In the centrosymmetric title compound, [Cu(C
10H
7N
2O
2)
2(H
2O)
2], the Cu
II ion occupies an inversion centre and exhibits a distorted octahedral geometry. The phenyl and pyrazole rings of the ligand are twisted by an angle of 11.36 (8)°. In the crystal structure, molecules are linked into a two-dimensional network parallel to the (010) plane by O—H

O and N—H

O hydrogen bonds.
Supporting information
CCDC reference: 677455
Key indicators
- Single-crystal X-ray study
- T = 292 K
- Mean
(C-C) = 0.004 Å
- R factor = 0.037
- wR factor = 0.084
- Data-to-parameter ratio = 15.0
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Cu1 - O3 .. 5.16 su
PLAT731_ALERT_1_C Bond Calc 0.83(3), Rep 0.827(10) ...... 3.00 su-Ra
O3 -H1W 1.555 1.555
PLAT731_ALERT_1_C Bond Calc 0.83(3), Rep 0.825(10) ...... 3.00 su-Ra
O3 -H2W 1.555 1.555
Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 3
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
3 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
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
5-Phenyl-1H-pyrazole-3-carboxylic acid was synthesized according to the
reported procedure (Gharbaoui et al., 2007;Crane et al., 1999).
5-Phenyl-1H-pyrazole-3-carboxylic acid (1.0 g, 5.3 mmol) and
Cu(OAc)2.2H2O (0.75 g, 2.7 mmol) were heated in H2O (200 ml) for 4 h
with stirring. The resulting precipitate was filtered off to obtain the title
compound (1.0 g, 80%). Single crystals suitable for X-ray diffraction were
obtained by recrystallization from dimethylformamide-water (1:1
v/v) solution.
The water H atoms were located and isotropically refined, with the O—H and
H···H distances restrained to 0.84 (1) and 1.37 (2) Å, respectively. The
remaining H atoms were positioned geometrically (N—H = 0.86 Å and C—H =
0.93 Å) and constrained to ride on their parent atoms, with Uiso(H)
= 1.2Ueq(C).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
Diaquabis(5-phenyl-1
H-pyrazole-3-carboxylato)copper(II)
top
Crystal data top
[Cu(C10H7N2O2)2(H2O)2] | F(000) = 486 |
Mr = 473.92 | Dx = 1.599 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2772 reflections |
a = 5.0443 (6) Å | θ = 2.5–26.6° |
b = 32.161 (4) Å | µ = 1.16 mm−1 |
c = 6.3234 (8) Å | T = 292 K |
β = 106.293 (1)° | Block, blue |
V = 984.6 (2) Å3 | 0.35 × 0.25 × 0.17 mm |
Z = 2 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2254 independent reflections |
Radiation source: fine-focus sealed tube | 1907 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
ϕ and ω scans | θmax = 27.5°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −6→6 |
Tmin = 0.690, Tmax = 0.829 | k = −41→39 |
8611 measured reflections | l = −8→8 |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.084 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0302P)2 + 0.72P] where P = (Fo2 + 2Fc2)/3 |
2254 reflections | (Δ/σ)max = 0.001 |
150 parameters | Δρmax = 0.34 e Å−3 |
3 restraints | Δρmin = −0.32 e Å−3 |
Crystal data top
[Cu(C10H7N2O2)2(H2O)2] | V = 984.6 (2) Å3 |
Mr = 473.92 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 5.0443 (6) Å | µ = 1.16 mm−1 |
b = 32.161 (4) Å | T = 292 K |
c = 6.3234 (8) Å | 0.35 × 0.25 × 0.17 mm |
β = 106.293 (1)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2254 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1907 reflections with I > 2σ(I) |
Tmin = 0.690, Tmax = 0.829 | Rint = 0.027 |
8611 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.037 | 3 restraints |
wR(F2) = 0.084 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.34 e Å−3 |
2254 reflections | Δρmin = −0.32 e Å−3 |
150 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 | |
Cu1 | 0.5000 | 0.0000 | 0.0000 | 0.03166 (13) | |
O1 | 0.3462 (3) | 0.01796 (5) | 0.2440 (2) | 0.0325 (3) | |
O2 | 0.3301 (4) | 0.07235 (5) | 0.4604 (3) | 0.0404 (4) | |
O3 | 0.0850 (4) | 0.03336 (6) | −0.2706 (3) | 0.0380 (4) | |
N1 | 0.6670 (4) | 0.05536 (5) | 0.0513 (3) | 0.0294 (4) | |
N2 | 0.8212 (4) | 0.08034 (5) | −0.0348 (3) | 0.0301 (4) | |
H2 | 0.8956 | 0.0730 | −0.1359 | 0.036* | |
C1 | 0.4084 (4) | 0.05525 (7) | 0.3144 (3) | 0.0288 (5) | |
C2 | 0.5895 (4) | 0.07783 (7) | 0.2015 (3) | 0.0277 (4) | |
C3 | 0.6964 (4) | 0.11779 (7) | 0.2111 (4) | 0.0302 (5) | |
H3 | 0.6732 | 0.1395 | 0.3017 | 0.036* | |
C4 | 0.8454 (4) | 0.11852 (6) | 0.0569 (4) | 0.0282 (4) | |
C5 | 1.0091 (5) | 0.15138 (7) | −0.0085 (4) | 0.0328 (5) | |
C6 | 1.0740 (6) | 0.18727 (8) | 0.1155 (5) | 0.0473 (6) | |
H6 | 1.0067 | 0.1911 | 0.2368 | 0.057* | |
C7 | 1.2389 (7) | 0.21770 (9) | 0.0605 (6) | 0.0641 (9) | |
H7 | 1.2821 | 0.2417 | 0.1454 | 0.077* | |
C8 | 1.3376 (6) | 0.21240 (9) | −0.1183 (6) | 0.0642 (9) | |
H8 | 1.4482 | 0.2328 | −0.1543 | 0.077* | |
C9 | 1.2744 (6) | 0.17720 (10) | −0.2448 (5) | 0.0565 (8) | |
H9 | 1.3419 | 0.1738 | −0.3663 | 0.068* | |
C10 | 1.1097 (5) | 0.14664 (8) | −0.1918 (4) | 0.0438 (6) | |
H10 | 1.0662 | 0.1229 | −0.2786 | 0.053* | |
H1W | 0.138 (6) | 0.0417 (9) | −0.376 (4) | 0.069 (10)* | |
H2W | −0.041 (5) | 0.0163 (8) | −0.312 (5) | 0.075 (11)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0386 (2) | 0.0297 (2) | 0.0341 (2) | −0.00911 (17) | 0.02227 (17) | −0.00583 (17) |
O1 | 0.0365 (9) | 0.0338 (8) | 0.0339 (8) | −0.0071 (7) | 0.0207 (7) | −0.0019 (7) |
O2 | 0.0523 (11) | 0.0407 (9) | 0.0388 (9) | −0.0031 (8) | 0.0301 (8) | −0.0036 (7) |
O3 | 0.0416 (10) | 0.0443 (10) | 0.0361 (9) | −0.0093 (8) | 0.0239 (8) | −0.0051 (8) |
N1 | 0.0332 (10) | 0.0304 (10) | 0.0301 (9) | −0.0060 (7) | 0.0177 (8) | −0.0028 (7) |
N2 | 0.0334 (10) | 0.0325 (10) | 0.0311 (10) | −0.0064 (8) | 0.0203 (8) | −0.0029 (8) |
C1 | 0.0276 (11) | 0.0349 (12) | 0.0264 (11) | 0.0006 (9) | 0.0115 (9) | 0.0032 (9) |
C2 | 0.0286 (11) | 0.0311 (11) | 0.0260 (10) | 0.0004 (8) | 0.0119 (9) | −0.0003 (8) |
C3 | 0.0315 (11) | 0.0298 (11) | 0.0320 (12) | 0.0002 (9) | 0.0133 (9) | −0.0033 (9) |
C4 | 0.0282 (10) | 0.0277 (11) | 0.0296 (11) | 0.0005 (8) | 0.0094 (9) | 0.0016 (9) |
C5 | 0.0285 (11) | 0.0303 (11) | 0.0402 (12) | 0.0008 (9) | 0.0108 (9) | 0.0071 (10) |
C6 | 0.0478 (15) | 0.0366 (14) | 0.0641 (18) | −0.0063 (11) | 0.0264 (13) | −0.0051 (12) |
C7 | 0.0610 (19) | 0.0357 (15) | 0.104 (3) | −0.0135 (13) | 0.0363 (19) | −0.0046 (15) |
C8 | 0.0521 (18) | 0.0476 (17) | 0.101 (3) | −0.0060 (14) | 0.0345 (18) | 0.0248 (17) |
C9 | 0.0530 (17) | 0.0655 (19) | 0.0588 (18) | −0.0018 (14) | 0.0287 (14) | 0.0232 (15) |
C10 | 0.0481 (15) | 0.0462 (15) | 0.0411 (14) | −0.0060 (11) | 0.0189 (12) | 0.0055 (11) |
Geometric parameters (Å, º) top
Cu1—N1 | 1.9572 (17) | C3—C4 | 1.388 (3) |
Cu1—N1i | 1.9573 (17) | C3—H3 | 0.93 |
Cu1—O1i | 1.9968 (14) | C4—C5 | 1.470 (3) |
Cu1—O1 | 1.9968 (14) | C5—C6 | 1.382 (3) |
Cu1—O3 | 2.5400 (19) | C5—C10 | 1.398 (3) |
O1—C1 | 1.287 (3) | C6—C7 | 1.390 (4) |
O2—C1 | 1.231 (3) | C6—H6 | 0.93 |
O3—H1W | 0.827 (10) | C7—C8 | 1.368 (5) |
O3—H2W | 0.825 (10) | C7—H7 | 0.93 |
N1—C2 | 1.336 (3) | C8—C9 | 1.371 (5) |
N1—N2 | 1.336 (2) | C8—H8 | 0.93 |
N2—C4 | 1.349 (3) | C9—C10 | 1.387 (3) |
N2—H2 | 0.86 | C9—H9 | 0.93 |
C1—C2 | 1.496 (3) | C10—H10 | 0.93 |
C2—C3 | 1.388 (3) | | |
| | | |
N1—Cu1—N1i | 180 | C3—C2—C1 | 135.23 (19) |
N1—Cu1—O1i | 98.56 (6) | C4—C3—C2 | 105.36 (19) |
N1i—Cu1—O1i | 81.44 (6) | C4—C3—H3 | 127.3 |
N1—Cu1—O1 | 81.44 (6) | C2—C3—H3 | 127.3 |
N1i—Cu1—O1 | 98.56 (6) | N2—C4—C3 | 106.56 (18) |
O1i—Cu1—O1 | 180 | N2—C4—C5 | 121.60 (19) |
N1—Cu1—O3 | 87.85 (7) | C3—C4—C5 | 131.8 (2) |
N1i—Cu1—O3 | 92.15 (7) | C6—C5—C10 | 118.6 (2) |
O1i—Cu1—O3 | 91.56 (6) | C6—C5—C4 | 120.2 (2) |
O1—Cu1—O3 | 88.44 (6) | C10—C5—C4 | 121.2 (2) |
C1—O1—Cu1 | 115.29 (13) | C5—C6—C7 | 120.6 (3) |
Cu1—O3—H1W | 107 (2) | C5—C6—H6 | 119.7 |
Cu1—O3—H2W | 110 (2) | C7—C6—H6 | 119.7 |
H1W—O3—H2W | 111 (2) | C8—C7—C6 | 120.1 (3) |
C2—N1—N2 | 106.51 (17) | C8—C7—H7 | 120.0 |
C2—N1—Cu1 | 114.33 (14) | C6—C7—H7 | 120.0 |
N2—N1—Cu1 | 138.77 (14) | C7—C8—C9 | 120.4 (3) |
N1—N2—C4 | 111.41 (17) | C7—C8—H8 | 119.8 |
N1—N2—H2 | 124.3 | C9—C8—H8 | 119.8 |
C4—N2—H2 | 124.3 | C8—C9—C10 | 120.1 (3) |
O2—C1—O1 | 125.27 (19) | C8—C9—H9 | 120.0 |
O2—C1—C2 | 120.58 (19) | C10—C9—H9 | 120.0 |
O1—C1—C2 | 114.14 (18) | C9—C10—C5 | 120.3 (3) |
N1—C2—C3 | 110.16 (18) | C9—C10—H10 | 119.9 |
N1—C2—C1 | 114.60 (18) | C5—C10—H10 | 119.9 |
| | | |
N1—Cu1—O1—C1 | 2.75 (15) | O1—C1—C2—C3 | 176.1 (2) |
N1i—Cu1—O1—C1 | −177.25 (15) | N1—C2—C3—C4 | 0.0 (2) |
O3—Cu1—O1—C1 | −85.31 (15) | C1—C2—C3—C4 | −178.6 (2) |
O1i—Cu1—N1—C2 | 175.94 (15) | N1—N2—C4—C3 | −0.1 (2) |
O1—Cu1—N1—C2 | −4.06 (15) | N1—N2—C4—C5 | 179.06 (19) |
O3—Cu1—N1—C2 | 84.69 (16) | C2—C3—C4—N2 | 0.1 (2) |
O1i—Cu1—N1—N2 | 4.4 (2) | C2—C3—C4—C5 | −179.0 (2) |
O1—Cu1—N1—N2 | −175.6 (2) | N2—C4—C5—C6 | −167.6 (2) |
O3—Cu1—N1—N2 | −86.8 (2) | C3—C4—C5—C6 | 11.3 (4) |
C2—N1—N2—C4 | 0.1 (2) | N2—C4—C5—C10 | 10.3 (3) |
Cu1—N1—N2—C4 | 172.02 (17) | C3—C4—C5—C10 | −170.8 (2) |
Cu1—O1—C1—O2 | 178.61 (18) | C10—C5—C6—C7 | −0.8 (4) |
Cu1—O1—C1—C2 | −1.0 (2) | C4—C5—C6—C7 | 177.2 (3) |
N2—N1—C2—C3 | 0.0 (2) | C5—C6—C7—C8 | 0.3 (5) |
Cu1—N1—C2—C3 | −174.22 (15) | C6—C7—C8—C9 | 0.2 (5) |
N2—N1—C2—C1 | 178.84 (17) | C7—C8—C9—C10 | −0.1 (5) |
Cu1—N1—C2—C1 | 4.7 (2) | C8—C9—C10—C5 | −0.5 (4) |
O2—C1—C2—N1 | 178.0 (2) | C6—C5—C10—C9 | 0.9 (4) |
O1—C1—C2—N1 | −2.4 (3) | C4—C5—C10—C9 | −177.1 (2) |
O2—C1—C2—C3 | −3.5 (4) | | |
Symmetry code: (i) −x+1, −y, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H1W···O2ii | 0.83 (3) | 1.88 (3) | 2.679 (3) | 161 (3) |
N2—H2···O3iii | 0.86 | 1.93 | 2.719 (3) | 152 |
O3—H2W···O1iv | 0.83 (3) | 2.04 (3) | 2.773 (3) | 149 (3) |
Symmetry codes: (ii) x, y, z−1; (iii) x+1, y, z; (iv) −x, −y, −z. |
Experimental details
Crystal data |
Chemical formula | [Cu(C10H7N2O2)2(H2O)2] |
Mr | 473.92 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 292 |
a, b, c (Å) | 5.0443 (6), 32.161 (4), 6.3234 (8) |
β (°) | 106.293 (1) |
V (Å3) | 984.6 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.16 |
Crystal size (mm) | 0.35 × 0.25 × 0.17 |
|
Data collection |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.690, 0.829 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8611, 2254, 1907 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.084, 1.08 |
No. of reflections | 2254 |
No. of parameters | 150 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.34, −0.32 |
Selected geometric parameters (Å, º) topCu1—N1 | 1.9572 (17) | Cu1—O3 | 2.5400 (19) |
Cu1—O1 | 1.9968 (14) | | |
| | | |
N1—Cu1—N1i | 180 | N1—Cu1—O3 | 87.85 (7) |
N1—Cu1—O1i | 98.56 (6) | N1i—Cu1—O3 | 92.15 (7) |
N1—Cu1—O1 | 81.44 (6) | O1i—Cu1—O3 | 91.56 (6) |
O1i—Cu1—O1 | 180 | O1—Cu1—O3 | 88.44 (6) |
Symmetry code: (i) −x+1, −y, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H1W···O2ii | 0.83 (3) | 1.88 (3) | 2.679 (3) | 161 (3) |
N2—H2···O3iii | 0.86 | 1.93 | 2.719 (3) | 152 |
O3—H2W···O1iv | 0.83 (3) | 2.04 (3) | 2.773 (3) | 149 (3) |
Symmetry codes: (ii) x, y, z−1; (iii) x+1, y, z; (iv) −x, −y, −z. |
Nicotinic acid as a hypolipidemic agent appears to have good potential to increase HDL cholesterol levels to a greater extent (Knopp, 1999). However, it has severe skin flushing side effect. In the search for novel agonists for nicotinic acid receptor, substituted pyrazole-3-carboxylic acids were found have substantial affinity for cloned G protein-coupled nicotinic acid receptor (van Herk et al., 2003). We report here the crystal structure of the title CuII complex with 5-phenyl-1H-pyrazole-3-carboxylic acid.
The asymmetric unit contains one-half of a formula unit (Fig. 1). The CuII ion occupies an inversion centre and exhibits a distorted octahedral geometry. The phenyl (C5—C10) and pyrazole (N1/N2/C2/C3/C4) rings form a dihedral angle of 11.36 (8)°. The dihedral angle between the Cu1/O1/C1/C2/N1 and N1/N2/C2/C3/C4 planes is 3.8 (1)°.
The molecules are linked into a two-dimensional network parallel to the (0 1 0) plane by O—H···O and N—H···O hydrogen bonds (Table 2).