In the title complex, [Cu(C6H6O2)(C10H9N3)(H2O)]·3H2O, the Cu atom has a distorted cis-square-pyramidal geometry formed by two O atoms of a bidentate cyclobutane-1,1-dicarboxylate anion, two N atoms of a bidentate di-2-pyridylamine (bpa) molecule and a water O atom. In the crystal structure, the complex molecules are connected by hydrogen bonds through the water molecules, and by π–π stacking interactions between bpa ligands.
Supporting information
CCDC reference: 636817
Key indicators
- Single-crystal X-ray study
- T = 123 K
- Mean (C-C) = 0.002 Å
- R factor = 0.021
- wR factor = 0.060
- Data-to-parameter ratio = 15.8
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT148_ALERT_3_B su on the a - Axis is Too Large (x 1000) . 9 Ang.
Alert level C
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 3000 Deg.
PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.74 Ratio
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Cu1 - O3 .. 5.10 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Cu1 - N2 .. 5.01 su
0 ALERT level A = In general: serious problem
1 ALERT level B = Potentially serious problem
4 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
3 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
0 ALERT type 5 Informative message, check
Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2005) and
CRYSTALS (Betteridge et al., 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: CrystalStructure.
Aqua(cyclobutane-1,1-dicarboxylato-
κ2O,
O')(di-2-pyridylamine-
κ2N,
N')copper(II) trihydrate
top
Crystal data top
[Cu(C6H6O2)(C10H9N3)(H2O)]·3H2O | Z = 2 |
Mr = 448.92 | F(000) = 466 |
Triclinic, P1 | Dx = 1.558 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.7107 Å |
a = 8.810 (9) Å | Cell parameters from 9199 reflections |
b = 11.19 (1) Å | θ = 3.1–27.5° |
c = 11.203 (9) Å | µ = 1.19 mm−1 |
α = 70.31 (3)° | T = 123 K |
β = 80.18 (3)° | Prism, blue |
γ = 67.11 (3)° | 0.30 × 0.30 × 0.20 mm |
V = 957.0 (15) Å3 | |
Data collection top
Rigaku R-AXIS RAPID diffractometer | 4099 reflections with F2 > 2σ(F2) |
Detector resolution: 10.0 pixels mm-1 | Rint = 0.011 |
ω scans | θmax = 27.5° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −11→11 |
Tmin = 0.712, Tmax = 0.789 | k = −14→13 |
9508 measured reflections | l = −14→14 |
4401 independent reflections | |
Refinement top
Refinement on F2 | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.021 | w = 1/[σ2(Fo2) + (0.0317P)2 + 0.4273P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.060 | (Δ/σ)max < 0.001 |
S = 1.08 | Δρmax = 0.38 e Å−3 |
4401 reflections | Δρmin = −0.37 e Å−3 |
278 parameters | |
Special details top
Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY |
Refinement. Refinement using all reflections. The weighted R-factor (wR) and
goodness of fit (S) are based on F2. R-factor (gt) are
based on F. The threshold expression of F2 > 2.0
σ(F2) is used only for calculating R-factor (gt). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu1 | 0.32486 (2) | 0.26739 (1) | 0.35005 (1) | 0.01211 (6) | |
O1 | 0.5404 (1) | 0.11967 (9) | 0.37828 (8) | 0.0155 (2) | |
O2 | 0.7971 (1) | 0.0256 (1) | 0.31116 (9) | 0.0191 (2) | |
O3 | 0.3294 (1) | 0.2433 (1) | 0.18422 (9) | 0.0185 (2) | |
O4 | 0.4803 (1) | 0.1756 (1) | 0.02323 (9) | 0.0206 (2) | |
O5 | 0.1651 (1) | 0.1409 (1) | 0.43572 (9) | 0.0172 (2) | |
O6 | 0.2642 (1) | 0.0369 (1) | 0.05094 (9) | 0.0206 (2) | |
O7 | 0.1225 (1) | 0.0033 (1) | 0.2911 (1) | 0.0198 (2) | |
O8 | 0.1810 (1) | 0.7658 (1) | 0.5043 (1) | 0.0238 (2) | |
N1 | 0.1480 (1) | 0.4507 (1) | 0.2973 (1) | 0.0147 (2) | |
N2 | 0.3484 (1) | 0.2981 (1) | 0.5091 (1) | 0.0132 (2) | |
N3 | 0.2311 (1) | 0.5375 (1) | 0.4301 (1) | 0.0171 (2) | |
C1 | 0.0482 (2) | 0.4761 (1) | 0.2046 (1) | 0.0203 (3) | |
C2 | −0.0570 (2) | 0.6034 (2) | 0.1454 (1) | 0.0247 (3) | |
C3 | −0.0626 (2) | 0.7128 (1) | 0.1814 (1) | 0.0244 (3) | |
C4 | 0.0330 (2) | 0.6893 (1) | 0.2770 (1) | 0.0209 (3) | |
C5 | 0.1374 (2) | 0.5557 (1) | 0.3347 (1) | 0.0148 (2) | |
C6 | 0.3154 (1) | 0.4211 (1) | 0.5209 (1) | 0.0137 (2) | |
C7 | 0.3666 (2) | 0.4372 (1) | 0.6249 (1) | 0.0187 (3) | |
C8 | 0.4461 (2) | 0.3240 (1) | 0.7196 (1) | 0.0209 (3) | |
C9 | 0.4736 (2) | 0.1957 (1) | 0.7105 (1) | 0.0192 (3) | |
C10 | 0.4257 (2) | 0.1871 (1) | 0.6047 (1) | 0.0161 (2) | |
C11 | 0.6132 (2) | 0.2215 (1) | 0.1636 (1) | 0.0155 (2) | |
C12 | 0.7604 (2) | 0.2301 (2) | 0.0683 (1) | 0.0260 (3) | |
C13 | 0.7653 (2) | 0.3446 (2) | 0.1133 (2) | 0.0373 (4) | |
C14 | 0.5892 (2) | 0.3643 (1) | 0.1732 (1) | 0.0229 (3) | |
C15 | 0.6568 (2) | 0.1138 (1) | 0.2928 (1) | 0.0142 (2) | |
C16 | 0.4651 (2) | 0.2121 (1) | 0.1193 (1) | 0.0152 (2) | |
H1 | 0.0517 | 0.4034 | 0.1802 | 0.024* | |
H2 | −0.1233 | 0.6166 | 0.0824 | 0.030* | |
H3 | −0.1306 | 0.8007 | 0.1409 | 0.029* | |
H4 | 0.0290 | 0.7608 | 0.3036 | 0.025* | |
H5 | 0.3468 | 0.5236 | 0.6293 | 0.022* | |
H6 | 0.4813 | 0.3325 | 0.7890 | 0.025* | |
H7 | 0.5236 | 0.1176 | 0.7751 | 0.023* | |
H8 | 0.4470 | 0.1014 | 0.5978 | 0.019* | |
H9 | 0.2382 | 0.6108 | 0.4337 | 0.021* | |
H10 | 0.8582 | 0.1484 | 0.0866 | 0.031* | |
H11 | 0.7332 | 0.2590 | −0.0198 | 0.031* | |
H12 | 0.8482 | 0.3138 | 0.1747 | 0.045* | |
H13 | 0.7733 | 0.4229 | 0.0445 | 0.045* | |
H14 | 0.5034 | 0.4390 | 0.1211 | 0.027* | |
H15 | 0.5764 | 0.3687 | 0.2595 | 0.027* | |
H16 | 0.1673 | 0.0967 | 0.3904 | 0.026* | |
H17 | 0.1842 | 0.0914 | 0.5070 | 0.026* | |
H18 | 0.3226 | −0.0289 | 0.0312 | 0.031* | |
H19 | 0.3206 | 0.0831 | 0.0407 | 0.031* | |
H20 | 0.1622 | 0.0128 | 0.2198 | 0.030* | |
H21 | 0.0246 | 0.0219 | 0.2852 | 0.030* | |
H22 | 0.0850 | 0.7881 | 0.5285 | 0.036* | |
H23 | 0.1861 | 0.8306 | 0.4458 | 0.036* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.01284 (8) | 0.01218 (8) | 0.01185 (8) | −0.00338 (6) | −0.00055 (5) | −0.00554 (6) |
O1 | 0.0157 (4) | 0.0134 (4) | 0.0139 (4) | −0.0032 (4) | 0.0023 (3) | −0.0035 (3) |
O2 | 0.0133 (4) | 0.0220 (5) | 0.0197 (5) | −0.0041 (4) | 0.0003 (4) | −0.0064 (4) |
O3 | 0.0163 (5) | 0.0251 (5) | 0.0181 (5) | −0.0067 (4) | 0.0001 (4) | −0.0125 (4) |
O4 | 0.0228 (5) | 0.0267 (5) | 0.0152 (5) | −0.0076 (4) | 0.0005 (4) | −0.0119 (4) |
O5 | 0.0205 (5) | 0.0178 (5) | 0.0152 (4) | −0.0089 (4) | −0.0003 (4) | −0.0050 (4) |
O6 | 0.0192 (5) | 0.0218 (5) | 0.0195 (5) | −0.0043 (4) | −0.0024 (4) | −0.0073 (4) |
O7 | 0.0153 (5) | 0.0255 (5) | 0.0199 (5) | −0.0083 (4) | 0.0009 (4) | −0.0080 (4) |
O8 | 0.0225 (5) | 0.0162 (5) | 0.0321 (6) | −0.0060 (4) | 0.0030 (4) | −0.0096 (4) |
N1 | 0.0136 (5) | 0.0157 (5) | 0.0137 (5) | −0.0036 (4) | −0.0013 (4) | −0.0047 (4) |
N2 | 0.0135 (5) | 0.0125 (5) | 0.0124 (5) | −0.0032 (4) | −0.0012 (4) | −0.0038 (4) |
N3 | 0.0224 (6) | 0.0107 (5) | 0.0186 (5) | −0.0040 (4) | −0.0057 (4) | −0.0046 (4) |
C1 | 0.0158 (6) | 0.0265 (7) | 0.0195 (6) | −0.0055 (6) | −0.0021 (5) | −0.0097 (6) |
C2 | 0.0171 (7) | 0.0327 (8) | 0.0191 (7) | −0.0035 (6) | −0.0059 (5) | −0.0053 (6) |
C3 | 0.0185 (7) | 0.0218 (7) | 0.0211 (7) | −0.0002 (6) | −0.0040 (5) | 0.0012 (5) |
C4 | 0.0215 (7) | 0.0144 (6) | 0.0212 (7) | −0.0025 (5) | −0.0021 (5) | −0.0026 (5) |
C5 | 0.0144 (6) | 0.0144 (6) | 0.0133 (6) | −0.0043 (5) | −0.0002 (4) | −0.0027 (5) |
C6 | 0.0135 (6) | 0.0140 (6) | 0.0133 (6) | −0.0044 (5) | −0.0002 (4) | −0.0046 (5) |
C7 | 0.0222 (7) | 0.0193 (7) | 0.0178 (6) | −0.0076 (5) | −0.0019 (5) | −0.0088 (5) |
C8 | 0.0218 (7) | 0.0279 (7) | 0.0148 (6) | −0.0086 (6) | −0.0029 (5) | −0.0079 (5) |
C9 | 0.0177 (6) | 0.0202 (7) | 0.0138 (6) | −0.0030 (5) | −0.0029 (5) | −0.0014 (5) |
C10 | 0.0159 (6) | 0.0136 (6) | 0.0149 (6) | −0.0030 (5) | −0.0002 (5) | −0.0025 (5) |
C11 | 0.0169 (6) | 0.0184 (6) | 0.0126 (6) | −0.0092 (5) | 0.0014 (5) | −0.0041 (5) |
C12 | 0.0237 (7) | 0.0384 (9) | 0.0172 (7) | −0.0176 (7) | 0.0051 (5) | −0.0051 (6) |
C13 | 0.042 (1) | 0.047 (1) | 0.0355 (9) | −0.0349 (9) | 0.0076 (7) | −0.0089 (8) |
C14 | 0.0334 (8) | 0.0196 (7) | 0.0205 (7) | −0.0165 (6) | −0.0023 (6) | −0.0032 (5) |
C15 | 0.0162 (6) | 0.0150 (6) | 0.0145 (6) | −0.0073 (5) | −0.0001 (5) | −0.0065 (5) |
C16 | 0.0183 (6) | 0.0140 (6) | 0.0131 (6) | −0.0056 (5) | −0.0014 (5) | −0.0036 (5) |
Geometric parameters (Å, º) top
Cu1—O1 | 1.962 (2) | C2—H2 | 0.9301 |
Cu1—O3 | 1.957 (1) | C3—C4 | 1.368 (2) |
Cu1—O5 | 2.254 (3) | C3—H3 | 0.9300 |
Cu1—N1 | 1.999 (2) | C4—C5 | 1.407 (2) |
Cu1—N2 | 1.983 (1) | C4—H4 | 0.9300 |
O1—C15 | 1.276 (2) | C6—C7 | 1.406 (2) |
O2—C15 | 1.243 (1) | C7—C8 | 1.371 (2) |
O3—C16 | 1.276 (2) | C7—H5 | 0.9300 |
O4—C16 | 1.244 (2) | C8—C9 | 1.396 (2) |
O5—H16 | 0.8136 | C8—H6 | 0.9300 |
O5—H17 | 0.8050 | C9—C10 | 1.369 (2) |
O6—H18 | 0.7951 | C9—H7 | 0.9301 |
O6—H19 | 0.8167 | C10—H8 | 0.9301 |
O7—H20 | 0.8048 | C11—C12 | 1.545 (2) |
O7—H21 | 0.8137 | C11—C14 | 1.566 (2) |
O8—H22 | 0.8091 | C11—C15 | 1.532 (2) |
O8—H23 | 0.8073 | C11—C16 | 1.524 (2) |
N1—C1 | 1.360 (2) | C12—C13 | 1.545 (3) |
N1—C5 | 1.340 (2) | C12—H10 | 0.9700 |
N2—C6 | 1.340 (2) | C12—H11 | 0.9700 |
N2—C10 | 1.359 (1) | C13—C14 | 1.544 (3) |
N3—C5 | 1.375 (2) | C13—H12 | 0.9700 |
N3—C6 | 1.376 (1) | C13—H13 | 0.9700 |
N3—H9 | 0.8601 | C14—H14 | 0.9700 |
C1—N1 | 1.360 (2) | C14—H15 | 0.9700 |
C1—C2 | 1.368 (2) | H1—C1 | 0.9300 |
C1—H1 | 0.9300 | H18—O6 | 0.7951 |
C2—C1 | 1.368 (2) | H21—O7 | 0.8137 |
C2—C3 | 1.394 (3) | | |
| | | |
O1—Cu1—O3 | 88.28 (4) | H4—C4—C3 | 120.3843 |
O1—Cu1—O5 | 98.10 (4) | C7—C6—N2 | 121.8 (1) |
O1—Cu1—N1 | 162.85 (5) | C7—C6—N3 | 117.2 (1) |
O1—Cu1—N2 | 87.89 (4) | C8—C7—C6 | 119.1 (2) |
O3—Cu1—O5 | 91.06 (5) | C8—C7—H5 | 120.4225 |
O3—Cu1—N1 | 90.91 (4) | H5—C7—C6 | 120.4319 |
O3—Cu1—N2 | 171.99 (5) | C9—C8—C7 | 119.1 (2) |
O5—Cu1—N1 | 99.04 (4) | C9—C8—H6 | 120.4364 |
O5—Cu1—N2 | 96.45 (5) | H6—C8—C7 | 120.4363 |
N1—Cu1—N2 | 90.68 (5) | C10—C9—C8 | 118.8 (1) |
C15—O1—Cu1 | 121.73 (7) | C10—C9—H7 | 120.6231 |
C16—O3—Cu1 | 120.4 (1) | H7—C9—C8 | 120.6266 |
H16—O5—Cu1 | 110.8889 | H8—C10—N2 | 118.5232 |
H16—O5—H17 | 109.1213 | H8—C10—C9 | 118.5282 |
H17—O5—Cu1 | 116.1636 | C12—C11—C14 | 88.8 (1) |
H18—O6—H19 | 105.8306 | C12—C11—C15 | 115.7 (1) |
H20—O7—H21 | 105.8582 | C12—C11—C16 | 118.5 (1) |
H22—O8—H23 | 104.3396 | C14—C11—C15 | 110.1 (1) |
C1—N1—Cu1 | 118.2 (1) | C14—C11—C16 | 115.4 (1) |
C1—N1—C5 | 117.7 (1) | C15—C11—C16 | 107.4 (1) |
C5—N1—Cu1 | 123.38 (9) | C13—C12—C11 | 88.7 (1) |
C6—N2—Cu1 | 123.80 (8) | C13—C12—H10 | 113.8605 |
C6—N2—C10 | 118.1 (1) | C13—C12—H11 | 113.8637 |
C10—N2—Cu1 | 117.3 (1) | H10—C12—C11 | 113.8620 |
C5—N3—C6 | 130.4 (1) | H10—C12—H11 | 111.0768 |
C5—N3—H9 | 114.7920 | H11—C12—C11 | 113.8674 |
C6—N3—H9 | 114.7896 | C14—C13—C12 | 89.6 (2) |
N1—C1—H1 | 118.3673 | C14—C13—H12 | 113.7223 |
N1—C1—C2 | 123.3 (2) | C14—C13—H13 | 113.7171 |
C2—C1—H1 | 118.3670 | H12—C13—C12 | 113.7217 |
C1—C2—C3 | 118.7 (2) | H12—C13—H13 | 110.9605 |
C1—C2—H2 | 120.6652 | H13—C13—C12 | 113.7149 |
C3—C2—H2 | 120.6684 | H14—C14—C11 | 113.9872 |
C4—C3—C2 | 119.1 (1) | H14—C14—H15 | 111.1899 |
C4—C3—H3 | 120.4208 | H14—C14—C13 | 113.9953 |
H3—C3—C2 | 120.4308 | H15—C14—C11 | 113.9871 |
C5—C4—H4 | 120.3750 | H15—C14—C13 | 113.9904 |
C5—C4—C3 | 119.2 (2) | | |
| | | |
O3—Cu1—O1—C15 | 45.5 (1) | N1—C1—C2—C3 | 0.1 (2) |
O1—Cu1—O3—C16 | −35.9 (1) | C1—C2—C3—C4 | −1.9 (2) |
O1—Cu1—O5—H16 | −71.7 | C2—C3—C4—C5 | 1.4 (2) |
O1—Cu1—N1—C1 | 112.3 (2) | C3—C4—C5—N1 | 1.1 (2) |
O1—Cu1—N2—C6 | 134.7 (1) | C3—C4—C5—N3 | 179.9 (1) |
Cu1—O1—C15—O2 | 175.7 (1) | N2—C6—C7—C8 | −3.0 (2) |
Cu1—O1—C15—C11 | −5.1 (2) | C6—C7—C8—C9 | −0.2 (2) |
Cu1—O3—C16—O4 | 168.8 (1) | C7—C8—C9—C10 | 2.4 (2) |
Cu1—O3—C16—C11 | −11.4 (2) | C8—C9—C10—N2 | −1.8 (2) |
Cu1—N1—C1—C2 | −168.2 (1) | C14—C11—C12—C13 | 16.7 (1) |
Cu1—N1—C5—N3 | −11.7 (2) | C12—C11—C14—C13 | −16.8 (1) |
Cu1—N1—C5—C4 | 167.1 (1) | C12—C11—C15—O1 | 169.7 (1) |
Cu1—N2—C6—N3 | 13.2 (2) | C12—C11—C15—O2 | −11.1 (2) |
Cu1—N2—C10—C9 | 169.0 (1) | C12—C11—C16—O3 | −160.8 (1) |
C6—N3—C5—N1 | −16.8 (2) | C12—C11—C16—O4 | 19.0 (2) |
C6—N3—C5—C4 | 164.4 (1) | C11—C12—C13—C14 | −17.0 (1) |
C5—N3—C6—N2 | 16.1 (2) | C12—C13—C14—C11 | 16.8 (1) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H9···O8 | 0.86 | 2.00 | 2.799 (2) | 154 |
O5—H16···O7 | 0.81 | 1.93 | 2.734 (2) | 168 |
O5—H17···O2i | 0.81 | 2.01 | 2.811 (3) | 173 (1) |
O6—H18···O4ii | 0.79 | 2.04 | 2.818 (3) | 164 (2) |
O6—H19···O4 | 0.82 | 2.00 | 2.810 (2) | 173 |
O7—H20···O6 | 0.81 | 1.93 | 2.734 (3) | 178 |
O7—H21···O2iii | 0.81 | 1.96 | 2.756 (2) | 164 (1) |
O8—H22···O5iv | 0.81 | 2.05 | 2.852 (3) | 172 (1) |
O8—H23···O7v | 0.81 | 2.07 | 2.848 (3) | 161 (2) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y, −z; (iii) x−1, y, z; (iv) −x, −y+1, −z+1; (v) x, y+1, z. |