The Zr atom in the title compound, {(C5H11N2)[Zr(C2O4)3]}n, is chelated by four oxalate groups in a square-antiprismatic geometry. Bridging by one of the three oxalate groups in the asymmetric unit gives rises to a helical tris(oxalato)zirconate chain that propagates along the b axis of the unit cell. The dications surround the chains and are tightly hydrogen bonded to them, resulting in a three-dimensional network.
Supporting information
CCDC reference: 269576
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C) = 0.002 Å
- R factor = 0.019
- wR factor = 0.054
- Data-to-parameter ratio = 13.3
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 ..... ?
PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C3 - C4 ... 1.54 Ang.
PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C5 - C6 ... 1.54 Ang.
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
4 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
2 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
0 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
catena-Poly[
N-methylpiperazinium(2+)
[[bis(oxalato-
κ2-O,
O')zirconate(IV)]-µ
2-oxalato-
κ4O,
O':
O'',
O''']]
top
Crystal data top
(C5H11N2)[Zr(C2O4)3] | F(000) = 920 |
Mr = 457.46 | Dx = 2.098 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5754 reflections |
a = 9.5936 (5) Å | θ = 2.4–28.5° |
b = 11.3569 (5) Å | µ = 0.84 mm−1 |
c = 13.9792 (7) Å | T = 295 K |
β = 108.023 (1)° | Prism, colorless |
V = 1448.4 (1) Å3 | 0.38 × 0.29 × 0.20 mm |
Z = 4 | |
Data collection top
Bruker APEX area-detector diffractometer | 3273 independent reflections |
Radiation source: fine-focus sealed tube | 3114 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
φ and ω scans | θmax = 27.5°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −12→12 |
Tmin = 0.712, Tmax = 0.850 | k = −14→14 |
15328 measured reflections | l = −18→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)] = 0.019 | Hydrogen site location: difmap (N-H) and geom (C-H) |
wR(F2) = 0.054 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.033P)2 + 0.4993P] where P = (Fo2 + 2Fc2)/3 |
3273 reflections | (Δ/σ)max = 0.001 |
247 parameters | Δρmax = 0.32 e Å−3 |
3 restraints | Δρmin = −0.54 e Å−3 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Zr1 | 0.40531 (1) | 0.61472 (1) | 0.23939 (1) | 0.01225 (6) | |
O1 | 0.6077 (1) | 0.4936 (1) | 0.2636 (1) | 0.0186 (2) | |
O2 | 0.6764 (1) | 0.3025 (1) | 0.2752 (1) | 0.0180 (2) | |
O3 | 0.3347 (1) | 0.4277 (1) | 0.2314 (1) | 0.0186 (2) | |
O4 | 0.4056 (1) | 0.2390 (1) | 0.2481 (1) | 0.0177 (2) | |
O5 | 0.2496 (1) | 0.6116 (1) | 0.3232 (1) | 0.0192 (2) | |
O6 | 0.2142 (1) | 0.6073 (1) | 0.4741 (1) | 0.0330 (3) | |
O7 | 0.5241 (1) | 0.6283 (1) | 0.3955 (1) | 0.0221 (2) | |
O8 | 0.5242 (1) | 0.6361 (1) | 0.5547 (1) | 0.0266 (2) | |
O9 | 0.1869 (1) | 0.6149 (1) | 0.1280 (1) | 0.0210 (2) | |
O10 | 0.0619 (1) | 0.6209 (1) | −0.0358 (1) | 0.0337 (3) | |
O11 | 0.4349 (1) | 0.6068 (1) | 0.0951 (1) | 0.0221 (2) | |
O12 | 0.3312 (2) | 0.6238 (1) | −0.0715 (1) | 0.0340 (3) | |
N1 | 0.8003 (1) | 0.7599 (1) | 0.5989 (1) | 0.0249 (3) | |
N2 | 1.0445 (1) | 0.6961 (1) | 0.7717 (1) | 0.0266 (3) | |
C1 | 0.5861 (1) | 0.3860 (1) | 0.2638 (1) | 0.0149 (3) | |
C2 | 0.4290 (1) | 0.3470 (1) | 0.2471 (1) | 0.0150 (2) | |
C3 | 0.2933 (2) | 0.6142 (1) | 0.4214 (1) | 0.0196 (3) | |
C4 | 0.4613 (2) | 0.6275 (1) | 0.4648 (1) | 0.0187 (3) | |
C5 | 0.1762 (2) | 0.6175 (1) | 0.0343 (1) | 0.0214 (3) | |
C6 | 0.3253 (2) | 0.6163 (1) | 0.0135 (1) | 0.0213 (3) | |
C7 | 0.9129 (2) | 0.6723 (1) | 0.5911 (1) | 0.0286 (3) | |
C8 | 0.9829 (2) | 0.6096 (1) | 0.6899 (1) | 0.0301 (4) | |
C9 | 0.9313 (2) | 0.7801 (2) | 0.7814 (1) | 0.0279 (3) | |
C10 | 0.8637 (2) | 0.8440 (1) | 0.6834 (1) | 0.0260 (3) | |
C11 | 0.7405 (2) | 0.8263 (2) | 0.5022 (1) | 0.0348 (4) | |
H11 | 0.731 (2) | 0.719 (2) | 0.607 (1) | 0.035 (5)* | |
H21 | 1.112 (2) | 0.737 (2) | 0.759 (1) | 0.035 (5)* | |
H22 | 1.075 (2) | 0.662 (2) | 0.829 (1) | 0.048 (6)* | |
H7a | 0.9883 | 0.7125 | 0.5707 | 0.034* | |
H7b | 0.8671 | 0.6147 | 0.5398 | 0.034* | |
H8a | 0.9102 | 0.5613 | 0.7065 | 0.036* | |
H8b | 1.0604 | 0.5583 | 0.6835 | 0.036* | |
H9a | 0.9755 | 0.8366 | 0.8341 | 0.034* | |
H9b | 0.8558 | 0.7378 | 0.8001 | 0.034* | |
H10a | 0.7871 | 0.8961 | 0.6901 | 0.031* | |
H10b | 0.9378 | 0.8919 | 0.6681 | 0.031* | |
H11a | 0.6996 | 0.7718 | 0.4483 | 0.052* | |
H11b | 0.8180 | 0.8700 | 0.4888 | 0.052* | |
H11c | 0.6656 | 0.8796 | 0.5076 | 0.052* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zr1 | 0.01299 (8) | 0.01007 (8) | 0.01343 (8) | 0.00006 (4) | 0.00371 (5) | −0.00019 (4) |
O1 | 0.0182 (5) | 0.0121 (5) | 0.0257 (5) | −0.0010 (3) | 0.0072 (4) | −0.0002 (3) |
O2 | 0.0170 (4) | 0.0125 (4) | 0.0254 (5) | 0.0008 (3) | 0.0080 (4) | −0.0002 (4) |
O3 | 0.0157 (4) | 0.0121 (4) | 0.0270 (5) | 0.0007 (3) | 0.0053 (4) | −0.0005 (4) |
O4 | 0.0167 (5) | 0.0113 (5) | 0.0250 (5) | −0.0007 (3) | 0.0063 (4) | −0.0006 (3) |
O5 | 0.0181 (5) | 0.0217 (5) | 0.0179 (5) | −0.0013 (4) | 0.0055 (4) | −0.0016 (3) |
O6 | 0.0306 (6) | 0.0469 (7) | 0.0269 (6) | −0.0023 (5) | 0.0168 (5) | 0.0001 (5) |
O7 | 0.0185 (5) | 0.0306 (5) | 0.0165 (5) | −0.0007 (4) | 0.0045 (4) | −0.0009 (4) |
O8 | 0.0305 (6) | 0.0311 (5) | 0.0163 (5) | −0.0037 (5) | 0.0044 (4) | −0.0005 (4) |
O9 | 0.0179 (5) | 0.0241 (5) | 0.0189 (5) | −0.0001 (4) | 0.0026 (4) | 0.0007 (4) |
O10 | 0.0255 (6) | 0.0451 (7) | 0.0232 (6) | −0.0029 (5) | −0.0030 (5) | 0.0052 (5) |
O11 | 0.0221 (5) | 0.0270 (5) | 0.0174 (5) | 0.0019 (4) | 0.0065 (4) | 0.0007 (4) |
O12 | 0.0432 (7) | 0.0413 (7) | 0.0186 (5) | 0.0057 (5) | 0.0112 (5) | 0.0031 (4) |
N1 | 0.0201 (6) | 0.0265 (6) | 0.0244 (6) | −0.0067 (5) | 0.0016 (5) | 0.0043 (5) |
N2 | 0.0183 (6) | 0.0319 (7) | 0.0262 (7) | −0.0038 (5) | 0.0019 (5) | 0.0055 (5) |
C1 | 0.0163 (7) | 0.0148 (7) | 0.0141 (6) | −0.0001 (4) | 0.0056 (5) | −0.0002 (4) |
C2 | 0.0170 (6) | 0.0148 (6) | 0.0132 (6) | −0.0005 (5) | 0.0049 (5) | 0.0002 (5) |
C3 | 0.0233 (7) | 0.0162 (6) | 0.0204 (7) | −0.0002 (5) | 0.0080 (6) | 0.0001 (5) |
C4 | 0.0232 (7) | 0.0147 (6) | 0.0177 (6) | −0.0001 (5) | 0.0056 (5) | −0.0005 (5) |
C5 | 0.0250 (7) | 0.0158 (7) | 0.0204 (7) | −0.0002 (5) | 0.0026 (6) | 0.0013 (5) |
C6 | 0.0282 (8) | 0.0160 (7) | 0.0191 (7) | 0.0014 (5) | 0.0063 (6) | 0.0004 (5) |
C7 | 0.0344 (8) | 0.0233 (7) | 0.0262 (7) | −0.0039 (6) | 0.0066 (6) | −0.0026 (6) |
C8 | 0.0285 (8) | 0.0222 (8) | 0.0355 (9) | −0.0031 (6) | 0.0040 (7) | 0.0030 (6) |
C9 | 0.0217 (7) | 0.0384 (9) | 0.0233 (7) | −0.0040 (6) | 0.0063 (6) | −0.0023 (6) |
C10 | 0.0226 (7) | 0.0263 (7) | 0.0281 (7) | −0.0019 (6) | 0.0063 (6) | −0.0023 (6) |
C11 | 0.0358 (9) | 0.0329 (9) | 0.0275 (8) | −0.0070 (7) | −0.0022 (7) | 0.0093 (7) |
Geometric parameters (Å, º) top
Zr1—O1 | 2.318 (1) | N1—C11 | 1.499 (2) |
Zr1—O2i | 2.260 (1) | N2—C9 | 1.483 (2) |
Zr1—O3 | 2.222 (1) | N2—C8 | 1.484 (2) |
Zr1—O4i | 2.263 (1) | C1—C2 | 1.517 (2) |
Zr1—O5 | 2.165 (1) | C3—C4 | 1.544 (2) |
Zr1—O7 | 2.132 (1) | C5—C6 | 1.545 (2) |
Zr1—O9 | 2.190 (1) | C7—C8 | 1.514 (2) |
Zr1—O11 | 2.124 (1) | C9—C10 | 1.509 (2) |
O1—C1 | 1.240 (2) | N1—H11 | 0.85 (1) |
O2—C1 | 1.261 (2) | N2—H21 | 0.86 (1) |
O3—C2 | 1.258 (2) | N2—H22 | 0.86 (1) |
O4—C2 | 1.248 (2) | C7—H7a | 0.97 |
O5—C3 | 1.306 (2) | C7—H7b | 0.97 |
O6—C3 | 1.212 (2) | C8—H8a | 0.97 |
O7—C4 | 1.289 (2) | C8—H8b | 0.97 |
O8—C4 | 1.218 (2) | C9—H9a | 0.97 |
O9—C5 | 1.281 (2) | C9—H9b | 0.97 |
O10—C5 | 1.225 (2) | C10—H10a | 0.97 |
O11—C6 | 1.295 (2) | C10—H10b | 0.97 |
O12—C6 | 1.210 (2) | C11—H11a | 0.96 |
N1—C10 | 1.494 (2) | C11—H11b | 0.96 |
N1—C7 | 1.497 (2) | C11—H11c | 0.96 |
| | | |
O1—Zr1—O2i | 145.59 (3) | O5—C3—C4 | 111.8 (1) |
O1—Zr1—O3 | 70.63 (3) | O8—C4—O7 | 125.3 (1) |
O1—Zr1—O4i | 75.13 (4) | O8—C4—C3 | 122.4 (1) |
O1—Zr1—O5 | 126.76 (3) | O7—C4—C3 | 112.3 (1) |
O1—Zr1—O7 | 74.66 (4) | O10—C5—O9 | 125.9 (2) |
O1—Zr1—O9 | 132.70 (3) | O10—C5—C6 | 120.1 (1) |
O1—Zr1—O11 | 76.18 (4) | O9—C5—C6 | 114.0 (1) |
O2i—Zr1—O3 | 143.72 (4) | O12—C6—O11 | 126.8 (2) |
O2i—Zr1—O4i | 70.46 (3) | O12—C6—C5 | 120.8 (1) |
O2i—Zr1—O5 | 77.67 (3) | O11—C6—C5 | 112.4 (1) |
O2i—Zr1—O7 | 94.87 (4) | N1—C7—C8 | 111.9 (1) |
O2i—Zr1—O9 | 72.92 (3) | N2—C8—C7 | 110.5 (1) |
O2i—Zr1—O11 | 95.67 (4) | N2—C9—C10 | 110.3 (1) |
O3—Zr1—O4i | 145.59 (3) | N1—C10—C9 | 111.5 (1) |
O3—Zr1—O5 | 76.15 (3) | C10—N1—H11 | 113 (1) |
O3—Zr1—O7 | 100.27 (4) | C7—N1—H11 | 105 (1) |
O3—Zr1—O9 | 75.85 (3) | C11—N1—H11 | 107 (1) |
O3—Zr1—O11 | 92.30 (4) | C9—N2—H21 | 107 (1) |
O4i—Zr1—O5 | 129.76 (3) | C8—N2—H21 | 110 (1) |
O4i—Zr1—O7 | 73.39 (4) | C9—N2—H22 | 105 (2) |
O4i—Zr1—O9 | 128.49 (3) | C8—N2—H22 | 111 (2) |
O4i—Zr1—O11 | 76.12 (4) | H21—N2—H22 | 112 (2) |
O5—Zr1—O7 | 71.76 (4) | N1—C7—H7a | 109.2 |
O5—Zr1—O9 | 73.52 (4) | C8—C7—H7a | 109.2 |
O5—Zr1—O11 | 146.14 (4) | N1—C7—H7b | 109.2 |
O7—Zr1—O9 | 144.93 (4) | C8—C7—H7b | 109.2 |
O7—Zr1—O11 | 142.09 (4) | H7a—C7—H7b | 107.9 |
O9—Zr1—O11 | 72.80 (4) | N2—C8—H8a | 109.6 |
C1—O1—Zr1 | 116.9 (1) | C7—C8—H8a | 109.6 |
C1—O2—Zr1ii | 119.5 (1) | N2—C8—H8b | 109.6 |
C2—O3—Zr1 | 119.7 (1) | C7—C8—H8b | 109.6 |
C2—O4—Zr1ii | 118.1 (1) | H8a—C8—H8b | 108.1 |
C3—O5—Zr1 | 121.2 (1) | N2—C9—H9a | 109.6 |
C4—O7—Zr1 | 122.9 (1) | C10—C9—H9a | 109.6 |
C5—O9—Zr1 | 118.9 (1) | N2—C9—H9b | 109.6 |
C6—O11—Zr1 | 121.5 (1) | C10—C9—H9b | 109.6 |
C10—N1—C7 | 110.8 (1) | H9a—C9—H9b | 108.1 |
C10—N1—C11 | 109.9 (1) | N1—C10—H10a | 109.3 |
C7—N1—C11 | 110.6 (1) | C9—C10—H10a | 109.3 |
C9—N2—C8 | 111.6 (1) | N1—C10—H10b | 109.3 |
O1—C1—O2 | 129.2 (1) | C9—C10—H10b | 109.3 |
O1—C1—C2 | 116.5 (1) | H10a—C10—H10b | 108.0 |
O2—C1—C2 | 114.3 (1) | N1—C11—H11a | 109.5 |
O4—C2—O3 | 126.5 (1) | N1—C11—H11b | 109.5 |
O4—C2—C1 | 117.3 (1) | H11a—C11—H11b | 109.5 |
O3—C2—C1 | 116.2 (1) | N1—C11—H11c | 109.5 |
O6—C3—O5 | 125.4 (1) | H11a—C11—H11c | 109.5 |
O6—C3—C4 | 122.8 (1) | H11b—C11—H11c | 109.5 |
| | | |
O11—Zr1—O1—C1 | −99.3 (1) | O2i—Zr1—O11—C6 | −63.8 (1) |
O7—Zr1—O1—C1 | 105.2 (1) | O4i—Zr1—O11—C6 | −132.1 (1) |
O5—Zr1—O1—C1 | 52.8 (1) | O1—Zr1—O11—C6 | 150.1 (1) |
O9—Zr1—O1—C1 | −49.2 (1) | Zr1—O1—C1—O2 | 179.9 (1) |
O3—Zr1—O1—C1 | −1.9 (1) | Zr1—O1—C1—C2 | 0.6 (1) |
O2i—Zr1—O1—C1 | −179.0 (1) | Zr1ii—O2—C1—O1 | −175.8 (1) |
O4i—Zr1—O1—C1 | −178.4 (1) | Zr1ii—O2—C1—C2 | 3.5 (1) |
O11—Zr1—O3—C2 | 77.7 (1) | Zr1ii—O4—C2—O3 | 173.0 (1) |
O7—Zr1—O3—C2 | −66.4 (1) | Zr1ii—O4—C2—C1 | −5.4 (1) |
O5—Zr1—O3—C2 | −134.6 (1) | Zr1—O3—C2—O4 | 177.7 (1) |
O9—Zr1—O3—C2 | 149.3 (1) | Zr1—O3—C2—C1 | −4.0 (2) |
O2i—Zr1—O3—C2 | −179.5 (1) | O1—C1—C2—O4 | −179.3 (1) |
O4i—Zr1—O3—C2 | 9.1 (1) | O2—C1—C2—O4 | 1.3 (2) |
O1—Zr1—O3—C2 | 3.2 (1) | O1—C1—C2—O3 | 2.1 (2) |
O11—Zr1—O5—C3 | 176.3 (1) | O2—C1—C2—O3 | −177.3 (1) |
O7—Zr1—O5—C3 | −2.6 (1) | Zr1—O5—C3—O6 | −176.4 (1) |
O9—Zr1—O5—C3 | −177.6 (1) | Zr1—O5—C3—C4 | 3.6 (1) |
O3—Zr1—O5—C3 | 103.4 (1) | Zr1—O7—C4—O8 | −179.3 (1) |
O2i—Zr1—O5—C3 | −102.0 (1) | Zr1—O7—C4—C3 | 0.7 (2) |
O4i—Zr1—O5—C3 | −50.8 (1) | O6—C3—C4—O8 | −2.7 (2) |
O1—Zr1—O5—C3 | 51.0 (1) | O5—C3—C4—O8 | 177.3 (1) |
O11—Zr1—O7—C4 | −178.2 (1) | O6—C3—C4—O7 | 177.3 (1) |
O5—Zr1—O7—C4 | 0.8 (1) | O5—C3—C4—O7 | −2.7 (2) |
O9—Zr1—O7—C4 | 9.2 (1) | Zr1—O9—C5—O10 | −178.1 (1) |
O3—Zr1—O7—C4 | −70.8 (1) | Zr1—O9—C5—C6 | 1.9 (1) |
O2i—Zr1—O7—C4 | 76.1 (1) | Zr1—O11—C6—O12 | 172.7 (1) |
O4i—Zr1—O7—C4 | 144.0 (1) | Zr1—O11—C6—C5 | −7.2 (1) |
O1—Zr1—O7—C4 | −137.3 (1) | O10—C5—C6—O12 | 3.3 (2) |
O11—Zr1—O9—C5 | −4.1 (1) | O9—C5—C6—O12 | −176.7 (1) |
O7—Zr1—O9—C5 | 171.2 (1) | O10—C5—C6—O11 | −176.8 (1) |
O5—Zr1—O9—C5 | 179.5 (1) | O9—C5—C6—O11 | 3.2 (2) |
O3—Zr1—O9—C5 | −101.1 (1) | C10—N1—C7—C8 | 54.0 (2) |
O2i—Zr1—O9—C5 | 97.7 (1) | C11—N1—C7—C8 | 176.1 (1) |
O4i—Zr1—O9—C5 | 51.4 (1) | C9—N2—C8—C7 | 56.7 (2) |
O1—Zr1—O9—C5 | −55.3 (1) | N1—C7—C8—N2 | −54.7 (2) |
O7—Zr1—O11—C6 | −169.3 (1) | C8—N2—C9—C10 | −57.7 (2) |
O5—Zr1—O11—C6 | 12.4 (1) | C7—N1—C10—C9 | −54.8 (2) |
O9—Zr1—O11—C6 | 6.3 (1) | C11—N1—C10—C9 | −177.4 (1) |
O3—Zr1—O11—C6 | 80.7 (1) | N2—C9—C10—N1 | 56.6 (2) |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, y−1/2, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H11···O8 | 0.85 (1) | 2.11 (1) | 2.892 (2) | 153 (2) |
N2—H21···O2iii | 0.86 (1) | 2.27 (2) | 2.948 (2) | 136 (2) |
N2—H21···O5iv | 0.86 (1) | 2.19 (2) | 2.879 (2) | 137 (2) |
N2—H22···O10v | 0.86 (1) | 1.99 (1) | 2.780 (2) | 153 (2) |
N2—H22···O12v | 0.86 (1) | 2.46 (2) | 3.052 (2) | 127 (2) |
Symmetry codes: (iii) −x+2, −y+1, −z+1; (iv) x+1, −y+3/2, z+1/2; (v) x+1, y, z+1. |