cyclo-Tris(μ₂-3-phenyl-1H-pyrazole)tricopper(I)

The crystal structure of the title compound, [Cu₃(C₉H₇N₂)₃], consists of discrete Cu^I–phenyl­pyrazolyl trimers, with Cu atoms bridged by exo-bidentate phenyl­pyrazolyl ligands having short intra­molecular Cu...Cu contacts [3.2076 (14)–3.2402 (14) Å]. The Cu₃N₆ nine-membered rings are essentially planar.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.012 Å
• R factor = 0.055
• wR factor = 0.131
• Data-to-parameter ratio = 14.5

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT601_ALERT_2_B Structure Contains Solvent Accessible VOIDS of .     141.00 A   3  

Alert level C
GOODF01_ALERT_2_C  The least squares goodness of fit parameter lies
            outside the range 0.80 <> 2.00
            Goodness of fit given =      0.793
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low ....         43 Perc.
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.94
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...         12

   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

   0 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
   2 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).

cyclo-Tris(µ₂-3-phenyl-1H-pyrazole)tricopper(I)

Crystal data

[Cu3(C9H7N2)3]	Dx = 1.620 Mg m^−3
Mr = 620.12	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4/n	Cell parameters from 6575 reflections
Hall symbol: -P 4a	θ = 2.3–24.8°
a = 26.6249 (19) Å	µ = 2.51 mm^−1
c = 7.1739 (7) Å	T = 173 K
V = 5085.5 (7) Å^3	Needle, colourless
Z = 8	0.19 × 0.09 × 0.08 mm
F(000) = 2496

Data collection

Stoe IPDS-II two-circle diffractometer	4701 independent reflections
Radiation source: fine-focus sealed tube	2005 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.090
ω scans	θmax = 25.5°, θmin = 2.2°
Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995)	h = −32→32
Tmin = 0.647, Tmax = 0.824	k = −32→32
29854 measured reflections	l = −8→7

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.131	H-atom parameters constrained
S = 0.79	w = 1/[σ^2(Fo^2) + (0.0458P)^2] where P = (Fo^2 + 2Fc^2)/3
4701 reflections	(Δ/σ)max < 0.001
325 parameters	Δρmax = 1.93 e Å^−3
0 restraints	Δρmin = −0.66 e Å^−3

Special details

Experimental. ;

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 (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.56636 (4)	0.46194 (4)	0.32062 (15)	0.0294 (3)
Cu2	0.48996 (4)	0.55369 (4)	0.23322 (16)	0.0312 (3)
Cu3	0.45712 (4)	0.43990 (4)	0.15080 (15)	0.0306 (3)
N1	0.5036 (3)	0.3886 (3)	0.1711 (11)	0.0325 (17)
N2	0.5509 (2)	0.3971 (2)	0.2450 (10)	0.0291 (17)
C3	0.5780 (3)	0.3549 (3)	0.2229 (13)	0.028 (2)
C4	0.5491 (3)	0.3183 (3)	0.1346 (14)	0.034 (2)
H4	0.5585	0.2850	0.1027	0.041*
C5	0.5028 (4)	0.3421 (3)	0.1038 (14)	0.037 (2)
H5	0.4749	0.3270	0.0433	0.044*
N11	0.5825 (2)	0.5272 (3)	0.3869 (10)	0.0274 (17)
N12	0.5511 (2)	0.5668 (2)	0.3507 (10)	0.0267 (16)
C13	0.5724 (3)	0.6095 (3)	0.4118 (12)	0.028 (2)
C14	0.6184 (3)	0.5973 (3)	0.4912 (12)	0.027 (2)
H14	0.6416	0.6200	0.5468	0.032*
C15	0.6239 (3)	0.5462 (3)	0.4740 (12)	0.026 (2)
H15	0.6519	0.5272	0.5158	0.032*
N21	0.4263 (3)	0.5411 (3)	0.1434 (10)	0.0305 (17)
N22	0.4102 (2)	0.4914 (3)	0.1236 (10)	0.0276 (17)
C23	0.3600 (3)	0.4913 (3)	0.0924 (13)	0.029 (2)
C24	0.3429 (3)	0.5409 (3)	0.0878 (13)	0.034 (2)
H24	0.3096	0.5523	0.0651	0.041*
C25	0.3850 (3)	0.5699 (3)	0.1236 (12)	0.031 (2)
H25	0.3848	0.6055	0.1329	0.037*
C31	0.6312 (3)	0.3510 (3)	0.2823 (13)	0.031 (2)
C32	0.6643 (3)	0.3209 (3)	0.1812 (14)	0.037 (2)
H32	0.6528	0.3031	0.0747	0.044*
C33	0.7146 (4)	0.3171 (3)	0.2375 (17)	0.050 (3)
H33	0.7371	0.2964	0.1692	0.060*
C34	0.7320 (4)	0.3432 (3)	0.3911 (16)	0.048 (3)
H34	0.7658	0.3400	0.4308	0.057*
C35	0.6987 (4)	0.3743 (4)	0.4864 (15)	0.044 (3)
H35	0.7104	0.3931	0.5900	0.052*
C36	0.6495 (3)	0.3782 (3)	0.4340 (14)	0.036 (2)
H36	0.6276	0.3997	0.5015	0.043*
C41	0.5479 (3)	0.6582 (3)	0.3860 (11)	0.0221 (19)
C42	0.5768 (3)	0.7012 (3)	0.3579 (13)	0.033 (2)
H42	0.6123	0.6988	0.3631	0.040*
C43	0.5546 (4)	0.7476 (3)	0.3225 (13)	0.041 (2)
H43	0.5750	0.7762	0.3007	0.049*
C44	0.5029 (4)	0.7518 (3)	0.3190 (14)	0.043 (3)
H44	0.4875	0.7833	0.2937	0.052*
C45	0.4735 (3)	0.7094 (3)	0.3530 (13)	0.038 (2)
H45	0.4379	0.7120	0.3533	0.045*
C46	0.4963 (3)	0.6637 (3)	0.3864 (13)	0.030 (2)
H46	0.4759	0.6351	0.4103	0.036*
C51	0.3323 (3)	0.4446 (3)	0.0778 (12)	0.026 (2)
C52	0.2846 (3)	0.4408 (3)	0.1607 (13)	0.032 (2)
H52	0.2695	0.4696	0.2155	0.038*
C53	0.2595 (3)	0.3952 (4)	0.1627 (15)	0.043 (2)
H53	0.2275	0.3928	0.2209	0.051*
C54	0.2804 (3)	0.3532 (4)	0.0812 (14)	0.043 (3)
H54	0.2628	0.3222	0.0802	0.052*
C55	0.3278 (4)	0.3571 (4)	0.0003 (13)	0.038 (2)
H55	0.3430	0.3281	−0.0527	0.045*
C56	0.3528 (3)	0.4016 (4)	−0.0039 (12)	0.030 (2)
H56	0.3846	0.4035	−0.0633	0.036*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0327 (6)	0.0252 (6)	0.0304 (6)	0.0013 (5)	−0.0015 (5)	0.0003 (5)
Cu2	0.0265 (6)	0.0322 (6)	0.0349 (7)	−0.0030 (5)	−0.0035 (5)	0.0030 (5)
Cu3	0.0260 (6)	0.0349 (6)	0.0310 (6)	0.0016 (5)	−0.0014 (5)	0.0042 (6)
N1	0.030 (4)	0.035 (4)	0.033 (5)	0.001 (3)	−0.002 (4)	0.004 (4)
N2	0.030 (4)	0.028 (4)	0.029 (4)	0.000 (3)	0.002 (4)	0.006 (3)
C3	0.027 (5)	0.029 (5)	0.029 (6)	0.002 (4)	0.003 (4)	−0.001 (4)
C4	0.045 (6)	0.020 (4)	0.038 (6)	0.001 (4)	0.002 (5)	−0.004 (4)
C5	0.048 (6)	0.030 (5)	0.034 (6)	0.000 (5)	−0.004 (5)	−0.004 (4)
N11	0.027 (4)	0.034 (4)	0.021 (4)	0.000 (3)	−0.001 (3)	0.001 (3)
N12	0.028 (4)	0.027 (4)	0.025 (4)	0.004 (3)	0.002 (3)	0.003 (4)
C13	0.028 (5)	0.027 (5)	0.027 (5)	−0.008 (4)	0.008 (4)	−0.001 (4)
C14	0.025 (5)	0.032 (5)	0.023 (5)	−0.009 (4)	0.000 (4)	0.005 (4)
C15	0.023 (5)	0.034 (5)	0.022 (5)	0.007 (4)	0.000 (4)	0.008 (4)
N21	0.032 (4)	0.029 (4)	0.030 (5)	−0.007 (4)	−0.001 (4)	0.008 (4)
N22	0.025 (4)	0.037 (4)	0.021 (5)	0.000 (3)	−0.006 (3)	0.003 (3)
C23	0.028 (5)	0.030 (5)	0.030 (6)	0.004 (4)	−0.002 (4)	0.004 (4)
C24	0.023 (5)	0.044 (6)	0.036 (6)	0.002 (4)	−0.004 (4)	0.000 (5)
C25	0.036 (5)	0.031 (5)	0.026 (6)	−0.004 (4)	0.000 (4)	0.007 (4)
C31	0.034 (5)	0.024 (5)	0.036 (6)	0.005 (4)	0.006 (4)	0.010 (4)
C32	0.037 (5)	0.032 (5)	0.041 (6)	0.005 (4)	0.006 (5)	−0.001 (5)
C33	0.038 (6)	0.032 (5)	0.079 (9)	0.012 (4)	0.019 (6)	−0.001 (6)
C34	0.038 (6)	0.037 (6)	0.068 (8)	0.003 (5)	−0.009 (6)	−0.002 (6)
C35	0.037 (6)	0.036 (6)	0.058 (8)	−0.004 (5)	−0.011 (5)	0.005 (5)
C36	0.035 (6)	0.032 (5)	0.040 (6)	0.012 (4)	−0.004 (5)	−0.001 (5)
C41	0.028 (5)	0.022 (4)	0.017 (5)	0.000 (4)	0.005 (4)	0.000 (4)
C42	0.030 (5)	0.029 (5)	0.041 (6)	−0.005 (4)	0.001 (5)	−0.010 (4)
C43	0.057 (6)	0.033 (5)	0.033 (6)	−0.007 (5)	−0.004 (5)	0.000 (5)
C44	0.056 (7)	0.030 (5)	0.042 (7)	0.010 (5)	−0.005 (5)	−0.003 (5)
C45	0.039 (5)	0.041 (6)	0.033 (6)	0.002 (5)	0.007 (5)	−0.009 (5)
C46	0.029 (5)	0.027 (5)	0.033 (6)	−0.003 (4)	0.002 (4)	0.000 (4)
C51	0.021 (5)	0.035 (5)	0.022 (5)	0.006 (4)	−0.001 (4)	−0.003 (4)
C52	0.020 (4)	0.041 (5)	0.034 (6)	0.005 (4)	−0.004 (4)	−0.002 (5)
C53	0.034 (5)	0.053 (6)	0.041 (6)	0.002 (5)	0.007 (5)	0.005 (5)
C54	0.032 (6)	0.055 (7)	0.043 (6)	−0.002 (5)	−0.005 (5)	0.008 (5)
C55	0.040 (6)	0.035 (6)	0.039 (6)	0.009 (5)	0.001 (5)	−0.005 (4)
C56	0.022 (5)	0.046 (6)	0.023 (6)	0.001 (5)	−0.002 (4)	0.001 (4)

Geometric parameters (Å, º)

Cu1—N11	1.852 (7)	C32—C33	1.404 (12)
Cu1—N2	1.857 (7)	C32—H32	0.9500
Cu2—N21	1.845 (7)	C33—C34	1.381 (14)
Cu2—N12	1.867 (7)	C33—H33	0.9500
Cu3—N1	1.849 (7)	C34—C35	1.391 (14)
Cu3—N22	1.864 (7)	C34—H34	0.9500
N1—C5	1.330 (11)	C35—C36	1.367 (12)
N1—N2	1.384 (9)	C35—H35	0.9500
N2—C3	1.345 (10)	C36—H36	0.9500
C3—C4	1.395 (11)	C41—C46	1.381 (11)
C3—C31	1.482 (11)	C41—C42	1.394 (11)
C4—C5	1.402 (12)	C42—C43	1.392 (12)
C4—H4	0.9500	C42—H42	0.9500
C5—H5	0.9500	C43—C44	1.382 (12)
N11—C15	1.363 (11)	C43—H43	0.9500
N11—N12	1.370 (9)	C44—C45	1.395 (12)
N12—C13	1.343 (10)	C44—H44	0.9500
C13—C14	1.388 (12)	C45—C46	1.381 (12)
C13—C41	1.463 (11)	C45—H45	0.9500
C14—C15	1.376 (12)	C46—H46	0.9500
C14—H14	0.9500	C51—C56	1.397 (11)
C15—H15	0.9500	C51—C52	1.407 (11)
N21—C25	1.348 (10)	C52—C53	1.387 (12)
N21—N22	1.398 (9)	C52—H52	0.9500
N22—C23	1.356 (10)	C53—C54	1.379 (13)
C23—C24	1.399 (12)	C53—H53	0.9500
C23—C51	1.448 (11)	C54—C55	1.394 (13)
C24—C25	1.386 (11)	C54—H54	0.9500
C24—H24	0.9500	C55—C56	1.359 (13)
C25—H25	0.9500	C55—H55	0.9500
C31—C32	1.394 (11)	C56—H56	0.9500
C31—C36	1.395 (12)
N11—Cu1—N2	177.8 (3)	C31—C32—C33	119.7 (9)
N21—Cu2—N12	173.6 (3)	C31—C32—H32	120.2
N1—Cu3—N22	178.5 (3)	C33—C32—H32	120.2
C5—N1—N2	107.7 (7)	C34—C33—C32	120.8 (9)
C5—N1—Cu3	130.5 (6)	C34—C33—H33	119.6
N2—N1—Cu3	121.2 (5)	C32—C33—H33	119.6
C3—N2—N1	107.9 (7)	C33—C34—C35	118.6 (9)
C3—N2—Cu1	133.8 (6)	C33—C34—H34	120.7
N1—N2—Cu1	117.7 (5)	C35—C34—H34	120.7
N2—C3—C4	109.8 (7)	C36—C35—C34	121.4 (10)
N2—C3—C31	122.5 (7)	C36—C35—H35	119.3
C4—C3—C31	127.6 (8)	C34—C35—H35	119.3
C3—C4—C5	104.0 (7)	C35—C36—C31	120.6 (9)
C3—C4—H4	128.0	C35—C36—H36	119.7
C5—C4—H4	128.0	C31—C36—H36	119.7
N1—C5—C4	110.5 (8)	C46—C41—C42	117.5 (7)
N1—C5—H5	124.8	C46—C41—C13	122.6 (7)
C4—C5—H5	124.8	C42—C41—C13	120.0 (7)
C15—N11—N12	107.1 (6)	C43—C42—C41	121.5 (8)
C15—N11—Cu1	130.7 (6)	C43—C42—H42	119.3
N12—N11—Cu1	122.2 (5)	C41—C42—H42	119.3
C13—N12—N11	109.4 (6)	C44—C43—C42	119.9 (9)
C13—N12—Cu2	132.4 (6)	C44—C43—H43	120.1
N11—N12—Cu2	118.2 (5)	C42—C43—H43	120.1
N12—C13—C14	108.0 (7)	C43—C44—C45	119.3 (8)
N12—C13—C41	121.3 (7)	C43—C44—H44	120.4
C14—C13—C41	130.7 (8)	C45—C44—H44	120.4
C15—C14—C13	106.7 (8)	C46—C45—C44	119.8 (8)
C15—C14—H14	126.7	C46—C45—H45	120.1
C13—C14—H14	126.7	C44—C45—H45	120.1
N11—C15—C14	108.8 (7)	C41—C46—C45	122.0 (8)
N11—C15—H15	125.6	C41—C46—H46	119.0
C14—C15—H15	125.6	C45—C46—H46	119.0
C25—N21—N22	106.2 (6)	C56—C51—C52	118.0 (8)
C25—N21—Cu2	133.0 (6)	C56—C51—C23	122.4 (8)
N22—N21—Cu2	119.2 (5)	C52—C51—C23	119.5 (7)
C23—N22—N21	108.7 (6)	C53—C52—C51	120.2 (8)
C23—N22—Cu3	132.6 (6)	C53—C52—H52	119.9
N21—N22—Cu3	118.7 (5)	C51—C52—H52	119.9
N22—C23—C24	108.9 (7)	C54—C53—C52	120.7 (9)
N22—C23—C51	121.1 (7)	C54—C53—H53	119.6
C24—C23—C51	130.0 (8)	C52—C53—H53	119.6
C25—C24—C23	105.0 (8)	C53—C54—C55	118.8 (9)
C25—C24—H24	127.5	C53—C54—H54	120.6
C23—C24—H24	127.5	C55—C54—H54	120.6
N21—C25—C24	111.2 (8)	C56—C55—C54	121.1 (9)
N21—C25—H25	124.4	C56—C55—H55	119.4
C24—C25—H25	124.4	C54—C55—H55	119.4
C32—C31—C36	118.9 (8)	C55—C56—C51	121.1 (8)
C32—C31—C3	119.6 (8)	C55—C56—H56	119.5
C36—C31—C3	121.5 (8)	C51—C56—H56	119.5
C5—N1—N2—C3	−0.7 (10)	C23—C24—C25—N21	1.9 (11)
Cu3—N1—N2—C3	−173.2 (6)	N2—C3—C31—C32	−147.0 (8)
C5—N1—N2—Cu1	171.8 (6)	C4—C3—C31—C32	31.2 (13)
Cu3—N1—N2—Cu1	−0.7 (9)	N2—C3—C31—C36	30.7 (13)
N1—N2—C3—C4	0.0 (10)	C4—C3—C31—C36	−151.1 (9)
Cu1—N2—C3—C4	−170.8 (7)	C36—C31—C32—C33	2.4 (13)
N1—N2—C3—C31	178.5 (8)	C3—C31—C32—C33	−179.9 (8)
Cu1—N2—C3—C31	7.7 (13)	C31—C32—C33—C34	−0.6 (14)
N2—C3—C4—C5	0.7 (10)	C32—C33—C34—C35	−1.5 (15)
C31—C3—C4—C5	−177.7 (9)	C33—C34—C35—C36	1.8 (15)
N2—N1—C5—C4	1.2 (10)	C34—C35—C36—C31	0.0 (14)
Cu3—N1—C5—C4	172.7 (7)	C32—C31—C36—C35	−2.1 (13)
C3—C4—C5—N1	−1.2 (10)	C3—C31—C36—C35	−179.8 (8)
C15—N11—N12—C13	0.5 (9)	N12—C13—C41—C46	32.3 (13)
Cu1—N11—N12—C13	−179.4 (6)	C14—C13—C41—C46	−149.3 (9)
C15—N11—N12—Cu2	−179.3 (5)	N12—C13—C41—C42	−147.0 (8)
Cu1—N11—N12—Cu2	0.8 (8)	C14—C13—C41—C42	31.3 (14)
N11—N12—C13—C14	−0.6 (9)	C46—C41—C42—C43	−3.1 (13)
Cu2—N12—C13—C14	179.2 (6)	C13—C41—C42—C43	176.3 (8)
N11—N12—C13—C41	178.1 (7)	C41—C42—C43—C44	1.6 (14)
Cu2—N12—C13—C41	−2.1 (12)	C42—C43—C44—C45	0.6 (15)
N12—C13—C14—C15	0.5 (9)	C43—C44—C45—C46	−1.2 (15)
C41—C13—C14—C15	−178.0 (8)	C42—C41—C46—C45	2.5 (13)
N12—N11—C15—C14	−0.2 (9)	C13—C41—C46—C45	−176.8 (8)
Cu1—N11—C15—C14	179.7 (6)	C44—C45—C46—C41	−0.5 (14)
C13—C14—C15—N11	−0.2 (10)	N22—C23—C51—C56	−35.5 (13)
C25—N21—N22—C23	0.0 (9)	C24—C23—C51—C56	147.9 (10)
Cu2—N21—N22—C23	167.9 (6)	N22—C23—C51—C52	139.6 (9)
C25—N21—N22—Cu3	−177.9 (6)	C24—C23—C51—C52	−37.1 (15)
Cu2—N21—N22—Cu3	−10.0 (8)	C56—C51—C52—C53	1.1 (13)
N21—N22—C23—C24	1.2 (10)	C23—C51—C52—C53	−174.2 (8)
Cu3—N22—C23—C24	178.7 (6)	C51—C52—C53—C54	−1.1 (14)
N21—N22—C23—C51	−176.1 (7)	C52—C53—C54—C55	1.5 (15)
Cu3—N22—C23—C51	1.4 (14)	C53—C54—C55—C56	−2.0 (14)
N22—C23—C24—C25	−1.9 (11)	C54—C55—C56—C51	2.0 (13)
C51—C23—C24—C25	175.1 (9)	C52—C51—C56—C55	−1.5 (13)
N22—N21—C25—C24	−1.2 (9)	C23—C51—C56—C55	173.6 (8)
Cu2—N21—C25—C24	−166.7 (7)