.53166 (12) | 0.7764 (2) | 0.0393 (6) | |
C15 | 0.2028 (3) | 0.51068 (14) | 0.8677 (2) | 0.0486 (7) | |
H15A | 0.1498 | 0.5346 | 0.8983 | 0.058* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn | 0.0438 (3) | 0.0402 (3) | 0.0327 (2) | 0.000 | −0.00015 (19) | 0.000 |
S1 | 0.0499 (4) | 0.0316 (3) | 0.0458 (4) | 0.0035 (3) | −0.0082 (3) | −0.0008 (3) |
O1 | 0.0510 (15) | 0.095 (2) | 0.0670 (16) | 0.0160 (15) | −0.0110 (13) | −0.0421 (16) |
O2 | 0.0423 (17) | 0.0390 (17) | 0.087 (2) | 0.000 | −0.0084 (17) | 0.000 |
O3 | 0.0445 (17) | 0.0561 (18) | 0.0349 (15) | 0.000 | 0.0009 (13) | 0.000 |
O4 | 0.0663 (16) | 0.0561 (14) | 0.0778 (18) | 0.0017 (12) | −0.0350 (13) | −0.0046 (12) |
O5 | 0.0641 (14) | 0.0371 (10) | 0.0563 (13) | 0.0076 (10) | 0.0041 (11) | −0.0052 (9) |
O6 | 0.0677 (14) | 0.0416 (11) | 0.0449 (12) | −0.0003 (10) | 0.0038 (10) | 0.0052 (9) |
N1 | 0.0406 (13) | 0.0414 (12) | 0.0442 (13) | −0.0023 (10) | 0.0003 (10) | 0.0057 (10) |
N2 | 0.054 (2) | 0.0332 (16) | 0.0354 (16) | 0.000 | −0.0077 (15) | 0.000 |
N3 | 0.0511 (14) | 0.0411 (12) | 0.0382 (12) | −0.0007 (11) | −0.0051 (11) | 0.0041 (10) |
N4 | 0.0758 (19) | 0.0357 (12) | 0.0349 (12) | 0.0067 (12) | −0.0084 (12) | 0.0020 (10) |
N5 | 0.064 (2) | 0.063 (2) | 0.0337 (18) | 0.000 | 0.0008 (18) | 0.000 |
C1 | 0.0526 (18) | 0.0438 (16) | 0.071 (2) | −0.0014 (14) | −0.0004 (16) | 0.0086 (16) |
C2 | 0.056 (2) | 0.056 (2) | 0.100 (3) | −0.0105 (17) | −0.011 (2) | 0.033 (2) |
C3 | 0.053 (2) | 0.090 (3) | 0.079 (3) | −0.016 (2) | −0.0024 (19) | 0.047 (2) |
C4 | 0.0444 (17) | 0.096 (3) | 0.0467 (18) | −0.0018 (18) | 0.0038 (14) | 0.0224 (19) |
C5 | 0.0303 (13) | 0.0608 (17) | 0.0376 (14) | −0.0021 (12) | −0.0008 (11) | 0.0089 (13) |
C6 | 0.0425 (15) | 0.0381 (14) | 0.0368 (14) | 0.0009 (11) | −0.0094 (11) | 0.0027 (11) |
C7 | 0.098 (4) | 0.123 (4) | 0.095 (4) | −0.038 (3) | 0.007 (3) | 0.022 (3) |
C8 | 0.038 (2) | 0.049 (2) | 0.038 (2) | 0.000 | −0.0039 (16) | 0.000 |
C9 | 0.081 (3) | 0.084 (3) | 0.0393 (17) | −0.011 (2) | −0.0023 (17) | 0.0125 (17) |
C10 | 0.070 (2) | 0.0414 (15) | 0.0368 (14) | 0.0017 (15) | 0.0014 (14) | −0.0007 (12) |
C11 | 0.0555 (18) | 0.0329 (13) | 0.0408 (15) | 0.0004 (12) | −0.0107 (13) | 0.0022 (11) |
C12 | 0.0474 (17) | 0.0424 (15) | 0.063 (2) | 0.0073 (13) | 0.0045 (15) | 0.0081 (14) |
C13 | 0.0487 (16) | 0.0417 (15) | 0.0535 (17) | 0.0023 (13) | 0.0058 (14) | 0.0092 (13) |
C14 | 0.0439 (15) | 0.0323 (13) | 0.0416 (14) | −0.0005 (11) | −0.0081 (12) | −0.0022 (11) |
C15 | 0.0619 (19) | 0.0391 (15) | 0.0447 (16) | 0.0079 (14) | 0.0044 (14) | −0.0041 (12) |
Zn—O1 | 2.059 (3) | C1—C2 | 1.387 (5) |
Zn—O1i | 2.059 (3) | C1—H1B | 0.9300 |
Zn—O2 | 2.112 (3) | C2—C3 | 1.354 (6) |
Zn—N1i | 2.122 (2) | C2—H2C | 0.9300 |
Zn—N1 | 2.122 (2) | C3—C4 | 1.380 (6) |
Zn—O3 | 2.135 (3) | C3—H3C | 0.9300 |
S1—O4 | 1.441 (2) | C4—C5 | 1.388 (4) |
S1—O6 | 1.450 (2) | C4—H4C | 0.9300 |
S1—O5 | 1.460 (2) | C5—C5i | 1.487 (6) |
S1—C14 | 1.766 (3) | C7—C9 | 1.495 (6) |
O1—H1 | 0.829 (19) | C7—H7A | 0.9600 |
O1—H2 | 0.825 (19) | C7—H7B | 0.9600 |
O2—H3 | 0.840 (18) | C7—H7C | 0.9600 |
O3—H4 | 0.841 (19) | C8—N3ii | 1.347 (3) |
O3—H5 | 0.83 (2) | C9—H9A | 0.9700 |
N1—C1 | 1.341 (4) | C9—H9B | 0.9700 |
N1—C5 | 1.344 (4) | C10—C15 | 1.379 (4) |
N2—C6 | 1.346 (3) | C10—C11 | 1.386 (4) |
N2—C6ii | 1.346 (3) | C10—H10A | 0.9300 |
N3—C6 | 1.326 (4) | C11—C12 | 1.394 (4) |
N3—C8 | 1.347 (3) | C12—C13 | 1.385 (4) |
N4—C6 | 1.365 (4) | C12—H12A | 0.9300 |
N4—C11 | 1.410 (3) | C13—C14 | 1.376 (4) |
N4—H4A | 0.8600 | C13—H13A | 0.9300 |
N5—C8 | 1.355 (5) | C14—C15 | 1.387 (4) |
N5—C9 | 1.464 (4) | C15—H15A | 0.9300 |
N5—C9ii | 1.464 (4) | ||
O1—Zn—O1i | 92.1 (2) | C2—C3—C4 | 120.1 (3) |
O1—Zn—O2 | 88.25 (11) | C2—C3—H3C | 119.9 |
O1i—Zn—O2 | 88.25 (11) | C4—C3—H3C | 119.9 |
O1—Zn—N1i | 172.70 (12) | C3—C4—C5 | 118.9 (4) |
O1i—Zn—N1i | 95.18 (12) | C3—C4—H4C | 120.6 |
O2—Zn—N1i | 91.38 (11) | C5—C4—H4C | 120.6 |
O1—Zn—N1 | 95.18 (12) | N1—C5—C4 | 121.0 (3) |
O1i—Zn—N1 | 172.70 (12) | N1—C5—C5i | 115.81 (16) |
O2—Zn—N1 | 91.38 (11) | C4—C5—C5i | 123.2 (2) |
N1i—Zn—N1 | 77.54 (14) | N3—C6—N2 | 126.1 (3) |
O1—Zn—O3 | 88.68 (10) | N3—C6—N4 | 118.3 (2) |
O1i—Zn—O3 | 88.68 (10) | N2—C6—N4 | 115.5 (2) |
O2—Zn—O3 | 175.57 (14) | C9—C7—H7A | 109.5 |
N1i—Zn—O3 | 92.07 (9) | C9—C7—H7B | 109.5 |
N1—Zn—O3 | 92.07 (9) | H7A—C7—H7B | 109.5 |
O4—S1—O6 | 112.06 (16) | C9—C7—H7C | 109.5 |
O4—S1—O5 | 112.78 (16) | H7A—C7—H7C | 109.5 |
O6—S1—O5 | 112.01 (13) | H7B—C7—H7C | 109.5 |
O4—S1—C14 | 106.48 (14) | N3—C8—N3ii | 125.1 (4) |
O6—S1—C14 | 107.15 (14) | N3—C8—N5 | 117.42 (18) |
O5—S1—C14 | 105.83 (13) | N3ii—C8—N5 | 117.42 (18) |
Zn—O1—H1 | 122 (3) | N5—C9—C7 | 113.7 (4) |
Zn—O1—H2 | 122 (3) | N5—C9—H9A | 108.8 |
H1—O1—H2 | 115 (4) | C7—C9—H9A | 108.8 |
Zn—O2—H3 | 123 (3) | N5—C9—H9B | 108.8 |
Zn—O3—H4 | 116 (4) | C7—C9—H9B | 108.8 |
Zn—O3—H5 | 135 (6) | H9A—C9—H9B | 107.7 |
H4—O3—H5 | 108 (6) | C15—C10—C11 | 120.3 (3) |
C1—N1—C5 | 119.4 (3) | C15—C10—H10A | 119.9 |
C1—N1—Zn | 125.2 (2) | C11—C10—H10A | 119.9 |
C5—N1—Zn | 115.41 (19) | C10—C11—C12 | 119.1 (3) |
C6—N2—C6ii | 113.7 (3) | C10—C11—N4 | 118.2 (3) |
C6—N3—C8 | 114.4 (3) | C12—C11—N4 | 122.6 (3) |
C6—N4—C11 | 125.5 (2) | C13—C12—C11 | 120.0 (3) |
C6—N4—H4A | 117.2 | C13—C12—H12A | 120.0 |
C11—N4—H4A | 117.2 | C11—C12—H12A | 120.0 |
C8—N5—C9 | 120.3 (2) | C14—C13—C12 | 120.3 (3) |
C8—N5—C9ii | 120.3 (2) | C14—C13—H13A | 119.8 |
C9—N5—C9ii | 119.5 (4) | C12—C13—H13A | 119.8 |
N1—C1—C2 | 121.7 (4) | C13—C14—C15 | 119.6 (3) |
N1—C1—H1B | 119.1 | C13—C14—S1 | 120.5 (2) |
C2—C1—H1B | 119.1 | C15—C14—S1 | 119.7 (2) |
C3—C2—C1 | 118.9 (4) | C10—C15—C14 | 120.3 (3) |
C3—C2—H2C | 120.6 | C10—C15—H15A | 119.8 |
C1—C2—H2C | 120.6 | C14—C15—H15A | 119.8 |
O1—Zn—N1—C1 | 1.3 (3) | C6—N3—C8—N5 | 179.3 (3) |
O2—Zn—N1—C1 | 89.7 (3) | C9—N5—C8—N3 | 0.2 (6) |
N1i—Zn—N1—C1 | −179.2 (2) | C9ii—N5—C8—N3 | −177.9 (4) |
O3—Zn—N1—C1 | −87.5 (3) | C9—N5—C8—N3ii | 177.9 (4) |
O1—Zn—N1—C5 | −178.9 (2) | C9ii—N5—C8—N3ii | −0.2 (6) |
O2—Zn—N1—C5 | −90.6 (2) | C8—N5—C9—C7 | 87.6 (5) |
N1i—Zn—N1—C5 | 0.5 (2) | C9ii—N5—C9—C7 | −94.3 (5) |
O3—Zn—N1—C5 | 92.2 (2) | C15—C10—C11—C12 | 4.2 (5) |
C5—N1—C1—C2 | 1.0 (5) | C15—C10—C11—N4 | −175.1 (3) |
Zn—N1—C1—C2 | −179.2 (3) | C6—N4—C11—C10 | 134.4 (3) |
N1—C1—C2—C3 | −1.0 (6) | C6—N4—C11—C12 | −44.9 (5) |
C1—C2—C3—C4 | 0.2 (6) | C10—C11—C12—C13 | −4.7 (5) |
C2—C3—C4—C5 | 0.6 (6) | N4—C11—C12—C13 | 174.6 (3) |
C1—N1—C5—C4 | −0.2 (4) | C11—C12—C13—C14 | 0.7 (5) |
Zn—N1—C5—C4 | −179.9 (2) | C12—C13—C14—C15 | 3.7 (5) |
C1—N1—C5—C5i | 179.3 (2) | C12—C13—C14—S1 | −171.3 (2) |
Zn—N1—C5—C5i | −0.5 (2) | O4—S1—C14—C13 | 90.6 (3) |
C3—C4—C5—N1 | −0.6 (5) | O6—S1—C14—C13 | −29.5 (3) |
C3—C4—C5—C5i | 180.0 (2) | O5—S1—C14—C13 | −149.2 (2) |
C8—N3—C6—N2 | 0.9 (5) | O4—S1—C14—C15 | −84.4 (3) |
C8—N3—C6—N4 | −177.0 (3) | O6—S1—C14—C15 | 155.6 (2) |
C6ii—N2—C6—N3 | −3.1 (6) | O5—S1—C14—C15 | 35.9 (3) |
C6ii—N2—C6—N4 | 174.8 (2) | C11—C10—C15—C14 | 0.2 (5) |
C11—N4—C6—N3 | 15.7 (5) | C13—C14—C15—C10 | −4.2 (5) |
C11—N4—C6—N2 | −162.4 (3) | S1—C14—C15—C10 | 170.9 (2) |
C6—N3—C8—N3ii | 1.8 (6) |
Symmetry codes: (i) x, −y+3/2, z; (ii) x, −y+1/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O6 | 0.83 (2) | 1.92 (2) | 2.743 (4) | 177 (4) |
O1—H2···O5iii | 0.83 (2) | 1.99 (2) | 2.798 (4) | 165 (5) |
O2—H3···O5 | 0.84 (2) | 1.90 (2) | 2.734 (3) | 174 (4) |
O3—H4···N2iv | 0.84 (2) | 1.91 (2) | 2.753 (4) | 176 (5) |
Symmetry codes: (iii) x+1/2, y, −z+3/2; (iv) −x+1, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C10H8N2)(H2O)4](C19H20N6O6S2) |
Mr | 786.19 |
Crystal system, space group | Orthorhombic, Pnma |
Temperature (K) | 293 |
a, b, c (Å) | 12.758 (3), 21.015 (6), 12.828 (4) |
V (Å3) | 3439.3 (17) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.90 |
Crystal size (mm) | 0.30 × 0.10 × 0.08 |
Data collection | |
Diffractometer | Rigaku Mercury CCD |
Absorption correction | Multi-scan (SPHERE in CrystalStructure; Molecular Structure Corporation & Rigaku, 2000)' |
Tmin, Tmax | 0.886, 0.930 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 25765, 4045, 3553 |
Rint | 0.045 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.136, 1.07 |
No. of reflections | 4045 |
No. of parameters | 253 |
No. of restraints | 5 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.34, −0.28 |
Computer programs: CrystalClear (Molecular Structure Corporation & Rigaku, 2000), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), CrystalStructure (Molecular Structure Corporation & Rigaku, 2000).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O6 | 0.829 (19) | 1.915 (19) | 2.743 (4) | 177 (4) |
O1—H2···O5i | 0.825 (19) | 1.99 (2) | 2.798 (4) | 165 (5) |
O2—H3···O5 | 0.840 (18) | 1.898 (18) | 2.734 (3) | 174 (4) |
O3—H4···N2ii | 0.841 (19) | 1.91 (2) | 2.753 (4) | 176 (5) |
Symmetry codes: (i) x+1/2, y, −z+3/2; (ii) −x+1, −y+1, −z+2. |
It is well known that chlorine atoms in cyanuric chloride are easily replaced by other organic groups (Thurston et al., 1951). Using cyanuric chloride as reactant and controlling stoichiometry and reaction temperature, we have synthesized a new triazine derivative, 2,4-bis(4-sulfophenylamino) -6-diethylamino-1,3,5-triazine (H2DSNT). Reaction of H2DSNT and 2,2-bipy with ZnCl2 in water yields a supramolecular compound [Zn(2,2'-bipy)(H2O)4]DSNT.
In the title compound, as shown in Fig. 1, the coordination geometry of ZnII is octahedral, with two nitrogen atoms from 2,2-bipy and four oxygen atoms from coordinated water. The Zn—N distance is 2.122 (2)Å and Zn—O distances are in the range of 2.059 (3)Å to 2.135 (3) Å. DSNT2- does not coordinate directly to ZnII but balances the charge of the ZnII cation. Previous studies revealed that the first row, divalent, transition metal ions have no tendency to coordinate to arenesulfonate (Kosnic et al., 1992; Shubnell et al., 1994; Gunderman et al., 1997). The crystal of the title compound is stablized not only by electrostatic interactions but also by abundant hydrogen-bonding interactions between the cation [Zn(2,2'-bipy)(H2O)4]2+ and the anion DSNT2- (Fig. 2). All of the four coordinated waters build up an intricate hydrogen-bonding network with sulfonic oxygen (O5 and O6) and triazine nitrogen (N2) in the anion DSNT2-.