(1,4,7,10-Tetra­aza­cyclo­dodecane-κ4N1,N4,N7,N10)(tetra­oxidomolybdato-κO)copper(II) monohydrate

Rohde, D.; Merzweiler, K.

doi:10.1107/S1600536810026000

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Page m894

https://doi.org/10.1107/S1600536810026000

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(1,4,7,10-Tetraazacyclododecane-κ⁴N¹,N⁴,N⁷,N¹⁰)(tetraoxidomolybdato-κO)copper(II) monohydrate

Dorothea Rohde ^a and Kurt Merzweiler ^a ^*

^aInstitut für Chemie, Naturwisssenchaftliche Fakultät II, Martin-Luther-Universität Halle-Wittenberg, Kurt-Mothes-Strasse 2, 06120 Halle, Germany
^*Correspondence e-mail: kurt.merzweiler@chemie.uni-halle.de

(Received 11 June 2010; accepted 1 July 2010; online 7 July 2010)

In the title compound, [CuMoO₄(C₈H₂₀N₄)]·H₂O, the Cu^II atom is coordinated by four N atoms of the 1,4,7,10-tetraazacyclododecane (cyclen) ligand and one O atom of the molybdate unit in a distorted square-pyramidal environment. The water molecules are linked to the complex unit to form centrosymmetric dimers [R₄⁴(12) and R₄⁴(16)] and discrete D₃²(9), D₃³(11) and D₃³(13) chains by O—H⋯O and N—H⋯O interactions. Additionally, the complex molecules are linked into C₄⁴(18) chain motifs by N—H⋯O interactions. As a result [(cyclen)CuMoO₄] units and water molecules are linked to layers that are oriented parallel to the ac plane. The stacking of the layers in the b-axis direction is supported by weak C—H⋯O hydrogen bridges.

Related literature

For inorganic–organic hybrid materials based on copper complexes with bridging molybdate ligands, see, for example: Rarig et al. (2002 ); Hagrman et al. (1998 ). For copper complexes with the cyclen ligand, see: Clay et al. (1979 ); Lu et al. (1997 ); Yeung et al. (2000 ); Guo et al. (2008 ). For related literature, see: Bernstein et al. (1995 ); Choi et al. (2004 ).

Experimental

Crystal data

[CuMoO₄(C₈H₂₀N₄)]·H₂O
M_r = 413.78
Triclinic, $[P \overline 1]$
a = 8.6985 (6) Å
b = 8.9784 (6) Å
c = 9.0055 (6) Å
α = 90.358 (6)°
β = 91.949 (6)°
γ = 100.742 (5)°
V = 690.54 (8) Å³
Z = 2
Mo Kα radiation
μ = 2.47 mm⁻¹
T = 200 K
0.22 × 0.21 × 0.13 mm

Data collection

Stoe IPDS 2T diffractometer
Absorption correction: numerical (X-RED; Stoe & Cie, 2009 ) T_min = 0.612, T_max = 0.737
9700 measured reflections
3017 independent reflections
2788 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.063
S = 1.04
3017 reflections
196 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.48 e Å⁻³
Δρ_min = −1.05 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5⋯O4ⁱ	0.83 (2)	1.95 (2)	2.770 (2)	169 (3)
N1—H1⋯O5ⁱⁱ	0.86 (2)	2.35 (2)	3.156 (3)	156 (3)
N2—H2⋯O1ⁱⁱ	0.89 (2)	2.19 (2)	2.949 (2)	143 (3)
N3—H3⋯O4ⁱ	0.88 (2)	2.28 (3)	2.955 (3)	133 (3)
N4—H4⋯O5ⁱⁱⁱ	0.88 (2)	2.10 (2)	2.928 (3)	157 (3)
O5—H6⋯O2^iv	0.84 (2)	1.85 (2)	2.666 (3)	163 (4)
C3—H3B⋯O3^v	0.99	2.36	3.345 (3)	175
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x+2, -y+1, -z+1; (iii) x, y, z+1; (iv) x, y, z-1; (v) x, y-1, z.

Data collection: X-AREA (Stoe & Cie, 2009); cell refinement: X-AREA; data reduction: X-RED (Stoe & Cie, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2009 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810026000/bx2287sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810026000/bx2287Isup2.hkl

checkCIF report

Comment top

In the title compound (I) the central copper atom is coordinated by four nitrogen atoms of the cyclen ligand and one oxygen atom of the molydate group. This leads to a distorted square pyramidal coordination environment with the four N atoms in the basal positions and the molybdate oxygen atom at the apex. The arrangement of the four nitrogen atoms is nearly co-planar within a maximum deviation of 0.015 Å and the copper atom lies 0.569 Å above this plane. The Cu—N distances ranging from 2.033 (2) to 2.049 (2) Å which is comparable to the Cu—N bond lengths oberserved in other cyclen copper complexes, like [(cyclen)Cu(NO₃)]NO₃ (Clay et al., 1979), [(cyclen)Cu(SCN)]₂[Ca(NCS)₆] H₂O (Lu et al., 1997), [(cyclen)Cu(Ag(CN)₂)][Ag(CN)₂] (Yeung et al., 2000) and [(cyclen)Cu(MnN(CN)₅)] (Guo et al., 2008). The molybdate unit coordinates as a monodentate ligand with a Cu—O distance of 2.104 (2) Å. The Mo—O distances ranging from 1.749 to 1.765 Å for the terminal oxygen atoms. In the case of the µ-bridging O atom O1 the Mo—O distance is slightly enlarged to 1.796 (2) Å. A similar monodentate coordination of molybdate has been observed in the copper complex [LCuMoO₄]₂ 5H₂O (L = 1,3,10, 12,16,19-hexaazatetracyclo[17,3,1,1^12.16,0^4.9]tetracosane with Cu—O distances of 2.320 (12) and 2.418 (11) Å and Mo—O distances ranging from 1.621 to 1.849 Å (Choi et al., 2004).

Compound (I) contains a water molecule which is involved into two strong hydrogen bonds to the molybdate O2 and O4 oxygen atoms . This leads to [(cyclen)CuMoO₄]₂(H₂O)₂ dimers containing a centrosymmetric Mo₂O₆H₄ ring of the type R₄⁴(12) (Fig. 2) (Bernstein et al., 1995). Additionally the NH groups of the cyclen ligand are also involved in hydrogen bonds either to water molecules (N1H1 and N4H4) or to molybdate groups (N2H2 and N3H3). As a resuslt of these hydrogen bonds [(cyclen)CuMoO₄] units and water are interlinked to layers which are oriented parallel to the crystallographic a-c plane. The stacking of the layers in direction of the crystallographic b axis is supported by weak C—H···O hydrogen bonds (C···O 3.35 Å) between cyclen ligands and molydate units.

Related literature top

For inorganic–organic hybrid materials based on copper complexes with bridging molybdate ligands, see for example: Rarig et al. (2002); Hagrman et al. (1998). For copper complexes with the cyclen ligand, see: Clay et al. (1979); Lu et al. (1997); Yeung et al. (2000); Guo et al. (2008). For related literature, see: Bernstein et al. (1995); Choi et al. (2004).

Experimental top

To a stirred suspension of 0.440 mg (2.0 mmol) CuMoO₄ in 70 ml of aqueous methanol (90%) 0.350 mg (2.0 mmol) cyclen was added. After four hours the blue suspension was filtered and the filtrate evaporated to dryness.Yield. 420 mg (50%). The residue was dissolved in 3 ml of methanol and then the solution was layered with 2-propanol. After one week single crystals of (I) were formed at the methanol/2-propanol interface. IR(cm^-1): 3172(s), 2960(w), 2937(w), 2920(w), 2869(w), 1631(w), 1592(w), 824(s); Elemental Analysis [Cu(cyclen)MoO₄] H₂O (413.78), C 23.0 (calc. 23.2), H 5.4 (5.4), N 13.1 (13.5) %.

Structure description top

Computing details top

Data collection: X-AREA (Stoe & Cie, 2009); cell refinement: X-AREA (Stoe & Cie, 2009); data reduction: X-RED (Stoe & Cie, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. Molecular structure of the [(cyclen)CuMoO₄] unit. Thermal ellipsoids are drawn at the 50% probability level.
	Fig. 2. [(cyclen)CuMoO₄]₂(H₂O)₂ dimers formed by hydrogen bonds. Symmetry codes: (i) 1 - x, 1 - y, 1 - z; (iv) x, y, -1 + z
	Fig. 3. N—H···O hydrogen bonds around the [(cyclen)CuMoO₄] unit. Symmetry codes (i) 1 - x, 1 - y, 1 - z; (ii) 2 - x, 1 - y, 1 - z; (iii) x, y, 1 + z
	Fig. 4. Stacking of the [(cyclen)CuMoO₄]H₂O layers along the crystallographic b axis.

(1,4,7,10-Tetraazacyclododecane- κ⁴N¹,N⁴,N⁷,N¹⁰)(tetraoxidomolybdato- κO)copper(II) monohydrate top

Crystal data top

[CuMoO₄(C₈H₂₀N₄)]·H₂O	Z = 2
M_r = 413.78	F(000) = 418
Triclinic, P1	D_x = 1.990 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.6985 (6) Å	Cell parameters from 16326 reflections
b = 8.9784 (6) Å	θ = 3.0–29.6°
c = 9.0055 (6) Å	µ = 2.47 mm⁻¹
α = 90.358 (6)°	T = 200 K
β = 91.949 (6)°	Plate, blue
γ = 100.742 (5)°	0.22 × 0.21 × 0.13 mm
V = 690.54 (8) Å³

Data collection top

Stoe IPDS 2T diffractometer	3017 independent reflections
Radiation source: fine-focus sealed tube	2788 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
Detector resolution: 6.67 pixels mm^-1	θ_max = 27.0°, θ_min = 3.0°
rotation method scans	h = −11→11
Absorption correction: numerical (X-RED; Stoe & Cie, 2009)	k = −11→11
T_min = 0.612, T_max = 0.737	l = −11→10
9700 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.063	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0403P)² + 0.2037P] where P = (F_o² + 2F_c²)/3
3017 reflections	(Δ/σ)_max = 0.002
196 parameters	Δρ_max = 0.48 e Å⁻³
6 restraints	Δρ_min = −1.05 e Å⁻³
0 constraints

Crystal data top

[CuMoO₄(C₈H₂₀N₄)]·H₂O	γ = 100.742 (5)°
M_r = 413.78	V = 690.54 (8) Å³
Triclinic, P1	Z = 2
a = 8.6985 (6) Å	Mo Kα radiation
b = 8.9784 (6) Å	µ = 2.47 mm⁻¹
c = 9.0055 (6) Å	T = 200 K
α = 90.358 (6)°	0.22 × 0.21 × 0.13 mm
β = 91.949 (6)°

Data collection top

Stoe IPDS 2T diffractometer	3017 independent reflections
Absorption correction: numerical (X-RED; Stoe & Cie, 2009)	2788 reflections with I > 2σ(I)
T_min = 0.612, T_max = 0.737	R_int = 0.037
9700 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	6 restraints
wR(F²) = 0.063	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.48 e Å⁻³
3017 reflections	Δρ_min = −1.05 e Å⁻³
196 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
C1	1.0572 (3)	0.1738 (3)	0.7826 (3)	0.0250 (4)
H1B	0.9796	0.0794	0.7636	0.030*
H1A	1.1463	0.1485	0.8422	0.030*
C2	1.1135 (3)	0.2435 (3)	0.6371 (3)	0.0262 (5)
H2B	1.2008	0.3300	0.6565	0.031*
H2A	1.1523	0.1675	0.5757	0.031*
C3	0.8796 (3)	0.1769 (2)	0.4653 (2)	0.0226 (4)
H3B	0.8488	0.0845	0.5248	0.027*
H3A	0.9349	0.1504	0.3775	0.027*
C4	0.7365 (3)	0.2401 (3)	0.4169 (3)	0.0264 (5)
H4B	0.7672	0.3273	0.3506	0.032*
H4A	0.6610	0.1614	0.3615	0.032*
C5	0.5518 (3)	0.1652 (2)	0.6197 (3)	0.0227 (4)
H5B	0.5989	0.0732	0.6275	0.027*
H5A	0.4539	0.1403	0.5579	0.027*
C6	0.5167 (3)	0.2183 (3)	0.7734 (3)	0.0246 (5)
H6B	0.4571	0.3019	0.7645	0.030*
H6A	0.4521	0.1338	0.8261	0.030*
C7	0.7290 (3)	0.1527 (3)	0.9414 (3)	0.0272 (5)
H7B	0.7284	0.0635	0.8761	0.033*
H7A	0.6640	0.1198	1.0277	0.033*
C8	0.8955 (3)	0.2202 (3)	0.9938 (3)	0.0289 (5)
H8B	0.8945	0.3004	1.0695	0.035*
H8A	0.9460	0.1405	1.0393	0.035*
N1	0.9846 (2)	0.2852 (2)	0.8642 (2)	0.0224 (4)
H1	1.060 (3)	0.356 (3)	0.895 (3)	0.027 (7)*
N2	0.9827 (2)	0.2966 (2)	0.5561 (2)	0.0214 (4)
H2	1.023 (3)	0.370 (3)	0.494 (3)	0.028 (7)*
N3	0.6625 (2)	0.2895 (2)	0.5510 (2)	0.0216 (4)
H3	0.616 (3)	0.365 (3)	0.526 (4)	0.036 (8)*
N4	0.6657 (2)	0.2715 (2)	0.8587 (2)	0.0218 (4)
H4	0.650 (4)	0.339 (3)	0.924 (3)	0.032 (8)*
O1	0.86208 (19)	0.58802 (17)	0.7174 (2)	0.0254 (3)
O2	0.6912 (2)	0.7196 (2)	0.9423 (2)	0.0353 (4)
O3	0.7520 (2)	0.87043 (18)	0.6678 (2)	0.0310 (4)
O4	0.5312 (2)	0.58763 (19)	0.6764 (2)	0.0290 (4)
Cu	0.83378 (3)	0.35012 (3)	0.71091 (3)	0.01771 (8)
Mo	0.70937 (2)	0.692556 (18)	0.750742 (19)	0.01796 (7)
O5	0.6967 (2)	0.4797 (2)	0.1142 (2)	0.0292 (4)
H5	0.621 (3)	0.452 (3)	0.168 (3)	0.033 (8)*
H6	0.678 (5)	0.556 (3)	0.069 (4)	0.058 (12)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0261 (11)	0.0227 (10)	0.0282 (11)	0.0109 (9)	−0.0037 (9)	−0.0040 (9)
C2	0.0220 (11)	0.0245 (11)	0.0330 (12)	0.0070 (9)	0.0008 (9)	−0.0045 (9)
C3	0.0269 (11)	0.0193 (10)	0.0219 (10)	0.0044 (8)	0.0027 (8)	−0.0037 (8)
C4	0.0320 (12)	0.0280 (11)	0.0195 (10)	0.0068 (9)	−0.0017 (9)	−0.0009 (8)
C5	0.0204 (10)	0.0188 (10)	0.0281 (11)	0.0021 (8)	−0.0020 (9)	−0.0031 (8)
C6	0.0189 (10)	0.0226 (10)	0.0319 (12)	0.0029 (8)	0.0021 (9)	−0.0027 (9)
C7	0.0331 (13)	0.0239 (11)	0.0247 (11)	0.0047 (9)	0.0038 (9)	0.0039 (9)
C8	0.0357 (13)	0.0306 (12)	0.0215 (11)	0.0099 (10)	−0.0027 (9)	−0.0001 (9)
N1	0.0219 (9)	0.0202 (9)	0.0251 (9)	0.0053 (7)	−0.0039 (7)	−0.0042 (7)
N2	0.0231 (9)	0.0162 (8)	0.0247 (9)	0.0028 (7)	0.0027 (7)	−0.0005 (7)
N3	0.0233 (9)	0.0183 (8)	0.0245 (9)	0.0078 (7)	−0.0026 (7)	0.0005 (7)
N4	0.0255 (9)	0.0164 (8)	0.0238 (9)	0.0048 (7)	0.0005 (7)	−0.0032 (7)
O1	0.0254 (8)	0.0135 (7)	0.0378 (9)	0.0048 (6)	0.0036 (7)	0.0007 (6)
O2	0.0475 (11)	0.0360 (10)	0.0237 (9)	0.0112 (8)	0.0024 (8)	−0.0024 (7)
O3	0.0388 (10)	0.0194 (8)	0.0370 (10)	0.0095 (7)	0.0086 (8)	0.0038 (7)
O4	0.0268 (9)	0.0279 (8)	0.0325 (9)	0.0062 (7)	−0.0039 (7)	−0.0001 (7)
Cu	0.01851 (14)	0.01362 (13)	0.02126 (14)	0.00388 (10)	−0.00018 (10)	−0.00115 (10)
Mo	0.02191 (11)	0.01353 (10)	0.01901 (11)	0.00478 (7)	0.00084 (7)	0.00004 (7)
O5	0.0301 (9)	0.0259 (8)	0.0324 (9)	0.0067 (7)	0.0048 (7)	−0.0017 (7)

Geometric parameters (Å, º) top

C1—N1	1.482 (3)	C7—C8	1.520 (4)
C1—C2	1.513 (3)	C7—H7B	0.9900
C1—H1B	0.9900	C7—H7A	0.9900
C1—H1A	0.9900	C8—N1	1.484 (3)
C2—N2	1.484 (3)	C8—H8B	0.9900
C2—H2B	0.9900	C8—H8A	0.9900
C2—H2A	0.9900	N1—Cu	2.034 (2)
C3—N2	1.486 (3)	N1—H1	0.864 (17)
C3—C4	1.513 (3)	N2—Cu	2.0493 (19)
C3—H3B	0.9900	N2—H2	0.890 (17)
C3—H3A	0.9900	N3—Cu	2.033 (2)
C4—N3	1.491 (3)	N3—H3	0.881 (18)
C4—H4B	0.9900	N4—Cu	2.0413 (19)
C4—H4A	0.9900	N4—H4	0.875 (17)
C5—N3	1.485 (3)	O1—Mo	1.7955 (16)
C5—C6	1.520 (3)	O1—Cu	2.1043 (15)
C5—H5B	0.9900	O2—Mo	1.7571 (18)
C5—H5A	0.9900	O3—Mo	1.7490 (16)
C6—N4	1.482 (3)	O4—Mo	1.7652 (17)
C6—H6B	0.9900	O5—H5	0.829 (18)
C6—H6A	0.9900	O5—H6	0.838 (19)
C7—N4	1.482 (3)

N1—C1—C2	108.15 (18)	N1—C8—H8A	109.9
N1—C1—H1B	110.1	C7—C8—H8A	109.9
C2—C1—H1B	110.1	H8B—C8—H8A	108.3
N1—C1—H1A	110.1	C1—N1—C8	113.52 (18)
C2—C1—H1A	110.1	C1—N1—Cu	103.80 (14)
H1B—C1—H1A	108.4	C8—N1—Cu	109.08 (15)
N2—C2—C1	109.64 (18)	C1—N1—H1	107 (2)
N2—C2—H2B	109.7	C8—N1—H1	109 (2)
C1—C2—H2B	109.7	Cu—N1—H1	115 (2)
N2—C2—H2A	109.7	C2—N2—C3	114.06 (17)
C1—C2—H2A	109.7	C2—N2—Cu	107.64 (14)
H2B—C2—H2A	108.2	C3—N2—Cu	102.43 (13)
N2—C3—C4	107.08 (18)	C2—N2—H2	108.6 (19)
N2—C3—H3B	110.3	C3—N2—H2	107.2 (19)
C4—C3—H3B	110.3	Cu—N2—H2	117 (2)
N2—C3—H3A	110.3	C5—N3—C4	113.35 (17)
C4—C3—H3A	110.3	C5—N3—Cu	103.78 (14)
H3B—C3—H3A	108.6	C4—N3—Cu	107.78 (14)
N3—C4—C3	109.07 (18)	C5—N3—H3	111 (2)
N3—C4—H4B	109.9	C4—N3—H3	109 (2)
C3—C4—H4B	109.9	Cu—N3—H3	112 (2)
N3—C4—H4A	109.9	C6—N4—C7	115.36 (18)
C3—C4—H4A	109.9	C6—N4—Cu	107.91 (14)
H4B—C4—H4A	108.3	C7—N4—Cu	104.25 (14)
N3—C5—C6	108.09 (17)	C6—N4—H4	108 (2)
N3—C5—H5B	110.1	C7—N4—H4	107 (2)
C6—C5—H5B	110.1	Cu—N4—H4	114.3 (19)
N3—C5—H5A	110.1	Mo—O1—Cu	125.18 (8)
C6—C5—H5A	110.1	N3—Cu—N1	148.36 (7)
H5B—C5—H5A	108.4	N3—Cu—N4	85.93 (8)
N4—C6—C5	109.38 (18)	N1—Cu—N4	84.96 (8)
N4—C6—H6B	109.8	N3—Cu—N2	85.57 (8)
C5—C6—H6B	109.8	N1—Cu—N2	85.70 (8)
N4—C6—H6A	109.8	N4—Cu—N2	146.84 (7)
C5—C6—H6A	109.8	N3—Cu—O1	102.97 (7)
H6B—C6—H6A	108.2	N1—Cu—O1	108.66 (7)
N4—C7—C8	107.65 (18)	N4—Cu—O1	106.23 (7)
N4—C7—H7B	110.2	N2—Cu—O1	106.91 (7)
C8—C7—H7B	110.2	O3—Mo—O2	108.43 (9)
N4—C7—H7A	110.2	O3—Mo—O4	110.51 (9)
C8—C7—H7A	110.2	O2—Mo—O4	108.75 (9)
H7B—C7—H7A	108.5	O3—Mo—O1	110.04 (8)
N1—C8—C7	108.83 (19)	O2—Mo—O1	110.65 (9)
N1—C8—H8B	109.9	O4—Mo—O1	108.45 (8)
C7—C8—H8B	109.9	H5—O5—H6	106 (4)

N1—C1—C2—N2	−53.5 (2)	C1—N1—Cu—N4	121.02 (14)
N2—C3—C4—N3	−55.8 (2)	C8—N1—Cu—N4	−0.30 (15)
N3—C5—C6—N4	−53.4 (2)	C1—N1—Cu—N2	−27.13 (14)
N4—C7—C8—N1	−53.0 (2)	C8—N1—Cu—N2	−148.44 (15)
C2—C1—N1—C8	168.05 (19)	C1—N1—Cu—O1	−133.53 (13)
C2—C1—N1—Cu	49.76 (19)	C8—N1—Cu—O1	105.15 (15)
C7—C8—N1—C1	−87.1 (2)	C6—N4—Cu—N3	−1.03 (14)
C7—C8—N1—Cu	28.1 (2)	C7—N4—Cu—N3	122.10 (15)
C1—C2—N2—C3	−84.7 (2)	C6—N4—Cu—N1	−150.70 (15)
C1—C2—N2—Cu	28.2 (2)	C7—N4—Cu—N1	−27.57 (14)
C4—C3—N2—C2	168.62 (18)	C6—N4—Cu—N2	−76.5 (2)
C4—C3—N2—Cu	52.62 (18)	C7—N4—Cu—N2	46.6 (2)
C6—C5—N3—C4	165.92 (19)	C6—N4—Cu—O1	101.31 (14)
C6—C5—N3—Cu	49.29 (19)	C7—N4—Cu—O1	−135.56 (14)
C3—C4—N3—C5	−85.7 (2)	C2—N2—Cu—N3	−150.00 (14)
C3—C4—N3—Cu	28.5 (2)	C3—N2—Cu—N3	−29.46 (13)
C5—C6—N4—C7	−87.4 (2)	C2—N2—Cu—N1	−0.44 (13)
C5—C6—N4—Cu	28.7 (2)	C3—N2—Cu—N1	120.10 (14)
C8—C7—N4—C6	168.22 (19)	C2—N2—Cu—N4	−74.40 (19)
C8—C7—N4—Cu	50.08 (19)	C3—N2—Cu—N4	46.1 (2)
C5—N3—Cu—N1	46.9 (2)	C2—N2—Cu—O1	107.77 (13)
C4—N3—Cu—N1	−73.6 (2)	C3—N2—Cu—O1	−131.69 (13)
C5—N3—Cu—N4	−26.66 (13)	Mo—O1—Cu—N3	56.76 (13)
C4—N3—Cu—N4	−147.15 (14)	Mo—O1—Cu—N1	−122.84 (11)
C5—N3—Cu—N2	121.25 (14)	Mo—O1—Cu—N4	−32.74 (13)
C4—N3—Cu—N2	0.77 (14)	Mo—O1—Cu—N2	146.02 (11)
C5—N3—Cu—O1	−132.40 (13)	Cu—O1—Mo—O3	−153.37 (11)
C4—N3—Cu—O1	107.12 (14)	Cu—O1—Mo—O2	86.82 (12)
C1—N1—Cu—N3	47.2 (2)	Cu—O1—Mo—O4	−32.38 (13)
C8—N1—Cu—N3	−74.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O4ⁱ	0.83 (2)	1.95 (2)	2.770 (2)	169 (3)
N1—H1···O5ⁱⁱ	0.86 (2)	2.35 (2)	3.156 (3)	156 (3)
N2—H2···O1ⁱⁱ	0.89 (2)	2.19 (2)	2.949 (2)	143 (3)
N3—H3···O4ⁱ	0.88 (2)	2.28 (3)	2.955 (3)	133 (3)
N4—H4···O5ⁱⁱⁱ	0.88 (2)	2.10 (2)	2.928 (3)	157 (3)
O5—H6···O2^iv	0.84 (2)	1.85 (2)	2.666 (3)	163 (4)
C3—H3B···O3^v	0.99	2.36	3.345 (3)	175

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

Experimental details

Crystal data
Chemical formula	[CuMoO₄(C₈H₂₀N₄)]·H₂O
M_r	413.78
Crystal system, space group	Triclinic, P1
Temperature (K)	200
a, b, c (Å)	8.6985 (6), 8.9784 (6), 9.0055 (6)
α, β, γ (°)	90.358 (6), 91.949 (6), 100.742 (5)
V (Å³)	690.54 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.47
Crystal size (mm)	0.22 × 0.21 × 0.13

Data collection
Diffractometer	Stoe IPDS 2T
Absorption correction	Numerical (X-RED; Stoe & Cie, 2009)
T_min, T_max	0.612, 0.737
No. of measured, independent and observed [I > 2σ(I)] reflections	9700, 3017, 2788
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.063, 1.04
No. of reflections	3017
No. of parameters	196
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.48, −1.05

Computer programs: X-AREA (Stoe & Cie, 2009), X-RED (Stoe & Cie, 2009), SHELXS97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2009), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O4ⁱ	0.829 (18)	1.952 (19)	2.770 (2)	169 (3)
N1—H1···O5ⁱⁱ	0.864 (17)	2.35 (2)	3.156 (3)	156 (3)
N2—H2···O1ⁱⁱ	0.890 (17)	2.19 (2)	2.949 (2)	143 (3)
N3—H3···O4ⁱ	0.881 (18)	2.28 (3)	2.955 (3)	133 (3)
N4—H4···O5ⁱⁱⁱ	0.875 (17)	2.10 (2)	2.928 (3)	157 (3)
O5—H6···O2^iv	0.838 (19)	1.85 (2)	2.666 (3)	163 (4)
C3—H3B···O3^v	0.99	2.36	3.345 (3)	174.6

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

References

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Volume 66| Part 8| August 2010| Page m894

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