Bis(1-methyl­guanidinium) tetra­chloro­cuprate(II) and 4-(2-pyrimidin-1-io)­piperazinium tetra­chloro­cuprate(II)

The crystal structures of the title compounds, (C₂N₃H₈)₂[CuCl₄], (I), and (C₈H₁₄N₄)[CuCl₄], (II), have been studied by X-ray diffraction. The structures consist of discrete [CuCl₄]^2- anions with two monoprotonated (C₂N₃H₈)⁺ cations for (I) and a diprotonated (C₈N₄H₁₄)²⁺ cation for (II). The [CuCl₄]^2- anions of both compounds have flattened tetrahedral geometries. There are several N-H...Cl weak bonds that join the [CuCl₄]^2- anions and the organic cations helping retain the pseudo-tetrahedral geometries of the anions.

Computing details

For both compounds, data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CRYSDA (Beurskens et al., 1992); data reduction: REFLEX (García-Granda et al., 2000); program(s) used to solve structure: DIRDIF (Beurskens et al., 1992); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: PARST (Nardelli, 1995) and SHELXL97.

(I) bis(1-methylguanidinium) Tetrachlorocuprate(II)

Crystal data

(C2N3H8)2[CuCl4]	F(000) = 716
Mr = 353.57	Dx = 1.700 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.372 (3) Å	Cell parameters from 25 reflections
b = 8.042 (2) Å	θ = 15–20°
c = 15.621 (9) Å	µ = 2.34 mm^−1
β = 104.71 (2)°	T = 293 K
V = 1381.8 (9) Å^3	Prismatic, green
Z = 4	0.46 × 0.26 × 0.17 mm

Data collection

Nonius CAD-4 diffractometer	2078 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.034
Graphite monochromator	θmax = 35.0°, θmin = 2.7°
ω–2θ scans	h = −18→17
Absorption correction: empirical (using intensity measurements) (XABS2; Parkin et al., 1995)	k = 0→12
Tmin = 0.335, Tmax = 0.672	l = 0→25
3302 measured reflections	3 standard reflections every 200 reflections
3039 independent reflections	intensity decay: 10.9%

Refinement

Refinement on F^2	Primary atom site location: Patterson
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.117	H-atom parameters constrained
S = 1.09	Calculated w = 1/[σ^2(Fo^2) + (0.0651P)^2 + 0.3729P] where P = (Fo^2 + 2Fc^2)/3
3039 reflections	(Δ/σ)max < 0.001
69 parameters	Δρmax = 0.50 e Å^−3
0 restraints	Δρmin = −1.41 e Å^−3

Special details

Experimental. Nonius CAD4 single-crystal diffractometer

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	0.0000	0.15875 (4)	0.2500	0.03172 (10)
Cl1	0.19436 (5)	0.24426 (7)	0.29103 (3)	0.04420 (14)
Cl2	0.00624 (5)	0.07638 (7)	0.11282 (3)	0.04416 (14)
N1	0.7776 (2)	0.4536 (3)	0.02025 (14)	0.0515 (5)
H1A	0.7981	0.4278	0.0755	0.062*
H1B	0.7200	0.4003	−0.0156	0.062*
N2	0.8024 (2)	0.6138 (3)	−0.09476 (13)	0.0482 (4)
H2A	0.7446	0.5600	−0.1302	0.058*
H2B	0.8391	0.6927	−0.1147	0.058*
N3	0.92352 (18)	0.6583 (2)	0.04463 (13)	0.0440 (4)
H3	0.9628	0.7303	0.0221	0.053*
C1	0.83473 (18)	0.5752 (2)	−0.00962 (13)	0.0352 (4)
C2	0.9588 (2)	0.6354 (3)	0.14004 (17)	0.0525 (6)
H2C	1.0250	0.7085	0.1657	0.063*
H2D	0.9836	0.5223	0.1535	0.063*
H2E	0.8909	0.6603	0.1640	0.063*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.03675 (17)	0.03306 (17)	0.02444 (14)	0.000	0.00611 (11)	0.000
Cl1	0.0403 (2)	0.0565 (3)	0.0336 (2)	−0.0086 (2)	0.00535 (18)	−0.0025 (2)
Cl2	0.0503 (3)	0.0522 (3)	0.0321 (2)	−0.0133 (2)	0.01437 (19)	−0.01294 (19)
N1	0.0556 (12)	0.0516 (11)	0.0413 (9)	−0.0211 (9)	0.0010 (8)	0.0102 (8)
N2	0.0550 (11)	0.0515 (10)	0.0363 (8)	−0.0074 (9)	0.0086 (8)	0.0064 (8)
N3	0.0449 (9)	0.0452 (10)	0.0408 (9)	−0.0111 (8)	0.0091 (7)	0.0012 (7)
C1	0.0367 (9)	0.0339 (9)	0.0350 (8)	0.0007 (7)	0.0092 (7)	0.0013 (7)
C2	0.0540 (13)	0.0532 (14)	0.0438 (11)	−0.0042 (11)	0.0004 (10)	0.0002 (10)

Geometric parameters (Å, º)

Cu1—Cl1^i	2.2471 (8)	N2—H2A	0.8600
Cu1—Cl1	2.2471 (8)	N2—H2B	0.8600
Cu1—Cl2^i	2.2610 (12)	N3—C1	1.323 (3)
Cu1—Cl2	2.2611 (12)	N3—C2	1.453 (3)
N1—C1	1.323 (3)	N3—H3	0.8600
N1—H1A	0.8600	C2—H2C	0.9600
N1—H1B	0.8600	C2—H2D	0.9600
N2—C1	1.324 (3)	C2—H2E	0.9600
Cl1^i—Cu1—Cl1	144.36 (4)	C1—N3—C2	124.0 (2)
Cl1^i—Cu1—Cl2^i	95.44 (3)	C1—N3—H3	118.0
Cl1—Cu1—Cl2^i	94.86 (3)	C2—N3—H3	118.0
Cl1^i—Cu1—Cl2	94.85 (3)	N1—C1—N3	120.71 (19)
Cl1—Cu1—Cl2	95.43 (3)	N1—C1—N2	119.5 (2)
Cl2^i—Cu1—Cl2	145.93 (4)	N3—C1—N2	119.8 (2)
C1—N1—H1A	120.0	N3—C2—H2C	109.5
C1—N1—H1B	120.0	N3—C2—H2D	109.5
H1A—N1—H1B	120.0	H2C—C2—H2D	109.5
C1—N2—H2A	120.0	N3—C2—H2E	109.5
C1—N2—H2B	120.0	H2C—C2—H2E	109.5
H2A—N2—H2B	120.0	H2D—C2—H2E	109.5
C2—N3—C1—N1	−5.5 (4)	C2—N3—C1—N2	174.5 (2)

Symmetry code: (i) −x, y, −z+1/2.

(II) N-(2-pyrimidinyl)-piperazine Tetrachlorocuprate(II)

Crystal data

(C8N4H14)[CuCl4]	F(000) = 748
Mr = 371.57	Dx = 1.793 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.205 (7) Å	Cell parameters from 25 reflections
b = 16.13 (3) Å	θ = 15–20°
c = 9.391 (7) Å	µ = 2.35 mm^−1
β = 99.24 (6)°	T = 293 K
V = 1376 (3) Å^3	Prismatic, brown
Z = 4	0.28 × 0.23 × 0.20 mm

Data collection

Nonius CAD-4 diffractometer	2756 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.079
Graphite monochromator	θmax = 30.0°, θmin = 2.2°
ω–2θ scans	h = −12→12
Absorption correction: empirical (using intensity measurements) (XABS2; Parkin et al., 1995)	k = 0→22
Tmin = 0.532, Tmax = 0.626	l = 0→13
4363 measured reflections	3 standard reflections every 200 reflections
3994 independent reflections	intensity decay: 3.2%

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.135	H-atom parameters constrained
S = 1.04	Calculated w = 1/[σ^2(Fo^2) + (0.0669P)^2 + 0.6687P] where P = (Fo^2 + 2Fc^2)/3
3994 reflections	(Δ/σ)max < 0.001
154 parameters	Δρmax = 0.53 e Å^−3
0 restraints	Δρmin = −0.99 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	0.13591 (5)	0.05351 (3)	0.16568 (5)	0.03290 (14)
Cl1	0.36211 (10)	0.05335 (6)	0.09497 (11)	0.0375 (2)
Cl2	−0.00591 (11)	0.12939 (6)	0.29619 (10)	0.0392 (2)
Cl3	0.20705 (10)	−0.03617 (6)	0.35258 (9)	0.0331 (2)
Cl4	0.02347 (12)	0.10424 (8)	−0.04539 (11)	0.0496 (3)
N1	−0.6003 (3)	−0.13904 (19)	0.1105 (3)	0.0325 (7)
H1	−0.5943	−0.0865	0.1262	0.039*
N2	−0.5172 (4)	−0.2725 (2)	0.1767 (4)	0.0415 (8)
N3	−0.4186 (3)	−0.16079 (19)	0.3117 (4)	0.0363 (7)
N4	−0.1283 (3)	−0.0979 (2)	0.3738 (3)	0.0345 (7)
H4A	−0.0448	−0.0837	0.3416	0.041*
H4B	−0.1154	−0.0877	0.4692	0.041*
C1	−0.6969 (4)	−0.1673 (3)	−0.0006 (5)	0.0404 (9)
H1A	−0.7554	−0.1305	−0.0609	0.048*
C2	−0.7088 (5)	−0.2503 (3)	−0.0245 (5)	0.0474 (11)
H2	−0.7759	−0.2723	−0.0995	0.057*
C3	−0.6163 (5)	−0.2998 (3)	0.0681 (5)	0.0468 (11)
H3	−0.6234	−0.3568	0.0537	0.056*
C4	−0.5118 (4)	−0.1905 (2)	0.1987 (4)	0.0297 (7)
C5	−0.3006 (4)	−0.2125 (3)	0.3893 (5)	0.0408 (9)
H5A	−0.3205	−0.2703	0.3655	0.049*
H5B	−0.2973	−0.2058	0.4924	0.049*
C6	−0.1549 (4)	−0.1883 (3)	0.3493 (5)	0.0394 (9)
H6A	−0.0769	−0.2197	0.4071	0.047*
H6B	−0.1540	−0.2014	0.2486	0.047*
C7	−0.2512 (4)	−0.0450 (2)	0.3004 (4)	0.0337 (8)
H7A	−0.2577	−0.0496	0.1966	0.040*
H7B	−0.2326	0.0126	0.3270	0.040*
C8	−0.3937 (4)	−0.0728 (2)	0.3449 (5)	0.0354 (8)
H8A	−0.3899	−0.0638	0.4475	0.042*
H8B	−0.4745	−0.0404	0.2940	0.042*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0332 (2)	0.0355 (3)	0.0303 (2)	0.00891 (19)	0.00621 (17)	0.00798 (19)
Cl1	0.0338 (5)	0.0301 (5)	0.0508 (5)	0.0034 (4)	0.0132 (4)	0.0071 (4)
Cl2	0.0448 (5)	0.0387 (5)	0.0343 (4)	0.0119 (4)	0.0069 (4)	0.0002 (4)
Cl3	0.0349 (4)	0.0310 (5)	0.0314 (4)	0.0014 (3)	−0.0010 (3)	0.0063 (3)
Cl4	0.0472 (6)	0.0695 (8)	0.0323 (5)	0.0210 (5)	0.0069 (4)	0.0121 (5)
N1	0.0280 (15)	0.0221 (15)	0.0453 (18)	−0.0007 (12)	−0.0004 (13)	−0.0024 (13)
N2	0.0436 (19)	0.0213 (15)	0.058 (2)	−0.0045 (14)	0.0029 (16)	−0.0045 (15)
N3	0.0342 (16)	0.0211 (15)	0.0489 (18)	−0.0024 (13)	−0.0080 (14)	−0.0006 (14)
N4	0.0302 (15)	0.0398 (19)	0.0341 (16)	−0.0050 (13)	0.0070 (12)	0.0022 (13)
C1	0.0298 (19)	0.044 (2)	0.046 (2)	0.0006 (17)	0.0000 (16)	−0.0059 (18)
C2	0.033 (2)	0.050 (3)	0.057 (3)	−0.0075 (19)	0.0015 (19)	−0.019 (2)
C3	0.045 (2)	0.028 (2)	0.067 (3)	−0.0122 (18)	0.009 (2)	−0.016 (2)
C4	0.0253 (16)	0.0215 (16)	0.0427 (19)	−0.0042 (13)	0.0068 (14)	−0.0010 (14)
C5	0.040 (2)	0.031 (2)	0.048 (2)	−0.0013 (17)	−0.0054 (17)	0.0111 (17)
C6	0.039 (2)	0.035 (2)	0.044 (2)	0.0078 (17)	0.0054 (17)	0.0033 (17)
C7	0.042 (2)	0.0229 (18)	0.0341 (18)	−0.0043 (15)	0.0008 (15)	−0.0003 (14)
C8	0.0338 (19)	0.0240 (18)	0.045 (2)	0.0005 (15)	−0.0030 (16)	−0.0099 (15)

Geometric parameters (Å, º)

Cu1—Cl4	2.2386 (19)	C1—C2	1.359 (7)
Cu1—Cl2	2.284 (2)	C1—H1A	0.9300
Cu1—Cl1	2.2849 (19)	C2—C3	1.371 (7)
Cu1—Cl3	2.287 (2)	C2—H2	0.9300
N1—C1	1.338 (5)	C3—H3	0.9300
N1—C4	1.349 (5)	C5—C6	1.501 (6)
N1—H1	0.8600	C5—H5A	0.9700
N2—C3	1.330 (6)	C5—H5B	0.9700
N2—C4	1.339 (5)	C6—H6A	0.9700
N3—C4	1.341 (5)	C6—H6B	0.9700
N3—C8	1.464 (5)	C7—C8	1.507 (5)
N3—C5	1.467 (5)	C7—H7A	0.9700
N4—C6	1.491 (6)	C7—H7B	0.9700
N4—C7	1.494 (5)	C8—H8A	0.9700
N4—H4A	0.9000	C8—H8B	0.9700
N4—H4B	0.9000
Cl4—Cu1—Cl2	93.23 (8)	N2—C4—N3	118.6 (3)
Cl4—Cu1—Cl1	93.24 (7)	N2—C4—N1	120.6 (3)
Cl2—Cu1—Cl1	141.49 (6)	N3—C4—N1	120.8 (3)
Cl4—Cu1—Cl3	160.96 (5)	N3—C5—C6	110.4 (3)
Cl2—Cu1—Cl3	92.58 (9)	N3—C5—H5A	109.6
Cl1—Cu1—Cl3	93.46 (6)	C6—C5—H5A	109.6
C1—N1—C4	122.0 (3)	N3—C5—H5B	109.6
C1—N1—H1	119.0	C6—C5—H5B	109.6
C4—N1—H1	119.0	H5A—C5—H5B	108.1
C3—N2—C4	116.7 (4)	N4—C6—C5	110.3 (3)
C4—N3—C8	125.0 (3)	N4—C6—H6A	109.6
C4—N3—C5	121.2 (3)	C5—C6—H6A	109.6
C8—N3—C5	111.6 (3)	N4—C6—H6B	109.6
C6—N4—C7	113.2 (3)	C5—C6—H6B	109.6
C6—N4—H4A	108.9	H6A—C6—H6B	108.1
C7—N4—H4A	108.9	N4—C7—C8	109.3 (3)
C6—N4—H4B	108.9	N4—C7—H7A	109.8
C7—N4—H4B	108.9	C8—C7—H7A	109.8
H4A—N4—H4B	107.7	N4—C7—H7B	109.8
N1—C1—C2	119.3 (4)	C8—C7—H7B	109.8
N1—C1—H1A	120.3	H7A—C7—H7B	108.3
C2—C1—H1A	120.3	N3—C8—C7	110.1 (3)
C1—C2—C3	116.4 (4)	N3—C8—H8A	109.6
C1—C2—H2	121.8	C7—C8—H8A	109.6
C3—C2—H2	121.8	N3—C8—H8B	109.6
N2—C3—C2	125.0 (4)	C7—C8—H8B	109.6
N2—C3—H3	117.5	H8A—C8—H8B	108.2
C2—C3—H3	117.5
C4—N1—C1—C2	1.2 (6)	C1—N1—C4—N2	0.6 (6)
N1—C1—C2—C3	−1.2 (6)	C1—N1—C4—N3	−178.2 (4)
C4—N2—C3—C2	2.2 (7)	C4—N3—C5—C6	104.3 (4)
C1—C2—C3—N2	−0.5 (7)	C8—N3—C5—C6	−59.5 (5)
C3—N2—C4—N3	176.7 (4)	C7—N4—C6—C5	−53.4 (4)
C3—N2—C4—N1	−2.2 (6)	N3—C5—C6—N4	54.5 (4)
C8—N3—C4—N2	176.1 (4)	C6—N4—C7—C8	54.2 (4)
C5—N3—C4—N2	14.5 (6)	C4—N3—C8—C7	−102.4 (4)
C8—N3—C4—N1	−5.0 (6)	C5—N3—C8—C7	60.7 (4)
C5—N3—C4—N1	−166.6 (4)	N4—C7—C8—N3	−56.6 (4)