Temperature-dependent analysis of thermal motion, disorder and structures of tris(ethylenediamine)zinc(II) sulfate and tris(ethylenediamine)copper(II) sulfate

The crystal structures of the title compounds have been determined in the temperature range 140–290 K for the zinc complex, and 190–270 K for the copper complex. The two structures are isostructural in the trigonal space group with the sulfate anion severely disordered on a site with 32 (D₃) symmetry. This sulfate disorder leads to a disordered three-dimensional hydrogen-bond network, with the N—H atoms acting as donors and the sulfate O atoms as acceptors. The displacement parameters of the N and C atoms in both compounds contain disorder contributions in the out-of-ligand plane direction owing to ring puckering and/or disorder in hydrogen bonding. In the Zn compound the vibrational amplitudes in the bond directions are closely similar. Their differences show no significant deviations from rigid-bond behaviour. In the Cu compound, a (presumably) dynamic Jahn–Teller effect is identified from a temperature-independent contribution to the displacement ellipsoids of the N atom along the N—Cu bond. These conclusions derive from analyses of the atomic displacement parameters with the Hirshfeld test, with rigid-body models at different temperatures, and with a normal coordinate analysis. This analysis considers the atomic displacement parameters (ADPs) from all different temperatures simultaneously and provides a detailed description of both the thermal motion and the disorder in the cation. The Jahn–Teller radii of the Cu compound derived on the basis of the ADP analysis and from the bond distances in the statically distorted low-temperature phase [Lutz (2010). Acta Cryst. C66, m330–m335] are found to be the same.

Computing details

For all structures, data collection: COLLECT (Nonius, 1999); cell refinement: PEAKREF (Schreurs, 2005); data reduction: EVAL15 (Schreurs et al., 2010), SADABS2008/1 (Sheldrick, 2008b); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008a); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008a).

(1a)

Crystal data

C6H24N6Zn·O4S	Dx = 1.708 Mg m^−3
Mr = 341.74	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P31c	Cell parameters from 11284 reflections
Hall symbol: -P 3 2c	θ = 2.1–35.0°
a = 8.9594 (1) Å	µ = 2.02 mm^−1
c = 9.5583 (1) Å	T = 140 K
V = 664.46 (2) Å^3	Needle, colourless
Z = 2	0.30 × 0.09 × 0.09 mm
F(000) = 360

Data collection

Nonius KappaCCD diffractometer	683 independent reflections
Radiation source: rotating anode	649 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
φ and ω scans	θmax = 30.5°, θmin = 2.6°
Absorption correction: analytical SADABS-2008/1 (Sheldrick, 2008b)	h = −12→12
Tmin = 0.619, Tmax = 0.878	k = −12→12
10729 measured reflections	l = −13→13

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)] = 0.020	Hydrogen site location: difference Fourier map
wR(F^2) = 0.048	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ^2(Fo^2) + (0.0206P)^2 + 0.4531P] where P = (Fo^2 + 2Fc^2)/3
683 reflections	(Δ/σ)max < 0.001
49 parameters	Δρmax = 0.56 e Å^−3
16 restraints	Δρmin = −0.25 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	Occ. (<1)
Zn1	0.6667	0.3333	0.2500	0.01092 (9)
N1	0.45179 (14)	0.30945 (15)	0.12505 (12)	0.0197 (2)
H1N	0.436 (3)	0.393 (3)	0.136 (2)	0.033 (5)*
H2N	0.470 (3)	0.304 (3)	0.040 (2)	0.035 (5)*
C1	0.29463 (16)	0.15271 (17)	0.17058 (13)	0.0199 (2)
H1A	0.2912	0.0497	0.1292	0.024*
H1B	0.1915	0.1565	0.1386	0.024*
S1	0.3333	0.6667	0.2500	0.01097 (13)
O1	0.3589 (9)	0.5639 (7)	0.1489 (3)	0.0623 (18)	0.33333
O2	0.2850 (10)	0.7776 (9)	0.1764 (4)	0.093 (3)	0.33333

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.01117 (11)	0.01117 (11)	0.01043 (15)	0.00559 (6)	0.000	0.000
N1	0.0162 (5)	0.0244 (5)	0.0171 (5)	0.0090 (4)	−0.0021 (4)	0.0045 (4)
C1	0.0133 (5)	0.0228 (6)	0.0200 (5)	0.0063 (4)	−0.0032 (4)	−0.0023 (4)
S1	0.01203 (18)	0.01203 (18)	0.0089 (3)	0.00601 (9)	0.000	0.000
O1	0.156 (6)	0.075 (3)	0.0164 (16)	0.103 (4)	0.004 (2)	−0.0032 (18)
O2	0.212 (8)	0.136 (6)	0.026 (2)	0.158 (6)	0.020 (3)	0.024 (3)

Geometric parameters (Å, º)

Zn1—N1^i	2.1832 (11)	S1—O1^vi	1.431 (3)
Zn1—N1^ii	2.1832 (11)	S1—O1^vii	1.431 (3)
Zn1—N1	2.1832 (11)	S1—O1	1.431 (3)
Zn1—N1^iii	2.1833 (11)	S1—O1^viii	1.431 (3)
Zn1—N1^iv	2.1833 (11)	S1—O1^ix	1.431 (3)
Zn1—N1^v	2.1833 (11)	S1—O1^v	1.431 (3)
N1—C1	1.4720 (17)	S1—O2^viii	1.449 (4)
N1—H1N	0.84 (2)	S1—O2^ix	1.450 (4)
N1—H2N	0.84 (2)	S1—O2^vi	1.450 (4)
C1—C1^ii	1.521 (3)	S1—O2	1.450 (4)
C1—H1A	0.9900	S1—O2^vii	1.450 (4)
C1—H1B	0.9900	S1—O2^v	1.450 (4)
N1^i—Zn1—N1^ii	94.50 (7)	Zn1—N1—H1N	112.5 (14)
N1^i—Zn1—N1	92.93 (4)	C1—N1—H2N	110.8 (14)
N1^ii—Zn1—N1	80.43 (6)	Zn1—N1—H2N	110.2 (15)
N1^i—Zn1—N1^iii	92.93 (4)	H1N—N1—H2N	107 (2)
N1^ii—Zn1—N1^iii	170.26 (6)	N1—C1—C1^ii	108.98 (9)
N1—Zn1—N1^iii	92.93 (4)	N1—C1—H1A	109.9
N1^i—Zn1—N1^iv	80.43 (6)	C1^ii—C1—H1A	109.9
N1^ii—Zn1—N1^iv	92.93 (4)	N1—C1—H1B	109.9
N1—Zn1—N1^iv	170.26 (6)	C1^ii—C1—H1B	109.9
N1^iii—Zn1—N1^iv	94.50 (7)	H1A—C1—H1B	108.3
N1^i—Zn1—N1^v	170.26 (6)	O1^vii—S1—O1	112.2 (5)
N1^ii—Zn1—N1^v	92.93 (4)	O1^vii—S1—O2	110.5 (4)
N1—Zn1—N1^v	94.50 (7)	O1—S1—O2	108.2 (2)
N1^iii—Zn1—N1^v	80.43 (6)	O1^vii—S1—O2^vii	108.2 (2)
N1^iv—Zn1—N1^v	92.93 (4)	O1—S1—O2^vii	110.5 (4)
C1—N1—Zn1	107.92 (8)	O2—S1—O2^vii	107.1 (6)
C1—N1—H1N	108.0 (14)
N1^i—Zn1—N1—C1	79.09 (11)	N1^v—Zn1—N1—C1	−107.21 (9)
N1^ii—Zn1—N1—C1	−14.99 (6)	Zn1—N1—C1—C1^ii	42.08 (14)
N1^iii—Zn1—N1—C1	172.18 (8)

Symmetry codes: (i) −y+1, x−y, z; (ii) x, x−y, −z+1/2; (iii) −x+y+1, −x+1, z; (iv) −x+y+1, y, −z+1/2; (v) −y+1, −x+1, −z+1/2; (vi) −x+y, −x+1, z; (vii) −x+y, y, −z+1/2; (viii) −y+1, x−y+1, z; (ix) x, x−y+1, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1	0.84 (2)	1.97 (2)	2.799 (3)	170 (2)
N1—H2N···O2^x	0.84 (2)	2.12 (2)	2.951 (4)	178 (2)

Symmetry code: (x) x−y+1, x, −z.

(1b)

Crystal data

C6H24N6Zn·O4S	Dx = 1.704 Mg m^−3
Mr = 341.74	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P31c	Cell parameters from 11070 reflections
Hall symbol: -P 3 2c	θ = 2.1–35.0°
a = 8.9649 (1) Å	µ = 2.02 mm^−1
c = 9.5685 (1) Å	T = 170 K
V = 665.99 (2) Å^3	Needle, colourless
Z = 2	0.30 × 0.09 × 0.09 mm
F(000) = 360

Data collection

Nonius KappaCCD diffractometer	689 independent reflections
Radiation source: rotating anode	650 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
φ and ω scans	θmax = 30.5°, θmin = 2.6°
Absorption correction: analytical SADABS-2008/1 (Sheldrick, 2008b)	h = −12→12
Tmin = 0.625, Tmax = 0.876	k = −12→12
10818 measured reflections	l = −13→13

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)] = 0.021	Hydrogen site location: difference Fourier map
wR(F^2) = 0.051	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0226P)^2 + 0.4729P] where P = (Fo^2 + 2Fc^2)/3
689 reflections	(Δ/σ)max < 0.001
49 parameters	Δρmax = 0.53 e Å^−3
16 restraints	Δρmin = −0.26 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	Occ. (<1)
Zn1	0.6667	0.3333	0.2500	0.01325 (10)
N1	0.45189 (15)	0.30936 (16)	0.12505 (12)	0.0222 (2)
H1N	0.437 (3)	0.393 (3)	0.136 (2)	0.031 (5)*
H2N	0.472 (3)	0.305 (3)	0.038 (2)	0.038 (6)*
C1	0.29493 (17)	0.15272 (18)	0.17071 (14)	0.0231 (3)
H1A	0.2916	0.0498	0.1296	0.028*
H1B	0.1918	0.1563	0.1387	0.028*
S1	0.3333	0.6667	0.2500	0.01318 (14)
O1	0.3574 (10)	0.5636 (7)	0.1483 (4)	0.071 (2)	0.33333
O2	0.2849 (10)	0.7773 (9)	0.1777 (5)	0.100 (3)	0.33333

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.01350 (12)	0.01350 (12)	0.01276 (16)	0.00675 (6)	0.000	0.000
N1	0.0190 (5)	0.0270 (6)	0.0198 (5)	0.0109 (4)	−0.0024 (4)	0.0040 (4)
C1	0.0155 (5)	0.0262 (6)	0.0235 (6)	0.0074 (5)	−0.0040 (4)	−0.0035 (5)
S1	0.01415 (19)	0.01415 (19)	0.0112 (3)	0.00707 (9)	0.000	0.000
O1	0.171 (7)	0.086 (4)	0.0215 (18)	0.114 (5)	0.005 (3)	−0.004 (2)
O2	0.222 (9)	0.145 (6)	0.032 (2)	0.166 (7)	0.020 (4)	0.027 (3)

Geometric parameters (Å, º)

Zn1—N1^i	2.1838 (11)	S1—O1^vi	1.430 (3)
Zn1—N1	2.1838 (11)	S1—O1^vii	1.430 (3)
Zn1—N1^ii	2.1838 (11)	S1—O1	1.430 (3)
Zn1—N1^iii	2.1838 (11)	S1—O1^viii	1.430 (3)
Zn1—N1^iv	2.1838 (11)	S1—O1^ix	1.430 (3)
Zn1—N1^v	2.1839 (11)	S1—O1^iii	1.430 (3)
N1—C1	1.4720 (18)	S1—O2	1.443 (4)
N1—H1N	0.83 (2)	S1—O2^vii	1.443 (4)
N1—H2N	0.85 (2)	S1—O2^iii	1.443 (4)
C1—C1^ii	1.520 (3)	S1—O2^viii	1.443 (4)
C1—H1A	0.9900	S1—O2^vi	1.443 (4)
C1—H1B	0.9900	S1—O2^ix	1.443 (4)
N1^i—Zn1—N1	92.89 (4)	Zn1—N1—H1N	112.1 (14)
N1^i—Zn1—N1^ii	170.22 (7)	C1—N1—H2N	111.4 (15)
N1—Zn1—N1^ii	80.44 (6)	Zn1—N1—H2N	110.0 (15)
N1^i—Zn1—N1^iii	80.44 (6)	H1N—N1—H2N	107 (2)
N1—Zn1—N1^iii	94.58 (7)	N1—C1—C1^ii	109.01 (9)
N1^ii—Zn1—N1^iii	92.89 (4)	N1—C1—H1A	109.9
N1^i—Zn1—N1^iv	92.89 (4)	C1^ii—C1—H1A	109.9
N1—Zn1—N1^iv	92.89 (4)	N1—C1—H1B	109.9
N1^ii—Zn1—N1^iv	94.58 (7)	C1^ii—C1—H1B	109.9
N1^iii—Zn1—N1^iv	170.22 (7)	H1A—C1—H1B	108.3
N1^i—Zn1—N1^v	94.57 (7)	O1^vii—S1—O1	112.0 (5)
N1—Zn1—N1^v	170.22 (7)	O1^vii—S1—O2	110.7 (4)
N1^ii—Zn1—N1^v	92.89 (4)	O1—S1—O2	108.2 (2)
N1^iii—Zn1—N1^v	92.89 (4)	O1^vii—S1—O2^vii	108.2 (2)
N1^iv—Zn1—N1^v	80.44 (6)	O1—S1—O2^vii	110.7 (4)
C1—N1—Zn1	107.86 (8)	O2—S1—O2^vii	106.9 (6)
C1—N1—H1N	108.5 (14)
N1^i—Zn1—N1—C1	172.21 (9)	N1^iv—Zn1—N1—C1	79.17 (12)
N1^ii—Zn1—N1—C1	−14.99 (6)	Zn1—N1—C1—C1^ii	42.12 (15)
N1^iii—Zn1—N1—C1	−107.16 (10)

Symmetry codes: (i) −x+y+1, −x+1, z; (ii) x, x−y, −z+1/2; (iii) −y+1, −x+1, −z+1/2; (iv) −y+1, x−y, z; (v) −x+y+1, y, −z+1/2; (vi) −x+y, −x+1, z; (vii) −x+y, y, −z+1/2; (viii) −y+1, x−y+1, z; (ix) x, x−y+1, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1	0.83 (2)	1.99 (2)	2.810 (4)	169 (2)
N1—H2N···O2^x	0.85 (2)	2.11 (2)	2.966 (5)	177 (2)

Symmetry code: (x) x−y+1, x, −z.

(1c)

Crystal data

C6H24N6Zn·O4S	Dx = 1.700 Mg m^−3
Mr = 341.74	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P31c	Cell parameters from 10704 reflections
Hall symbol: -P 3 2c	θ = 2.1–35.0°
a = 8.9696 (2) Å	µ = 2.01 mm^−1
c = 9.5842 (1) Å	T = 200 K
V = 667.78 (3) Å^3	Needle, colourless
Z = 2	0.30 × 0.09 × 0.09 mm
F(000) = 360

Data collection

Nonius KappaCCD diffractometer	690 independent reflections
Radiation source: rotating anode	652 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
φ and ω scans	θmax = 30.5°, θmin = 2.6°
Absorption correction: analytical SADABS-2008/1 (Sheldrick, 2008b)	h = −12→12
Tmin = 0.622, Tmax = 0.882	k = −12→12
10832 measured reflections	l = −13→13

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)] = 0.022	Hydrogen site location: difference Fourier map
wR(F^2) = 0.058	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0316P)^2 + 0.3881P] where P = (Fo^2 + 2Fc^2)/3
690 reflections	(Δ/σ)max = 0.001
49 parameters	Δρmax = 0.56 e Å^−3
16 restraints	Δρmin = −0.25 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	Occ. (<1)
Zn1	0.6667	0.3333	0.2500	0.01591 (11)
N1	0.45178 (16)	0.30936 (17)	0.12531 (13)	0.0251 (3)
H1N	0.434 (3)	0.394 (3)	0.137 (2)	0.040 (6)*
H2N	0.472 (3)	0.305 (3)	0.039 (2)	0.036 (5)*
C1	0.29525 (18)	0.1529 (2)	0.17090 (16)	0.0278 (3)
H1A	0.2921	0.0501	0.1298	0.033*
H1B	0.1920	0.1562	0.1389	0.033*
S1	0.3333	0.6667	0.2500	0.01605 (15)
O1	0.3538 (11)	0.5626 (8)	0.1466 (4)	0.082 (3)	0.33333
O2	0.2837 (11)	0.7780 (10)	0.1814 (5)	0.105 (3)	0.33333

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.01605 (13)	0.01605 (13)	0.01564 (17)	0.00802 (7)	0.000	0.000
N1	0.0225 (6)	0.0308 (6)	0.0222 (5)	0.0136 (5)	−0.0030 (4)	0.0028 (4)
C1	0.0187 (6)	0.0320 (7)	0.0287 (7)	0.0096 (5)	−0.0048 (5)	−0.0044 (5)
S1	0.0165 (2)	0.0165 (2)	0.0152 (3)	0.00825 (10)	0.000	0.000
O1	0.190 (8)	0.099 (5)	0.028 (2)	0.125 (6)	0.010 (3)	−0.003 (3)
O2	0.223 (10)	0.152 (7)	0.042 (3)	0.170 (8)	0.018 (4)	0.027 (4)

Geometric parameters (Å, º)

Zn1—N1^i	2.1852 (12)	S1—O1^vi	1.435 (4)
Zn1—N1^ii	2.1852 (12)	S1—O1^vii	1.435 (4)
Zn1—N1	2.1852 (12)	S1—O1^viii	1.435 (4)
Zn1—N1^iii	2.1852 (12)	S1—O1^ix	1.435 (4)
Zn1—N1^iv	2.1852 (12)	S1—O1	1.435 (4)
Zn1—N1^v	2.1852 (12)	S1—O1^ii	1.435 (4)
N1—C1	1.470 (2)	S1—O2^ii	1.439 (4)
N1—H1N	0.86 (3)	S1—O2	1.439 (4)
N1—H2N	0.86 (2)	S1—O2^ix	1.439 (4)
C1—C1^iii	1.519 (3)	S1—O2^vii	1.439 (4)
C1—H1A	0.9900	S1—O2^vi	1.439 (4)
C1—H1B	0.9900	S1—O2^viii	1.439 (4)
N1^i—Zn1—N1^ii	80.38 (7)	Zn1—N1—H1N	113.1 (16)
N1^i—Zn1—N1	92.95 (5)	C1—N1—H2N	111.5 (15)
N1^ii—Zn1—N1	94.52 (7)	Zn1—N1—H2N	110.0 (15)
N1^i—Zn1—N1^iii	170.22 (7)	H1N—N1—H2N	107 (2)
N1^ii—Zn1—N1^iii	92.94 (5)	N1—C1—C1^iii	109.03 (10)
N1—Zn1—N1^iii	80.38 (7)	N1—C1—H1A	109.9
N1^i—Zn1—N1^iv	92.94 (5)	C1^iii—C1—H1A	109.9
N1^ii—Zn1—N1^iv	170.22 (7)	N1—C1—H1B	109.9
N1—Zn1—N1^iv	92.95 (5)	C1^iii—C1—H1B	109.9
N1^iii—Zn1—N1^iv	94.52 (7)	H1A—C1—H1B	108.3
N1^i—Zn1—N1^v	94.52 (7)	O1^ix—S1—O1	111.4 (6)
N1^ii—Zn1—N1^v	92.94 (5)	O1^ix—S1—O2	110.9 (4)
N1—Zn1—N1^v	170.22 (7)	O1—S1—O2	108.7 (3)
N1^iii—Zn1—N1^v	92.94 (5)	O1^ix—S1—O2^ix	108.7 (3)
N1^iv—Zn1—N1^v	80.38 (7)	O1—S1—O2^ix	110.9 (4)
C1—N1—Zn1	107.80 (9)	O2—S1—O2^ix	106.2 (7)
C1—N1—H1N	107.0 (16)
N1^i—Zn1—N1—C1	172.18 (10)	N1^iv—Zn1—N1—C1	79.08 (12)
N1^ii—Zn1—N1—C1	−107.24 (10)	Zn1—N1—C1—C1^iii	42.20 (17)
N1^iii—Zn1—N1—C1	−15.02 (7)

Symmetry codes: (i) −x+y+1, −x+1, z; (ii) −y+1, −x+1, −z+1/2; (iii) x, x−y, −z+1/2; (iv) −y+1, x−y, z; (v) −x+y+1, y, −z+1/2; (vi) −x+y, −x+1, z; (vii) −y+1, x−y+1, z; (viii) x, x−y+1, −z+1/2; (ix) −x+y, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1	0.86 (3)	1.97 (3)	2.823 (5)	170 (2)
N1—H2N···O2^x	0.86 (2)	2.15 (2)	3.006 (5)	177 (2)

Symmetry code: (x) x−y+1, x, −z.

(1d)

Crystal data

C6H24N6Zn·O4S	Dx = 1.694 Mg m^−3
Mr = 341.74	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P31c	Cell parameters from 10489 reflections
Hall symbol: -P 3 2c	θ = 2.1–35.0°
a = 8.9790 (1) Å	µ = 2.01 mm^−1
c = 9.5973 (2) Å	T = 230 K
V = 670.09 (2) Å^3	Needle, colourless
Z = 2	0.30 × 0.09 × 0.09 mm
F(000) = 360

Data collection

Nonius KappaCCD diffractometer	694 independent reflections
Radiation source: rotating anode	649 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
φ and ω scans	θmax = 30.5°, θmin = 2.6°
Absorption correction: analytical SADABS-2008/1 (Sheldrick, 2008b)	h = −12→12
Tmin = 0.625, Tmax = 0.878	k = −12→12
10896 measured reflections	l = −13→13

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)] = 0.023	Hydrogen site location: difference Fourier map
wR(F^2) = 0.061	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0331P)^2 + 0.3399P] where P = (Fo^2 + 2Fc^2)/3
694 reflections	(Δ/σ)max < 0.001
49 parameters	Δρmax = 0.59 e Å^−3
16 restraints	Δρmin = −0.24 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	Occ. (<1)
Zn1	0.6667	0.3333	0.2500	0.01825 (12)
N1	0.45172 (17)	0.30921 (18)	0.12541 (14)	0.0278 (3)
H1N	0.434 (3)	0.395 (3)	0.138 (3)	0.043 (6)*
H2N	0.471 (3)	0.305 (3)	0.040 (2)	0.046 (6)*
C1	0.29538 (19)	0.1530 (2)	0.17114 (17)	0.0312 (3)
H1A	0.2921	0.0513	0.1305	0.037*
H1B	0.1933	0.1564	0.1396	0.037*
S1	0.3333	0.6667	0.2500	0.01843 (16)
O1	0.3535 (11)	0.5634 (9)	0.1464 (5)	0.089 (3)	0.33333
O2	0.2836 (11)	0.7783 (10)	0.1823 (6)	0.110 (4)	0.33333

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.01837 (14)	0.01837 (14)	0.01802 (18)	0.00918 (7)	0.000	0.000
N1	0.0254 (6)	0.0340 (7)	0.0248 (6)	0.0153 (5)	−0.0031 (5)	0.0026 (5)
C1	0.0212 (6)	0.0354 (8)	0.0328 (7)	0.0109 (6)	−0.0055 (5)	−0.0055 (6)
S1	0.0188 (2)	0.0188 (2)	0.0177 (3)	0.00939 (11)	0.000	0.000
O1	0.196 (9)	0.106 (5)	0.035 (2)	0.127 (7)	0.014 (4)	−0.004 (3)
O2	0.228 (10)	0.156 (8)	0.049 (3)	0.173 (8)	0.019 (5)	0.028 (4)

Geometric parameters (Å, º)

Zn1—N1^i	2.1871 (13)	S1—O1^vi	1.432 (4)
Zn1—N1^ii	2.1871 (13)	S1—O1^vii	1.432 (4)
Zn1—N1^iii	2.1871 (13)	S1—O1^viii	1.432 (4)
Zn1—N1^iv	2.1871 (13)	S1—O1	1.432 (4)
Zn1—N1^v	2.1871 (13)	S1—O1^ix	1.432 (4)
Zn1—N1	2.1871 (13)	S1—O1^i	1.432 (4)
N1—C1	1.470 (2)	S1—O2^i	1.440 (4)
N1—H1N	0.87 (3)	S1—O2	1.440 (4)
N1—H2N	0.84 (2)	S1—O2^vii	1.440 (4)
C1—C1^ii	1.517 (3)	S1—O2^vi	1.440 (4)
C1—H1A	0.9800	S1—O2^ix	1.440 (4)
C1—H1B	0.9800	S1—O2^viii	1.440 (4)
N1^i—Zn1—N1^ii	92.96 (5)	Zn1—N1—H1N	112.3 (16)
N1^i—Zn1—N1^iii	92.96 (5)	C1—N1—H2N	111.4 (17)
N1^ii—Zn1—N1^iii	92.96 (5)	Zn1—N1—H2N	110.3 (17)
N1^i—Zn1—N1^iv	80.33 (7)	H1N—N1—H2N	108 (2)
N1^ii—Zn1—N1^iv	170.16 (8)	N1—C1—C1^ii	109.14 (11)
N1^iii—Zn1—N1^iv	94.55 (8)	N1—C1—H1A	109.9
N1^i—Zn1—N1^v	170.16 (8)	C1^ii—C1—H1A	109.9
N1^ii—Zn1—N1^v	94.55 (8)	N1—C1—H1B	109.9
N1^iii—Zn1—N1^v	80.33 (7)	C1^ii—C1—H1B	109.9
N1^iv—Zn1—N1^v	92.96 (5)	H1A—C1—H1B	108.3
N1^i—Zn1—N1	94.55 (8)	O1^vii—S1—O1	111.8 (6)
N1^ii—Zn1—N1	80.33 (7)	O1^vii—S1—O2	110.8 (5)
N1^iii—Zn1—N1	170.16 (8)	O1—S1—O2	108.7 (3)
N1^iv—Zn1—N1	92.96 (5)	O1^vii—S1—O2^vii	108.7 (3)
N1^v—Zn1—N1	92.96 (5)	O1—S1—O2^vii	110.8 (5)
C1—N1—Zn1	107.79 (9)	O2—S1—O2^vii	105.9 (7)
C1—N1—H1N	107.2 (16)
N1^i—Zn1—N1—C1	−107.19 (11)	N1^v—Zn1—N1—C1	79.17 (13)
N1^ii—Zn1—N1—C1	−14.95 (7)	Zn1—N1—C1—C1^ii	42.11 (18)
N1^iv—Zn1—N1—C1	172.29 (10)

Symmetry codes: (i) −y+1, −x+1, −z+1/2; (ii) x, x−y, −z+1/2; (iii) −x+y+1, y, −z+1/2; (iv) −x+y+1, −x+1, z; (v) −y+1, x−y, z; (vi) x, x−y+1, −z+1/2; (vii) −x+y, y, −z+1/2; (viii) −x+y, −x+1, z; (ix) −y+1, x−y+1, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1	0.87 (3)	1.98 (3)	2.835 (5)	169 (2)
N1—H2N···O2^x	0.84 (2)	2.18 (2)	3.019 (6)	177 (2)

Symmetry code: (x) x−y+1, x, −z.

(1e)

Crystal data

C6H24N6Zn·O4S	Dx = 1.690 Mg m^−3
Mr = 341.74	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P31c	Cell parameters from 10365 reflections
Hall symbol: -P 3 2c	θ = 2.1–35.0°
a = 8.9855 (2) Å	µ = 2.00 mm^−1
c = 9.6043 (1) Å	T = 260 K
V = 671.55 (3) Å^3	Needle, colourless
Z = 2	0.30 × 0.09 × 0.09 mm
F(000) = 360

Data collection

Nonius KappaCCD diffractometer	694 independent reflections
Radiation source: rotating anode	653 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
φ and ω scans	θmax = 30.5°, θmin = 2.6°
Absorption correction: analytical SADABS-2008/1 (Sheldrick, 2008b)	h = −12→12
Tmin = 0.621, Tmax = 0.874	k = −12→12
11110 measured reflections	l = −13→13

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)] = 0.024	Hydrogen site location: difference Fourier map
wR(F^2) = 0.063	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0373P)^2 + 0.3022P] where P = (Fo^2 + 2Fc^2)/3
694 reflections	(Δ/σ)max < 0.001
49 parameters	Δρmax = 0.66 e Å^−3
16 restraints	Δρmin = −0.29 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	Occ. (<1)
Zn1	0.6667	0.3333	0.2500	0.02039 (13)
N1	0.45185 (18)	0.30916 (19)	0.12549 (14)	0.0302 (3)
H1N	0.432 (3)	0.393 (4)	0.136 (3)	0.048 (6)*
H2N	0.471 (3)	0.303 (3)	0.038 (2)	0.045 (6)*
C1	0.2958 (2)	0.1531 (2)	0.17122 (18)	0.0343 (3)
H1A	0.2927	0.0525	0.1311	0.041*
H1B	0.1948	0.1563	0.1399	0.041*
S1	0.3333	0.6667	0.2500	0.02050 (17)
O1	0.3538 (12)	0.5637 (9)	0.1465 (5)	0.096 (3)	0.33333
O2	0.2838 (11)	0.7780 (10)	0.1822 (6)	0.115 (4)	0.33333

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.02054 (15)	0.02054 (15)	0.02010 (19)	0.01027 (7)	0.000	0.000
N1	0.0281 (6)	0.0368 (7)	0.0268 (6)	0.0170 (5)	−0.0035 (5)	0.0027 (5)
C1	0.0232 (6)	0.0385 (8)	0.0365 (8)	0.0118 (6)	−0.0063 (6)	−0.0058 (6)
S1	0.0207 (2)	0.0207 (2)	0.0201 (3)	0.01036 (11)	0.000	0.000
O1	0.202 (10)	0.112 (6)	0.042 (3)	0.131 (7)	0.013 (4)	−0.007 (3)
O2	0.233 (11)	0.158 (8)	0.058 (4)	0.175 (9)	0.018 (5)	0.029 (4)

Geometric parameters (Å, º)

Zn1—N1^i	2.1871 (13)	S1—O1^vi	1.432 (4)
Zn1—N1^ii	2.1871 (13)	S1—O1	1.432 (4)
Zn1—N1^iii	2.1871 (13)	S1—O1^iv	1.432 (4)
Zn1—N1	2.1872 (13)	S1—O1^vii	1.432 (4)
Zn1—N1^iv	2.1872 (13)	S1—O1^viii	1.432 (4)
Zn1—N1^v	2.1872 (13)	S1—O1^ix	1.432 (4)
N1—C1	1.469 (2)	S1—O2^vii	1.438 (5)
N1—H1N	0.86 (3)	S1—O2^ix	1.438 (5)
N1—H2N	0.87 (2)	S1—O2^viii	1.438 (5)
C1—C1^iii	1.516 (3)	S1—O2^iv	1.438 (5)
C1—H1A	0.9700	S1—O2	1.438 (5)
C1—H1B	0.9700	S1—O2^vi	1.438 (5)
N1^i—Zn1—N1^ii	80.31 (7)	Zn1—N1—H1N	114.1 (18)
N1^i—Zn1—N1^iii	92.96 (5)	C1—N1—H2N	110.9 (16)
N1^ii—Zn1—N1^iii	94.58 (8)	Zn1—N1—H2N	110.3 (17)
N1^i—Zn1—N1	170.13 (8)	H1N—N1—H2N	107 (2)
N1^ii—Zn1—N1	92.96 (5)	N1—C1—C1^iii	109.13 (11)
N1^iii—Zn1—N1	80.31 (7)	N1—C1—H1A	109.9
N1^i—Zn1—N1^iv	92.96 (5)	C1^iii—C1—H1A	109.9
N1^ii—Zn1—N1^iv	170.13 (8)	N1—C1—H1B	109.9
N1^iii—Zn1—N1^iv	92.96 (5)	C1^iii—C1—H1B	109.9
N1—Zn1—N1^iv	94.58 (8)	H1A—C1—H1B	108.3
N1^i—Zn1—N1^v	94.58 (8)	O1^vi—S1—O1	111.9 (6)
N1^ii—Zn1—N1^v	92.96 (5)	O1^vi—S1—O2	110.8 (5)
N1^iii—Zn1—N1^v	170.13 (8)	O1—S1—O2	108.7 (3)
N1—Zn1—N1^v	92.96 (5)	O1^vi—S1—O2^vi	108.7 (3)
N1^iv—Zn1—N1^v	80.31 (7)	O1—S1—O2^vi	110.8 (5)
C1—N1—Zn1	107.76 (10)	O2—S1—O2^vi	105.9 (7)
C1—N1—H1N	106.6 (17)
N1^ii—Zn1—N1—C1	79.17 (13)	N1^v—Zn1—N1—C1	172.29 (10)
N1^iii—Zn1—N1—C1	−14.98 (8)	Zn1—N1—C1—C1^iii	42.19 (18)
N1^iv—Zn1—N1—C1	−107.20 (11)

Symmetry codes: (i) −x+y+1, y, −z+1/2; (ii) −y+1, x−y, z; (iii) x, x−y, −z+1/2; (iv) −y+1, −x+1, −z+1/2; (v) −x+y+1, −x+1, z; (vi) −x+y, y, −z+1/2; (vii) x, x−y+1, −z+1/2; (viii) −x+y, −x+1, z; (ix) −y+1, x−y+1, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1	0.86 (3)	1.99 (3)	2.839 (5)	172 (3)
N1—H2N···O2^x	0.87 (2)	2.16 (2)	3.022 (6)	177 (2)

Symmetry code: (x) x−y+1, x, −z.

(1f)

Crystal data

C6H24N6Zn·O4S	Dx = 1.686 Mg m^−3
Mr = 341.74	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P31c	Cell parameters from 10072 reflections
Hall symbol: -P 3 2c	θ = 2.1–34.9°
a = 8.9929 (2) Å	µ = 2.00 mm^−1
c = 9.6101 (2) Å	T = 290 K
V = 673.07 (3) Å^3	Needle, colourless
Z = 2	0.30 × 0.09 × 0.09 mm
F(000) = 360

Data collection

Nonius KappaCCD diffractometer	696 independent reflections
Radiation source: rotating anode	647 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
φ and ω scans	θmax = 30.5°, θmin = 2.6°
Absorption correction: analytical SADABS-2008/1 (Sheldrick, 2008b)	h = −12→12
Tmin = 0.627, Tmax = 0.872	k = −12→12
11155 measured reflections	l = −13→13

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)] = 0.023	Hydrogen site location: difference Fourier map
wR(F^2) = 0.064	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0402P)^2 + 0.1924P] where P = (Fo^2 + 2Fc^2)/3
696 reflections	(Δ/σ)max < 0.001
49 parameters	Δρmax = 0.62 e Å^−3
16 restraints	Δρmin = −0.29 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	Occ. (<1)
Zn1	0.6667	0.3333	0.2500	0.02240 (13)
N1	0.45193 (17)	0.30908 (19)	0.12575 (14)	0.0328 (3)
H1N	0.432 (3)	0.392 (4)	0.136 (3)	0.053 (6)*
H2N	0.469 (3)	0.304 (3)	0.038 (2)	0.050 (6)*
C1	0.2960 (2)	0.1532 (2)	0.17146 (18)	0.0375 (3)
H1A	0.2929	0.0527	0.1314	0.045*
H1B	0.1951	0.1564	0.1402	0.045*
S1	0.3333	0.6667	0.2500	0.02259 (16)
O1	0.3543 (12)	0.5644 (9)	0.1464 (5)	0.100 (3)	0.33333
O2	0.2843 (11)	0.7782 (10)	0.1825 (6)	0.119 (4)	0.33333

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.02248 (15)	0.02248 (15)	0.02224 (19)	0.01124 (7)	0.000	0.000
N1	0.0302 (6)	0.0399 (7)	0.0295 (6)	0.0185 (5)	−0.0038 (5)	0.0024 (5)
C1	0.0255 (6)	0.0417 (8)	0.0407 (8)	0.0134 (6)	−0.0072 (6)	−0.0070 (6)
S1	0.0230 (2)	0.0230 (2)	0.0218 (3)	0.01150 (11)	0.000	0.000
O1	0.206 (10)	0.116 (6)	0.045 (3)	0.131 (7)	0.015 (4)	−0.008 (3)
O2	0.239 (11)	0.159 (8)	0.063 (4)	0.177 (9)	0.020 (5)	0.028 (4)

Geometric parameters (Å, º)

Zn1—N1^i	2.1866 (13)	S1—O1^v	1.430 (4)
Zn1—N1^ii	2.1866 (13)	S1—O1^vi	1.430 (4)
Zn1—N1^iii	2.1866 (13)	S1—O1	1.430 (4)
Zn1—N1	2.1866 (13)	S1—O1^vii	1.430 (4)
Zn1—N1^iv	2.1866 (13)	S1—O1^viii	1.430 (4)
Zn1—N1^v	2.1867 (13)	S1—O1^ix	1.430 (4)
N1—C1	1.469 (2)	S1—O2^vii	1.436 (5)
N1—H1N	0.86 (3)	S1—O2	1.436 (5)
N1—H2N	0.86 (2)	S1—O2^ix	1.436 (5)
C1—C1^iii	1.512 (3)	S1—O2^vi	1.436 (5)
C1—H1A	0.9700	S1—O2^viii	1.436 (5)
C1—H1B	0.9700	S1—O2^v	1.436 (5)
N1^i—Zn1—N1^ii	80.22 (7)	Zn1—N1—H1N	114.3 (18)
N1^i—Zn1—N1^iii	93.02 (5)	C1—N1—H2N	110.8 (16)
N1^ii—Zn1—N1^iii	94.56 (8)	Zn1—N1—H2N	111.4 (17)
N1^i—Zn1—N1	170.09 (8)	H1N—N1—H2N	106 (2)
N1^ii—Zn1—N1	93.02 (5)	N1—C1—C1^iii	109.14 (11)
N1^iii—Zn1—N1	80.22 (7)	N1—C1—H1A	109.9
N1^i—Zn1—N1^iv	94.56 (8)	C1^iii—C1—H1A	109.9
N1^ii—Zn1—N1^iv	93.02 (5)	N1—C1—H1B	109.9
N1^iii—Zn1—N1^iv	170.09 (8)	C1^iii—C1—H1B	109.9
N1—Zn1—N1^iv	93.02 (5)	H1A—C1—H1B	108.3
N1^i—Zn1—N1^v	93.02 (5)	O1^vi—S1—O1	112.3 (6)
N1^ii—Zn1—N1^v	170.09 (8)	O1^vi—S1—O2	110.7 (5)
N1^iii—Zn1—N1^v	93.02 (5)	O1—S1—O2	108.7 (3)
N1—Zn1—N1^v	94.56 (8)	O1^vi—S1—O2^vi	108.7 (3)
N1^iv—Zn1—N1^v	80.22 (7)	O1—S1—O2^vi	110.7 (5)
C1—N1—Zn1	107.80 (10)	O2—S1—O2^vi	105.6 (7)
C1—N1—H1N	106.5 (18)
N1^ii—Zn1—N1—C1	79.15 (13)	N1^v—Zn1—N1—C1	−107.24 (11)
N1^iii—Zn1—N1—C1	−14.96 (8)	Zn1—N1—C1—C1^iii	42.21 (18)
N1^iv—Zn1—N1—C1	172.34 (10)

Symmetry codes: (i) −x+y+1, y, −z+1/2; (ii) −y+1, x−y, z; (iii) x, x−y, −z+1/2; (iv) −x+y+1, −x+1, z; (v) −y+1, −x+1, −z+1/2; (vi) −x+y, y, −z+1/2; (vii) x, x−y+1, −z+1/2; (viii) −y+1, x−y+1, z; (ix) −x+y, −x+1, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1	0.86 (3)	1.99 (3)	2.846 (6)	172 (3)
N1—H2N···O2^x	0.86 (2)	2.17 (2)	3.029 (6)	178 (2)

Symmetry code: (x) x−y+1, x, −z.

(2a)

Crystal data

C6H24CuN6·O4S	Dx = 1.704 Mg m^−3
Mr = 339.91	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P31c	Cell parameters from 9767 reflections
Hall symbol: -P 3 2c	θ = 2.1–35.0°
a = 8.9387 (1) Å	µ = 1.82 mm^−1
c = 9.5766 (1) Å	T = 190 K
V = 662.66 (2) Å^3	Plate, blue
Z = 2	0.33 × 0.15 × 0.06 mm
F(000) = 358

Data collection

Nonius KappaCCD diffractometer	683 independent reflections
Radiation source: rotating anode	644 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
φ and ω scans	θmax = 30.5°, θmin = 2.6°
Absorption correction: analytical SADABS-2008/1 (Sheldrick, 2008b)	h = −12→12
Tmin = 0.580, Tmax = 0.940	k = −12→12
9708 measured reflections	l = −13→13

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)] = 0.022	Hydrogen site location: difference Fourier map
wR(F^2) = 0.056	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ^2(Fo^2) + (0.0277P)^2 + 0.3168P] where P = (Fo^2 + 2Fc^2)/3
683 reflections	(Δ/σ)max < 0.001
49 parameters	Δρmax = 0.45 e Å^−3
16 restraints	Δρmin = −0.28 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	Occ. (<1)
Cu1	0.6667	0.3333	0.2500	0.01628 (11)
N1	0.45572 (19)	0.31150 (19)	0.12709 (15)	0.0333 (3)
H1N	0.435 (3)	0.390 (3)	0.135 (2)	0.039 (6)*
H2N	0.471 (3)	0.305 (3)	0.042 (2)	0.050 (6)*
C1	0.29734 (18)	0.1540 (2)	0.17112 (16)	0.0298 (3)
H1A	0.2940	0.0509	0.1297	0.036*
H1B	0.1943	0.1583	0.1390	0.036*
S1	0.3333	0.6667	0.2500	0.01729 (15)
O1	0.3523 (10)	0.5611 (8)	0.1455 (4)	0.081 (2)	0.33333
O2	0.2834 (10)	0.7788 (9)	0.1815 (6)	0.104 (3)	0.33333

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.01773 (13)	0.01773 (13)	0.01339 (17)	0.00886 (7)	0.000	0.000
N1	0.0369 (7)	0.0313 (6)	0.0302 (6)	0.0159 (6)	0.0085 (5)	0.0030 (5)
C1	0.0216 (6)	0.0342 (7)	0.0292 (7)	0.0105 (5)	−0.0037 (5)	−0.0036 (5)
S1	0.0185 (2)	0.0185 (2)	0.0150 (3)	0.00923 (10)	0.000	0.000
O1	0.170 (7)	0.102 (5)	0.032 (2)	0.114 (5)	−0.003 (3)	−0.016 (3)
O2	0.210 (9)	0.133 (6)	0.058 (3)	0.154 (7)	0.013 (4)	0.024 (4)

Geometric parameters (Å, º)

Cu1—N1	2.1473 (16)	S1—O1^vi	1.442 (4)
Cu1—N1^i	2.1473 (16)	S1—O1^vii	1.442 (4)
Cu1—N1^ii	2.1473 (16)	S1—O1^viii	1.442 (4)
Cu1—N1^iii	2.1473 (16)	S1—O1	1.442 (4)
Cu1—N1^iv	2.1473 (16)	S1—O1^v	1.442 (4)
Cu1—N1^v	2.1473 (16)	S1—O1^ix	1.442 (4)
N1—C1	1.473 (2)	S1—O2^vii	1.443 (4)
N1—H1N	0.81 (3)	S1—O2^vi	1.443 (4)
N1—H2N	0.83 (2)	S1—O2	1.443 (4)
C1—C1^iv	1.514 (3)	S1—O2^ix	1.443 (4)
C1—H1A	0.9900	S1—O2^v	1.443 (4)
C1—H1B	0.9900	S1—O2^viii	1.443 (4)
N1—Cu1—N1^i	92.83 (5)	Cu1—N1—H1N	115.8 (16)
N1—Cu1—N1^ii	92.82 (5)	C1—N1—H2N	109.0 (17)
N1^i—Cu1—N1^ii	92.83 (5)	Cu1—N1—H2N	111.8 (18)
N1—Cu1—N1^iii	170.97 (8)	H1N—N1—H2N	106 (2)
N1^i—Cu1—N1^iii	80.99 (7)	N1—C1—C1^iv	108.40 (10)
N1^ii—Cu1—N1^iii	94.04 (8)	N1—C1—H1A	110.0
N1—Cu1—N1^iv	80.99 (7)	C1^iv—C1—H1A	110.0
N1^i—Cu1—N1^iv	94.04 (8)	N1—C1—H1B	110.0
N1^ii—Cu1—N1^iv	170.97 (8)	C1^iv—C1—H1B	110.0
N1^iii—Cu1—N1^iv	92.82 (5)	H1A—C1—H1B	108.4
N1—Cu1—N1^v	94.04 (8)	O1^viii—S1—O1	111.0 (5)
N1^i—Cu1—N1^v	170.97 (8)	O1^viii—S1—O2	111.3 (4)
N1^ii—Cu1—N1^v	80.99 (7)	O1—S1—O2	108.5 (3)
N1^iii—Cu1—N1^v	92.82 (5)	O1^viii—S1—O2^viii	108.5 (3)
N1^iv—Cu1—N1^v	92.82 (5)	O1—S1—O2^viii	111.3 (4)
C1—N1—Cu1	108.09 (10)	O2—S1—O2^viii	106.0 (6)
C1—N1—H1N	105.9 (16)
N1^i—Cu1—N1—C1	78.55 (13)	N1^v—Cu1—N1—C1	−107.32 (11)
N1^ii—Cu1—N1—C1	171.52 (10)	Cu1—N1—C1—C1^iv	42.31 (17)
N1^iv—Cu1—N1—C1	−15.09 (7)

Symmetry codes: (i) −y+1, x−y, z; (ii) −x+y+1, −x+1, z; (iii) −x+y+1, y, −z+1/2; (iv) x, x−y, −z+1/2; (v) −y+1, −x+1, −z+1/2; (vi) −y+1, x−y+1, z; (vii) −x+y, −x+1, z; (viii) −x+y, y, −z+1/2; (ix) x, x−y+1, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1	0.81 (3)	2.01 (3)	2.816 (5)	172 (2)
N1—H2N···O2^x	0.83 (2)	2.19 (2)	3.017 (6)	179 (2)

Symmetry code: (x) x−y+1, x, −z.

(2b)

Crystal data

C6H24CuN6·O4S	Dx = 1.700 Mg m^−3
Mr = 339.91	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P31c	Cell parameters from 9618 reflections
Hall symbol: -P 3 2c	θ = 2.1–35.0°
a = 8.9445 (1) Å	µ = 1.82 mm^−1
c = 9.5826 (1) Å	T = 210 K
V = 663.94 (2) Å^3	Plate, blue
Z = 2	0.33 × 0.15 × 0.06 mm
F(000) = 358

Data collection

Nonius KappaCCD diffractometer	685 independent reflections
Radiation source: rotating anode	637 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
φ and ω scans	θmax = 30.5°, θmin = 2.6°
Absorption correction: analytical SADABS-2008/1 (Sheldrick, 2008b)	h = −12→12
Tmin = 0.581, Tmax = 0.940	k = −12→12
9739 measured reflections	l = −13→13

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)] = 0.022	Hydrogen site location: difference Fourier map
wR(F^2) = 0.057	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0302P)^2 + 0.2851P] where P = (Fo^2 + 2Fc^2)/3
685 reflections	(Δ/σ)max < 0.001
49 parameters	Δρmax = 0.46 e Å^−3
16 restraints	Δρmin = −0.26 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	Occ. (<1)
Cu1	0.6667	0.3333	0.2500	0.01760 (12)
N1	0.4559 (2)	0.31159 (19)	0.12711 (15)	0.0352 (3)
H1N	0.435 (3)	0.390 (3)	0.135 (2)	0.047 (6)*
H2N	0.468 (3)	0.304 (3)	0.042 (2)	0.051 (6)*
C1	0.29761 (19)	0.1542 (2)	0.17121 (16)	0.0319 (3)
H1A	0.2942	0.0522	0.1302	0.038*
H1B	0.1956	0.1584	0.1394	0.038*
S1	0.3333	0.6667	0.2500	0.01877 (15)
O1	0.3531 (11)	0.5622 (9)	0.1458 (5)	0.087 (2)	0.33333
O2	0.2842 (11)	0.7787 (9)	0.1813 (6)	0.107 (3)	0.33333

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.01900 (14)	0.01900 (14)	0.01480 (17)	0.00950 (7)	0.000	0.000
N1	0.0385 (7)	0.0341 (7)	0.0318 (6)	0.0173 (6)	0.0084 (5)	0.0036 (5)
C1	0.0240 (6)	0.0358 (7)	0.0319 (7)	0.0120 (5)	−0.0045 (5)	−0.0041 (6)
S1	0.0200 (2)	0.0200 (2)	0.0163 (3)	0.01000 (10)	0.000	0.000
O1	0.177 (8)	0.108 (5)	0.037 (2)	0.117 (6)	−0.002 (3)	−0.018 (3)
O2	0.212 (10)	0.139 (7)	0.064 (3)	0.157 (8)	0.018 (5)	0.028 (4)

Geometric parameters (Å, º)

Cu1—N1^i	2.1479 (16)	S1—O1^ii	1.438 (4)
Cu1—N1^ii	2.1479 (16)	S1—O1^vi	1.438 (4)
Cu1—N1^iii	2.1479 (16)	S1—O1^vii	1.438 (4)
Cu1—N1	2.1479 (16)	S1—O1	1.438 (4)
Cu1—N1^iv	2.1479 (16)	S1—O1^viii	1.438 (4)
Cu1—N1^v	2.1479 (16)	S1—O1^ix	1.438 (4)
N1—C1	1.474 (2)	S1—O2	1.439 (4)
N1—H1N	0.81 (3)	S1—O2^vii	1.439 (4)
N1—H2N	0.83 (2)	S1—O2^ii	1.439 (4)
C1—C1^iii	1.513 (3)	S1—O2^vi	1.439 (4)
C1—H1A	0.9800	S1—O2^ix	1.439 (4)
C1—H1B	0.9800	S1—O2^viii	1.439 (4)
N1^i—Cu1—N1^ii	92.82 (5)	Cu1—N1—H1N	115.9 (17)
N1^i—Cu1—N1^iii	92.82 (5)	C1—N1—H2N	108.0 (17)
N1^ii—Cu1—N1^iii	92.82 (5)	Cu1—N1—H2N	113.4 (18)
N1^i—Cu1—N1	171.00 (8)	H1N—N1—H2N	105 (2)
N1^ii—Cu1—N1	94.02 (8)	N1—C1—C1^iii	108.45 (11)
N1^iii—Cu1—N1	81.02 (7)	N1—C1—H1A	110.0
N1^i—Cu1—N1^iv	94.02 (8)	C1^iii—C1—H1A	110.0
N1^ii—Cu1—N1^iv	81.02 (7)	N1—C1—H1B	110.0
N1^iii—Cu1—N1^iv	171.00 (8)	C1^iii—C1—H1B	110.0
N1—Cu1—N1^iv	92.82 (5)	H1A—C1—H1B	108.4
N1^i—Cu1—N1^v	81.02 (7)	O1^vii—S1—O1	111.5 (6)
N1^ii—Cu1—N1^v	171.00 (8)	O1^vii—S1—O2	111.4 (5)
N1^iii—Cu1—N1^v	94.02 (8)	O1—S1—O2	108.3 (3)
N1—Cu1—N1^v	92.82 (5)	O2—S1—O2^vii	105.8 (7)
N1^iv—Cu1—N1^v	92.82 (5)	O1^vii—S1—O2^vii	108.3 (3)
C1—N1—Cu1	108.04 (10)	O1—S1—O2^vii	111.4 (5)
C1—N1—H1N	105.8 (17)
N1^ii—Cu1—N1—C1	−107.29 (11)	N1^v—Cu1—N1—C1	78.56 (13)
N1^iii—Cu1—N1—C1	−15.07 (7)	Cu1—N1—C1—C1^iii	42.28 (17)
N1^iv—Cu1—N1—C1	171.52 (10)

Symmetry codes: (i) −x+y+1, y, −z+1/2; (ii) −y+1, −x+1, −z+1/2; (iii) x, x−y, −z+1/2; (iv) −x+y+1, −x+1, z; (v) −y+1, x−y, z; (vi) x, x−y+1, −z+1/2; (vii) −x+y, y, −z+1/2; (viii) −y+1, x−y+1, z; (ix) −x+y, −x+1, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1	0.81 (3)	2.01 (3)	2.821 (5)	172 (2)
N1—H2N···O2^x	0.83 (2)	2.19 (2)	3.017 (6)	179 (2)

Symmetry code: (x) x−y+1, x, −z.

(2c)

Crystal data

C6H24CuN6·O4S	Dx = 1.697 Mg m^−3
Mr = 339.91	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P31c	Cell parameters from 9445 reflections
Hall symbol: -P 3 2c	θ = 2.1–35.0°
a = 8.9513 (1) Å	µ = 1.82 mm^−1
c = 9.5876 (1) Å	T = 230 K
V = 665.29 (2) Å^3	Plate, blue
Z = 2	0.33 × 0.15 × 0.06 mm
F(000) = 358

Data collection

Nonius KappaCCD diffractometer	687 independent reflections
Radiation source: rotating anode	642 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
φ and ω scans	θmax = 30.5°, θmin = 2.6°
Absorption correction: analytical SADABS-2008/1 (Sheldrick, 2008b)	h = −12→12
Tmin = 0.578, Tmax = 0.937	k = −12→12
9736 measured reflections	l = −13→13

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)] = 0.023	Hydrogen site location: difference Fourier map
wR(F^2) = 0.060	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ^2(Fo^2) + (0.0315P)^2 + 0.2737P] where P = (Fo^2 + 2Fc^2)/3
687 reflections	(Δ/σ)max < 0.001
49 parameters	Δρmax = 0.51 e Å^−3
16 restraints	Δρmin = −0.28 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	Occ. (<1)
Cu1	0.6667	0.3333	0.2500	0.01892 (12)
N1	0.4561 (2)	0.3115 (2)	0.12728 (16)	0.0369 (3)
H1N	0.437 (3)	0.390 (4)	0.135 (3)	0.048 (7)*
H2N	0.469 (3)	0.304 (3)	0.043 (3)	0.052 (7)*
C1	0.2978 (2)	0.1543 (2)	0.17130 (17)	0.0339 (3)
H1A	0.2944	0.0523	0.1303	0.041*
H1B	0.1960	0.1586	0.1395	0.041*
S1	0.3333	0.6667	0.2500	0.02010 (16)
O1	0.3538 (11)	0.5626 (9)	0.1460 (5)	0.091 (3)	0.33333
O2	0.2842 (11)	0.7787 (10)	0.1816 (6)	0.113 (4)	0.33333

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.02039 (15)	0.02039 (15)	0.01598 (18)	0.01020 (7)	0.000	0.000
N1	0.0410 (8)	0.0362 (7)	0.0327 (7)	0.0186 (6)	0.0079 (6)	0.0036 (5)
C1	0.0248 (7)	0.0386 (8)	0.0340 (7)	0.0126 (6)	−0.0049 (5)	−0.0044 (6)
S1	0.0214 (2)	0.0214 (2)	0.0176 (3)	0.01069 (11)	0.000	0.000
O1	0.187 (9)	0.112 (5)	0.040 (3)	0.123 (6)	0.002 (4)	−0.016 (3)
O2	0.225 (11)	0.142 (7)	0.069 (4)	0.164 (8)	0.016 (5)	0.029 (4)

Geometric parameters (Å, º)

Cu1—N1^i	2.1466 (17)	S1—O1^vi	1.437 (4)
Cu1—N1^ii	2.1466 (17)	S1—O1^vii	1.437 (4)
Cu1—N1^iii	2.1467 (17)	S1—O1^viii	1.437 (4)
Cu1—N1	2.1467 (17)	S1—O1^ii	1.437 (4)
Cu1—N1^iv	2.1467 (17)	S1—O1^ix	1.437 (4)
Cu1—N1^v	2.1467 (17)	S1—O1	1.437 (4)
N1—C1	1.474 (2)	S1—O2^vi	1.439 (4)
N1—H1N	0.80 (3)	S1—O2^vii	1.439 (4)
N1—H2N	0.83 (2)	S1—O2	1.439 (4)
C1—C1^iii	1.512 (3)	S1—O2^ix	1.439 (4)
C1—H1A	0.9800	S1—O2^viii	1.439 (4)
C1—H1B	0.9800	S1—O2^ii	1.439 (4)
N1^i—Cu1—N1^ii	80.98 (8)	Cu1—N1—H1N	115.6 (18)
N1^i—Cu1—N1^iii	170.96 (9)	C1—N1—H2N	108.0 (18)
N1^ii—Cu1—N1^iii	92.83 (6)	Cu1—N1—H2N	113.1 (19)
N1^i—Cu1—N1	92.83 (6)	H1N—N1—H2N	105 (3)
N1^ii—Cu1—N1	94.04 (9)	N1—C1—C1^iii	108.42 (11)
N1^iii—Cu1—N1	80.98 (8)	N1—C1—H1A	110.0
N1^i—Cu1—N1^iv	92.83 (6)	C1^iii—C1—H1A	110.0
N1^ii—Cu1—N1^iv	170.96 (9)	N1—C1—H1B	110.0
N1^iii—Cu1—N1^iv	94.04 (9)	C1^iii—C1—H1B	110.0
N1—Cu1—N1^iv	92.83 (6)	H1A—C1—H1B	108.4
N1^i—Cu1—N1^v	94.04 (9)	O1^ix—S1—O1	111.7 (6)
N1^ii—Cu1—N1^v	92.83 (6)	O1^ix—S1—O2	111.1 (5)
N1^iii—Cu1—N1^v	92.83 (6)	O1—S1—O2	108.5 (3)
N1—Cu1—N1^v	170.96 (9)	O1^ix—S1—O2^ix	108.5 (3)
N1^iv—Cu1—N1^v	80.98 (8)	O1—S1—O2^ix	111.1 (5)
C1—N1—Cu1	108.12 (11)	O2—S1—O2^ix	105.7 (7)
C1—N1—H1N	106.4 (18)
N1^i—Cu1—N1—C1	171.56 (11)	N1^iv—Cu1—N1—C1	78.58 (14)
N1^ii—Cu1—N1—C1	−107.29 (12)	Cu1—N1—C1—C1^iii	42.25 (18)
N1^iii—Cu1—N1—C1	−15.06 (8)

Symmetry codes: (i) −x+y+1, −x+1, z; (ii) −y+1, −x+1, −z+1/2; (iii) x, x−y, −z+1/2; (iv) −y+1, x−y, z; (v) −x+y+1, y, −z+1/2; (vi) −x+y, −x+1, z; (vii) −y+1, x−y+1, z; (viii) x, x−y+1, −z+1/2; (ix) −x+y, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1	0.80 (3)	2.03 (3)	2.825 (6)	172 (3)
N1—H2N···O2^x	0.83 (2)	2.20 (3)	3.022 (6)	179 (2)

Symmetry code: (x) x−y+1, x, −z.

(2d)

Crystal data

C6H24CuN6·O4S	Dx = 1.694 Mg m^−3
Mr = 339.91	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P31c	Cell parameters from 9343 reflections
Hall symbol: -P 3 2c	θ = 2.1–35.0°
a = 8.9572 (1) Å	µ = 1.81 mm^−1
c = 9.5926 (1) Å	T = 250 K
V = 666.52 (2) Å^3	Plate, blue
Z = 2	0.33 × 0.15 × 0.06 mm
F(000) = 358

Data collection

Nonius KappaCCD diffractometer	687 independent reflections
Radiation source: rotating anode	638 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
φ and ω scans	θmax = 30.5°, θmin = 2.6°
Absorption correction: analytical SADABS-2008/1 (Sheldrick, 2008b)	h = −12→12
Tmin = 0.579, Tmax = 0.947	k = −12→12
9785 measured reflections	l = −13→13

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)] = 0.024	Hydrogen site location: difference Fourier map
wR(F^2) = 0.061	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ^2(Fo^2) + (0.031P)^2 + 0.3143P] where P = (Fo^2 + 2Fc^2)/3
687 reflections	(Δ/σ)max < 0.001
49 parameters	Δρmax = 0.52 e Å^−3
16 restraints	Δρmin = −0.29 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	Occ. (<1)
Cu1	0.6667	0.3333	0.2500	0.02025 (13)
N1	0.4560 (2)	0.3115 (2)	0.12733 (17)	0.0385 (3)
H1N	0.436 (3)	0.390 (4)	0.135 (3)	0.048 (7)*
H2N	0.469 (3)	0.304 (3)	0.043 (3)	0.056 (7)*
C1	0.2980 (2)	0.1544 (2)	0.17132 (18)	0.0361 (3)
H1A	0.2946	0.0526	0.1303	0.043*
H1B	0.1962	0.1587	0.1396	0.043*
S1	0.3333	0.6667	0.2500	0.02154 (16)
O1	0.3551 (12)	0.5636 (9)	0.1464 (5)	0.096 (3)	0.33333
O2	0.2847 (11)	0.7790 (10)	0.1813 (7)	0.116 (4)	0.33333

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.02168 (15)	0.02168 (15)	0.01737 (19)	0.01084 (7)	0.000	0.000
N1	0.0427 (8)	0.0376 (7)	0.0347 (7)	0.0198 (6)	0.0076 (6)	0.0034 (6)
C1	0.0266 (7)	0.0402 (8)	0.0370 (8)	0.0134 (6)	−0.0056 (6)	−0.0050 (6)
S1	0.0227 (2)	0.0227 (2)	0.0193 (3)	0.01133 (11)	0.000	0.000
O1	0.191 (9)	0.119 (6)	0.045 (3)	0.127 (7)	0.001 (4)	−0.019 (3)
O2	0.222 (11)	0.145 (8)	0.075 (4)	0.163 (9)	0.019 (5)	0.032 (5)

Geometric parameters (Å, º)

Cu1—N1^i	2.1479 (17)	S1—O1^vi	1.434 (4)
Cu1—N1^ii	2.1479 (17)	S1—O1^vii	1.434 (4)
Cu1—N1	2.1479 (17)	S1—O1	1.434 (4)
Cu1—N1^iii	2.1479 (17)	S1—O1^viii	1.434 (4)
Cu1—N1^iv	2.1479 (17)	S1—O1^iii	1.434 (4)
Cu1—N1^v	2.1479 (17)	S1—O1^ix	1.434 (4)
N1—C1	1.473 (2)	S1—O2^viii	1.440 (5)
N1—H1N	0.81 (3)	S1—O2^ix	1.440 (5)
N1—H2N	0.83 (3)	S1—O2	1.440 (5)
C1—C1^i	1.513 (3)	S1—O2^vii	1.440 (5)
C1—H1A	0.9800	S1—O2^vi	1.440 (5)
C1—H1B	0.9800	S1—O2^iii	1.440 (5)
N1^i—Cu1—N1^ii	94.01 (9)	Cu1—N1—H1N	116.1 (18)
N1^i—Cu1—N1	80.96 (8)	C1—N1—H2N	108.4 (18)
N1^ii—Cu1—N1	92.85 (6)	Cu1—N1—H2N	113.0 (19)
N1^i—Cu1—N1^iii	92.85 (6)	H1N—N1—H2N	105 (3)
N1^ii—Cu1—N1^iii	170.97 (9)	N1—C1—C1^i	108.44 (12)
N1—Cu1—N1^iii	94.01 (9)	N1—C1—H1A	110.0
N1^i—Cu1—N1^iv	92.85 (6)	C1^i—C1—H1A	110.0
N1^ii—Cu1—N1^iv	80.96 (8)	N1—C1—H1B	110.0
N1—Cu1—N1^iv	170.97 (9)	C1^i—C1—H1B	110.0
N1^iii—Cu1—N1^iv	92.85 (6)	H1A—C1—H1B	108.4
N1^i—Cu1—N1^v	170.97 (9)	O1^vi—S1—O1	112.3 (6)
N1^ii—Cu1—N1^v	92.85 (6)	O1^vi—S1—O2	110.8 (5)
N1—Cu1—N1^v	92.85 (6)	O1—S1—O2	108.6 (3)
N1^iii—Cu1—N1^v	80.96 (8)	O1^vi—S1—O2^vi	108.6 (3)
N1^iv—Cu1—N1^v	94.01 (9)	O1—S1—O2^vi	110.8 (5)
C1—N1—Cu1	108.10 (11)	O2—S1—O2^vi	105.6 (7)
C1—N1—H1N	106.3 (18)
N1^i—Cu1—N1—C1	−15.06 (8)	N1^v—Cu1—N1—C1	171.55 (11)
N1^ii—Cu1—N1—C1	78.55 (15)	Cu1—N1—C1—C1^i	42.26 (19)
N1^iii—Cu1—N1—C1	−107.32 (12)

Symmetry codes: (i) x, x−y, −z+1/2; (ii) −y+1, x−y, z; (iii) −y+1, −x+1, −z+1/2; (iv) −x+y+1, y, −z+1/2; (v) −x+y+1, −x+1, z; (vi) −x+y, y, −z+1/2; (vii) −x+y, −x+1, z; (viii) x, x−y+1, −z+1/2; (ix) −y+1, x−y+1, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1	0.81 (3)	2.02 (3)	2.827 (6)	173 (3)
N1—H2N···O2^x	0.83 (3)	2.19 (3)	3.022 (7)	180 (3)

Symmetry code: (x) x−y+1, x, −z.

(2e)

Crystal data

C6H24CuN6·O4S	Dx = 1.689 Mg m^−3
Mr = 339.91	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P31c	Cell parameters from 8734 reflections
Hall symbol: -P 3 2c	θ = 2.1–35.0°
a = 8.9664 (1) Å	µ = 1.81 mm^−1
c = 9.5996 (1) Å	T = 270 K
V = 668.38 (2) Å^3	Plate, blue
Z = 2	0.33 × 0.15 × 0.06 mm
F(000) = 358

Data collection

Nonius KappaCCD diffractometer	690 independent reflections
Radiation source: rotating anode	639 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
φ and ω scans	θmax = 30.5°, θmin = 2.6°
Absorption correction: analytical SADABS-2008/1 (Sheldrick, 2008b)	h = −12→12
Tmin = 0.578, Tmax = 0.947	k = −12→12
9819 measured reflections	l = −13→13

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)] = 0.025	Hydrogen site location: difference Fourier map
wR(F^2) = 0.065	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ^2(Fo^2) + (0.0364P)^2 + 0.2214P] where P = (Fo^2 + 2Fc^2)/3
690 reflections	(Δ/σ)max < 0.001
49 parameters	Δρmax = 0.56 e Å^−3
16 restraints	Δρmin = −0.35 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	Occ. (<1)
Cu1	0.6667	0.3333	0.2500	0.02174 (13)
N1	0.4561 (2)	0.3115 (2)	0.12731 (17)	0.0405 (3)
H1N	0.434 (4)	0.389 (4)	0.134 (3)	0.054 (7)*
H2N	0.469 (4)	0.304 (3)	0.042 (3)	0.057 (7)*
C1	0.2983 (2)	0.1545 (2)	0.17148 (18)	0.0387 (4)
H1A	0.2951	0.0537	0.1310	0.046*
H1B	0.1976	0.1585	0.1401	0.046*
S1	0.3333	0.6667	0.2500	0.02308 (17)
O1	0.3561 (12)	0.5645 (10)	0.1468 (6)	0.102 (3)	0.33333
O2	0.2845 (11)	0.7783 (10)	0.1814 (7)	0.121 (4)	0.33333

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.02328 (15)	0.02328 (15)	0.01866 (19)	0.01164 (8)	0.000	0.000
N1	0.0443 (8)	0.0405 (8)	0.0364 (7)	0.0210 (6)	0.0076 (6)	0.0038 (6)
C1	0.0290 (7)	0.0438 (9)	0.0398 (8)	0.0155 (6)	−0.0060 (6)	−0.0052 (7)
S1	0.0242 (2)	0.0242 (2)	0.0208 (3)	0.01211 (11)	0.000	0.000
O1	0.201 (10)	0.126 (6)	0.050 (3)	0.134 (7)	0.003 (4)	−0.019 (4)
O2	0.226 (11)	0.156 (8)	0.081 (4)	0.171 (9)	0.020 (6)	0.035 (5)

Geometric parameters (Å, º)

Cu1—N1^i	2.1495 (18)	S1—O1^vi	1.431 (5)
Cu1—N1	2.1495 (18)	S1—O1^vii	1.431 (5)
Cu1—N1^ii	2.1495 (18)	S1—O1^viii	1.431 (5)
Cu1—N1^iii	2.1495 (18)	S1—O1	1.431 (5)
Cu1—N1^iv	2.1495 (18)	S1—O1^ix	1.431 (5)
Cu1—N1^v	2.1495 (18)	S1—O1^i	1.431 (5)
N1—C1	1.474 (2)	S1—O2^ix	1.437 (5)
N1—H1N	0.82 (3)	S1—O2^vii	1.437 (5)
N1—H2N	0.84 (3)	S1—O2^vi	1.437 (5)
C1—C1^ii	1.511 (4)	S1—O2	1.437 (5)
C1—H1A	0.9700	S1—O2^viii	1.437 (5)
C1—H1B	0.9700	S1—O2^i	1.437 (5)
N1^i—Cu1—N1	94.03 (9)	Cu1—N1—H1N	117.2 (19)
N1^i—Cu1—N1^ii	92.85 (6)	C1—N1—H2N	108.1 (18)
N1—Cu1—N1^ii	80.96 (8)	Cu1—N1—H2N	113.0 (19)
N1^i—Cu1—N1^iii	80.96 (8)	H1N—N1—H2N	105 (3)
N1—Cu1—N1^iii	92.85 (6)	N1—C1—C1^ii	108.48 (12)
N1^ii—Cu1—N1^iii	170.97 (9)	N1—C1—H1A	110.0
N1^i—Cu1—N1^iv	170.96 (9)	C1^ii—C1—H1A	110.0
N1—Cu1—N1^iv	92.85 (6)	N1—C1—H1B	110.0
N1^ii—Cu1—N1^iv	94.02 (9)	C1^ii—C1—H1B	110.0
N1^iii—Cu1—N1^iv	92.84 (6)	H1A—C1—H1B	108.4
N1^i—Cu1—N1^v	92.85 (6)	O1^viii—S1—O1	112.7 (6)
N1—Cu1—N1^v	170.96 (9)	O1^viii—S1—O2	110.5 (5)
N1^ii—Cu1—N1^v	92.84 (6)	O1—S1—O2	108.6 (3)
N1^iii—Cu1—N1^v	94.02 (9)	O1^viii—S1—O2^viii	108.6 (3)
N1^iv—Cu1—N1^v	80.96 (8)	O1—S1—O2^viii	110.5 (5)
C1—N1—Cu1	108.01 (11)	O2—S1—O2^viii	105.8 (7)
C1—N1—H1N	105.2 (19)
N1^i—Cu1—N1—C1	−107.30 (12)	N1^iv—Cu1—N1—C1	78.57 (15)
N1^ii—Cu1—N1—C1	−15.06 (8)	Cu1—N1—C1—C1^ii	42.33 (19)
N1^iii—Cu1—N1—C1	171.56 (11)

Symmetry codes: (i) −y+1, −x+1, −z+1/2; (ii) x, x−y, −z+1/2; (iii) −x+y+1, −x+1, z; (iv) −y+1, x−y, z; (v) −x+y+1, y, −z+1/2; (vi) −x+y, −x+1, z; (vii) x, x−y+1, −z+1/2; (viii) −x+y, y, −z+1/2; (ix) −y+1, x−y+1, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1	0.82 (3)	2.01 (3)	2.832 (6)	175 (3)
N1—H2N···O2^x	0.84 (3)	2.19 (3)	3.025 (7)	180 (3)

Symmetry code: (x) x−y+1, x, −z.