Dichloro­tetra­kis(1H-pyrazole-κN²)copper(II)

The reaction of CuCl₂ and pyrazole (Hpz) in methanol solution at room temperature yields the title mononuclear complex, [CuCl₂(C₃H₄N₂)₄]. The Cu atom is six-coordinated by four N atoms from four pyrazole ligands and by two Cl⁻ ions. The overall symmetry of the complex is . The structure features N—H...Cl and C—H...Cl hydrogen bonds, yielding a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.049
• wR factor = 0.159
• Data-to-parameter ratio = 16.1

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Cu1    -   Cl1     ..      45.72 su

Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.92
PLAT230_ALERT_2_C Hirshfeld Test Diff for    N3     -   N4      ..       6.09 su
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          7
PLAT420_ALERT_2_C D-H Without Acceptor       N2     -   H2A    ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N4     -   H4A    ...          ?
PLAT480_ALERT_4_C Long H...A H-Bond Reported H2A    ..  CL1     ..       2.89 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H2A    ..  CL1     ..       2.95 Ang.

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.921
            Tmax scaled      0.780 Tmin scaled      0.635
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   7 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 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

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Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: SHELXTL (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Dichlorotetrakis(1H-pyrazole-κN²)copper(II)

Crystal data

[CuCl2(C3H4N2)4]	F(000) = 828
Mr = 406.77	Dx = 1.637 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4803 reflections
a = 13.674 (8) Å	θ = 2.8–26.5°
b = 9.172 (5) Å	µ = 1.66 mm^−1
c = 14.750 (8) Å	T = 293 K
β = 116.852 (9)°	Plate, blue
V = 1650.5 (16) Å^3	0.23 × 0.20 × 0.15 mm
Z = 4

Data collection

Bruker P4 diffractometer	1710 independent reflections
Radiation source: fine-focus sealed tube	1603 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
ω scans	θmax = 26.5°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −17→16
Tmin = 0.690, Tmax = 0.847	k = −11→10
4803 measured reflections	l = −14→18

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.159	H-atom parameters constrained
S = 1.17	w = 1/[σ^2(Fo^2) + (0.0886P)^2 + 4.2919P] where P = (Fo^2 + 2Fc^2)/3
1710 reflections	(Δ/σ)max = 0.001
106 parameters	Δρmax = 0.72 e Å^−3
0 restraints	Δρmin = −0.71 e Å^−3

Special details

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	0.2500	0.2500	0.5000	0.0385 (3)
Cl1	0.06447 (7)	0.06419 (10)	0.41053 (7)	0.0421 (3)
N1	0.2600 (3)	0.2681 (3)	0.3676 (2)	0.0347 (7)
N3	0.1476 (2)	0.4204 (3)	0.4574 (2)	0.0354 (6)
C1	0.3365 (3)	0.3452 (3)	0.3543 (3)	0.0315 (7)
H1A	0.3923	0.3981	0.4052	0.038*
N2	0.1963 (3)	0.2101 (4)	0.2783 (3)	0.0502 (8)
H2A	0.1401	0.1562	0.2655	0.060*
N4	0.1650 (3)	0.5620 (4)	0.4660 (3)	0.0550 (9)
H4A	0.2282	0.6021	0.4992	0.066*
C2	0.3221 (4)	0.3358 (5)	0.2594 (3)	0.0489 (9)
H2B	0.3646	0.3804	0.2329	0.059*
C6	0.0677 (4)	0.6377 (4)	0.4142 (4)	0.0510 (10)
H6A	0.0584	0.7384	0.4088	0.061*
C3	0.2331 (4)	0.2486 (4)	0.2079 (3)	0.0503 (11)
H3A	0.2035	0.2208	0.1401	0.060*
C5	−0.0108 (3)	0.5350 (5)	0.3732 (4)	0.0540 (11)
H5A	−0.0855	0.5511	0.3339	0.065*
C4	0.0397 (3)	0.4045 (4)	0.4001 (3)	0.0349 (7)
H4B	0.0041	0.3150	0.3812	0.042*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0450 (4)	0.0387 (4)	0.0335 (4)	0.0177 (2)	0.0194 (3)	0.0083 (2)
Cl1	0.0363 (5)	0.0390 (5)	0.0457 (5)	−0.0053 (3)	0.0138 (4)	−0.0006 (3)
N1	0.0342 (15)	0.0336 (15)	0.0351 (15)	0.0030 (11)	0.0146 (13)	0.0009 (11)
N3	0.0357 (15)	0.0319 (14)	0.0370 (15)	0.0074 (11)	0.0150 (12)	0.0034 (11)
C1	0.0291 (15)	0.0264 (14)	0.0392 (17)	0.0000 (12)	0.0156 (13)	0.0008 (13)
N2	0.0472 (19)	0.0532 (19)	0.0445 (18)	−0.0013 (16)	0.0158 (16)	−0.0014 (16)
N4	0.049 (2)	0.049 (2)	0.063 (2)	0.0020 (16)	0.0219 (18)	−0.0010 (17)
C2	0.054 (2)	0.045 (2)	0.056 (2)	0.0079 (18)	0.033 (2)	0.0124 (18)
C6	0.050 (2)	0.0320 (19)	0.071 (3)	0.0106 (16)	0.028 (2)	0.0081 (17)
C3	0.058 (3)	0.057 (3)	0.035 (2)	0.0103 (18)	0.020 (2)	0.0048 (15)
C5	0.0351 (19)	0.047 (2)	0.070 (3)	0.0132 (17)	0.0157 (19)	0.012 (2)
C4	0.0271 (15)	0.0277 (15)	0.0440 (18)	0.0043 (12)	0.0107 (14)	0.0033 (14)

Geometric parameters (Å, º)

Cu1—N3^i	2.001 (3)	N2—H2A	0.8600
Cu1—N3	2.001 (3)	N4—C6	1.385 (6)
Cu1—N1	2.025 (3)	N4—H4A	0.8600
Cu1—N1^i	2.025 (3)	C2—C3	1.364 (7)
Cu1—Cl1	2.8386 (15)	C2—H2B	0.9300
N1—N2	1.319 (5)	C6—C5	1.349 (7)
N1—C1	1.348 (5)	C6—H6A	0.9300
N3—N4	1.317 (5)	C3—H3A	0.9300
N3—C4	1.336 (5)	C5—C4	1.350 (5)
C1—C2	1.324 (5)	C5—H5A	0.9300
C1—H1A	0.9300	C4—H4B	0.9300
N2—C3	1.389 (6)
N3^i—Cu1—N3	180.000 (1)	N3—N4—C6	110.8 (4)
N3^i—Cu1—N1	91.40 (12)	N3—N4—H4A	124.6
N3—Cu1—N1	88.60 (12)	C6—N4—H4A	124.6
N3^i—Cu1—N1^i	88.60 (12)	C1—C2—C3	107.2 (4)
N3—Cu1—N1^i	91.40 (12)	C1—C2—H2B	126.4
N1—Cu1—N1^i	180.000 (1)	C3—C2—H2B	126.4
N2—N1—C1	105.8 (3)	C5—C6—N4	105.6 (4)
N2—N1—Cu1	128.9 (3)	C5—C6—H6A	127.2
C1—N1—Cu1	125.3 (3)	N4—C6—H6A	127.2
N4—N3—C4	105.6 (3)	C2—C3—N2	105.4 (4)
N4—N3—Cu1	132.1 (3)	C2—C3—H3A	127.3
C4—N3—Cu1	121.9 (2)	N2—C3—H3A	127.3
C2—C1—N1	111.4 (3)	C6—C5—C4	106.8 (4)
C2—C1—H1A	124.3	C6—C5—H5A	126.6
N1—C1—H1A	124.3	C4—C5—H5A	126.6
N1—N2—C3	110.2 (4)	N3—C4—C5	111.2 (3)
N1—N2—H2A	124.9	N3—C4—H4B	124.4
C3—N2—H2A	124.9	C5—C4—H4B	124.4
N3^i—Cu1—N1—N2	92.6 (3)	Cu1—N1—N2—C3	−179.2 (3)
N3—Cu1—N1—N2	−87.4 (3)	C4—N3—N4—C6	0.2 (5)
N3^i—Cu1—N1—C1	−87.3 (3)	Cu1—N3—N4—C6	173.0 (3)
N3—Cu1—N1—C1	92.7 (3)	N1—C1—C2—C3	−0.4 (4)
N1—Cu1—N3—N4	−85.4 (4)	N3—N4—C6—C5	0.0 (5)
N1^i—Cu1—N3—N4	94.6 (4)	C1—C2—C3—N2	0.9 (5)
N1—Cu1—N3—C4	86.5 (3)	N1—N2—C3—C2	−1.0 (5)
N1^i—Cu1—N3—C4	−93.5 (3)	N4—C6—C5—C4	−0.3 (5)
N2—N1—C1—C2	−0.3 (4)	N4—N3—C4—C5	−0.4 (5)
Cu1—N1—C1—C2	179.7 (3)	Cu1—N3—C4—C5	−174.1 (3)
C1—N1—N2—C3	0.8 (4)	C6—C5—C4—N3	0.4 (5)

Symmetry code: (i) −x+1/2, −y+1/2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···Cl1^i	0.93	2.53	3.211 (4)	130
C1—H1A···Cl1^ii	0.93	2.77	3.479 (5)	133
N2—H2A···Cl1	0.86	2.89	3.467 (5)	126
N2—H2A···Cl1^iii	0.86	2.95	3.646 (5)	139

Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) x+1/2, y+1/2, z; (iii) −x, y, −z+1/2.