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Acta Cryst. (2012). E68, m503    [ doi:10.1107/S160053681201241X ]

Di-[mu]-methanolato-[kappa]4O:O-bis[bis(3-methyl-5-phenyl-1H-pyrazole-[kappa]N2)(nitrato-[kappa]O)copper(II)]

X.-G. Li, M.-M. Gao and S. W. Ng

Abstract top

Copper nitrate in methanol solution cleaves the N-Cmethanol bond when reacted with 3-methyl-5-phenylpyrazole-1-methanol to yield the centrosymmetric dinuclear title compound, [Cu2(CH3O)2(NO3)2(C10H10N2)4], in which the CuII atom is linked to a nitrate ion, two methanolate ions and two pyrazole ligands in a distorted square-pyramidal environment. The O atom of the nitrate anion occupies the apical site. The crystal structure features intramolecular N-H...O hydrogen bonds.

Comment top

Copper nitrate in methanol solution cleaves the N–Cmethanol bond when reacted with 3-methyl-5-phenylpyrazole-1-methanol to yield the dinuclear title compound (Scheme I, Fig. 1). The molecule lies on a center-of-inversion; the CuII atom is linked to a nitrate ion, two methanolate ions and two of the pyrazole ligands in a square-pyramidal environment. In the perchlorate analog, [Cu(OCH3)(C10H10N2)2]2(ClO4)2,the counterion is not connected to the copper atom, whose geometry is a square pyramid. The compound was synthesized by directly reacting 3-methyl-5-phenylpyrazole with copper perchlorate in methanol medium (He & Sykes, 2007).

Related literature top

For a related structure, see: He & Sykes (2007). For the synthesis of 3-methyl-5-phenylpyrazole-1-methanol, see: Zhu et al. (2004).

Experimental top

3-Methyl-5-phenylpyrazole-1-methanol was synthesized by using a literature procedure (Zhu et al., 2004). The ligand (0.065 g, 0.4 mmol) was dissolved in dichloromethane (10 mol) and this was mixed with a methanol solution (10 ml) of copper nitrate trihydrate (0.024 g, 0.1 mmol). The clear blue solution was filtered and then set aside for the growth of deep blue crystals. CH&N elemental analysis. Calc. for C42H46Cu2N10O8: C 53.33, H 4.90; N 14.81%. Found: C 56.36, H 5.18, N 15.02%.

Refinement top

Carbon-bound H-atoms were placed in calculated positions (C—H 0.93 to 0.96 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2 to 1.5U(C).

The amino H-atoms were located in a difference Fourier map, and were refined with a distance restraint of N–H 0.88±0.01 Å; their temperature factors were freely refined.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of centrosymmetric [Cu(OCH3)(NO3)(C10H10N2)2]2 at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. Inversion-related atoms are not labeled.
Di-µ-methanolato-κ4O:O-bis[bis(3-methyl-5-phenyl-1H- pyrazole-κN2)(nitrato-κO)copper(II)] top
Crystal data top
[Cu2(CH3O)2(NO3)2(C10H10N2)4]Z = 1
Mr = 945.97F(000) = 490
Triclinic, P1Dx = 1.419 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.3896 (8) ÅCell parameters from 2170 reflections
b = 11.2569 (11) Åθ = 2.5–24.5°
c = 12.7200 (12) ŵ = 1.02 mm−1
α = 106.120 (2)°T = 293 K
β = 103.025 (2)°Prism, blue
γ = 95.853 (2)°0.12 × 0.11 × 0.10 mm
V = 1106.85 (18) Å3
Data collection top
Bruker SMART-1000
diffractometer		4898 independent reflections
Radiation source: fine-focus sealed tube3461 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.015
ω scansθmax = 27.5°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −10→10
Tmin = 0.887, Tmax = 0.905k = −12→14
6768 measured reflectionsl = −16→10
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)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116H atoms treated by a mixture of independent and constrained refinement
S = 1.02 w = 1/[σ2(Fo2) + (0.0516P)2 + 0.4958P]
where P = (Fo2 + 2Fc2)/3
4898 reflections(Δ/σ)max = 0.001
290 parametersΔρmax = 0.38 e Å−3
2 restraintsΔρmin = −0.30 e Å−3
Crystal data top
[Cu2(CH3O)2(NO3)2(C10H10N2)4]γ = 95.853 (2)°
Mr = 945.97V = 1106.85 (18) Å3
Triclinic, P1Z = 1
a = 8.3896 (8) ÅMo Kα radiation
b = 11.2569 (11) ŵ = 1.02 mm−1
c = 12.7200 (12) ÅT = 293 K
α = 106.120 (2)°0.12 × 0.11 × 0.10 mm
β = 103.025 (2)°
Data collection top
Bruker SMART-1000
diffractometer		4898 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		3461 reflections with I > 2σ(I)
Tmin = 0.887, Tmax = 0.905Rint = 0.015
6768 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.042H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.116Δρmax = 0.38 e Å−3
S = 1.02Δρmin = −0.30 e Å−3
4898 reflectionsAbsolute structure: ?
290 parametersFlack parameter: ?
2 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.54841 (4)0.37278 (3)0.47584 (3)0.04912 (14)
O10.7401 (3)0.4733 (3)0.3606 (2)0.0769 (7)
O20.6684 (3)0.6571 (2)0.3847 (2)0.0768 (7)
O30.5511 (3)0.5059 (2)0.23096 (17)0.0703 (6)
O40.3871 (2)0.46286 (18)0.41469 (14)0.0464 (5)
N10.7022 (3)0.3017 (2)0.57615 (18)0.0508 (6)
N20.6938 (3)0.3252 (2)0.68576 (19)0.0507 (6)
N30.4722 (3)0.2251 (2)0.3377 (2)0.0576 (6)
N40.4708 (3)0.2394 (3)0.2345 (2)0.0573 (6)
N50.6566 (3)0.5464 (3)0.3264 (2)0.0535 (6)
C10.9035 (5)0.2356 (4)0.4677 (3)0.0793 (11)
H1A0.81490.23700.40560.119*
H1B0.93300.15350.45250.119*
H1C0.99830.29650.47640.119*
C20.8479 (4)0.2663 (3)0.5748 (2)0.0519 (7)
C30.9314 (4)0.2661 (3)0.6822 (2)0.0545 (7)
H31.03500.24400.70280.065*
C40.8307 (3)0.3052 (3)0.7523 (2)0.0469 (6)
C50.8519 (3)0.3269 (3)0.8744 (2)0.0493 (7)
C60.7739 (4)0.4139 (3)0.9353 (3)0.0603 (8)
H60.70850.46030.89900.072*
C70.7932 (4)0.4319 (4)1.0499 (3)0.0730 (10)
H70.74080.49061.09010.088*
C80.8892 (4)0.3639 (4)1.1049 (3)0.0753 (11)
H80.89930.37481.18150.090*
C90.9694 (4)0.2801 (4)1.0461 (3)0.0717 (10)
H91.03620.23531.08350.086*
C100.9524 (4)0.2610 (3)0.9315 (3)0.0579 (8)
H101.00820.20400.89250.069*
C110.3473 (6)0.0666 (4)0.4104 (3)0.0996 (15)
H11A0.43990.10100.47630.149*
H11B0.3330−0.02340.38700.149*
H11C0.24840.09250.42810.149*
C120.3794 (5)0.1132 (3)0.3157 (3)0.0659 (9)
C130.3201 (5)0.0571 (3)0.1989 (3)0.0731 (10)
H130.2534−0.02140.16180.088*
C140.3786 (4)0.1393 (3)0.1488 (3)0.0582 (8)
C150.3536 (4)0.1299 (3)0.0279 (3)0.0616 (8)
C160.4062 (5)0.2286 (4)−0.0078 (3)0.0764 (10)
H160.45970.30520.04560.092*
C170.3799 (5)0.2146 (5)−0.1229 (3)0.0884 (12)
H170.41660.2815−0.14610.106*
C180.3000 (6)0.1023 (5)−0.2022 (3)0.0935 (14)
H180.28280.0925−0.27920.112*
C190.2461 (7)0.0050 (5)−0.1673 (3)0.1131 (18)
H190.1906−0.0708−0.22120.136*
C200.2722 (6)0.0169 (4)−0.0533 (3)0.0944 (14)
H200.2353−0.0507−0.03100.113*
C210.2225 (4)0.4090 (3)0.3499 (3)0.0620 (8)
H21A0.16670.47270.32900.093*
H21B0.16470.37300.39400.093*
H21C0.22410.34460.28250.093*
H20.602 (2)0.349 (3)0.698 (3)0.061 (10)*
H40.510 (4)0.3130 (18)0.231 (3)0.079 (12)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0482 (2)0.0578 (2)0.03230 (18)0.00578 (16)−0.00269 (13)0.01163 (15)
O10.0655 (15)0.0950 (19)0.0817 (17)0.0317 (14)0.0191 (13)0.0398 (15)
O20.0714 (16)0.0622 (15)0.0842 (17)0.0014 (13)0.0201 (13)0.0070 (14)
O30.0657 (14)0.0978 (18)0.0423 (12)0.0083 (13)0.0082 (10)0.0205 (12)
O40.0393 (10)0.0574 (12)0.0334 (9)0.0009 (9)−0.0025 (8)0.0123 (9)
N10.0506 (14)0.0663 (16)0.0343 (11)0.0126 (12)0.0056 (10)0.0174 (11)
N20.0439 (14)0.0703 (17)0.0409 (12)0.0157 (13)0.0089 (11)0.0217 (12)
N30.0634 (16)0.0554 (16)0.0418 (13)0.0061 (13)−0.0030 (11)0.0109 (12)
N40.0658 (17)0.0528 (16)0.0400 (13)0.0032 (13)0.0029 (12)0.0047 (12)
N50.0435 (14)0.0709 (18)0.0501 (14)0.0076 (13)0.0165 (11)0.0225 (14)
C10.074 (2)0.114 (3)0.0451 (18)0.029 (2)0.0173 (17)0.011 (2)
C20.0500 (17)0.0613 (19)0.0406 (15)0.0102 (14)0.0093 (13)0.0118 (14)
C30.0439 (16)0.068 (2)0.0475 (16)0.0148 (15)0.0051 (13)0.0148 (15)
C40.0457 (15)0.0516 (17)0.0411 (14)0.0053 (13)0.0041 (12)0.0180 (13)
C50.0423 (15)0.0620 (19)0.0402 (14)0.0003 (13)0.0032 (12)0.0199 (14)
C60.0504 (18)0.081 (2)0.0470 (16)0.0099 (16)0.0088 (14)0.0196 (16)
C70.053 (2)0.107 (3)0.0500 (18)0.0045 (19)0.0137 (15)0.0134 (19)
C80.056 (2)0.119 (3)0.0397 (16)−0.012 (2)0.0029 (15)0.025 (2)
C90.060 (2)0.095 (3)0.0545 (19)0.0006 (19)−0.0066 (16)0.037 (2)
C100.0499 (17)0.073 (2)0.0492 (16)0.0066 (15)0.0039 (13)0.0259 (16)
C110.140 (4)0.077 (3)0.071 (2)−0.007 (3)0.002 (3)0.035 (2)
C120.078 (2)0.0510 (19)0.0567 (19)0.0079 (17)−0.0037 (17)0.0158 (16)
C130.085 (3)0.0482 (19)0.062 (2)−0.0004 (18)−0.0088 (18)0.0060 (16)
C140.0610 (19)0.0508 (18)0.0482 (17)0.0117 (15)−0.0006 (14)0.0035 (14)
C150.061 (2)0.064 (2)0.0430 (16)0.0170 (16)−0.0007 (14)−0.0006 (15)
C160.073 (2)0.088 (3)0.0516 (19)−0.003 (2)0.0066 (17)0.0086 (19)
C170.078 (3)0.122 (4)0.059 (2)0.008 (3)0.017 (2)0.024 (2)
C180.098 (3)0.125 (4)0.045 (2)0.033 (3)0.015 (2)0.006 (2)
C190.162 (5)0.090 (3)0.048 (2)0.022 (3)0.000 (3)−0.017 (2)
C200.138 (4)0.065 (2)0.052 (2)0.007 (2)0.003 (2)−0.0041 (18)
C210.0456 (17)0.071 (2)0.0514 (17)−0.0038 (15)−0.0093 (13)0.0134 (16)
Geometric parameters (Å, º) top
Cu1—O4i1.9185 (19)C7—C81.377 (5)
Cu1—O41.9256 (18)C7—H70.9300
Cu1—N31.979 (2)C8—C91.366 (5)
Cu1—N11.992 (2)C8—H80.9300
Cu1—Cu1i2.9939 (8)C9—C101.385 (4)
O1—N51.239 (3)C9—H90.9300
O2—N51.242 (3)C10—H100.9300
O3—N51.261 (3)C11—C121.505 (5)
O4—C211.412 (3)C11—H11A0.9600
O4—Cu1i1.9185 (19)C11—H11B0.9600
N1—C21.326 (4)C11—H11C0.9600
N1—N21.364 (3)C12—C131.391 (4)
N2—C41.344 (3)C13—C141.370 (5)
N2—H20.873 (10)C13—H130.9300
N3—C121.333 (4)C14—C151.478 (4)
N3—N41.363 (3)C15—C161.380 (5)
N4—C141.348 (4)C15—C201.388 (5)
N4—H40.874 (10)C16—C171.392 (5)
C1—C21.501 (4)C16—H160.9300
C1—H1A0.9600C17—C181.370 (6)
C1—H1B0.9600C17—H170.9300
C1—H1C0.9600C18—C191.365 (6)
C2—C31.388 (4)C18—H180.9300
C3—C41.379 (4)C19—C201.383 (6)
C3—H30.9300C19—H190.9300
C4—C51.469 (4)C20—H200.9300
C5—C61.387 (4)C21—H21A0.9600
C5—C101.393 (4)C21—H21B0.9600
C6—C71.383 (4)C21—H21C0.9600
C6—H60.9300
O4i—Cu1—O477.69 (8)C8—C7—H7119.6
O4i—Cu1—N3166.83 (9)C6—C7—H7119.6
O4—Cu1—N391.96 (9)C9—C8—C7119.4 (3)
O4i—Cu1—N191.67 (9)C9—C8—H8120.3
O4—Cu1—N1165.30 (9)C7—C8—H8120.3
N3—Cu1—N199.88 (10)C8—C9—C10120.8 (3)
O4i—Cu1—Cu1i38.93 (5)C8—C9—H9119.6
O4—Cu1—Cu1i38.76 (5)C10—C9—H9119.6
N3—Cu1—Cu1i130.23 (7)C5—C10—C9120.1 (3)
N1—Cu1—Cu1i129.86 (7)C5—C10—H10119.9
C21—O4—Cu1i124.42 (19)C9—C10—H10119.9
C21—O4—Cu1125.07 (19)C12—C11—H11A109.5
Cu1i—O4—Cu1102.31 (8)C12—C11—H11B109.5
C2—N1—N2105.4 (2)H11A—C11—H11B109.5
C2—N1—Cu1133.5 (2)C12—C11—H11C109.5
N2—N1—Cu1117.77 (18)H11A—C11—H11C109.5
C4—N2—N1111.9 (2)H11B—C11—H11C109.5
C4—N2—H2133 (2)N3—C12—C13109.7 (3)
N1—N2—H2115 (2)N3—C12—C11120.9 (3)
C12—N3—N4105.7 (2)C13—C12—C11129.3 (3)
C12—N3—Cu1132.4 (2)C14—C13—C12107.1 (3)
N4—N3—Cu1119.6 (2)C14—C13—H13126.5
C14—N4—N3111.5 (3)C12—C13—H13126.5
C14—N4—H4128 (2)N4—C14—C13106.0 (3)
N3—N4—H4119 (2)N4—C14—C15123.3 (3)
O1—N5—O2122.3 (3)C13—C14—C15130.7 (3)
O1—N5—O3119.0 (3)C16—C15—C20118.7 (3)
O2—N5—O3118.6 (3)C16—C15—C14123.0 (3)
C2—C1—H1A109.5C20—C15—C14118.3 (3)
C2—C1—H1B109.5C15—C16—C17120.6 (4)
H1A—C1—H1B109.5C15—C16—H16119.7
C2—C1—H1C109.5C17—C16—H16119.7
H1A—C1—H1C109.5C18—C17—C16120.0 (4)
H1B—C1—H1C109.5C18—C17—H17120.0
N1—C2—C3110.3 (3)C16—C17—H17120.0
N1—C2—C1120.8 (3)C19—C18—C17119.5 (4)
C3—C2—C1128.8 (3)C19—C18—H18120.3
C4—C3—C2106.6 (3)C17—C18—H18120.3
C4—C3—H3126.7C18—C19—C20121.3 (4)
C2—C3—H3126.7C18—C19—H19119.4
N2—C4—C3105.7 (2)C20—C19—H19119.4
N2—C4—C5121.9 (3)C19—C20—C15119.8 (4)
C3—C4—C5132.4 (3)C19—C20—H20120.1
C6—C5—C10118.7 (3)C15—C20—H20120.1
C6—C5—C4120.9 (3)O4—C21—H21A109.5
C10—C5—C4120.4 (3)O4—C21—H21B109.5
C7—C6—C5120.2 (3)H21A—C21—H21B109.5
C7—C6—H6119.9O4—C21—H21C109.5
C5—C6—H6119.9H21A—C21—H21C109.5
C8—C7—C6120.7 (4)H21B—C21—H21C109.5
O4i—Cu1—O4—C21−149.3 (3)C2—C3—C4—C5−178.2 (3)
N3—Cu1—O4—C2138.9 (2)N2—C4—C5—C6−27.0 (4)
N1—Cu1—O4—C21−104.9 (4)C3—C4—C5—C6151.7 (3)
Cu1i—Cu1—O4—C21−149.3 (3)N2—C4—C5—C10153.5 (3)
O4i—Cu1—O4—Cu1i0.0C3—C4—C5—C10−27.7 (5)
N3—Cu1—O4—Cu1i−171.78 (10)C10—C5—C6—C7−1.5 (5)
N1—Cu1—O4—Cu1i44.5 (4)C4—C5—C6—C7179.0 (3)
O4i—Cu1—N1—C2−104.9 (3)C5—C6—C7—C8−0.2 (5)
O4—Cu1—N1—C2−148.1 (3)C6—C7—C8—C91.7 (5)
N3—Cu1—N1—C268.7 (3)C7—C8—C9—C10−1.4 (5)
Cu1i—Cu1—N1—C2−113.3 (3)C6—C5—C10—C91.8 (5)
O4i—Cu1—N1—N250.9 (2)C4—C5—C10—C9−178.7 (3)
O4—Cu1—N1—N27.7 (5)C8—C9—C10—C5−0.4 (5)
N3—Cu1—N1—N2−135.5 (2)N4—N3—C12—C130.2 (4)
Cu1i—Cu1—N1—N242.5 (2)Cu1—N3—C12—C13162.2 (3)
C2—N1—N2—C4−0.1 (3)N4—N3—C12—C11−177.8 (3)
Cu1—N1—N2—C4−162.1 (2)Cu1—N3—C12—C11−15.7 (5)
O4i—Cu1—N3—C12−141.7 (4)N3—C12—C13—C14−0.5 (4)
O4—Cu1—N3—C12−103.9 (3)C11—C12—C13—C14177.2 (4)
N1—Cu1—N3—C1267.3 (3)N3—N4—C14—C13−0.6 (4)
Cu1i—Cu1—N3—C12−110.6 (3)N3—N4—C14—C15179.3 (3)
O4i—Cu1—N3—N418.4 (6)C12—C13—C14—N40.7 (4)
O4—Cu1—N3—N456.2 (2)C12—C13—C14—C15−179.2 (3)
N1—Cu1—N3—N4−132.6 (2)N4—C14—C15—C16−7.8 (5)
Cu1i—Cu1—N3—N449.4 (3)C13—C14—C15—C16172.1 (4)
C12—N3—N4—C140.3 (4)N4—C14—C15—C20172.8 (3)
Cu1—N3—N4—C14−164.5 (2)C13—C14—C15—C20−7.3 (6)
N2—N1—C2—C30.5 (3)C20—C15—C16—C17−0.8 (6)
Cu1—N1—C2—C3158.4 (2)C14—C15—C16—C17179.8 (3)
N2—N1—C2—C1−178.3 (3)C15—C16—C17—C180.5 (6)
Cu1—N1—C2—C1−20.5 (5)C16—C17—C18—C190.3 (7)
N1—C2—C3—C4−0.8 (4)C17—C18—C19—C20−0.8 (8)
C1—C2—C3—C4178.0 (3)C18—C19—C20—C150.5 (8)
N1—N2—C4—C3−0.4 (3)C16—C15—C20—C190.3 (7)
N1—N2—C4—C5178.6 (3)C14—C15—C20—C19179.7 (4)
C2—C3—C4—N20.7 (3)
Symmetry code: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O2i0.87 (1)2.26 (2)3.012 (3)144 (3)
N4—H4···O30.87 (1)2.17 (2)3.022 (4)166 (3)
Symmetry code: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O2i0.87 (1)2.26 (2)3.012 (3)144 (3)
N4—H4···O30.87 (1)2.17 (2)3.022 (4)166 (3)
Symmetry code: (i) −x+1, −y+1, −z+1.
Acknowledgements top

The authors acknowledge support from the Scientific Research Project of Higher Education of Inner Mongolia (grant No. NJ09204) and the Ministry of Higher Education of Malaysia (grant No. UM.C/HIR/MOHE/SC/12).

references
References top

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