Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807061946/ng2377sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807061946/ng2377Isup2.hkl |
CCDC reference: 672779
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (C-C) = 0.005 Å
- Disorder in solvent or counterion
- R factor = 0.041
- wR factor = 0.099
- Data-to-parameter ratio = 13.6
checkCIF/PLATON results
No syntax errors found
Alert level A DIFF020_ALERT_1_A _diffrn_standards_interval_count and _diffrn_standards_interval_time are missing. Number of measurements between standards or time (min) between standards.
Author Response: CCD detector used |
Alert level B PLAT420_ALERT_2_B D-H Without Acceptor O1W - H1W ... ?
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97 PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 13.00 Perc. PLAT480_ALERT_4_C Long H...A H-Bond Reported H1W .. O2 .. 2.65 Ang.
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 21
1 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 2 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 2 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For metal complexes of pyridinedicarboxylic acids, see: Pocic et al. (2005); Zhou et al. (2006).
Copper chloride dihydrate and 2,4-pyridinedicarboxylic acid (H2PDC) were obtained commercially. N,N'-di(4-pyridylmethyl)piperazine (bpmp) was prepared via a published procedure (Pocic et al., 2005). Copper chloride dihydrate (0.044 g, 0.26 mmol) and H2PDC (0.031 g, 0.19 mmol) were dissolved in 4 ml water in a glass vial. A solution of bpmp (0.050 g, 0.19 mmol) in 4 ml me thanol was carefully layered on top. Blue blocks of the title compound were deposited (0.047 g, 0.17 mmol, 89% yield) after one week at 293 K.
All H atoms bound to C atoms were placed in calculated positions, with C—H = 0.95 (2) Å and refined in riding mode with Uiso = 1.2Ueq(C). The H atoms bound to O in the aqua ligands and unligated water molecules were found via Fourier difference map, restrained with O—H = 0.85 (2) Å, and refined with Uiso =1.2Ueq(O).
Data collection: COSMO (Bruker, 2006); cell refinement: APEX2 (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: CrystalMaker (Palmer, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
[Cu(C7H3NO4)(H2O)2]·0.625H2O | Dx = 2.006 Mg m−3 |
Mr = 275.94 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pnna | Cell parameters from 7418 reflections |
a = 20.324 (4) Å | θ = 2.0–28.3° |
b = 12.057 (2) Å | µ = 2.41 mm−1 |
c = 7.4706 (16) Å | T = 173 K |
V = 1830.7 (6) Å3 | Block, blue |
Z = 8 | 0.25 × 0.25 × 0.20 mm |
F(000) = 1114 |
Bruker APEXII diffractometer | 2152 independent reflections |
Radiation source: fine-focus sealed tube | 1517 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
ϕ and ω scans | θmax = 28.3°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −16→26 |
Tmin = 0.520, Tmax = 0.618 | k = −10→15 |
7418 measured reflections | l = −6→9 |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.099 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0426P)2 + 0.2838P] where P = (Fo2 + 2Fc2)/3 |
2152 reflections | (Δ/σ)max = 0.001 |
158 parameters | Δρmax = 0.68 e Å−3 |
21 restraints | Δρmin = −0.69 e Å−3 |
[Cu(C7H3NO4)(H2O)2]·0.625H2O | V = 1830.7 (6) Å3 |
Mr = 275.94 | Z = 8 |
Orthorhombic, Pnna | Mo Kα radiation |
a = 20.324 (4) Å | µ = 2.41 mm−1 |
b = 12.057 (2) Å | T = 173 K |
c = 7.4706 (16) Å | 0.25 × 0.25 × 0.20 mm |
Bruker APEXII diffractometer | 2152 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1517 reflections with I > 2σ(I) |
Tmin = 0.520, Tmax = 0.618 | Rint = 0.038 |
7418 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 21 restraints |
wR(F2) = 0.099 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | Δρmax = 0.68 e Å−3 |
2152 reflections | Δρmin = −0.69 e Å−3 |
158 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cu1 | 0.631799 (18) | 0.45906 (4) | 0.18172 (6) | 0.01542 (15) | |
O1 | 0.67326 (11) | 0.7225 (2) | 0.4821 (3) | 0.0251 (7) | |
O1W | 0.7500 | 0.5000 | −0.3147 (6) | 0.104 (3) | |
H1W | 0.7590 | 0.5513 | −0.3903 | 0.124* | |
O2W | 0.7243 (11) | 0.2500 | −0.2500 | 0.108 (10) | 0.25 |
H2W | 0.7513 | 0.2379 | −0.1577 | 0.130* | 0.25 |
O2 | 0.68258 (10) | 0.5671 (2) | 0.3219 (3) | 0.0174 (6) | |
O3 | 0.42732 (10) | 0.8454 (2) | 0.5840 (3) | 0.0166 (6) | |
O4 | 0.35590 (11) | 0.7053 (2) | 0.5432 (4) | 0.0320 (8) | |
O5 | 0.64138 (12) | 0.5631 (2) | −0.0813 (4) | 0.0231 (7) | |
H5A | 0.6535 (18) | 0.6282 (18) | −0.066 (5) | 0.028* | |
H5B | 0.6750 (13) | 0.560 (3) | −0.142 (4) | 0.028* | |
O6 | 0.71189 (11) | 0.3848 (2) | 0.1122 (4) | 0.0208 (6) | |
H6A | 0.7049 (18) | 0.3176 (17) | 0.106 (5) | 0.025* | |
H6B | 0.7394 (14) | 0.371 (3) | 0.188 (4) | 0.025* | |
N1 | 0.55748 (12) | 0.5464 (2) | 0.2784 (4) | 0.0128 (7) | |
C1 | 0.57573 (15) | 0.6319 (3) | 0.3852 (5) | 0.0129 (8) | |
C2 | 0.53100 (15) | 0.7009 (3) | 0.4690 (5) | 0.0136 (8) | |
H2 | 0.5454 | 0.7614 | 0.5407 | 0.016* | |
C3 | 0.46437 (15) | 0.6796 (3) | 0.4454 (5) | 0.0130 (8) | |
C4 | 0.44555 (15) | 0.5921 (3) | 0.3370 (4) | 0.0163 (8) | |
H4 | 0.4003 | 0.5766 | 0.3188 | 0.020* | |
C5 | 0.49278 (15) | 0.5276 (3) | 0.2556 (5) | 0.0154 (8) | |
H5 | 0.4793 | 0.4679 | 0.1808 | 0.018* | |
C6 | 0.64987 (15) | 0.6440 (3) | 0.4010 (5) | 0.0152 (8) | |
C7 | 0.41055 (15) | 0.7489 (3) | 0.5317 (5) | 0.0176 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.01020 (19) | 0.0141 (3) | 0.0220 (3) | −0.00002 (17) | −0.00034 (17) | −0.0044 (2) |
O1 | 0.0160 (11) | 0.0209 (16) | 0.0385 (17) | −0.0024 (11) | −0.0026 (11) | −0.0116 (14) |
O1W | 0.096 (4) | 0.190 (7) | 0.024 (3) | 0.102 (5) | 0.000 | 0.000 |
O2W | 0.095 (18) | 0.17 (3) | 0.057 (15) | 0.000 | 0.000 | −0.005 (18) |
O2 | 0.0103 (10) | 0.0161 (15) | 0.0258 (15) | 0.0003 (9) | 0.0015 (10) | −0.0046 (13) |
O3 | 0.0138 (11) | 0.0137 (15) | 0.0222 (14) | 0.0014 (10) | 0.0023 (10) | −0.0046 (13) |
O4 | 0.0158 (13) | 0.0252 (17) | 0.055 (2) | −0.0062 (11) | 0.0115 (12) | −0.0181 (16) |
O5 | 0.0194 (13) | 0.0228 (17) | 0.0270 (17) | −0.0053 (11) | 0.0009 (11) | −0.0024 (15) |
O6 | 0.0116 (11) | 0.0175 (16) | 0.0332 (17) | 0.0034 (11) | −0.0046 (11) | −0.0050 (15) |
N1 | 0.0119 (12) | 0.0108 (17) | 0.0157 (17) | 0.0004 (11) | 0.0002 (11) | −0.0010 (14) |
C1 | 0.0133 (14) | 0.011 (2) | 0.0141 (19) | −0.0028 (14) | 0.0008 (13) | 0.0007 (17) |
C2 | 0.0163 (15) | 0.009 (2) | 0.016 (2) | −0.0020 (13) | 0.0008 (14) | −0.0042 (16) |
C3 | 0.0148 (15) | 0.010 (2) | 0.014 (2) | 0.0003 (13) | 0.0032 (13) | 0.0028 (16) |
C4 | 0.0128 (15) | 0.014 (2) | 0.022 (2) | 0.0014 (14) | −0.0013 (14) | −0.0012 (18) |
C5 | 0.0155 (15) | 0.014 (2) | 0.0172 (19) | 0.0002 (14) | −0.0013 (14) | −0.0052 (17) |
C6 | 0.0127 (15) | 0.013 (2) | 0.020 (2) | −0.0002 (14) | −0.0018 (14) | 0.0009 (19) |
C7 | 0.0158 (16) | 0.017 (2) | 0.020 (2) | 0.0030 (15) | 0.0016 (14) | −0.0009 (19) |
Cu1—O6 | 1.931 (2) | O6—H6A | 0.824 (18) |
Cu1—O2 | 1.963 (2) | O6—H6B | 0.815 (18) |
Cu1—O3i | 1.964 (2) | N1—C5 | 1.348 (4) |
Cu1—N1 | 1.980 (3) | N1—C1 | 1.353 (4) |
Cu1—O5 | 2.339 (3) | C1—C2 | 1.383 (4) |
O1—C6 | 1.219 (4) | C1—C6 | 1.522 (4) |
O1W—H1W | 0.8563 | C2—C3 | 1.392 (4) |
O2W—H2W | 0.8920 | C2—H2 | 0.9500 |
O2—C6 | 1.285 (4) | C3—C4 | 1.382 (5) |
O3—C7 | 1.273 (4) | C3—C7 | 1.521 (4) |
O4—C7 | 1.234 (4) | C4—C5 | 1.378 (4) |
O5—H5A | 0.831 (18) | C4—H4 | 0.9500 |
O5—H5B | 0.822 (18) | C5—H5 | 0.9500 |
O6—Cu1—O2 | 90.46 (10) | N1—C1—C2 | 122.8 (3) |
O6—Cu1—O3i | 95.30 (11) | N1—C1—C6 | 113.0 (3) |
O2—Cu1—O3i | 169.33 (10) | C2—C1—C6 | 124.1 (3) |
O6—Cu1—N1 | 171.84 (11) | C1—C2—C3 | 118.3 (3) |
O2—Cu1—N1 | 81.58 (10) | C1—C2—H2 | 120.8 |
O3i—Cu1—N1 | 92.30 (10) | C3—C2—H2 | 120.8 |
O6—Cu1—O5 | 87.36 (11) | C4—C3—C2 | 119.0 (3) |
O2—Cu1—O5 | 92.78 (9) | C4—C3—C7 | 117.8 (3) |
O3i—Cu1—O5 | 96.48 (10) | C2—C3—C7 | 123.2 (3) |
N1—Cu1—O5 | 94.86 (11) | C5—C4—C3 | 119.6 (3) |
C6—O2—Cu1 | 116.7 (2) | C5—C4—H4 | 120.2 |
C7—O3—Cu1ii | 125.9 (2) | C3—C4—H4 | 120.2 |
Cu1—O5—H5A | 115 (3) | N1—C5—C4 | 122.1 (3) |
Cu1—O5—H5B | 120 (3) | N1—C5—H5 | 118.9 |
H5A—O5—H5B | 83 (3) | C4—C5—H5 | 118.9 |
Cu1—O6—H6A | 109 (3) | O1—C6—O2 | 125.8 (3) |
Cu1—O6—H6B | 119 (3) | O1—C6—C1 | 120.0 (3) |
H6A—O6—H6B | 87 (3) | O2—C6—C1 | 114.2 (3) |
C5—N1—C1 | 118.1 (3) | O4—C7—O3 | 127.6 (3) |
C5—N1—Cu1 | 127.7 (2) | O4—C7—C3 | 116.4 (3) |
C1—N1—Cu1 | 114.1 (2) | O3—C7—C3 | 116.0 (3) |
O6—Cu1—O2—C6 | 178.6 (3) | C2—C3—C4—C5 | 0.4 (5) |
O3i—Cu1—O2—C6 | −58.7 (7) | C7—C3—C4—C5 | 179.7 (3) |
N1—Cu1—O2—C6 | −3.2 (3) | C1—N1—C5—C4 | −0.1 (5) |
O5—Cu1—O2—C6 | 91.2 (3) | Cu1—N1—C5—C4 | 177.0 (3) |
O2—Cu1—N1—C5 | −176.9 (3) | C3—C4—C5—N1 | 0.3 (6) |
O3i—Cu1—N1—C5 | −5.7 (3) | Cu1—O2—C6—O1 | −174.1 (3) |
O5—Cu1—N1—C5 | 91.1 (3) | Cu1—O2—C6—C1 | 5.1 (4) |
O2—Cu1—N1—C1 | 0.3 (2) | N1—C1—C6—O1 | 174.5 (3) |
O3i—Cu1—N1—C1 | 171.5 (2) | C2—C1—C6—O1 | −4.9 (6) |
O5—Cu1—N1—C1 | −91.7 (2) | N1—C1—C6—O2 | −4.8 (5) |
C5—N1—C1—C2 | −0.9 (5) | C2—C1—C6—O2 | 175.8 (3) |
Cu1—N1—C1—C2 | −178.4 (3) | Cu1ii—O3—C7—O4 | −5.5 (6) |
C5—N1—C1—C6 | 179.7 (3) | Cu1ii—O3—C7—C3 | 174.6 (2) |
Cu1—N1—C1—C6 | 2.2 (4) | C4—C3—C7—O4 | 20.4 (5) |
N1—C1—C2—C3 | 1.6 (5) | C2—C3—C7—O4 | −160.3 (4) |
C6—C1—C2—C3 | −179.1 (3) | C4—C3—C7—O3 | −159.7 (3) |
C1—C2—C3—C4 | −1.3 (5) | C2—C3—C7—O3 | 19.6 (5) |
C1—C2—C3—C7 | 179.4 (3) |
Symmetry codes: (i) −x+1, y−1/2, z−1/2; (ii) −x+1, y+1/2, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···O2iii | 0.86 | 2.65 | 3.145 (5) | 117 |
O2W—H2W···O1iv | 0.89 | 2.02 | 2.904 (17) | 168 |
O5—H5A···O1v | 0.83 (2) | 1.95 (2) | 2.765 (4) | 168 (4) |
O5—H5B···O1W | 0.82 (2) | 2.12 (2) | 2.914 (4) | 162 (4) |
O6—H6A···O4i | 0.82 (2) | 1.89 (2) | 2.618 (4) | 146 (4) |
O6—H6B···O2vi | 0.82 (2) | 2.02 (2) | 2.719 (3) | 144 (4) |
Symmetry codes: (i) −x+1, y−1/2, z−1/2; (iii) x, y, z−1; (iv) −x+3/2, y−1/2, −z+1/2; (v) x, −y+3/2, −z+1/2; (vi) −x+3/2, −y+1, z. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C7H3NO4)(H2O)2]·0.625H2O |
Mr | 275.94 |
Crystal system, space group | Orthorhombic, Pnna |
Temperature (K) | 173 |
a, b, c (Å) | 20.324 (4), 12.057 (2), 7.4706 (16) |
V (Å3) | 1830.7 (6) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 2.41 |
Crystal size (mm) | 0.25 × 0.25 × 0.20 |
Data collection | |
Diffractometer | Bruker APEXII diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.520, 0.618 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7418, 2152, 1517 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.666 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.099, 1.09 |
No. of reflections | 2152 |
No. of parameters | 158 |
No. of restraints | 21 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.68, −0.69 |
Computer programs: COSMO (Bruker, 2006), APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), CrystalMaker (Palmer, 2005).
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···O2i | 0.86 | 2.65 | 3.145 (5) | 117.1 |
O2W—H2W···O1ii | 0.89 | 2.02 | 2.904 (17) | 168.4 |
O5—H5A···O1iii | 0.831 (18) | 1.95 (2) | 2.765 (4) | 168 (4) |
O5—H5B···O1W | 0.822 (18) | 2.12 (2) | 2.914 (4) | 162 (4) |
O6—H6A···O4iv | 0.824 (18) | 1.89 (2) | 2.618 (4) | 146 (4) |
O6—H6B···O2v | 0.815 (18) | 2.02 (2) | 2.719 (3) | 144 (4) |
Symmetry codes: (i) x, y, z−1; (ii) −x+3/2, y−1/2, −z+1/2; (iii) x, −y+3/2, −z+1/2; (iv) −x+1, y−1/2, z−1/2; (v) −x+3/2, −y+1, z. |
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- If you have already subscribed, you may need to register
Coordination polymers containing both pyridinedicarboxylate and organodiimine ligands have displayed intriguing structural morphologies and physical properties (Zhou et al., 2006). The title compound was prepared during an attempt to prepare a divalent copper coordination polymer containing both 2,4-pyridinedicarboxylate (PDC) and N,N'-di(4-pyridylmethyl)piperazine (bpmp) ligands.
The asymmetric unit of the title compound (Fig. 1) consists of a CuII ion, two aqua ligands, a single ligated PDC dianion, and waters molecule of crystallization located on crystallographic 2-fold axes (with 50% and 12.5% occupancies, respectively). The CuII ion manifests a Jahn–Teller distorted square pyramidal coordination, with cis aqua ligands occupying the axial position and one of the basal positions. The remainder of the basal coordination sites are occupied by an O atom from one PDC ligand, and an N donor and O donor from a second PDC ligand. The two O donors from the PDC ligands, from 2- and 4-carboxylate positions, are situated trans to each other.
Neighboring CuII ions are conjoined through exobidentate PDC ligands to form one-dimensional [Cu(H2O)2(PDC)]n chains that propagate along the [011] crystal direction (Fig. 2), with a Cu—Cu distance measuring 8.883 (3) Å. These are aggregated into double chain motifs (Fig. 3) through long-range Cu—O interactions (2.841 (2) Å).
Double [Cu(H2O)2(PDC)]n chains connect into pseudo layers, coincident with the bc crystal planes through hydrogen bonding between aqua ligands and unligated carboxylate O atoms. These subsequently stack into the pseudo three-dimensional crystal structure of the title compound through additional hydrogen bonding patterns involving the water molecules of crystallization (Fig. 4).