In the compound μ2-1,4-benzenedicarboxylate-κ2O,O′-bis{aquachloro[4-(1H-1,3,7,8-tetraazacyclopenta[l]phenanthren-2-yl)phenol-κ2N,N′]zinc(II)} dihydrate, [Zn2Cl2(1,4-BDC)(L)2(H2O)2]·2H2O, where 1,4-BDC is the 1,4-benzenedicarboxylate dianion, C8H4O42−, and L is 4-(1H-1,3,7,8-tetraazacyclopenta[l]phenanthren-2-yl)phenol, C19H12N4O, the ZnII atom is five-coordinated by two N atoms from one L ligand, one Cl− ion, an O atom from a 1,4-BDC anion and one water molecule in an approximate trigonal–bipyramidal geometry. The complete 1,4-BDC ligand is generated by inversion symmetry; it bridges two ZnII atoms to form a dinuclear complex. Neighbouring complexes interact through π–π contacts and various kinds of hydrogen bonds, leading to a two-dimensional supramolecular structure.
Supporting information
CCDC reference: 613695
Key indicators
- Single-crystal X-ray study
- T = 292 K
- Mean (C-C) = 0.006 Å
- R factor = 0.052
- wR factor = 0.113
- Data-to-parameter ratio = 14.9
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT420_ALERT_2_B D-H Without Acceptor O2W - HW22 ... ?
Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT480_ALERT_4_C Long H...A H-Bond Reported HW22 .. CL1 .. 2.85 Ang.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 4
0 ALERT level A = In general: serious problem
1 ALERT level B = Potentially serious problem
3 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
1 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
0 ALERT type 3 Indicator that the structure quality may be low
2 ALERT type 4 Improvement, methodology, query or suggestion
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); software used to prepare material for publication: SHELXL97.
µ
2-1,4-benzenedicarboxylate-
κ2O,
O'[bis[aquachloro-4-(1
H-1,3,7,8-
tetraazacyclopenta[
l]phenanthren-2-yl)phenol-
κ2N,
N']zinc(II)] dihydrate
top
Crystal data top
[Zn2Cl2(C8H4O4)(C19H12N4O)2(H2O)2]·2H2O | Z = 1 |
Mr = 1062.47 | F(000) = 542 |
Triclinic, P1 | Dx = 1.672 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.1608 (18) Å | Cell parameters from 7257 reflections |
b = 9.4769 (19) Å | θ = 3.3–27.5° |
c = 13.334 (3) Å | µ = 1.34 mm−1 |
α = 109.24 (3)° | T = 292 K |
β = 90.66 (3)° | Block, yellow |
γ = 104.02 (3)° | 0.29 × 0.25 × 0.21 mm |
V = 1055.1 (5) Å3 | |
Data collection top
Rigaku R-AXIS RAPID diffractometer | 4780 independent reflections |
Radiation source: rotating anode | 3065 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.059 |
Detector resolution: 10.0 pixels mm-1 | θmax = 27.5°, θmin = 3.3° |
ω scans | h = −11→11 |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −12→12 |
Tmin = 0.684, Tmax = 0.758 | l = −17→17 |
10429 measured reflections | |
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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.113 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0392P)2 + 0.7847P] where P = (Fo2 + 2Fc2)/3 |
4780 reflections | (Δ/σ)max = 0.001 |
321 parameters | Δρmax = 0.74 e Å−3 |
3 restraints | Δρmin = −0.43 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 | |
C1 | 0.9669 (4) | 0.7960 (5) | 0.3295 (3) | 0.0395 (10) | |
H1 | 1.0457 | 0.7649 | 0.3531 | 0.047* | |
C2 | 1.0013 (5) | 0.9286 (5) | 0.3025 (3) | 0.0415 (11) | |
H2 | 1.1014 | 0.9848 | 0.3082 | 0.050* | |
C3 | 0.8875 (4) | 0.9768 (5) | 0.2673 (3) | 0.0362 (10) | |
H3 | 0.9090 | 1.0664 | 0.2498 | 0.043* | |
C4 | 0.7374 (4) | 0.8882 (4) | 0.2580 (3) | 0.0255 (8) | |
C5 | 0.7119 (4) | 0.7549 (4) | 0.2870 (3) | 0.0268 (8) | |
C6 | 0.5606 (4) | 0.6583 (4) | 0.2806 (3) | 0.0244 (8) | |
C7 | 0.4110 (4) | 0.4480 (5) | 0.3136 (3) | 0.0319 (9) | |
H7 | 0.4022 | 0.3658 | 0.3385 | 0.038* | |
C8 | 0.2801 (5) | 0.4724 (5) | 0.2760 (3) | 0.0344 (9) | |
H8 | 0.1861 | 0.4073 | 0.2760 | 0.041* | |
C9 | 0.2908 (4) | 0.5925 (5) | 0.2393 (3) | 0.0313 (9) | |
H9 | 0.2044 | 0.6090 | 0.2128 | 0.038* | |
C10 | 0.4336 (4) | 0.6909 (4) | 0.2418 (3) | 0.0254 (8) | |
C11 | 0.4622 (4) | 0.8246 (4) | 0.2106 (3) | 0.0257 (8) | |
C12 | 0.6065 (4) | 0.9177 (4) | 0.2205 (3) | 0.0280 (8) | |
C13 | 0.4428 (4) | 1.0063 (4) | 0.1535 (3) | 0.0303 (9) | |
C14 | 0.3841 (4) | 1.1032 (4) | 0.1065 (3) | 0.0289 (8) | |
C15 | 0.2298 (5) | 1.0816 (5) | 0.0882 (3) | 0.0366 (9) | |
H15 | 0.1635 | 1.0053 | 0.1070 | 0.044* | |
C16 | 0.1720 (5) | 1.1704 (5) | 0.0427 (3) | 0.0405 (10) | |
H16 | 0.0680 | 1.1547 | 0.0319 | 0.049* | |
C17 | 0.2694 (5) | 1.2830 (5) | 0.0132 (3) | 0.0356 (9) | |
C18 | 0.4241 (5) | 1.3061 (5) | 0.0307 (3) | 0.0356 (9) | |
H18 | 0.4902 | 1.3820 | 0.0114 | 0.043* | |
C19 | 0.4805 (5) | 1.2169 (5) | 0.0768 (3) | 0.0335 (9) | |
H19 | 0.5846 | 1.2332 | 0.0881 | 0.040* | |
C20 | 0.6948 (4) | 0.2648 (4) | 0.4631 (3) | 0.0298 (9) | |
C21 | 0.5926 (4) | 0.1264 (4) | 0.4807 (3) | 0.0265 (8) | |
C22 | 0.4369 (4) | 0.0984 (4) | 0.4681 (3) | 0.0307 (9) | |
H22 | 0.3940 | 0.1645 | 0.4465 | 0.037* | |
C23 | 0.3454 (4) | −0.0261 (5) | 0.4872 (3) | 0.0318 (9) | |
H23 | 0.2409 | −0.0435 | 0.4787 | 0.038* | |
N1 | 0.8264 (3) | 0.7114 (4) | 0.3231 (2) | 0.0296 (7) | |
N2 | 0.5478 (3) | 0.5374 (3) | 0.3154 (2) | 0.0271 (7) | |
N3 | 0.3606 (3) | 0.8805 (4) | 0.1686 (2) | 0.0299 (7) | |
N4 | 0.5907 (4) | 1.0336 (4) | 0.1846 (2) | 0.0298 (7) | |
H4 | 0.6622 | 1.1100 | 0.1824 | 0.036* | |
O1 | 0.6346 (3) | 0.3325 (3) | 0.4135 (2) | 0.0405 (7) | |
O2 | 0.8287 (3) | 0.3067 (3) | 0.5005 (2) | 0.0449 (8) | |
O1W | 0.8694 (4) | 0.6100 (4) | 0.5082 (2) | 0.0419 (8) | |
O3 | 0.2213 (4) | 1.3747 (3) | −0.0318 (2) | 0.0481 (8) | |
H3A | 0.1285 | 1.3514 | −0.0388 | 0.072* | |
O2W | 0.0842 (4) | 0.6786 (4) | 0.0430 (3) | 0.0604 (9) | |
Zn1 | 0.75014 (5) | 0.50066 (5) | 0.35762 (4) | 0.03021 (14) | |
Cl1 | 0.86655 (11) | 0.35345 (12) | 0.22822 (8) | 0.0415 (3) | |
HW11 | 0.961 (7) | 0.641 (7) | 0.503 (4) | 0.07 (2)* | |
HW12 | 0.860 (6) | 0.527 (6) | 0.524 (4) | 0.059 (16)* | |
HW21 | 0.169 (4) | 0.733 (6) | 0.084 (3) | 0.089* | |
HW22 | 0.121 (5) | 0.626 (6) | −0.020 (2) | 0.089* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.024 (2) | 0.040 (3) | 0.060 (3) | 0.0024 (19) | −0.0022 (18) | 0.029 (2) |
C2 | 0.024 (2) | 0.041 (3) | 0.063 (3) | −0.0026 (19) | −0.0037 (18) | 0.031 (2) |
C3 | 0.032 (2) | 0.033 (2) | 0.049 (2) | 0.0008 (19) | 0.0004 (17) | 0.0253 (19) |
C4 | 0.027 (2) | 0.0231 (19) | 0.0273 (19) | 0.0043 (16) | 0.0021 (14) | 0.0114 (15) |
C5 | 0.027 (2) | 0.023 (2) | 0.0280 (19) | 0.0037 (16) | −0.0006 (14) | 0.0076 (15) |
C6 | 0.028 (2) | 0.0223 (19) | 0.0262 (18) | 0.0067 (16) | 0.0033 (14) | 0.0118 (14) |
C7 | 0.034 (2) | 0.030 (2) | 0.037 (2) | 0.0073 (18) | 0.0054 (16) | 0.0191 (17) |
C8 | 0.028 (2) | 0.032 (2) | 0.043 (2) | −0.0004 (18) | 0.0042 (16) | 0.0181 (18) |
C9 | 0.026 (2) | 0.033 (2) | 0.036 (2) | 0.0060 (18) | 0.0039 (15) | 0.0144 (17) |
C10 | 0.026 (2) | 0.026 (2) | 0.0255 (19) | 0.0069 (16) | 0.0051 (14) | 0.0108 (15) |
C11 | 0.0229 (19) | 0.025 (2) | 0.0295 (19) | 0.0066 (16) | 0.0042 (14) | 0.0101 (15) |
C12 | 0.031 (2) | 0.023 (2) | 0.031 (2) | 0.0065 (17) | −0.0009 (15) | 0.0117 (15) |
C13 | 0.036 (2) | 0.024 (2) | 0.033 (2) | 0.0095 (18) | 0.0002 (16) | 0.0124 (16) |
C14 | 0.033 (2) | 0.022 (2) | 0.032 (2) | 0.0070 (17) | −0.0029 (15) | 0.0110 (15) |
C15 | 0.031 (2) | 0.033 (2) | 0.051 (2) | 0.0077 (19) | −0.0003 (17) | 0.0229 (19) |
C16 | 0.040 (3) | 0.036 (2) | 0.050 (3) | 0.013 (2) | −0.0079 (19) | 0.019 (2) |
C17 | 0.050 (3) | 0.028 (2) | 0.034 (2) | 0.0144 (19) | −0.0033 (17) | 0.0139 (17) |
C18 | 0.041 (2) | 0.028 (2) | 0.042 (2) | 0.0085 (19) | 0.0038 (17) | 0.0179 (18) |
C19 | 0.033 (2) | 0.033 (2) | 0.040 (2) | 0.0123 (18) | 0.0014 (16) | 0.0166 (18) |
C20 | 0.029 (2) | 0.027 (2) | 0.034 (2) | −0.0001 (17) | 0.0022 (15) | 0.0164 (16) |
C21 | 0.030 (2) | 0.0227 (19) | 0.0246 (18) | −0.0005 (16) | 0.0042 (14) | 0.0110 (15) |
C22 | 0.029 (2) | 0.030 (2) | 0.041 (2) | 0.0070 (17) | 0.0016 (16) | 0.0216 (17) |
C23 | 0.028 (2) | 0.033 (2) | 0.034 (2) | 0.0002 (18) | −0.0016 (15) | 0.0164 (17) |
N1 | 0.0281 (18) | 0.0257 (18) | 0.0391 (18) | 0.0065 (14) | 0.0009 (13) | 0.0167 (14) |
N2 | 0.0249 (17) | 0.0241 (17) | 0.0354 (17) | 0.0025 (14) | 0.0041 (12) | 0.0170 (14) |
N3 | 0.0284 (18) | 0.0306 (18) | 0.0355 (17) | 0.0105 (15) | 0.0028 (13) | 0.0156 (14) |
N4 | 0.0285 (18) | 0.0256 (18) | 0.0395 (18) | 0.0047 (14) | −0.0013 (13) | 0.0182 (14) |
O1 | 0.0352 (17) | 0.0379 (17) | 0.0566 (18) | −0.0003 (13) | −0.0022 (13) | 0.0342 (15) |
O2 | 0.0293 (17) | 0.0437 (19) | 0.0643 (19) | −0.0067 (14) | −0.0057 (13) | 0.0338 (15) |
O1W | 0.036 (2) | 0.0391 (19) | 0.0515 (19) | −0.0017 (15) | 0.0010 (14) | 0.0250 (15) |
O3 | 0.054 (2) | 0.0438 (19) | 0.0597 (19) | 0.0187 (16) | −0.0018 (15) | 0.0306 (15) |
O2W | 0.047 (2) | 0.049 (2) | 0.075 (2) | 0.0107 (18) | −0.0118 (17) | 0.0103 (18) |
Zn1 | 0.0266 (3) | 0.0266 (3) | 0.0424 (3) | 0.00442 (19) | 0.00095 (17) | 0.02003 (19) |
Cl1 | 0.0323 (6) | 0.0324 (6) | 0.0596 (7) | 0.0079 (5) | 0.0084 (4) | 0.0159 (5) |
Geometric parameters (Å, º) top
Zn1—O1 | 2.049 (3) | C13—N3 | 1.325 (5) |
Zn1—O1W | 2.080 (3) | C13—N4 | 1.349 (5) |
Zn1—N1 | 2.150 (3) | C13—C14 | 1.462 (5) |
Zn1—N2 | 2.072 (3) | C14—C15 | 1.385 (5) |
Zn1—Cl1 | 2.2885 (14) | C14—C19 | 1.388 (5) |
C1—N1 | 1.327 (5) | C15—C16 | 1.379 (5) |
C1—C2 | 1.385 (5) | C15—H15 | 0.9300 |
C1—H1 | 0.9300 | C16—C17 | 1.382 (6) |
C2—C3 | 1.370 (6) | C16—H16 | 0.9300 |
C2—H2 | 0.9300 | C17—O3 | 1.354 (4) |
C3—C4 | 1.407 (5) | C17—C18 | 1.386 (6) |
C3—H3 | 0.9300 | C18—C19 | 1.381 (5) |
C4—C5 | 1.407 (5) | C18—H18 | 0.9300 |
C4—C12 | 1.416 (5) | C19—H19 | 0.9300 |
C5—N1 | 1.354 (5) | C20—O2 | 1.237 (4) |
C5—C6 | 1.448 (5) | C20—O1 | 1.263 (4) |
C6—N2 | 1.352 (4) | C20—C21 | 1.505 (5) |
C6—C10 | 1.407 (5) | C21—C22 | 1.384 (5) |
C7—N2 | 1.327 (5) | C21—C23i | 1.390 (5) |
C7—C8 | 1.392 (5) | C22—C23 | 1.373 (5) |
C7—H7 | 0.9300 | C22—H22 | 0.9300 |
C8—C9 | 1.363 (5) | C23—C21i | 1.390 (5) |
C8—H8 | 0.9300 | C23—H23 | 0.9300 |
C9—C10 | 1.403 (5) | N4—H4 | 0.8600 |
C9—H9 | 0.9300 | O1W—HW11 | 0.83 (6) |
C10—C11 | 1.427 (5) | O1W—HW12 | 0.87 (5) |
C11—N3 | 1.372 (4) | O3—H3A | 0.8200 |
C11—C12 | 1.378 (5) | O2W—HW21 | 0.88 (4) |
C12—N4 | 1.370 (4) | O2W—HW22 | 0.941 (19) |
| | | |
N1—C1—C2 | 122.8 (4) | O3—C17—C16 | 123.1 (4) |
N1—C1—H1 | 118.6 | O3—C17—C18 | 117.4 (4) |
C2—C1—H1 | 118.6 | C16—C17—C18 | 119.5 (4) |
C3—C2—C1 | 119.8 (4) | C19—C18—C17 | 120.2 (4) |
C3—C2—H2 | 120.1 | C19—C18—H18 | 119.9 |
C1—C2—H2 | 120.1 | C17—C18—H18 | 119.9 |
C2—C3—C4 | 118.8 (4) | C18—C19—C14 | 120.9 (4) |
C2—C3—H3 | 120.6 | C18—C19—H19 | 119.6 |
C4—C3—H3 | 120.6 | C14—C19—H19 | 119.6 |
C3—C4—C5 | 117.9 (3) | O2—C20—O1 | 124.9 (3) |
C3—C4—C12 | 126.6 (3) | O2—C20—C21 | 118.4 (3) |
C5—C4—C12 | 115.5 (3) | O1—C20—C21 | 116.6 (3) |
N1—C5—C4 | 122.0 (3) | C22—C21—C23i | 118.9 (3) |
N1—C5—C6 | 116.7 (3) | C22—C21—C20 | 121.2 (3) |
C4—C5—C6 | 121.3 (3) | C23i—C21—C20 | 119.8 (3) |
N2—C6—C10 | 122.0 (3) | C23—C22—C21 | 120.5 (4) |
N2—C6—C5 | 116.6 (3) | C23—C22—H22 | 119.8 |
C10—C6—C5 | 121.4 (3) | C21—C22—H22 | 119.8 |
N2—C7—C8 | 122.7 (4) | C22—C23—C21i | 120.6 (4) |
N2—C7—H7 | 118.7 | C22—C23—H23 | 119.7 |
C8—C7—H7 | 118.7 | C21i—C23—H23 | 119.7 |
C9—C8—C7 | 119.5 (4) | C1—N1—C5 | 118.7 (3) |
C9—C8—H8 | 120.3 | C1—N1—Zn1 | 128.5 (3) |
C7—C8—H8 | 120.3 | C5—N1—Zn1 | 112.8 (2) |
C8—C9—C10 | 119.3 (4) | C7—N2—C6 | 118.7 (3) |
C8—C9—H9 | 120.4 | C7—N2—Zn1 | 125.7 (3) |
C10—C9—H9 | 120.4 | C6—N2—Zn1 | 115.5 (2) |
C9—C10—C6 | 117.8 (3) | C13—N3—C11 | 105.1 (3) |
C9—C10—C11 | 125.7 (3) | C13—N4—C12 | 107.8 (3) |
C6—C10—C11 | 116.4 (3) | C13—N4—H4 | 126.1 |
N3—C11—C12 | 110.3 (3) | C12—N4—H4 | 126.1 |
N3—C11—C10 | 128.4 (3) | C20—O1—Zn1 | 125.1 (2) |
C12—C11—C10 | 121.3 (3) | Zn1—O1W—HW11 | 110 (4) |
N4—C12—C11 | 105.1 (3) | Zn1—O1W—HW12 | 96 (3) |
N4—C12—C4 | 130.7 (3) | HW11—O1W—HW12 | 106 (5) |
C11—C12—C4 | 124.1 (3) | C17—O3—H3A | 109.5 |
N3—C13—N4 | 111.7 (3) | HW21—O2W—HW22 | 101 (3) |
N3—C13—C14 | 125.1 (3) | O1—Zn1—N2 | 90.17 (11) |
N4—C13—C14 | 123.2 (3) | O1—Zn1—O1W | 87.43 (13) |
C15—C14—C19 | 118.0 (3) | N2—Zn1—O1W | 124.01 (13) |
C15—C14—C13 | 120.7 (3) | O1—Zn1—N1 | 163.57 (12) |
C19—C14—C13 | 121.2 (4) | N2—Zn1—N1 | 78.13 (12) |
C16—C15—C14 | 121.6 (4) | O1W—Zn1—N1 | 89.60 (13) |
C16—C15—H15 | 119.2 | O1—Zn1—Cl1 | 98.97 (10) |
C14—C15—H15 | 119.2 | N2—Zn1—Cl1 | 118.99 (9) |
C15—C16—C17 | 119.7 (4) | O1W—Zn1—Cl1 | 116.62 (11) |
C15—C16—H16 | 120.1 | N1—Zn1—Cl1 | 96.81 (9) |
C17—C16—H16 | 120.1 | | |
Symmetry code: (i) −x+1, −y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—HW12···O2 | 0.87 (5) | 1.95 (6) | 2.774 (5) | 158 (4) |
O1W—HW11···O2ii | 0.83 (6) | 1.88 (6) | 2.700 (5) | 172 (6) |
O3—H3A···O2Wiii | 0.82 | 1.90 | 2.713 (5) | 173 |
N4—H4···Cl1iv | 0.86 | 2.48 | 3.318 (4) | 165 |
O2W—HW21···N3 | 0.88 (4) | 2.01 (2) | 2.884 (5) | 172 (6) |
O2W—HW22···Cl1v | 0.94 (2) | 2.85 (4) | 3.571 (4) | 134 (5) |
Symmetry codes: (ii) −x+2, −y+1, −z+1; (iii) −x, −y+2, −z; (iv) x, y+1, z; (v) −x+1, −y+1, −z. |