(1,4,7,10-Tetra-aza-cyclo-dodecane-κN,N,N,N)(tetra-oxidomolybdato-κO)copper(II) monohydrate.

In the title compound, [CuMoO(4)(C(8)H(20)N(4))]·H(2)O, the Cu(II) atom is coordinated by four N atoms of the 1,4,7,10-tetra-aza-cyclo-dodecane (cyclen) ligand and one O atom of the molybdate unit in a distorted square-pyramidal environment. The water mol-ecules are linked to the complex unit to form centrosymmetric dimers [R(4) (4)(12) and R(4) (4)(16)] and discrete D(3) (2)(9), D(3) (3)(11) and D(3) (3)(13) chains by O-H⋯O and N-H⋯O inter-actions. Additionally, the complex mol-ecules are linked into C(4) (4)(18) chain motifs by N-H⋯O inter-actions. As a result [(cyclen)CuMoO(4)] 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 = 413.78

Triclinic,

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[F 2 > 2σ(F 2)] = 0.024

wR(F 2) = 0.063

S = 1.04

3017 reflections

196 parameters

6 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.48 e Å−3

Δρmin = −1.05 e Å−3

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 ▶).

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

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810026000/bx2287Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[CuMoO4(C8H20N4)]·H2O	Z = 2
Mr = 413.78	F(000) = 418
Triclinic, P1	Dx = 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

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

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(Fo2) + (0.0403P)2 + 0.2037P] where P = (Fo2 + 2Fc2)/3
3017 reflections	(Δ/σ)max = 0.002
196 parameters	Δρmax = 0.48 e Å−3
6 restraints	Δρmin = −1.05 e Å−3
0 constraints

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.

	x	y	z	Uiso*/Ueq
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)*

	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)

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)

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···O2iv	0.84 (2)	1.85 (2)	2.666 (3)	163 (4)
C3—H3B···O3v	0.99	2.36	3.345 (3)	175

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⋯O2iv	0.84 (2)	1.85 (2)	2.666 (3)	163 (4)
C3—H3B⋯O3v	0.99	2.36	3.345 (3)	175

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .