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Acta Cryst. (2008). E64, m1532    [ doi:10.1107/S160053680803626X ]

Tetrakis(3,5-dimethyl-1H-pyrazole-[kappa]N2)(nitrato-[kappa]2O,O')cadmium(II) nitrate

S.-Q. Wang and F.-F. Jian

Abstract top

The title compound, [Cd(NO3)(C5H8N2)4]NO3, was prepared by reaction of cadmium nitrate and 3,5-dimethylpyrazole in ethanol solution. The Cd atom adopts a distorted cis-CdO2N4 octahedral geometry involving four dimethylpyrazole molecules and one bidentate nitrate anion. The molecular structure and packing are stabilized by N-H...O and C-H...O inter- and intramolecular hydrogen-bonding interactions.

Comment top

It is also known that most of the Cd(II) in biological systems is not in the form of free Cd(II) ions, but is coordinated by the abundance of biological ligands (Dressing et al., 1982). Therefore the coordination chemistry of Cd(II) with ligands is of great interest. In this paper, we reported the synthesis and the crystal structure of tri(3,5-dimenthyl pyrazolyl)cadmium(II) nitrate (I).

In the molecule of (I) (Fig. 1), each Cd atoms is coordinated by four nitrogen atoms from four 3,5-dimethyl pyrazoles respectively and two oxygen atoms from nitrate anion. All the bond length and angle are in the normal range. Another nitrate anion exists in the crystal lattice.

The molecular structure and packing are stabilized by the N—H···O and C—H···O inter and intraintermolecular hydrogen-bonding intercations.

Related literature top

For background on the coordination chemistry

of Cd(II) in biological systems, see: Dressing et al. (1982). For related literature, see: Addison et al. (1984).

Experimental top

Solid 3,5-dimethyl pyrazole 0.96 g (0.01 mol) and cadmium nitrate 0.77 g (0.0025 mol) were added in 50 ml anhydrous alcohol under stirring. The mixture was refluxed for 3.5 h. The colourless solution was filtered and the filtrate was left to stand undisturbed. Upon slow evaporation at room temperature, a colourless crystalline solid appeared three days later and was separated by filtration.

Refinement top

H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H distances of 0.93 and 0.96 Å, and with Uiso(H) = 1.2 or 1.5Ueq of the parent atoms.

Computing details top

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: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure and atom-labeling scheme for (I), with displacement ellipsoids drawn at the 30% probability level.
Tetrakis(3,5-dimethyl-1H-pyrazole-κN2)(nitrato-κ2O,O')cadmium(II) nitrate top
Crystal data top
[Cd(NO3)(C5H8N2)4]NO3Z = 2
Mr = 620.97F(000) = 636
Triclinic, P1Dx = 1.509 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.1790 (18) ÅCell parameters from 6067 reflections
b = 11.353 (2) Åθ = 2.3–28.2°
c = 13.669 (3) ŵ = 0.85 mm−1
α = 94.79 (3)°T = 293 K
β = 105.61 (3)°Block, colourless
γ = 90.68 (3)°0.25 × 0.20 × 0.18 mm
V = 1366.2 (5) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer		4677 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.016
graphiteθmax = 25.5°, θmin = 2.3°
φ and ω scansh = −10→11
7482 measured reflectionsk = −13→13
5035 independent reflectionsl = −16→11
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.137H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0885P)2 + 1.8569P]
where P = (Fo2 + 2Fc2)/3
5035 reflections(Δ/σ)max < 0.001
319 parametersΔρmax = 1.66 e Å−3
1 restraintΔρmin = −0.87 e Å−3
Crystal data top
[Cd(NO3)(C5H8N2)4]NO3γ = 90.68 (3)°
Mr = 620.97V = 1366.2 (5) Å3
Triclinic, P1Z = 2
a = 9.1790 (18) ÅMo Kα radiation
b = 11.353 (2) ŵ = 0.85 mm−1
c = 13.669 (3) ÅT = 293 K
α = 94.79 (3)°0.25 × 0.20 × 0.18 mm
β = 105.61 (3)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		4677 reflections with I > 2σ(I)
7482 measured reflectionsRint = 0.016
5035 independent reflectionsθmax = 25.5°
Refinement top
R[F2 > 2σ(F2)] = 0.047H-atom parameters constrained
wR(F2) = 0.137Δρmax = 1.66 e Å−3
S = 1.06Δρmin = −0.87 e Å−3
5035 reflectionsAbsolute structure: ?
319 parametersFlack parameter: ?
1 restraintRogers parameter: ?
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
xyzUiso*/Ueq
Cd10.13316 (3)0.80806 (2)0.33031 (2)0.03976 (14)
O40.3597 (4)0.8966 (3)0.4877 (3)0.0559 (6)
O50.1497 (4)0.9850 (3)0.4459 (3)0.0538 (6)
O60.3174 (5)1.0465 (4)0.5840 (3)0.0679 (9)
N20.2219 (5)0.6381 (3)0.2677 (3)0.0492 (7)
N30.1348 (5)0.5493 (4)0.2059 (4)0.0600 (9)
H4A0.03770.54440.19180.072*
N4−0.2135 (4)0.7666 (4)0.1863 (3)0.0497 (7)
H5A−0.20400.69190.19090.060*
N5−0.1073 (4)0.8506 (3)0.2393 (3)0.0451 (6)
N6−0.0798 (5)0.7578 (3)0.4743 (3)0.0491 (7)
H7A−0.14260.80450.43970.059*
N70.0527 (5)0.7270 (3)0.4544 (3)0.0495 (6)
N80.2600 (4)0.9168 (3)0.2410 (3)0.0461 (6)
N90.3644 (4)1.0038 (3)0.2868 (3)0.0448 (7)
H10A0.40811.01200.35120.054*
N100.2779 (4)0.9758 (3)0.5082 (3)0.0464 (7)
C10.1461 (12)0.3654 (6)0.0977 (7)0.112 (3)
H1A0.22290.31870.07960.167*
H1B0.08000.39250.03730.167*
H1C0.08870.31830.13030.167*
C20.2191 (8)0.4702 (5)0.1697 (5)0.0705 (13)
C30.3657 (8)0.5085 (5)0.2081 (5)0.0731 (14)
H3A0.45030.47150.19670.088*
C40.3647 (6)0.6135 (4)0.2678 (4)0.0526 (9)
C50.4955 (6)0.6919 (6)0.3272 (5)0.0731 (16)
H5B0.45940.75720.36220.110*
H5C0.54800.72100.28160.110*
H5D0.56320.64780.37600.110*
C6−0.4658 (7)0.7409 (7)0.0621 (6)0.0848 (19)
H6A−0.54060.79090.02490.127*
H6B−0.50900.69670.10500.127*
H6C−0.43270.68720.01510.127*
C7−0.3346 (5)0.8148 (5)0.1261 (4)0.0537 (9)
C8−0.3053 (6)0.9339 (5)0.1395 (4)0.0543 (9)
H8A−0.36820.99120.10790.065*
C9−0.1645 (5)0.9538 (4)0.2091 (3)0.0464 (8)
C10−0.0833 (7)1.0697 (5)0.2516 (5)0.0689 (14)
H10B0.01281.05590.29790.103*
H10C−0.14291.11600.28730.103*
H10D−0.06761.11160.19690.103*
C11−0.2363 (8)0.7287 (5)0.5941 (5)0.0694 (13)
H11A−0.30110.78120.55200.104*
H11B−0.20420.76410.66300.104*
H11C−0.29060.65530.59200.104*
C12−0.1004 (6)0.7059 (4)0.5551 (3)0.0509 (8)
C130.0213 (7)0.6372 (4)0.5865 (4)0.0572 (9)
H13A0.03830.58920.64010.069*
C140.1155 (6)0.6525 (4)0.5233 (3)0.0475 (7)
C150.2634 (6)0.5992 (5)0.5268 (5)0.0657 (12)
H15A0.30060.62510.47260.099*
H15B0.25100.51450.51890.099*
H15C0.33450.62340.59120.099*
C160.1073 (7)0.8553 (6)0.0647 (4)0.0666 (14)
H16A0.07270.79370.09790.100*
H16B0.15470.82080.01500.100*
H16C0.02280.89980.03140.100*
C170.2195 (5)0.9358 (4)0.1424 (3)0.0462 (8)
C180.2983 (6)1.0353 (4)0.1273 (4)0.0528 (9)
H18A0.28911.06790.06580.063*
C190.3919 (5)1.0756 (4)0.2202 (4)0.0459 (8)
C200.5065 (7)1.1759 (5)0.2532 (5)0.0652 (13)
H20A0.55151.17810.32540.098*
H20B0.45781.24900.23730.098*
H20C0.58351.16500.21800.098*
N10.7643 (6)0.4506 (5)0.1574 (5)0.0806 (16)
O10.8224 (7)0.5308 (6)0.2225 (5)0.1116 (18)*
O20.7028 (11)0.3695 (9)0.1665 (7)0.164 (3)*
O30.7830 (17)0.4749 (13)0.0795 (12)0.247 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.0405 (2)0.0371 (2)0.0402 (2)−0.00263 (12)0.00835 (13)0.00418 (12)
O40.0536 (12)0.0644 (18)0.0442 (11)0.0005 (9)0.0059 (9)−0.0028 (10)
O50.0618 (15)0.0429 (11)0.0496 (14)0.0006 (11)0.0051 (9)−0.0030 (9)
O60.079 (2)0.068 (2)0.0463 (17)−0.0047 (17)0.0045 (13)−0.0119 (13)
N20.0505 (12)0.0401 (10)0.0565 (19)−0.0024 (10)0.0156 (13)−0.0010 (10)
N30.0675 (15)0.0397 (16)0.070 (3)−0.0119 (14)0.0175 (19)−0.0051 (14)
N40.0429 (13)0.0510 (12)0.051 (2)−0.0062 (11)0.0065 (11)0.0048 (14)
N50.0432 (9)0.0431 (12)0.0471 (15)−0.0030 (8)0.0076 (8)0.0091 (11)
N60.0595 (18)0.0430 (19)0.0497 (19)0.0036 (14)0.0214 (15)0.0103 (13)
N70.0581 (15)0.0460 (15)0.0482 (16)0.0079 (11)0.0175 (12)0.0144 (12)
N80.0434 (14)0.0460 (14)0.0456 (10)−0.0075 (11)0.0050 (10)0.0097 (11)
N90.0458 (18)0.0451 (18)0.0430 (12)−0.0069 (11)0.0113 (12)0.0045 (12)
N100.0557 (16)0.0430 (17)0.0392 (15)−0.0088 (11)0.0116 (10)0.0023 (9)
C10.148 (6)0.059 (4)0.116 (6)−0.019 (4)0.031 (5)−0.038 (3)
C20.093 (2)0.044 (2)0.072 (3)−0.0035 (19)0.022 (3)−0.0101 (18)
C30.0842 (19)0.053 (3)0.088 (4)0.004 (2)0.040 (3)−0.012 (2)
C40.0555 (13)0.045 (2)0.059 (3)0.0029 (12)0.0205 (19)0.0004 (15)
C50.0479 (17)0.077 (3)0.086 (4)0.002 (2)0.010 (3)−0.013 (3)
C60.054 (3)0.100 (3)0.082 (4)−0.009 (2)−0.010 (2)−0.004 (3)
C70.0426 (17)0.0707 (17)0.045 (2)0.0005 (13)0.0080 (12)0.0024 (18)
C80.0503 (19)0.0663 (15)0.045 (2)0.0131 (14)0.0091 (14)0.0079 (18)
C90.0482 (17)0.0466 (11)0.045 (2)0.0081 (10)0.0124 (13)0.0054 (15)
C100.071 (3)0.0418 (14)0.085 (4)0.0075 (18)0.006 (3)0.005 (2)
C110.089 (3)0.066 (3)0.064 (3)−0.009 (2)0.043 (3)0.000 (2)
C120.074 (2)0.039 (2)0.043 (2)−0.0074 (16)0.0224 (17)−0.0003 (14)
C130.081 (3)0.046 (2)0.044 (2)−0.0043 (18)0.0141 (18)0.0110 (15)
C140.0612 (19)0.033 (2)0.044 (2)−0.0021 (14)0.0061 (15)0.0065 (13)
C150.061 (2)0.051 (3)0.078 (4)0.0071 (19)0.003 (2)0.016 (2)
C160.067 (3)0.080 (3)0.0456 (19)−0.015 (2)0.0061 (19)−0.002 (2)
C170.047 (2)0.053 (2)0.0399 (11)−0.0012 (14)0.0138 (13)0.0033 (13)
C180.060 (3)0.057 (2)0.0459 (14)−0.0009 (16)0.0198 (16)0.0114 (15)
C190.047 (2)0.0426 (19)0.0525 (16)−0.0011 (13)0.0213 (15)0.0070 (14)
C200.071 (3)0.055 (3)0.076 (3)−0.0182 (19)0.032 (2)0.003 (2)
N10.074 (3)0.075 (3)0.085 (4)−0.042 (3)0.008 (3)0.012 (3)
Geometric parameters (Å, °) top
Cd1—N72.278 (4)C6—C71.486 (7)
Cd1—N22.293 (4)C6—H6A0.9600
Cd1—N52.303 (4)C6—H6B0.9600
Cd1—N82.314 (4)C6—H6C0.9600
Cd1—O52.427 (3)C7—C81.362 (7)
Cd1—O42.673 (3)C8—C91.386 (7)
O4—N101.240 (5)C8—H8A0.9300
O5—N101.264 (5)C9—C101.497 (7)
O6—N101.225 (5)C10—H10B0.9600
N2—C41.343 (6)C10—H10C0.9600
N2—N31.358 (6)C10—H10D0.9600
N3—C21.341 (8)C11—C121.500 (7)
N3—H4A0.8600C11—H11A0.9600
N4—C71.346 (6)C11—H11B0.9600
N4—N51.365 (5)C11—H11C0.9600
N4—H5A0.8600C12—C131.363 (8)
N5—C91.341 (6)C13—C141.396 (7)
N6—C121.350 (6)C13—H13A0.9300
N6—N71.359 (6)C14—C151.483 (7)
N6—H7A0.8600C15—H15A0.9600
N7—C141.337 (6)C15—H15B0.9600
N8—C171.335 (6)C15—H15C0.9600
N8—N91.356 (5)C16—C171.500 (7)
N9—C191.342 (6)C16—H16A0.9600
N9—H10A0.8600C16—H16B0.9600
C1—C21.505 (8)C16—H16C0.9600
C1—H1A0.9600C17—C181.393 (7)
C1—H1B0.9600C18—C191.366 (7)
C1—H1C0.9600C18—H18A0.9300
C2—C31.357 (9)C19—C201.495 (7)
C3—C41.389 (7)C20—H20A0.9600
C3—H3A0.9300C20—H20B0.9600
C4—C51.490 (7)C20—H20C0.9600
C5—H5B0.9600N1—O21.108 (10)
C5—H5C0.9600N1—O31.176 (15)
C5—H5D0.9600N1—O11.226 (8)
N7—Cd1—N296.81 (14)C7—C6—H6B109.5
N7—Cd1—N593.80 (14)H6A—C6—H6B109.5
N2—Cd1—N5113.69 (15)C7—C6—H6C109.5
N7—Cd1—N8164.83 (15)H6A—C6—H6C109.5
N2—Cd1—N889.43 (14)H6B—C6—H6C109.5
N5—Cd1—N896.33 (13)N4—C7—C8105.9 (4)
N7—Cd1—O581.49 (13)N4—C7—C6121.7 (5)
N2—Cd1—O5154.81 (14)C8—C7—C6132.3 (5)
N5—Cd1—O591.50 (13)C7—C8—C9107.4 (4)
N8—Cd1—O586.98 (13)C7—C8—H8A126.3
N7—Cd1—O483.20 (13)C9—C8—H8A126.3
N2—Cd1—O4105.38 (13)N5—C9—C8109.8 (4)
N5—Cd1—O4140.88 (12)N5—C9—C10122.0 (4)
N8—Cd1—O481.82 (12)C8—C9—C10128.2 (4)
O5—Cd1—O449.43 (12)C9—C10—H10B109.5
N10—O4—Cd190.4 (2)C9—C10—H10C109.5
N10—O5—Cd1101.7 (3)H10B—C10—H10C109.5
C4—N2—N3105.2 (4)C9—C10—H10D109.5
C4—N2—Cd1128.6 (3)H10B—C10—H10D109.5
N3—N2—Cd1125.3 (3)H10C—C10—H10D109.5
C2—N3—N2111.5 (5)C12—C11—H11A109.5
C2—N3—H4A124.2C12—C11—H11B109.5
N2—N3—H4A124.2H11A—C11—H11B109.5
C7—N4—N5112.0 (4)C12—C11—H11C109.5
C7—N4—H5A124.0H11A—C11—H11C109.5
N5—N4—H5A124.0H11B—C11—H11C109.5
C9—N5—N4104.9 (4)N6—C12—C13106.1 (4)
C9—N5—Cd1130.1 (3)N6—C12—C11121.7 (5)
N4—N5—Cd1123.7 (3)C13—C12—C11132.2 (5)
C12—N6—N7111.5 (4)C12—C13—C14107.2 (4)
C12—N6—H7A124.2C12—C13—H13A126.4
N7—N6—H7A124.2C14—C13—H13A126.4
C14—N7—N6105.9 (4)N7—C14—C13109.2 (4)
C14—N7—Cd1132.7 (3)N7—C14—C15122.2 (5)
N6—N7—Cd1121.3 (3)C13—C14—C15128.6 (5)
C17—N8—N9105.2 (4)C14—C15—H15A109.5
C17—N8—Cd1129.0 (3)C14—C15—H15B109.5
N9—N8—Cd1122.8 (3)H15A—C15—H15B109.5
C19—N9—N8112.3 (4)C14—C15—H15C109.5
C19—N9—H10A123.9H15A—C15—H15C109.5
N8—N9—H10A123.9H15B—C15—H15C109.5
O6—N10—O4123.0 (4)C17—C16—H16A109.5
O6—N10—O5119.2 (4)C17—C16—H16B109.5
O4—N10—O5117.8 (4)H16A—C16—H16B109.5
C2—C1—H1A109.5C17—C16—H16C109.5
C2—C1—H1B109.5H16A—C16—H16C109.5
H1A—C1—H1B109.5H16B—C16—H16C109.5
C2—C1—H1C109.5N8—C17—C18109.8 (4)
H1A—C1—H1C109.5N8—C17—C16121.7 (4)
H1B—C1—H1C109.5C18—C17—C16128.5 (4)
N3—C2—C3106.9 (5)C19—C18—C17106.8 (4)
N3—C2—C1120.8 (6)C19—C18—H18A126.6
C3—C2—C1132.3 (6)C17—C18—H18A126.6
C2—C3—C4106.6 (5)N9—C19—C18105.9 (4)
C2—C3—H3A126.7N9—C19—C20121.6 (5)
C4—C3—H3A126.7C18—C19—C20132.5 (5)
N2—C4—C3109.8 (5)C19—C20—H20A109.5
N2—C4—C5121.6 (4)C19—C20—H20B109.5
C3—C4—C5128.7 (5)H20A—C20—H20B109.5
C4—C5—H5B109.5C19—C20—H20C109.5
C4—C5—H5C109.5H20A—C20—H20C109.5
H5B—C5—H5C109.5H20B—C20—H20C109.5
C4—C5—H5D109.5O2—N1—O3124.1 (11)
H5B—C5—H5D109.5O2—N1—O1128.2 (8)
H5C—C5—H5D109.5O3—N1—O1107.6 (9)
C7—C6—H6A109.5
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H4A···O1i0.862.132.943 (8)157
N3—H4A···O3i0.862.503.289 (16)152
N4—H5A···O1i0.861.922.771 (8)171
N6—H7A···O6ii0.862.333.131 (6)156
N9—H10A···O40.862.503.106 (5)128
C5—H5B···O40.962.593.530 (7)166
C10—H10B···O50.962.293.157 (7)150
C13—H13A···O1iii0.932.493.375 (8)159
Symmetry codes: (i) x−1, y, z; (ii) −x, −y+2, −z+1; (iii) −x+1, −y+1, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H4A···O1i0.862.132.943 (8)157
N3—H4A···O3i0.862.503.289 (16)152
N4—H5A···O1i0.861.922.771 (8)171
N6—H7A···O6ii0.862.333.131 (6)156
N9—H10A···O40.862.503.106 (5)128
C5—H5B···O40.962.593.530 (7)166
C10—H10B···O50.962.293.157 (7)150
C13—H13A···O1iii0.932.493.375 (8)159
Symmetry codes: (i) x−1, y, z; (ii) −x, −y+2, −z+1; (iii) −x+1, −y+1, −z+1.
references
References top

Addison, A. W., Rao, T. N., Reedijk, J., Vanrijn, J. & Verschoor, G. C. (1984). J. Chem. Soc. Dalton Trans. pp. 1349–1356.

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Dressing, S. A., Mass, R. P. & Weiss, C. M. (1982). Bull. Environ. Contam. Toxicol. 28, 172–180.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.