Bis(nitrato-κO)(5,7,12,14-tetra­methyl-1,4,8,11-tetra­aza­cyclo­tetra­decane-6,13-diaminium-κ4N1,N4,N8,N11)copper(II) dinitrate tetra­hydrate

Liu, X.-Y.; Chu, H.-Y.

doi:10.1107/S1600536810023342

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page m837

doi:10.1107/S1600536810023342

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Bis(nitrato-κO)(5,7,12,14-tetramethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diaminium-κ⁴N¹,N⁴,N⁸,N¹¹)copper(II) dinitrate tetrahydrate

Xiang-Yun Liu ^a ^* and Hong-Ying Chu ^b

^aDepartment of Chemistry and Chemical Engineering, Henan University of Urban Construction, Pingdingshan 467044, People's Republic of China, and ^bDepartment of Environment and Chemical Engineering, Yellow River Conservancy Technical Institute, Kaifeng 475004, People's Republic of China
^*Correspondence e-mail: tianlin1288@163.com

(Received 27 May 2010; accepted 16 June 2010; online 23 June 2010)

In the title compound, [Cu(NO₃)₂(C₁₄H₃₆N₆)](NO₃)₂·4H₂O, the Cu^II atom, lying on an inversion center, is six-coordinated in a distorted octahedral environment by four N atoms from a centrosymmetric 14-membered tetraazacyclotetradecane macrocyclic ligand and two O atoms from two nitrate anions. The supramolecular network is consolidated by extensive O—H⋯O and N—H⋯O hydrogen-bonding interactions.

Related literature

For Cu(II) complexes of related macrocyclic ligands, see: Bernhardt (1999 ); Bernhardt & Sharpe (1998 ).

Experimental

Crystal data

[Cu(NO₃)₂(C₁₄H₃₆N₆)](NO₃)₂·4H₂O
M_r = 672.14
Monoclinic, P 2₁ /n
a = 9.201 (2) Å
b = 16.576 (4) Å
c = 9.278 (2) Å
β = 98.788 (4)°
V = 1398.4 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.87 mm⁻¹
T = 123 K
0.37 × 0.34 × 0.31 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.739, T_max = 0.774
6071 measured reflections
3021 independent reflections
2269 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.133
S = 1.03
3021 reflections
202 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.24 e Å⁻³
Δρ_min = −0.81 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯O3	0.93	2.43	3.155 (4)	134
N1—H1C⋯O2Wⁱ	0.93	2.28	3.096 (4)	146
N2—H2A⋯O3	0.93	2.52	3.244 (4)	135
N2—H2A⋯O4ⁱⁱ	0.93	2.47	3.249 (4)	141
N3—H3D⋯O4	0.91	2.08	2.924 (4)	155
N3—H3E⋯O1Wⁱⁱⁱ	0.91	1.86	2.748 (4)	164
N3—H3F⋯O2ⁱ	0.91	2.06	2.902 (4)	154
N3—H3F⋯O3ⁱ	0.91	2.32	3.108 (4)	145
O1W—H1WA⋯O2ⁱ	0.84 (4)	2.01 (3)	2.823 (4)	160 (5)
O1W—H1WB⋯O5^iv	0.84 (2)	1.97 (2)	2.795 (4)	168 (5)
O2W—H2WA⋯O6ⁱⁱ	0.93 (5)	2.00 (5)	2.913 (5)	166 (5)
O2W—H2WB⋯O6^v	0.92 (2)	2.18 (2)	3.084 (5)	167 (5)
Symmetry codes: (i) -x+1, -y, -z+1; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) x-1, y, z; (v) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810023342/hy2316sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810023342/hy2316Isup2.hkl

checkCIF report

Comment top

In the past, much attention has been given to the copper complexes of macrocyclic trans-5(R),7(R),12(R), 14(R)-tetramethyl-6, 13-dinitro-1,4,8,11-tetraazacyclotetradecane and related ligands (Bernhardt, 1999; Bernhardt & Sharpe, 1998). Recently, we have synthesized a Cu(II) complex based on 5,7,12,14-tetramethyl-6,13- diamino-1,4,8,11-tetraazacyclotetradecane and its structure is reported here.

The asymmetric unit of the title compound (Fig. 1) contains one Cu^II ion lying on an inversion center, one half of a 14-membered tetraazacyclotetradecane macrocyclic ligand, one coordinated nitrate anion, one uncoordinated nitrate anion and two solvent water molecules. The Cu^II ion has a slightly distorted octahedral coordination geometry, with two O atoms from two nitrate anions in the axial positions. The equatorial positions are occupied by four N atoms from the centrosymmetric 14-membered tetraazacyclotetradecane macrocyclic ligand [Cu1—N1 2.025 (2) and Cu1—N2 2.020 (2) Å]. The two uncoordinated nitrate anions are located above and below the 14-membered tetraazacyclotetradecane macrocycle and linked to the macrocycle via N—H···O hydrogen bonds (Table 1).

Related literature top

For Cu(II) complexes of related macrocyclic ligands, see: Bernhardt (1999); Bernhardt & Sharpe (1998).

Experimental top

An aqueous solution of 5,7,12,14-tetramethyl-6,13-diamino-1,4,8,11-tetraazacyclotetradecane (0.27 g, 1.0 mmol), Cu(NO₃)₂ (0.10 g, 0.5 mmol) and Na₂CO₃ (0.05 g, 0.5 mmol) was heated to reflux for 24 h. The reaction mixture was cooled to room temperature and red crystals of the title compound were obtained by slow evaporation of the solvent at room temperature.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are shown at the 30% probability level. H atoms have been omitted for clarity. [Symmetry code: (i) 2-x, -y, 1-z.]

Bis(nitrato-κO)(5,7,12,14-tetramethyl-1,4,8,11- tetraazacyclotetradecane-6,13-diaminium- κ⁴N¹,N⁴,N⁸,N¹¹)copper(II) dinitrate tetrahydrate top

Crystal data top

[Cu(NO₃)₂(C₁₄H₃₆N₆)](NO₃)₂·4H₂O	F(000) = 710
M_r = 672.14	D_x = 1.596 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2543 reflections
a = 9.201 (2) Å	θ = 2.5–27.0°
b = 16.576 (4) Å	µ = 0.87 mm⁻¹
c = 9.278 (2) Å	T = 123 K
β = 98.788 (4)°	Block, red
V = 1398.4 (5) Å³	0.37 × 0.34 × 0.31 mm
Z = 2

Data collection top

Bruker SMART 1000 CCD diffractometer	3021 independent reflections
Radiation source: fine-focus sealed tube	2269 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ϕ and ω scans	θ_max = 27.1°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −11→11
T_min = 0.739, T_max = 0.774	k = −21→17
6071 measured reflections	l = −10→11

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.133	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0649P)² + 2.4391P] where P = (F_o² + 2F_c²)/3
3021 reflections	(Δ/σ)_max = 0.036
202 parameters	Δρ_max = 1.24 e Å⁻³
6 restraints	Δρ_min = −0.81 e Å⁻³

Crystal data top

[Cu(NO₃)₂(C₁₄H₃₆N₆)](NO₃)₂·4H₂O	V = 1398.4 (5) Å³
M_r = 672.14	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.201 (2) Å	µ = 0.87 mm⁻¹
b = 16.576 (4) Å	T = 123 K
c = 9.278 (2) Å	0.37 × 0.34 × 0.31 mm
β = 98.788 (4)°

Data collection top

Bruker SMART 1000 CCD diffractometer	3021 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	2269 reflections with I > 2σ(I)
T_min = 0.739, T_max = 0.774	R_int = 0.027
6071 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	6 restraints
wR(F²) = 0.133	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 1.24 e Å⁻³
3021 reflections	Δρ_min = −0.81 e Å⁻³
202 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.8753 (4)	0.0883 (2)	0.2521 (3)	0.0169 (7)
H1A	0.9413	0.1356	0.2695	0.020*
H1B	0.7886	0.1039	0.1807	0.020*
C2	0.7676 (3)	0.13149 (18)	0.4684 (3)	0.0136 (6)
H2	0.8477	0.1722	0.4930	0.016*
C3	0.6400 (4)	0.1717 (2)	0.3687 (3)	0.0234 (8)
H3A	0.6749	0.1921	0.2809	0.035*
H3B	0.6019	0.2167	0.4205	0.035*
H3C	0.5616	0.1322	0.3408	0.035*
C4	0.7205 (3)	0.10160 (19)	0.6114 (3)	0.0129 (6)
H4	0.6574	0.0527	0.5888	0.016*
C5	0.8448 (3)	0.08013 (19)	0.7366 (3)	0.0137 (6)
H5	0.7973	0.0642	0.8224	0.016*
C6	0.9474 (3)	0.15076 (19)	0.7843 (3)	0.0167 (7)
H6A	1.0086	0.1378	0.8774	0.025*
H6B	0.8889	0.1991	0.7960	0.025*
H6C	1.0105	0.1608	0.7102	0.025*
C7	1.0453 (3)	−0.0192 (2)	0.8066 (3)	0.0170 (7)
H7A	1.0050	−0.0366	0.8947	0.020*
H7B	1.1144	0.0259	0.8342	0.020*
Cu1	1.0000	0.0000	0.5000	0.01124 (16)
N1	0.8274 (3)	0.06223 (16)	0.3922 (2)	0.0120 (5)
H1C	0.7509	0.0256	0.3683	0.014*
N2	0.9236 (3)	0.00785 (15)	0.6924 (3)	0.0128 (5)
H2A	0.8545	−0.0334	0.6882	0.015*
N3	0.6297 (3)	0.16570 (17)	0.6691 (3)	0.0173 (6)
H3D	0.6722	0.2147	0.6611	0.026*
H3E	0.6241	0.1555	0.7645	0.026*
H3F	0.5376	0.1657	0.6167	0.026*
N5	0.7860 (3)	0.36290 (18)	0.6169 (3)	0.0214 (6)
O4	0.6922 (3)	0.33861 (18)	0.6897 (3)	0.0377 (7)
O5	0.8513 (3)	0.31313 (17)	0.5511 (3)	0.0399 (7)
O6	0.8117 (3)	0.43623 (16)	0.6061 (4)	0.0402 (7)
O1W	0.1266 (3)	0.33514 (16)	0.4647 (3)	0.0236 (5)
O2W	0.4173 (4)	0.0272 (3)	0.8131 (4)	0.0592 (10)
H1WA	0.168 (5)	0.291 (2)	0.489 (6)	0.071*
H1WB	0.039 (3)	0.334 (3)	0.481 (6)	0.071*
H2WA	0.494 (5)	−0.008 (3)	0.846 (6)	0.071*
H2WB	0.396 (6)	0.045 (3)	0.901 (3)	0.071*
N4	0.7300 (3)	−0.14301 (18)	0.4733 (3)	0.0233 (6)
O1	0.8658 (2)	−0.13506 (15)	0.4843 (2)	0.0226 (5)
O2	0.6711 (3)	−0.21048 (15)	0.4441 (3)	0.0252 (6)
O3	0.6522 (3)	−0.08487 (18)	0.4963 (4)	0.0520 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0194 (16)	0.0188 (17)	0.0124 (14)	0.0044 (13)	0.0023 (11)	0.0043 (12)
C2	0.0175 (15)	0.0104 (15)	0.0122 (14)	0.0038 (12)	0.0004 (11)	0.0000 (11)
C3	0.0233 (18)	0.032 (2)	0.0150 (15)	0.0136 (15)	0.0039 (13)	0.0031 (14)
C4	0.0113 (14)	0.0153 (16)	0.0120 (13)	0.0026 (12)	0.0014 (11)	−0.0013 (11)
C5	0.0141 (15)	0.0155 (16)	0.0117 (13)	0.0025 (12)	0.0021 (11)	0.0011 (11)
C6	0.0171 (15)	0.0130 (16)	0.0192 (15)	0.0000 (12)	−0.0003 (12)	−0.0031 (12)
C7	0.0175 (15)	0.0232 (18)	0.0094 (13)	0.0068 (13)	−0.0009 (11)	0.0019 (11)
Cu1	0.0120 (3)	0.0135 (3)	0.0079 (2)	0.0030 (2)	0.00051 (17)	0.0002 (2)
N1	0.0121 (12)	0.0128 (13)	0.0112 (11)	0.0008 (10)	0.0022 (9)	−0.0003 (10)
N2	0.0123 (12)	0.0143 (14)	0.0113 (11)	0.0017 (10)	−0.0001 (9)	0.0009 (10)
N3	0.0161 (13)	0.0226 (16)	0.0134 (12)	0.0050 (11)	0.0030 (10)	−0.0006 (11)
N5	0.0167 (14)	0.0227 (16)	0.0244 (14)	0.0033 (12)	0.0021 (11)	0.0008 (12)
O4	0.0357 (16)	0.0389 (17)	0.0442 (16)	0.0024 (13)	0.0241 (13)	0.0093 (13)
O5	0.0442 (17)	0.0260 (15)	0.0558 (18)	−0.0001 (13)	0.0282 (14)	−0.0111 (13)
O6	0.0382 (16)	0.0149 (14)	0.071 (2)	−0.0009 (12)	0.0184 (14)	−0.0028 (13)
O1W	0.0252 (13)	0.0268 (14)	0.0192 (12)	−0.0001 (11)	0.0047 (10)	0.0005 (10)
O2W	0.051 (2)	0.068 (3)	0.056 (2)	0.0019 (19)	−0.0006 (17)	−0.0158 (19)
N4	0.0187 (14)	0.0206 (16)	0.0305 (16)	−0.0036 (12)	0.0031 (12)	−0.0016 (12)
O1	0.0153 (11)	0.0264 (14)	0.0268 (12)	−0.0057 (10)	0.0053 (9)	−0.0017 (10)
O2	0.0212 (12)	0.0197 (13)	0.0327 (13)	−0.0060 (10)	−0.0022 (10)	−0.0022 (10)
O3	0.0230 (15)	0.0230 (16)	0.111 (3)	0.0001 (12)	0.0151 (16)	−0.0074 (17)

Geometric parameters (Å, º) top

C1—N1	1.499 (4)	C7—C1ⁱ	1.505 (4)
C1—C7ⁱ	1.505 (4)	C7—H7A	0.9900
C1—H1A	0.9900	C7—H7B	0.9900
C1—H1B	0.9900	Cu1—N2	2.020 (2)
C2—N1	1.496 (4)	Cu1—N1	2.025 (2)
C2—C3	1.532 (4)	Cu1—O1	2.550 (2)
C2—C4	1.539 (4)	N1—H1C	0.9300
C2—H2	1.0000	N2—H2A	0.9300
C3—H3A	0.9800	N3—H3D	0.9100
C3—H3B	0.9800	N3—H3E	0.9100
C3—H3C	0.9800	N3—H3F	0.9100
C4—N3	1.500 (4)	N5—O5	1.235 (4)
C4—C5	1.542 (4)	N5—O4	1.241 (4)
C4—H4	1.0000	N5—O6	1.245 (4)
C5—N2	1.491 (4)	O1W—H1WA	0.84 (4)
C5—C6	1.526 (4)	O1W—H1WB	0.84 (2)
C5—H5	1.0000	O2W—H2WA	0.93 (5)
C6—H6A	0.9800	O2W—H2WB	0.91 (2)
C6—H6B	0.9800	N4—O3	1.239 (4)
C6—H6C	0.9800	N4—O1	1.245 (4)
C7—N2	1.488 (3)	N4—O2	1.254 (4)

N1—C1—C7ⁱ	108.5 (2)	N2—C7—H7A	109.9
N1—C1—H1A	110.0	C1ⁱ—C7—H7A	109.9
C7ⁱ—C1—H1A	110.0	N2—C7—H7B	109.9
N1—C1—H1B	110.0	C1ⁱ—C7—H7B	109.9
C7ⁱ—C1—H1B	110.0	H7A—C7—H7B	108.3
H1A—C1—H1B	108.4	N2ⁱ—Cu1—N1	87.06 (10)
N1—C2—C3	110.6 (2)	N2—Cu1—N1	92.94 (10)
N1—C2—C4	109.4 (2)	O1—Cu1—N1	94.74 (9)
C3—C2—C4	111.7 (3)	O1—Cu1—N2	82.89 (8)
N1—C2—H2	108.3	O1—Cu1—N1ⁱ	85.26 (9)
C3—C2—H2	108.3	O1—Cu1—N2ⁱ	97.11 (8)
C4—C2—H2	108.3	C2—N1—C1	111.5 (2)
C2—C3—H3A	109.5	C2—N1—Cu1	118.36 (17)
C2—C3—H3B	109.5	C1—N1—Cu1	105.27 (18)
H3A—C3—H3B	109.5	C2—N1—H1C	107.1
C2—C3—H3C	109.5	C1—N1—H1C	107.1
H3A—C3—H3C	109.5	Cu1—N1—H1C	107.1
H3B—C3—H3C	109.5	C7—N2—C5	113.0 (2)
N3—C4—C2	109.0 (2)	C7—N2—Cu1	106.55 (18)
N3—C4—C5	106.5 (2)	C5—N2—Cu1	123.02 (18)
C2—C4—C5	116.8 (3)	C7—N2—H2A	104.1
N3—C4—H4	108.1	C5—N2—H2A	104.1
C2—C4—H4	108.1	Cu1—N2—H2A	104.1
C5—C4—H4	108.1	C4—N3—H3D	109.5
N2—C5—C6	113.0 (2)	C4—N3—H3E	109.5
N2—C5—C4	108.3 (2)	H3D—N3—H3E	109.5
C6—C5—C4	113.3 (3)	C4—N3—H3F	109.5
N2—C5—H5	107.3	H3D—N3—H3F	109.5
C6—C5—H5	107.3	H3E—N3—H3F	109.5
C4—C5—H5	107.3	O5—N5—O4	118.9 (3)
C5—C6—H6A	109.5	O5—N5—O6	120.0 (3)
C5—C6—H6B	109.5	O4—N5—O6	121.1 (3)
H6A—C6—H6B	109.5	H1WA—O1W—H1WB	109 (4)
C5—C6—H6C	109.5	H2WA—O2W—H2WB	99 (4)
H6A—C6—H6C	109.5	O3—N4—O1	120.2 (3)
H6B—C6—H6C	109.5	O3—N4—O2	119.3 (3)
N2—C7—C1ⁱ	109.0 (2)	O1—N4—O2	120.5 (3)

N1—C2—C4—N3	−167.0 (2)	N2ⁱ—Cu1—N1—C2	−142.1 (2)
C3—C2—C4—N3	−44.1 (3)	N2—Cu1—N1—C2	37.9 (2)
N1—C2—C4—C5	72.4 (3)	N2ⁱ—Cu1—N1—C1	−16.78 (19)
C3—C2—C4—C5	−164.7 (3)	N2—Cu1—N1—C1	163.22 (19)
N3—C4—C5—N2	171.2 (2)	C1ⁱ—C7—N2—C5	−175.9 (3)
C2—C4—C5—N2	−66.9 (3)	C1ⁱ—C7—N2—Cu1	−37.9 (3)
N3—C4—C5—C6	−62.6 (3)	C6—C5—N2—C7	54.5 (3)
C2—C4—C5—C6	59.3 (3)	C4—C5—N2—C7	−179.2 (2)
C3—C2—N1—C1	56.7 (3)	C6—C5—N2—Cu1	−75.7 (3)
C4—C2—N1—C1	−179.9 (2)	C4—C5—N2—Cu1	50.7 (3)
C3—C2—N1—Cu1	178.9 (2)	N1ⁱ—Cu1—N2—C7	11.4 (2)
C4—C2—N1—Cu1	−57.6 (3)	N1—Cu1—N2—C7	−168.6 (2)
C7ⁱ—C1—N1—C2	171.5 (2)	N1ⁱ—Cu1—N2—C5	144.2 (2)
C7ⁱ—C1—N1—Cu1	42.0 (3)	N1—Cu1—N2—C5	−35.8 (2)

Symmetry code: (i) −x+2, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O3	0.93	2.43	3.155 (4)	134
N1—H1C···O2Wⁱⁱ	0.93	2.28	3.096 (4)	146
N2—H2A···O3	0.93	2.52	3.244 (4)	135
N2—H2A···O4ⁱⁱⁱ	0.93	2.47	3.249 (4)	141
N3—H3D···O4	0.91	2.08	2.924 (4)	155
N3—H3E···O1W^iv	0.91	1.86	2.748 (4)	164
N3—H3F···O2ⁱⁱ	0.91	2.06	2.902 (4)	154
N3—H3F···O3ⁱⁱ	0.91	2.32	3.108 (4)	145
O1W—H1WA···O2ⁱⁱ	0.84 (4)	2.01 (3)	2.823 (4)	160 (5)
O1W—H1WB···O5^v	0.84 (2)	1.97 (2)	2.795 (4)	168 (5)
O2W—H2WA···O6ⁱⁱⁱ	0.93 (5)	2.00 (5)	2.913 (5)	166 (5)
O2W—H2WB···O6^vi	0.92 (2)	2.18 (2)	3.084 (5)	167 (5)

Symmetry codes: (ii) −x+1, −y, −z+1; (iii) −x+3/2, y−1/2, −z+3/2; (iv) x+1/2, −y+1/2, z+1/2; (v) x−1, y, z; (vi) x−1/2, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	[Cu(NO₃)₂(C₁₄H₃₆N₆)](NO₃)₂·4H₂O
M_r	672.14
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	123
a, b, c (Å)	9.201 (2), 16.576 (4), 9.278 (2)
β (°)	98.788 (4)
V (Å³)	1398.4 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.87
Crystal size (mm)	0.37 × 0.34 × 0.31

Data collection
Diffractometer	Bruker SMART 1000 CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.739, 0.774
No. of measured, independent and observed [I > 2σ(I)] reflections	6071, 3021, 2269
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.641

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.133, 1.03
No. of reflections	3021
No. of parameters	202
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)	1.24, −0.81

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O3	0.93	2.43	3.155 (4)	134.4
N1—H1C···O2Wⁱ	0.93	2.28	3.096 (4)	146.1
N2—H2A···O3	0.93	2.52	3.244 (4)	134.8
N2—H2A···O4ⁱⁱ	0.93	2.47	3.249 (4)	140.9
N3—H3D···O4	0.91	2.08	2.924 (4)	154.7
N3—H3E···O1Wⁱⁱⁱ	0.91	1.86	2.748 (4)	164.1
N3—H3F···O2ⁱ	0.91	2.06	2.902 (4)	154.3
N3—H3F···O3ⁱ	0.91	2.32	3.108 (4)	144.7
O1W—H1WA···O2ⁱ	0.84 (4)	2.01 (3)	2.823 (4)	160 (5)
O1W—H1WB···O5^iv	0.84 (2)	1.97 (2)	2.795 (4)	168 (5)
O2W—H2WA···O6ⁱⁱ	0.93 (5)	2.00 (5)	2.913 (5)	166 (5)
O2W—H2WB···O6^v	0.92 (2)	2.18 (2)	3.084 (5)	167 (5)

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+3/2, y−1/2, −z+3/2; (iii) x+1/2, −y+1/2, z+1/2; (iv) x−1, y, z; (v) x−1/2, −y+1/2, z+1/2.

Acknowledgements

The authors acknowledge Henan University of Urban Construction for supporting this work.

References

Bernhardt, P. V. (1999). Inorg. Chem. 38, 3481–3483. Web of Science CSD CrossRef PubMed CAS Google Scholar
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Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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