The title compound, [Zn(H
2O)
6][ZnCl
3(C
8H
10N
4O
2)]
2·2H
2O, consists of two disordered water molecules, one hexahydrated Zn
II cation and two [Zn
IICl
3(caffeine)]
− anions, which are arranged around an inversion center. The coordination around the hexahydrated Zn
II cation is octahedral. This cation is linked with [Zn
IICl
3(caffeine)]
− anions and water molecules
via O—H
O hydrogen bonds. Moreover, O—H
O and O—H
Cl hydrogen bonds are co-operative in building up two-dimensional bilayers in which hexahydrated Zn
II cations are sandwiched between two layers of [Zn
IICl
3(caffeine)]
− anions, which are anti-parallel to each other.
Supporting information
CCDC reference: 283905
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.003 Å
- Disorder in solvent or counterion
- R factor = 0.027
- wR factor = 0.070
- Data-to-parameter ratio = 13.9
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ?
PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 11.00 Perc.
PLAT417_ALERT_2_C Short Inter D-H..H-D H4WB .. H6B2 .. 2.10 Ang.
PLAT432_ALERT_2_C Short Inter X...Y Contact Cl1 .. C2 .. 3.24 Ang.
PLAT432_ALERT_2_C Short Inter X...Y Contact O2 .. C5 .. 3.01 Ang.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 10
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 5.40 Deg.
H6A1 -O6A -H6B1 1.555 1.555 1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 18.20 Deg.
H6A1 -O6B -H6B1 1.555 1.555 1.555
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
9 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
5 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
2 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Hexaaquazinc(II) bis[trichloro(3,7-dihydro-1,3,7-trimethyl-1
H-purine-2,6-
dione-
κN9)zincate(II)] dihydrate
top
Crystal data top
[Zn(H2O)6][ZnCl3(C8H10N4O2)]2·2H2O | F(000) = 952 |
Mr = 941.40 | Dx = 1.767 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 890 reflections |
a = 8.8699 (6) Å | θ = 2.3–34.6° |
b = 19.7245 (13) Å | µ = 2.53 mm−1 |
c = 10.8701 (7) Å | T = 298 K |
β = 111.508 (1)° | Prism, colorless |
V = 1769.3 (2) Å3 | 0.30 × 0.25 × 0.20 mm |
Z = 2 | |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 3178 independent reflections |
Radiation source: fine-focus sealed tube | 2841 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
φ and ω scans | θmax = 25.2°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −10→10 |
Tmin = 0.473, Tmax = 0.603 | k = −23→21 |
9304 measured reflections | l = −13→9 |
Refinement top
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)] = 0.027 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.070 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0401P)2 + 0.441P] where P = (Fo2 + 2Fc2)/3 |
3178 reflections | (Δ/σ)max = 0.002 |
229 parameters | Δρmax = 0.29 e Å−3 |
15 restraints | Δρmin = −0.30 e Å−3 |
Special details top
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 (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Zn1 | 0.21334 (3) | 0.621062 (13) | −0.21379 (2) | 0.03608 (10) | |
Zn2 | 0.5000 | 0.5000 | 0.5000 | 0.04515 (12) | |
Cl1 | 0.27639 (9) | 0.51022 (3) | −0.22474 (8) | 0.05735 (19) | |
Cl2 | 0.28042 (7) | 0.68632 (3) | −0.35491 (6) | 0.04439 (15) | |
Cl3 | −0.05272 (7) | 0.62579 (3) | −0.24910 (7) | 0.05225 (17) | |
O1 | 0.89977 (18) | 0.63678 (9) | 0.14739 (17) | 0.0454 (4) | |
O2 | 0.6264 (2) | 0.69184 (8) | 0.41716 (16) | 0.0468 (4) | |
H5WA | 0.3296 (13) | 0.5307 (15) | 0.253 (2) | 0.056* | |
H5WB | 0.489 (2) | 0.5177 (13) | 0.269 (2) | 0.056* | |
O3 | 0.5211 (3) | 0.59944 (9) | 0.5645 (2) | 0.0594 (5) | |
H3WA | 0.557 (4) | 0.6267 (12) | 0.522 (3) | 0.071* | |
H3WB | 0.444 (3) | 0.6180 (13) | 0.580 (3) | 0.071* | |
O4 | 0.7462 (2) | 0.50523 (11) | 0.5222 (2) | 0.0655 (6) | |
H4WA | 0.771 (4) | 0.5013 (14) | 0.455 (2) | 0.079* | |
H4WB | 0.803 (3) | 0.5343 (13) | 0.576 (2) | 0.079* | |
O5 | 0.4274 (2) | 0.53339 (10) | 0.30504 (19) | 0.0541 (5) | |
N1 | 0.7617 (2) | 0.66264 (10) | 0.28088 (17) | 0.0364 (4) | |
N2 | 0.6258 (2) | 0.64270 (9) | 0.05206 (17) | 0.0338 (4) | |
N3 | 0.3292 (2) | 0.65318 (9) | −0.02286 (17) | 0.0347 (4) | |
N4 | 0.3201 (2) | 0.68648 (9) | 0.16949 (18) | 0.0342 (4) | |
C1 | 0.9173 (3) | 0.66488 (15) | 0.3938 (2) | 0.0515 (6) | |
H1A | 0.9774 | 0.6242 | 0.3952 | 0.077* | |
H1B | 0.8973 | 0.6684 | 0.4746 | 0.077* | |
H1C | 0.9786 | 0.7035 | 0.3852 | 0.077* | |
C2 | 0.7699 (2) | 0.64688 (11) | 0.1594 (2) | 0.0349 (5) | |
C3 | 0.6336 (3) | 0.62276 (15) | −0.0749 (3) | 0.0564 (7) | |
H3A | 0.5956 | 0.5770 | −0.0949 | 0.085* | |
H3B | 0.7437 | 0.6256 | −0.0702 | 0.085* | |
H3C | 0.5668 | 0.6525 | −0.1429 | 0.085* | |
C4 | 0.4835 (2) | 0.65680 (10) | 0.0695 (2) | 0.0302 (4) | |
C5 | 0.2358 (3) | 0.67222 (11) | 0.0445 (2) | 0.0360 (5) | |
H5 | 0.1234 | 0.6750 | 0.0069 | 0.043* | |
C6 | 0.2538 (3) | 0.71007 (15) | 0.2673 (3) | 0.0508 (6) | |
H6A | 0.1410 | 0.7206 | 0.2237 | 0.076* | |
H6B | 0.3112 | 0.7499 | 0.3105 | 0.076* | |
H6C | 0.2659 | 0.6751 | 0.3317 | 0.076* | |
C7 | 0.4811 (2) | 0.67663 (10) | 0.1878 (2) | 0.0320 (5) | |
C8 | 0.6223 (3) | 0.67877 (11) | 0.3056 (2) | 0.0351 (5) | |
O6A | 0.1101 (3) | 0.52958 (15) | 0.1408 (3) | 0.0694 (8) | 0.78 |
H6A1 | 0.0451 | 0.5587 | 0.1503 | 0.104* | 0.78 |
H6A2 | 0.0792 | 0.4898 | 0.1488 | 0.104* | 0.78 |
O6B | 0.1166 (12) | 0.5262 (6) | 0.2165 (8) | 0.0694 (8) | 0.22 |
H6B1 | 0.0652 | 0.5462 | 0.1440 | 0.104* | 0.22 |
H6B2 | 0.0774 | 0.5358 | 0.2747 | 0.104* | 0.22 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn1 | 0.03230 (15) | 0.04159 (17) | 0.03358 (16) | 0.00086 (10) | 0.01116 (11) | −0.00244 (10) |
Zn2 | 0.0455 (2) | 0.0442 (2) | 0.0553 (3) | 0.00373 (17) | 0.0297 (2) | 0.00146 (18) |
Cl1 | 0.0686 (4) | 0.0388 (3) | 0.0800 (5) | 0.0038 (3) | 0.0455 (4) | −0.0004 (3) |
Cl2 | 0.0498 (3) | 0.0448 (3) | 0.0420 (3) | 0.0060 (3) | 0.0209 (3) | 0.0048 (2) |
Cl3 | 0.0314 (3) | 0.0708 (4) | 0.0522 (4) | 0.0016 (3) | 0.0125 (3) | −0.0046 (3) |
O1 | 0.0274 (8) | 0.0544 (10) | 0.0534 (11) | 0.0009 (7) | 0.0135 (7) | −0.0028 (8) |
O2 | 0.0487 (10) | 0.0583 (11) | 0.0323 (9) | −0.0114 (8) | 0.0136 (7) | −0.0071 (8) |
O3 | 0.0744 (14) | 0.0460 (10) | 0.0779 (14) | 0.0022 (9) | 0.0517 (11) | −0.0010 (10) |
O4 | 0.0487 (11) | 0.0881 (16) | 0.0705 (14) | −0.0051 (10) | 0.0348 (10) | −0.0148 (11) |
O5 | 0.0503 (11) | 0.0621 (12) | 0.0560 (12) | 0.0054 (9) | 0.0266 (9) | 0.0077 (9) |
N1 | 0.0282 (9) | 0.0423 (11) | 0.0346 (10) | −0.0050 (8) | 0.0067 (8) | 0.0006 (8) |
N2 | 0.0282 (9) | 0.0407 (10) | 0.0331 (10) | 0.0003 (8) | 0.0118 (7) | −0.0013 (8) |
N3 | 0.0293 (9) | 0.0428 (10) | 0.0314 (10) | 0.0030 (8) | 0.0106 (7) | −0.0001 (8) |
N4 | 0.0321 (9) | 0.0382 (10) | 0.0355 (10) | −0.0029 (7) | 0.0162 (8) | −0.0032 (8) |
C1 | 0.0339 (12) | 0.0736 (18) | 0.0390 (14) | −0.0040 (12) | 0.0040 (10) | 0.0000 (12) |
C2 | 0.0298 (11) | 0.0345 (12) | 0.0392 (13) | −0.0007 (9) | 0.0111 (9) | 0.0020 (9) |
C3 | 0.0377 (13) | 0.096 (2) | 0.0381 (14) | 0.0027 (13) | 0.0173 (11) | −0.0106 (13) |
C4 | 0.0285 (10) | 0.0307 (10) | 0.0313 (11) | 0.0006 (8) | 0.0108 (8) | 0.0024 (9) |
C5 | 0.0294 (11) | 0.0432 (12) | 0.0352 (12) | 0.0013 (9) | 0.0117 (9) | 0.0007 (10) |
C6 | 0.0433 (13) | 0.0685 (17) | 0.0493 (15) | −0.0091 (12) | 0.0273 (12) | −0.0194 (13) |
C7 | 0.0297 (11) | 0.0333 (11) | 0.0350 (11) | −0.0041 (8) | 0.0143 (9) | −0.0016 (9) |
C8 | 0.0369 (12) | 0.0341 (11) | 0.0330 (12) | −0.0089 (9) | 0.0113 (9) | −0.0005 (9) |
O6A | 0.0549 (14) | 0.0688 (15) | 0.083 (2) | 0.0092 (12) | 0.0240 (17) | 0.0018 (18) |
O6B | 0.0549 (14) | 0.0688 (15) | 0.083 (2) | 0.0092 (12) | 0.0240 (17) | 0.0018 (18) |
Geometric parameters (Å, º) top
Zn1—N3 | 2.0495 (18) | N3—C5 | 1.345 (3) |
Zn1—Cl2 | 2.2435 (6) | N3—C4 | 1.371 (3) |
Zn1—Cl3 | 2.2497 (7) | N4—C5 | 1.318 (3) |
Zn1—Cl1 | 2.2707 (7) | N4—C7 | 1.381 (3) |
Zn2—O3i | 2.0684 (19) | N4—C6 | 1.467 (3) |
Zn2—O3 | 2.0684 (19) | C1—H1A | 0.9600 |
Zn2—O5 | 2.0830 (19) | C1—H1B | 0.9600 |
Zn2—O5i | 2.0830 (19) | C1—H1C | 0.9600 |
Zn2—O4 | 2.1101 (19) | C3—H3A | 0.9600 |
Zn2—O4i | 2.1101 (19) | C3—H3B | 0.9600 |
O1—C2 | 1.222 (3) | C3—H3C | 0.9600 |
O2—C8 | 1.227 (3) | C4—C7 | 1.352 (3) |
O3—H3WA | 0.84 (3) | C5—H5 | 0.9300 |
O3—H3WB | 0.85 (3) | C6—H6A | 0.9600 |
O4—H4WA | 0.84 (3) | C6—H6B | 0.9600 |
O4—H4WB | 0.84 (3) | C6—H6C | 0.9600 |
O5—H5WA | 0.84 (3) | C7—C8 | 1.426 (3) |
O5—H5WB | 0.84 (3) | O6A—H6A1 | 0.8471 |
N1—C2 | 1.384 (3) | O6A—H6A2 | 0.8462 |
N1—C8 | 1.395 (3) | O6A—H6B1 | 0.5264 |
N1—C1 | 1.474 (3) | O6B—H6A1 | 0.9977 |
N2—C4 | 1.372 (3) | O6B—H6A2 | 0.9945 |
N2—C2 | 1.382 (3) | O6B—H6B1 | 0.8489 |
N2—C3 | 1.460 (3) | O6B—H6B2 | 0.8478 |
| | | |
N3—Zn1—Cl2 | 110.79 (5) | N1—C1—H1A | 109.5 |
N3—Zn1—Cl3 | 105.37 (5) | N1—C1—H1B | 109.5 |
Cl2—Zn1—Cl3 | 112.59 (3) | H1A—C1—H1B | 109.5 |
N3—Zn1—Cl1 | 108.00 (6) | N1—C1—H1C | 109.5 |
Cl2—Zn1—Cl1 | 112.61 (3) | H1A—C1—H1C | 109.5 |
Cl3—Zn1—Cl1 | 107.10 (3) | H1B—C1—H1C | 109.5 |
O3i—Zn2—O3 | 180.00 (3) | O1—C2—N2 | 121.1 (2) |
O3i—Zn2—O5 | 89.94 (8) | O1—C2—N1 | 121.3 (2) |
O3—Zn2—O5 | 90.06 (8) | N2—C2—N1 | 117.57 (18) |
O3i—Zn2—O5i | 90.06 (8) | N2—C3—H3A | 109.5 |
O3—Zn2—O5i | 89.94 (8) | N2—C3—H3B | 109.5 |
O5—Zn2—O5i | 180.0 | H3A—C3—H3B | 109.5 |
O3i—Zn2—O4 | 92.66 (8) | N2—C3—H3C | 109.5 |
O3—Zn2—O4 | 87.34 (8) | H3A—C3—H3C | 109.5 |
O5—Zn2—O4 | 91.25 (8) | H3B—C3—H3C | 109.5 |
O5i—Zn2—O4 | 88.75 (8) | C7—C4—N3 | 110.60 (18) |
O3i—Zn2—O4i | 87.34 (8) | C7—C4—N2 | 121.77 (18) |
O3—Zn2—O4i | 92.66 (8) | N3—C4—N2 | 127.63 (19) |
O5—Zn2—O4i | 88.75 (8) | N4—C5—N3 | 112.98 (19) |
O5i—Zn2—O4i | 91.25 (8) | N4—C5—H5 | 123.5 |
O4—Zn2—O4i | 180.0 | N3—C5—H5 | 123.5 |
Zn2—O3—H3WA | 115 (2) | N4—C6—H6A | 109.5 |
Zn2—O3—H3WB | 120 (2) | N4—C6—H6B | 109.5 |
H3WA—O3—H3WB | 109 (2) | H6A—C6—H6B | 109.5 |
Zn2—O4—H4WA | 119 (2) | N4—C6—H6C | 109.5 |
Zn2—O4—H4WB | 116 (2) | H6A—C6—H6C | 109.5 |
H4WA—O4—H4WB | 112 (2) | H6B—C6—H6C | 109.5 |
Zn2—O5—H5WA | 121.1 (19) | C4—C7—N4 | 106.24 (18) |
Zn2—O5—H5WB | 110.1 (18) | C4—C7—C8 | 123.21 (19) |
H5WA—O5—H5WB | 111 (2) | N4—C7—C8 | 130.27 (19) |
C2—N1—C8 | 126.57 (18) | O2—C8—N1 | 122.1 (2) |
C2—N1—C1 | 116.12 (19) | O2—C8—C7 | 126.2 (2) |
C8—N1—C1 | 117.27 (19) | N1—C8—C7 | 111.64 (19) |
C4—N2—C2 | 118.97 (18) | H6A1—O6A—H6A2 | 110.8 |
C4—N2—C3 | 123.36 (18) | H6A1—O6A—H6B1 | 5.4 |
C2—N2—C3 | 117.67 (18) | H6A2—O6A—H6B1 | 106.8 |
C5—N3—C4 | 103.63 (18) | H6A1—O6B—H6A2 | 88.8 |
C5—N3—Zn1 | 117.24 (14) | H6A1—O6B—H6B1 | 18.2 |
C4—N3—Zn1 | 138.84 (15) | H6A2—O6B—H6B1 | 74.3 |
C5—N4—C7 | 106.54 (17) | H6A1—O6B—H6B2 | 93.9 |
C5—N4—C6 | 126.0 (2) | H6A2—O6B—H6B2 | 126.6 |
C7—N4—C6 | 127.45 (19) | H6B1—O6B—H6B2 | 111.3 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5WA···O6A | 0.84 (3) | 1.88 (1) | 2.725 (4) | 177 (3) |
O5—H5WA···O6B | 0.84 (3) | 1.78 (2) | 2.569 (11) | 154 (2) |
O5—H5WB···Cl1ii | 0.84 (3) | 2.36 (1) | 3.176 (2) | 162 (2) |
O3—H3WA···O2 | 0.84 (3) | 1.96 (3) | 2.803 (2) | 176 (3) |
O3—H3WB···Cl2iii | 0.85 (3) | 2.28 (3) | 3.1037 (19) | 167 (3) |
O4—H4WA···Cl1ii | 0.84 (3) | 2.39 (2) | 3.180 (2) | 156 (3) |
O4—H4WB···Cl3iv | 0.84 (3) | 2.60 (1) | 3.430 (2) | 173 (3) |
O6A—H6A1···O1v | 0.85 | 2.00 | 2.838 (3) | 170 |
O6A—H6A2···Cl3vi | 0.85 | 2.57 | 3.388 (3) | 161 |
O6B—H6B1···O1v | 0.85 | 2.32 | 2.821 (9) | 118 |
C1—H1B···O2 | 0.96 | 2.30 | 2.736 (3) | 107 |
C3—H3B···O1 | 0.96 | 2.27 | 2.703 (3) | 106 |
Symmetry codes: (ii) −x+1, −y+1, −z; (iii) x, y, z+1; (iv) x+1, y, z+1; (v) x−1, y, z; (vi) −x, −y+1, −z. |