In the title compound, diaquabis(1,10-phenanthroline-κ2N,N′)zinc(II) fumarate tetrahydrate, [Zn(phen)2(H2O)2]L·4H2O, where phen is 1,10-phenanthroline (C12H8N2) and L2− = fumarate (C4H2O4), the zinc(II) cation is six-coordinated by two water molecules and four N atoms from two phen molecules. Each of the two independent L2− anions is located about an inversion centre and does not coordinate to zinc(II) cations, acting rather as a counter-ion. The water molecules and L2− anions are linked through a complicated hydrogen-bonding network to form a three-dimensional structure.
Supporting information
CCDC reference: 214776
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.003 Å
- R factor = 0.026
- wR factor = 0.082
- Data-to-parameter ratio = 14.9
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level A:
DIFF_020 Alert A _diffrn_standards_interval_count and
_diffrn_standards_interval_time are missing. Number of measurements
between standards or time (min) between standards.
1 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
0 Alert Level C = Please check
A mixture of fumaric acid (0.116 g, 1 mmol) and ZnO (0.081 g, 1 mmol) in water (10 ml) was stirred at room temperature. Then 1,10-phenanthroline (0.198 g, 1 mmol) was added to the solution. Colourless crystals of (I) were obtained after several days; yield: 68% (based on Zn). Analysis calculated for C28H30N4O10Zn: C 51.86, H 4.63, N 8.64%; found: C 51.79, H 4.44, N 8.77%.
All H atoms on C atoms were generated geometrically and refined in the riding-model approximation, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C). The H atoms of water molecules were located from difference Fourier map and were refined with restrained O—H distances of 0.xx+/-0.01 Å.
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1990).
Crystal data top
[Zn(C12H8N2)2(H2O)2](C4H2O4)·4H2O | Z = 2 |
Mr = 647.93 | F(000) = 672 |
Triclinic, P1 | Dx = 1.500 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.481 (2) Å | Cell parameters from 7123 reflections |
b = 10.597 (2) Å | θ = 1.5–27.5° |
c = 13.568 (3) Å | µ = 0.92 mm−1 |
α = 97.12 (3)° | T = 293 K |
β = 93.55 (3)° | Block, colorless |
γ = 105.38 (3)° | 0.50 × 0.32 × 0.10 mm |
V = 1434.7 (6) Å3 | |
Data collection top
Rigaku R-AXIS-RAPID diffractometer | 6500 independent reflections |
Radiation source: rotating anode | 5423 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
ω scans | θmax = 27.5°, θmin = 1.5° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = 0→13 |
Tmin = 0.767, Tmax = 0.912 | k = −13→13 |
13836 measured reflections | l = −17→17 |
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)] = 0.026 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.082 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.052P)2] where P = (Fo2 + 2Fc2)/3 |
6500 reflections | (Δ/σ)max = 0.001 |
436 parameters | Δρmax = 0.51 e Å−3 |
10 restraints | Δρmin = −0.36 e Å−3 |
Crystal data top
[Zn(C12H8N2)2(H2O)2](C4H2O4)·4H2O | γ = 105.38 (3)° |
Mr = 647.93 | V = 1434.7 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.481 (2) Å | Mo Kα radiation |
b = 10.597 (2) Å | µ = 0.92 mm−1 |
c = 13.568 (3) Å | T = 293 K |
α = 97.12 (3)° | 0.50 × 0.32 × 0.10 mm |
β = 93.55 (3)° | |
Data collection top
Rigaku R-AXIS-RAPID diffractometer | 6500 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 5423 reflections with I > 2σ(I) |
Tmin = 0.767, Tmax = 0.912 | Rint = 0.021 |
13836 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.026 | 10 restraints |
wR(F2) = 0.082 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.51 e Å−3 |
6500 reflections | Δρmin = −0.36 e Å−3 |
436 parameters | |
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 | |
Zn | 0.740215 (19) | 0.419239 (18) | 0.744324 (13) | 0.01881 (7) | |
C1 | 0.97086 (17) | 0.12752 (16) | 0.60677 (12) | 0.0216 (3) | |
C2 | 1.00193 (17) | 0.01054 (16) | 0.54916 (12) | 0.0228 (3) | |
H2 | 1.0253 | −0.0507 | 0.5849 | 0.027* | |
C3 | 0.54292 (18) | 0.02698 (16) | 0.86601 (13) | 0.0235 (3) | |
C4 | 0.47368 (18) | −0.01899 (16) | 0.95322 (13) | 0.0243 (4) | |
H4 | 0.3889 | −0.0775 | 0.9411 | 0.029* | |
C101 | 0.99317 (18) | 0.62464 (17) | 0.85969 (13) | 0.0261 (4) | |
H101 | 1.0266 | 0.6251 | 0.7978 | 0.031* | |
C102 | 1.07059 (19) | 0.70882 (18) | 0.94182 (15) | 0.0306 (4) | |
H102 | 1.1526 | 0.7655 | 0.9340 | 0.037* | |
C103 | 1.0245 (2) | 0.70689 (18) | 1.03350 (14) | 0.0315 (4) | |
H103 | 1.0749 | 0.7625 | 1.0888 | 0.038* | |
C104 | 0.90064 (19) | 0.62054 (18) | 1.04408 (13) | 0.0263 (4) | |
C105 | 0.82702 (17) | 0.54245 (16) | 0.95724 (12) | 0.0209 (3) | |
C106 | 0.8483 (2) | 0.6072 (2) | 1.13893 (14) | 0.0342 (4) | |
H106 | 0.8963 | 0.6593 | 1.1965 | 0.041* | |
C107 | 0.7306 (2) | 0.5199 (2) | 1.14527 (13) | 0.0350 (5) | |
H107 | 0.7007 | 0.5095 | 1.2077 | 0.042* | |
C108 | 0.65013 (19) | 0.44266 (18) | 1.05770 (13) | 0.0272 (4) | |
C109 | 0.69740 (17) | 0.45544 (16) | 0.96346 (12) | 0.0212 (3) | |
C110 | 0.5225 (2) | 0.35677 (19) | 1.05962 (15) | 0.0321 (4) | |
H110 | 0.4879 | 0.3436 | 1.1202 | 0.039* | |
C111 | 0.44977 (19) | 0.29309 (18) | 0.97235 (15) | 0.0311 (4) | |
H111 | 0.3649 | 0.2371 | 0.9727 | 0.037* | |
C112 | 0.50449 (18) | 0.31296 (17) | 0.88209 (14) | 0.0259 (4) | |
H112 | 0.4539 | 0.2691 | 0.8230 | 0.031* | |
C201 | 0.7425 (2) | 0.72052 (18) | 0.73107 (14) | 0.0320 (4) | |
H201 | 0.8287 | 0.7440 | 0.7623 | 0.038* | |
C202 | 0.6849 (2) | 0.8212 (2) | 0.71208 (15) | 0.0402 (5) | |
H202 | 0.7327 | 0.9096 | 0.7294 | 0.048* | |
C203 | 0.5581 (2) | 0.7881 (2) | 0.66795 (14) | 0.0397 (5) | |
H203 | 0.5179 | 0.8540 | 0.6564 | 0.048* | |
C204 | 0.4882 (2) | 0.6552 (2) | 0.63988 (13) | 0.0321 (4) | |
C205 | 0.55409 (18) | 0.55977 (18) | 0.65993 (12) | 0.0236 (4) | |
C206 | 0.3553 (2) | 0.6121 (3) | 0.59199 (15) | 0.0416 (5) | |
H206 | 0.3109 | 0.6746 | 0.5797 | 0.050* | |
C207 | 0.2934 (2) | 0.4828 (3) | 0.56446 (15) | 0.0425 (5) | |
H207 | 0.2068 | 0.4575 | 0.5339 | 0.051* | |
C208 | 0.35877 (19) | 0.3835 (2) | 0.58153 (13) | 0.0329 (4) | |
C209 | 0.48906 (17) | 0.42196 (18) | 0.62991 (12) | 0.0247 (4) | |
C210 | 0.2998 (2) | 0.2477 (2) | 0.55319 (15) | 0.0426 (5) | |
H210 | 0.2141 | 0.2178 | 0.5209 | 0.051* | |
C211 | 0.3685 (2) | 0.1596 (2) | 0.57315 (16) | 0.0449 (6) | |
H211 | 0.3299 | 0.0693 | 0.5548 | 0.054* | |
C212 | 0.4980 (2) | 0.20611 (19) | 0.62162 (14) | 0.0343 (4) | |
H212 | 0.5440 | 0.1451 | 0.6347 | 0.041* | |
N1 | 0.87398 (14) | 0.54400 (14) | 0.86610 (10) | 0.0206 (3) | |
N2 | 0.62515 (14) | 0.39140 (13) | 0.87679 (10) | 0.0210 (3) | |
N3 | 0.67945 (15) | 0.59284 (14) | 0.70646 (10) | 0.0231 (3) | |
N4 | 0.55703 (15) | 0.33404 (14) | 0.64942 (10) | 0.0244 (3) | |
O1 | 0.95813 (14) | 0.12353 (13) | 0.69809 (9) | 0.0286 (3) | |
O2 | 0.95872 (15) | 0.22148 (13) | 0.56302 (10) | 0.0343 (3) | |
O3 | 0.66783 (13) | 0.07833 (13) | 0.87957 (9) | 0.0285 (3) | |
O4 | 0.47281 (13) | 0.01526 (13) | 0.78560 (9) | 0.0294 (3) | |
OW1 | 0.88141 (14) | 0.43684 (12) | 0.64255 (10) | 0.0288 (3) | |
OW2 | 0.76621 (13) | 0.23559 (12) | 0.75192 (10) | 0.0260 (3) | |
OW3 | 0.03549 (17) | 0.67433 (14) | 0.61186 (11) | 0.0406 (4) | |
OW4 | 0.21277 (19) | 0.85772 (18) | 0.75020 (14) | 0.0494 (4) | |
OW5 | 0.82287 (15) | 0.92593 (16) | 0.95644 (13) | 0.0407 (3) | |
OW6 | 0.04139 (16) | 0.98998 (17) | 0.84401 (11) | 0.0418 (4) | |
H32 | 0.039 (3) | 0.710 (2) | 0.5553 (14) | 0.050 (7)* | |
H21 | 0.729 (2) | 0.183 (2) | 0.7917 (16) | 0.050 (7)* | |
H22 | 0.8345 (19) | 0.204 (2) | 0.7301 (16) | 0.039 (6)* | |
H12 | 0.908 (3) | 0.368 (2) | 0.6194 (19) | 0.056 (8)* | |
H31 | 0.101 (2) | 0.727 (2) | 0.6501 (18) | 0.060 (8)* | |
H52 | 0.783 (3) | 0.979 (2) | 0.937 (2) | 0.058 (8)* | |
H61 | 0.026 (3) | 1.035 (3) | 0.796 (2) | 0.092 (11)* | |
H11 | 0.937 (2) | 0.5146 (19) | 0.6293 (19) | 0.057 (8)* | |
H51 | 0.853 (3) | 0.939 (3) | 1.0196 (15) | 0.085 (11)* | |
H62 | −0.033 (3) | 0.972 (4) | 0.875 (2) | 0.107 (13)* | |
H42 | 0.164 (3) | 0.897 (3) | 0.775 (2) | 0.052 (8)* | |
H41 | 0.290 (3) | 0.911 (3) | 0.757 (2) | 0.059 (8)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn | 0.01987 (11) | 0.01897 (10) | 0.01792 (10) | 0.00625 (7) | 0.00175 (7) | 0.00208 (7) |
C1 | 0.0224 (8) | 0.0201 (8) | 0.0226 (8) | 0.0067 (6) | 0.0056 (6) | 0.0013 (7) |
C2 | 0.0266 (9) | 0.0187 (8) | 0.0252 (8) | 0.0084 (7) | 0.0076 (7) | 0.0038 (7) |
C3 | 0.0288 (9) | 0.0187 (8) | 0.0266 (9) | 0.0102 (7) | 0.0079 (7) | 0.0058 (7) |
C4 | 0.0226 (9) | 0.0215 (8) | 0.0298 (9) | 0.0043 (7) | 0.0079 (7) | 0.0087 (7) |
C101 | 0.0240 (9) | 0.0277 (9) | 0.0271 (9) | 0.0057 (7) | 0.0009 (7) | 0.0100 (7) |
C102 | 0.0256 (9) | 0.0240 (9) | 0.0393 (10) | 0.0016 (7) | −0.0049 (8) | 0.0095 (8) |
C103 | 0.0354 (10) | 0.0239 (9) | 0.0318 (10) | 0.0085 (8) | −0.0125 (8) | −0.0020 (8) |
C104 | 0.0334 (10) | 0.0250 (8) | 0.0224 (8) | 0.0137 (7) | −0.0029 (7) | 0.0012 (7) |
C105 | 0.0267 (9) | 0.0196 (8) | 0.0188 (8) | 0.0109 (7) | 0.0013 (6) | 0.0031 (6) |
C106 | 0.0453 (12) | 0.0403 (11) | 0.0190 (8) | 0.0202 (9) | −0.0027 (8) | −0.0032 (8) |
C107 | 0.0500 (13) | 0.0452 (11) | 0.0181 (8) | 0.0258 (10) | 0.0082 (8) | 0.0056 (8) |
C108 | 0.0358 (10) | 0.0290 (9) | 0.0249 (9) | 0.0188 (8) | 0.0109 (7) | 0.0086 (7) |
C109 | 0.0274 (9) | 0.0200 (8) | 0.0206 (8) | 0.0131 (7) | 0.0057 (7) | 0.0034 (7) |
C110 | 0.0401 (11) | 0.0338 (10) | 0.0332 (10) | 0.0207 (8) | 0.0202 (8) | 0.0146 (8) |
C111 | 0.0294 (10) | 0.0230 (8) | 0.0465 (11) | 0.0103 (7) | 0.0184 (9) | 0.0117 (8) |
C112 | 0.0261 (9) | 0.0197 (8) | 0.0333 (9) | 0.0085 (7) | 0.0080 (7) | 0.0023 (7) |
C201 | 0.0413 (11) | 0.0253 (9) | 0.0298 (10) | 0.0121 (8) | 0.0000 (8) | 0.0007 (8) |
C202 | 0.0653 (15) | 0.0260 (10) | 0.0326 (10) | 0.0204 (10) | 0.0022 (10) | 0.0011 (8) |
C203 | 0.0638 (15) | 0.0397 (11) | 0.0287 (10) | 0.0358 (11) | 0.0076 (10) | 0.0058 (9) |
C204 | 0.0382 (11) | 0.0481 (12) | 0.0212 (8) | 0.0277 (9) | 0.0094 (8) | 0.0100 (8) |
C205 | 0.0255 (9) | 0.0336 (9) | 0.0164 (7) | 0.0146 (7) | 0.0051 (6) | 0.0055 (7) |
C206 | 0.0376 (12) | 0.0702 (16) | 0.0317 (10) | 0.0351 (12) | 0.0073 (9) | 0.0162 (11) |
C207 | 0.0240 (10) | 0.0801 (17) | 0.0311 (10) | 0.0229 (11) | 0.0033 (8) | 0.0176 (11) |
C208 | 0.0212 (9) | 0.0543 (12) | 0.0220 (9) | 0.0058 (8) | 0.0034 (7) | 0.0105 (9) |
C209 | 0.0216 (9) | 0.0369 (10) | 0.0167 (8) | 0.0081 (7) | 0.0041 (6) | 0.0065 (7) |
C210 | 0.0264 (10) | 0.0592 (14) | 0.0318 (10) | −0.0060 (9) | −0.0028 (8) | 0.0092 (10) |
C211 | 0.0433 (13) | 0.0390 (12) | 0.0366 (11) | −0.0139 (10) | −0.0029 (9) | 0.0042 (9) |
C212 | 0.0400 (11) | 0.0293 (9) | 0.0272 (9) | −0.0010 (8) | −0.0017 (8) | 0.0048 (8) |
N1 | 0.0214 (7) | 0.0219 (7) | 0.0194 (7) | 0.0065 (5) | 0.0018 (5) | 0.0055 (6) |
N2 | 0.0229 (7) | 0.0177 (6) | 0.0239 (7) | 0.0080 (5) | 0.0057 (6) | 0.0022 (6) |
N3 | 0.0260 (8) | 0.0238 (7) | 0.0207 (7) | 0.0095 (6) | 0.0015 (6) | 0.0023 (6) |
N4 | 0.0256 (8) | 0.0248 (7) | 0.0208 (7) | 0.0031 (6) | 0.0009 (6) | 0.0044 (6) |
O1 | 0.0397 (8) | 0.0322 (7) | 0.0207 (6) | 0.0199 (6) | 0.0087 (5) | 0.0043 (5) |
O2 | 0.0601 (10) | 0.0252 (6) | 0.0266 (7) | 0.0229 (6) | 0.0159 (6) | 0.0077 (5) |
O3 | 0.0239 (7) | 0.0331 (7) | 0.0311 (7) | 0.0068 (5) | 0.0097 (5) | 0.0137 (6) |
O4 | 0.0325 (7) | 0.0322 (7) | 0.0250 (6) | 0.0093 (5) | 0.0049 (5) | 0.0079 (5) |
OW1 | 0.0356 (8) | 0.0213 (6) | 0.0330 (7) | 0.0096 (5) | 0.0177 (6) | 0.0067 (5) |
OW2 | 0.0297 (7) | 0.0243 (6) | 0.0312 (7) | 0.0130 (5) | 0.0154 (5) | 0.0127 (5) |
OW3 | 0.0518 (10) | 0.0319 (7) | 0.0301 (8) | −0.0051 (7) | 0.0019 (7) | 0.0118 (6) |
OW4 | 0.0343 (9) | 0.0499 (10) | 0.0547 (10) | 0.0048 (8) | 0.0018 (8) | −0.0117 (8) |
OW5 | 0.0314 (8) | 0.0430 (9) | 0.0489 (10) | 0.0105 (7) | −0.0006 (7) | 0.0134 (8) |
OW6 | 0.0401 (9) | 0.0594 (10) | 0.0360 (8) | 0.0241 (8) | 0.0091 (7) | 0.0199 (7) |
Geometric parameters (Å, º) top
Zn—OW1 | 2.0742 (14) | C112—N2 | 1.328 (2) |
Zn—OW2 | 2.0493 (13) | C112—H112 | 0.9300 |
Zn—N1 | 2.1522 (16) | C201—N3 | 1.329 (2) |
Zn—N2 | 2.2323 (15) | C201—C202 | 1.400 (3) |
Zn—N3 | 2.2065 (15) | C201—H201 | 0.9300 |
Zn—N4 | 2.1554 (17) | C202—C203 | 1.360 (3) |
C1—O2 | 1.251 (2) | C202—H202 | 0.9300 |
C1—O1 | 1.259 (2) | C203—C204 | 1.396 (3) |
C1—C2 | 1.503 (2) | C203—H203 | 0.9300 |
C2—C2i | 1.321 (3) | C204—C205 | 1.410 (2) |
C2—H2 | 0.9300 | C204—C206 | 1.431 (3) |
C3—O4 | 1.251 (2) | C205—N3 | 1.359 (2) |
C3—O3 | 1.269 (2) | C205—C209 | 1.433 (3) |
C3—C4 | 1.492 (2) | C206—C207 | 1.345 (3) |
C4—C4ii | 1.322 (4) | C206—H206 | 0.9300 |
C4—H4 | 0.9300 | C207—C208 | 1.434 (3) |
C101—N1 | 1.328 (2) | C207—H207 | 0.9300 |
C101—C102 | 1.398 (3) | C208—C210 | 1.400 (3) |
C101—H101 | 0.9300 | C208—C209 | 1.410 (3) |
C102—C103 | 1.362 (3) | C209—N4 | 1.355 (2) |
C102—H102 | 0.9300 | C210—C211 | 1.364 (4) |
C103—C104 | 1.404 (3) | C210—H210 | 0.9300 |
C103—H103 | 0.9300 | C211—C212 | 1.404 (3) |
C104—C105 | 1.406 (2) | C211—H211 | 0.9300 |
C104—C106 | 1.438 (3) | C212—N4 | 1.328 (2) |
C105—N1 | 1.359 (2) | C212—H212 | 0.9300 |
C105—C109 | 1.440 (2) | OW1—H12 | 0.874 (17) |
C106—C107 | 1.346 (3) | OW1—H11 | 0.919 (17) |
C106—H106 | 0.9300 | OW2—H21 | 0.861 (16) |
C107—C108 | 1.436 (3) | OW2—H22 | 0.919 (16) |
C107—H107 | 0.9300 | OW3—H32 | 0.897 (16) |
C108—C110 | 1.409 (3) | OW3—H31 | 0.852 (17) |
C108—C109 | 1.409 (2) | OW4—H42 | 0.80 (3) |
C109—N2 | 1.355 (2) | OW4—H41 | 0.85 (3) |
C110—C111 | 1.362 (3) | OW5—H52 | 0.838 (17) |
C110—H110 | 0.9300 | OW5—H51 | 0.877 (18) |
C111—C112 | 1.400 (3) | OW6—H61 | 0.890 (18) |
C111—H111 | 0.9300 | OW6—H62 | 0.894 (19) |
| | | |
OW1—Zn—OW2 | 85.59 (6) | N2—C112—H112 | 118.4 |
OW1—Zn—N1 | 95.04 (6) | C111—C112—H112 | 118.4 |
OW1—Zn—N2 | 166.71 (5) | N3—C201—C202 | 122.9 (2) |
OW1—Zn—N3 | 93.27 (6) | N3—C201—H201 | 118.5 |
OW1—Zn—N4 | 102.31 (6) | C202—C201—H201 | 118.5 |
OW2—Zn—N1 | 103.74 (6) | C203—C202—C201 | 119.1 (2) |
OW2—Zn—N2 | 86.94 (6) | C203—C202—H202 | 120.5 |
OW2—Zn—N3 | 166.82 (5) | C201—C202—H202 | 120.5 |
OW2—Zn—N4 | 91.16 (6) | C202—C203—C204 | 120.12 (18) |
N1—Zn—N2 | 76.09 (6) | C202—C203—H203 | 119.9 |
N1—Zn—N3 | 89.43 (6) | C204—C203—H203 | 119.9 |
N1—Zn—N4 | 157.97 (6) | C203—C204—C205 | 117.32 (19) |
N2—Zn—N3 | 96.48 (6) | C203—C204—C206 | 123.59 (19) |
N2—Zn—N4 | 88.81 (6) | C205—C204—C206 | 119.1 (2) |
N3—Zn—N4 | 76.23 (6) | N3—C205—C204 | 122.55 (18) |
O2—C1—O1 | 123.89 (15) | N3—C205—C209 | 117.56 (16) |
O2—C1—C2 | 119.60 (15) | C204—C205—C209 | 119.89 (17) |
O1—C1—C2 | 116.52 (15) | C207—C206—C204 | 121.2 (2) |
C2i—C2—C1 | 124.0 (2) | C207—C206—H206 | 119.4 |
C2i—C2—H2 | 118.0 | C204—C206—H206 | 119.4 |
C1—C2—H2 | 118.0 | C206—C207—C208 | 121.06 (19) |
O4—C3—O3 | 124.88 (16) | C206—C207—H207 | 119.5 |
O4—C3—C4 | 117.41 (16) | C208—C207—H207 | 119.5 |
O3—C3—C4 | 117.69 (16) | C210—C208—C209 | 117.2 (2) |
C4ii—C4—C3 | 123.5 (2) | C210—C208—C207 | 123.5 (2) |
C4ii—C4—H4 | 118.2 | C209—C208—C207 | 119.4 (2) |
C3—C4—H4 | 118.2 | N4—C209—C208 | 122.89 (18) |
N1—C101—C102 | 122.94 (17) | N4—C209—C205 | 117.77 (16) |
N1—C101—H101 | 118.5 | C208—C209—C205 | 119.33 (17) |
C102—C101—H101 | 118.5 | C211—C210—C208 | 119.71 (19) |
C103—C102—C101 | 119.27 (18) | C211—C210—H210 | 120.1 |
C103—C102—H102 | 120.4 | C208—C210—H210 | 120.1 |
C101—C102—H102 | 120.4 | C210—C211—C212 | 119.6 (2) |
C102—C103—C104 | 119.64 (17) | C210—C211—H211 | 120.2 |
C102—C103—H103 | 120.2 | C212—C211—H211 | 120.2 |
C104—C103—H103 | 120.2 | N4—C212—C211 | 122.3 (2) |
C103—C104—C105 | 117.51 (17) | N4—C212—H212 | 118.8 |
C103—C104—C106 | 123.08 (17) | C211—C212—H212 | 118.8 |
C105—C104—C106 | 119.40 (18) | C101—N1—C105 | 118.04 (15) |
N1—C105—C104 | 122.53 (16) | C101—N1—Zn | 126.51 (12) |
N1—C105—C109 | 117.71 (15) | C105—N1—Zn | 115.38 (11) |
C104—C105—C109 | 119.75 (16) | C112—N2—C109 | 117.78 (15) |
C107—C106—C104 | 120.68 (18) | C112—N2—Zn | 129.07 (12) |
C107—C106—H106 | 119.7 | C109—N2—Zn | 112.79 (11) |
C104—C106—H106 | 119.7 | C201—N3—C205 | 117.98 (16) |
C106—C107—C108 | 121.38 (17) | C201—N3—Zn | 129.06 (13) |
C106—C107—H107 | 119.3 | C205—N3—Zn | 112.62 (12) |
C108—C107—H107 | 119.3 | C212—N4—C209 | 118.31 (17) |
C110—C108—C109 | 117.08 (18) | C212—N4—Zn | 126.62 (14) |
C110—C108—C107 | 123.62 (17) | C209—N4—Zn | 114.31 (12) |
C109—C108—C107 | 119.25 (18) | Zn—OW1—H12 | 120.3 (18) |
N2—C109—C108 | 123.06 (17) | Zn—OW1—H11 | 126.1 (16) |
N2—C109—C105 | 117.59 (15) | H12—OW1—H11 | 112 (2) |
C108—C109—C105 | 119.34 (16) | Zn—OW2—H21 | 124.7 (17) |
C111—C110—C108 | 119.72 (17) | Zn—OW2—H22 | 127.6 (15) |
C111—C110—H110 | 120.1 | H21—OW2—H22 | 105 (2) |
C108—C110—H110 | 120.1 | H32—OW3—H31 | 103 (2) |
C110—C111—C112 | 119.15 (18) | H42—OW4—H41 | 107 (3) |
C110—C111—H111 | 120.4 | H52—OW5—H51 | 117 (3) |
C112—C111—H111 | 120.4 | H61—OW6—H62 | 105 (3) |
N2—C112—C111 | 123.19 (18) | | |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+1, −y, −z+2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
OW1—H11···OW3iii | 0.92 (2) | 1.79 (2) | 2.702 (2) | 174 (2) |
OW3—H32···O2iv | 0.90 (2) | 1.84 (2) | 2.736 (2) | 178 (2) |
OW5—H51···OW6v | 0.88 (2) | 2.04 (2) | 2.898 (2) | 165 (2) |
OW4—H41···O4vi | 0.85 (3) | 1.93 (3) | 2.770 (2) | 172 (3) |
OW5—H52···O3vi | 0.84 (3) | 1.99 (3) | 2.817 (2) | 170 (2) |
OW6—H61···O1vii | 0.89 (3) | 1.92 (3) | 2.796 (2) | 169 (3) |
OW1—H12···O2 | 0.87 (3) | 1.87 (3) | 2.7399 (19) | 177 (3) |
OW2—H22···O1 | 0.92 (2) | 1.78 (2) | 2.6877 (18) | 172 (2) |
OW2—H21···O3 | 0.86 (2) | 1.76 (2) | 2.6202 (19) | 175 (2) |
OW3—H31···OW4 | 0.85 (2) | 1.90 (2) | 2.739 (3) | 166 (2) |
OW4—H42···OW6 | 0.80 (3) | 2.02 (3) | 2.826 (3) | 177 (3) |
OW6—H62···OW5viii | 0.90 (3) | 1.92 (3) | 2.810 (2) | 171 (3) |
Symmetry codes: (iii) x+1, y, z; (iv) −x+1, −y+1, −z+1; (v) −x+1, −y+2, −z+2; (vi) x, y+1, z; (vii) x−1, y+1, z; (viii) x−1, y, z. |
Experimental details
Crystal data |
Chemical formula | [Zn(C12H8N2)2(H2O)2](C4H2O4)·4H2O |
Mr | 647.93 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 10.481 (2), 10.597 (2), 13.568 (3) |
α, β, γ (°) | 97.12 (3), 93.55 (3), 105.38 (3) |
V (Å3) | 1434.7 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.92 |
Crystal size (mm) | 0.50 × 0.32 × 0.10 |
|
Data collection |
Diffractometer | Rigaku R-AXIS-RAPID diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.767, 0.912 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13836, 6500, 5423 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.082, 1.06 |
No. of reflections | 6500 |
No. of parameters | 436 |
No. of restraints | 10 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.51, −0.36 |
Selected geometric parameters (Å, º) topZn—OW1 | 2.0742 (14) | Zn—N2 | 2.2323 (15) |
Zn—OW2 | 2.0493 (13) | Zn—N3 | 2.2065 (15) |
Zn—N1 | 2.1522 (16) | Zn—N4 | 2.1554 (17) |
| | | |
OW1—Zn—OW2 | 85.59 (6) | OW2—Zn—N4 | 91.16 (6) |
OW1—Zn—N1 | 95.04 (6) | N1—Zn—N2 | 76.09 (6) |
OW1—Zn—N2 | 166.71 (5) | N1—Zn—N3 | 89.43 (6) |
OW1—Zn—N3 | 93.27 (6) | N1—Zn—N4 | 157.97 (6) |
OW1—Zn—N4 | 102.31 (6) | N2—Zn—N3 | 96.48 (6) |
OW2—Zn—N1 | 103.74 (6) | N2—Zn—N4 | 88.81 (6) |
OW2—Zn—N2 | 86.94 (6) | N3—Zn—N4 | 76.23 (6) |
OW2—Zn—N3 | 166.82 (5) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
OW1—H11···OW3i | 0.92 (2) | 1.79 (2) | 2.702 (2) | 174 (2) |
OW3—H32···O2ii | 0.90 (2) | 1.84 (2) | 2.736 (2) | 178 (2) |
OW5—H51···OW6iii | 0.88 (2) | 2.04 (2) | 2.898 (2) | 165 (2) |
OW4—H41···O4iv | 0.85 (3) | 1.93 (3) | 2.770 (2) | 172 (3) |
OW5—H52···O3iv | 0.84 (3) | 1.99 (3) | 2.817 (2) | 170 (2) |
OW6—H61···O1v | 0.89 (3) | 1.92 (3) | 2.796 (2) | 169 (3) |
OW1—H12···O2 | 0.87 (3) | 1.87 (3) | 2.7399 (19) | 177 (3) |
OW2—H22···O1 | 0.92 (2) | 1.78 (2) | 2.6877 (18) | 172 (2) |
OW2—H21···O3 | 0.86 (2) | 1.76 (2) | 2.6202 (19) | 175 (2) |
OW3—H31···OW4 | 0.85 (2) | 1.90 (2) | 2.739 (3) | 166 (2) |
OW4—H42···OW6 | 0.80 (3) | 2.02 (3) | 2.826 (3) | 177 (3) |
OW6—H62···OW5vi | 0.90 (3) | 1.92 (3) | 2.810 (2) | 171 (3) |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y+2, −z+2; (iv) x, y+1, z; (v) x−1, y+1, z; (vi) x−1, y, z. |
Interest in the synthesis and characterization of complexes with mixed ligands (Cariati et al., 1983) arises as these offer the advantage that their structural and chemical properties may be significantly varied depending on the choice of ligands used (Robl, 1992). On the basis of reported X-ray structures, the anion derived from fumaric acid has been found to be a versatile ligand and the coordination mode can be tailored by introducing different neutral ligands to the complex (Young et al., 1998). In this paper, we present the preparation and crystal structure of an aquazinc complex of 1,10-phenanthroline containing fumarate as a non-coordinating species, (I).
The structure determination of (I) shows the coordination environment of the zinc(II) cation to be defined by two water molecules and four N atoms, derived from two phen molecules (Fig. 1 and Table 1). Charge balance is provided for by two independent fumarate anions, each located about a centre of inversion. Finally, there are four non-coordinating water molecules in the asymmetric unit.
The presence of an uncoordinated carboxylate group for the L2− anion is somewhat unexpected because the carboxylate group is generally thought of as being a better coordinating group than water for zinc(II). In the related compound [Cu2(C4H2O4)(C14H33N3)2](ClO4)2 (Charpin et al., 1987), the carboxylate O atoms coordinate to copper(II) to form a dimer. The average Zn—N distance of 2.1866 (16) Å is near to that of [ZnL1.5(H2O)2](NO3)2·2H2O, where L is 1,1'-(1,4-butanediyl)bis(imidazole) (Ma et al., 2000).
In (I), the L2− anions and water molecules are linked through hydrogen bonds to form a complicated three-dimensional structure (Table 2). It is noted that there are 12 H atoms available for hydrogen bonding in the asymmetric unit and each of these participate in such interactions. The water molecules play a role as both acceptors and donors, while the carboxylate O atoms only as acceptors.