The Ni^II, Hg^II and Cu^II complexes of 12-membered-ring mixed-donor macrocycles

The structures of di­aqua(1,7-dioxa-4-thia-10-aza­cyclo­do­decane)­nickel dinitrate, [Ni(C₈H₁₇NO₂S)(H₂O)₂](NO₃)₂, (I), bis­(nitrato-O,O')(1,4,7-trioxa-10-aza­cyclo­do­decane)­mercury, [Hg(NO₃)₂(C₈H₁₇NO₃)], (II), and aqua­(nitrato-O)(1-oxa-4,7,10-tri­aza­cyclo­do­decane)copper nitrate, [Cu(NO₃)(C₈H₁₉N₃O)(H₂O)]NO₃, (III), reveal each macrocycle binding in a tetradentate manner. The conformations of the ligands in (I) and (III) are the same and distinct from that identified for (II). These differences are in agreement with molecular-mechanics predictions of ligand conformation as a function of metal-ion size.

Computing details

For all compounds, data collection: CAD4 Manual (Enraf-Nonius, 1988); cell refinement: SET4 in CAD4 Manual (Enraf-Nonius, 1988); data reduction: Xtal3.2 (Hall et al., 1992); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1990); software used to prepare material for publication: SHELXL97.

(I) diaqua(1,7-dioxa-4-thia-10-azacyclododecane)nickel(II) nitrate

Crystal data

[Ni(C8H17NO2S)(H2O)2](NO3)2	Dx = 1.671 Mg m^−3
Mr = 410.05	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P65	Cell parameters from 25 reflections
a = 8.7242 (3) Å	θ = 10–14°
c = 37.102 (3) Å	µ = 1.37 mm^−1
V = 2445.6 (2) Å^3	T = 295 K
Z = 6	Prism, blue
F(000) = 1284	0.40 × 0.40 × 0.40 mm

Data collection

Enraf-Nonius CAD4 diffractometer	1208 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.058
Graphite monochromator	θmax = 25.0°, θmin = 2.7°
ω–2θ scans	h = −10→8
Absorption correction: ψ scan (North et al., 1968)	k = 0→10
Tmin = 0.529, Tmax = 0.578	l = 0→44
4648 measured reflections	3 standard reflections every 120 min
1459 independent reflections	intensity decay: <5%

Refinement

Refinement on F^2	Hydrogen site location: constr
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.032	Calculated w = 1/[σ^2(Fo^2) + (0.0398P)^2 + 0.4947P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.078	(Δ/σ)max < 0.001
S = 1.06	Δρmax = 0.28 e Å^−3
1459 reflections	Δρmin = −0.26 e Å^−3
209 parameters	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.0010 (4)
Primary atom site location: Patterson	Absolute structure: Flack (1983)
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.00 (2)

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
Ni1	0.75006 (9)	0.41459 (9)	−0.000389 (18)	0.0430 (2)
S1	0.9037 (2)	0.3596 (2)	−0.04843 (5)	0.0582 (4)
N1	0.5691 (6)	0.3561 (7)	0.04125 (13)	0.0499 (12)
H1	0.5647	0.4549	0.0474	0.060*
O1	0.5335 (5)	0.1894 (6)	−0.02155 (11)	0.0520 (10)
O2	0.8233 (6)	0.2631 (6)	0.03031 (11)	0.0550 (11)
O3	0.6839 (6)	0.5672 (6)	−0.03044 (14)	0.0691 (13)
H31	0.6741	0.6504	−0.0151	0.083*
H32	0.7740	0.6299	−0.0482	0.083*
O4	0.9611 (6)	0.6302 (7)	0.02131 (16)	0.0859 (17)
H41	0.9223	0.7046	0.0323	0.103*
H42	1.0447	0.6945	0.0026	0.103*
C1	0.7108 (9)	0.1682 (10)	−0.06758 (19)	0.0665 (19)
H1A	0.7253	0.1670	−0.0935	0.080*
H1B	0.7024	0.0610	−0.0578	0.080*
C2	0.5431 (10)	0.1692 (12)	−0.0598 (2)	0.072 (2)
H2A	0.5421	0.2658	−0.0725	0.086*
H2B	0.4418	0.0589	−0.0676	0.086*
C3	0.3771 (9)	0.1881 (10)	−0.00996 (18)	0.067 (2)
H3A	0.2736	0.0756	−0.0159	0.080*
H3B	0.3665	0.2818	−0.0217	0.080*
C4	0.3920 (8)	0.2148 (10)	0.0299 (2)	0.069 (2)
H4A	0.3044	0.2449	0.0379	0.083*
H4B	0.3660	0.1048	0.0416	0.083*
C5	0.6395 (10)	0.3015 (11)	0.07165 (18)	0.0654 (19)
H5A	0.5486	0.2437	0.0899	0.078*
H5B	0.7383	0.4050	0.0825	0.078*
C6	0.6987 (10)	0.1761 (10)	0.05882 (19)	0.0652 (18)
H6A	0.7546	0.1484	0.0784	0.078*
H6B	0.5985	0.0668	0.0503	0.078*
C7	0.8742 (10)	0.1530 (9)	0.01084 (19)	0.0678 (19)
H7A	0.7697	0.0489	0.0017	0.081*
H7B	0.9364	0.1143	0.0268	0.081*
C8	0.9914 (9)	0.2567 (10)	−0.01959 (19)	0.0635 (18)
H8A	1.0148	0.1782	−0.0341	0.076*
H8B	1.1036	0.3478	−0.0099	0.076*
N2	0.8882 (8)	0.8688 (9)	0.08374 (19)	0.0651 (15)
O5	0.8887 (7)	0.9633 (9)	0.10823 (18)	0.102 (2)
O6	1.0205 (10)	0.9026 (10)	0.0676 (2)	0.118 (3)
O7	0.7530 (12)	0.7405 (11)	0.0759 (3)	0.156 (4)
N3	0.4020 (7)	0.7017 (7)	0.0053 (2)	0.0670 (18)
O8	0.3719 (11)	0.5637 (10)	0.0178 (2)	0.126 (2)
O9	0.5279 (9)	0.7712 (9)	−0.01627 (17)	0.106 (2)
O10	0.3128 (9)	0.7616 (9)	0.0127 (4)	0.155 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0387 (4)	0.0429 (4)	0.0466 (4)	0.0197 (3)	0.0031 (3)	−0.0004 (3)
S1	0.0593 (9)	0.0608 (10)	0.0587 (10)	0.0332 (8)	0.0139 (8)	0.0024 (8)
N1	0.047 (3)	0.054 (3)	0.049 (3)	0.026 (2)	0.004 (2)	−0.001 (2)
O1	0.046 (2)	0.059 (2)	0.050 (2)	0.025 (2)	−0.0055 (19)	−0.010 (2)
O2	0.060 (3)	0.066 (3)	0.049 (2)	0.038 (2)	−0.003 (2)	0.000 (2)
O3	0.075 (3)	0.066 (3)	0.079 (3)	0.045 (3)	0.021 (3)	0.022 (2)
O4	0.052 (3)	0.064 (3)	0.119 (4)	0.011 (2)	0.015 (3)	−0.037 (3)
C1	0.078 (5)	0.082 (5)	0.050 (4)	0.048 (4)	−0.004 (3)	−0.014 (4)
C2	0.070 (5)	0.080 (5)	0.069 (5)	0.040 (4)	−0.019 (4)	−0.023 (4)
C3	0.042 (3)	0.067 (4)	0.086 (6)	0.024 (3)	−0.011 (3)	−0.009 (4)
C4	0.041 (3)	0.081 (5)	0.077 (5)	0.024 (4)	0.012 (3)	0.008 (4)
C5	0.065 (4)	0.082 (5)	0.047 (4)	0.035 (4)	0.005 (3)	0.003 (3)
C6	0.068 (4)	0.079 (5)	0.053 (4)	0.040 (4)	0.007 (3)	0.018 (4)
C7	0.070 (4)	0.077 (5)	0.076 (5)	0.051 (4)	−0.014 (4)	−0.003 (4)
C8	0.056 (4)	0.071 (4)	0.074 (5)	0.040 (3)	0.000 (3)	−0.008 (4)
N2	0.060 (4)	0.059 (4)	0.082 (4)	0.035 (3)	0.010 (3)	0.000 (3)
O5	0.075 (4)	0.099 (4)	0.125 (6)	0.040 (4)	0.004 (3)	−0.051 (4)
O6	0.100 (5)	0.109 (5)	0.160 (7)	0.063 (4)	0.061 (5)	0.016 (5)
O7	0.122 (6)	0.101 (5)	0.176 (8)	0.005 (5)	0.031 (6)	−0.062 (5)
N3	0.053 (3)	0.047 (3)	0.094 (5)	0.020 (3)	0.005 (3)	−0.012 (3)
O8	0.131 (6)	0.093 (5)	0.151 (6)	0.055 (5)	−0.003 (5)	0.022 (5)
O9	0.097 (5)	0.103 (5)	0.099 (5)	0.036 (4)	0.031 (4)	0.014 (4)
O10	0.077 (4)	0.093 (5)	0.301 (13)	0.048 (4)	0.037 (6)	−0.031 (6)

Geometric parameters (Å, º)

Ni1—O4	2.028 (5)	O2—C6	1.432 (8)
Ni1—O3	2.029 (5)	O2—C7	1.438 (8)
Ni1—O2	2.073 (4)	C1—C2	1.495 (9)
Ni1—N1	2.082 (5)	C3—C4	1.494 (10)
Ni1—O1	2.082 (4)	C5—C6	1.502 (11)
Ni1—S1	2.4185 (17)	C7—C8	1.488 (10)
S1—C8	1.795 (7)	N2—O7	1.187 (10)
S1—C1	1.821 (7)	N2—O6	1.200 (8)
N1—C5	1.473 (9)	N2—O5	1.225 (8)
N1—C4	1.476 (8)	N3—O10	1.166 (10)
O1—C3	1.426 (7)	N3—O8	1.190 (9)
O1—C2	1.438 (8)	N3—O9	1.245 (9)
O4—Ni1—O3	91.9 (2)	C3—O1—C2	114.3 (5)
O4—Ni1—O2	87.0 (2)	C3—O1—Ni1	107.9 (4)
O3—Ni1—O2	178.8 (2)	C2—O1—Ni1	114.0 (4)
O4—Ni1—N1	99.1 (2)	C6—O2—C7	115.0 (5)
O3—Ni1—N1	98.0 (2)	C6—O2—Ni1	110.4 (4)
O2—Ni1—N1	82.75 (18)	C7—O2—Ni1	116.5 (4)
O4—Ni1—O1	178.5 (2)	C2—C1—S1	112.2 (5)
O3—Ni1—O1	89.45 (19)	O1—C2—C1	107.9 (6)
O2—Ni1—O1	91.66 (17)	O1—C3—C4	106.8 (5)
N1—Ni1—O1	80.19 (17)	N1—C4—C3	112.7 (5)
O4—Ni1—S1	98.07 (15)	N1—C5—C6	110.1 (6)
O3—Ni1—S1	95.33 (15)	O2—C6—C5	107.1 (6)
O2—Ni1—S1	84.27 (12)	O2—C7—C8	108.8 (6)
N1—Ni1—S1	157.83 (14)	C7—C8—S1	114.9 (5)
O1—Ni1—S1	82.31 (12)	O7—N2—O6	119.4 (8)
C8—S1—C1	101.7 (4)	O7—N2—O5	118.9 (7)
C8—S1—Ni1	94.4 (2)	O6—N2—O5	121.7 (8)
C1—S1—Ni1	96.9 (2)	O10—N3—O8	120.2 (9)
C5—N1—C4	112.3 (6)	O10—N3—O9	123.9 (8)
C5—N1—Ni1	105.1 (4)	O8—N3—O9	115.9 (8)
C4—N1—Ni1	110.0 (4)
O4—Ni1—S1—C8	78.3 (3)	O4—Ni1—O2—C6	109.6 (4)
O3—Ni1—S1—C8	171.0 (3)	O3—Ni1—O2—C6	137 (9)
O2—Ni1—S1—C8	−7.8 (3)	N1—Ni1—O2—C6	10.0 (4)
N1—Ni1—S1—C8	−62.2 (4)	O1—Ni1—O2—C6	−69.9 (4)
O1—Ni1—S1—C8	−100.2 (3)	S1—Ni1—O2—C6	−152.0 (4)
O4—Ni1—S1—C1	−179.3 (3)	O4—Ni1—O2—C7	−116.8 (5)
O3—Ni1—S1—C1	−86.5 (3)	O3—Ni1—O2—C7	−89 (9)
O2—Ni1—S1—C1	94.6 (3)	N1—Ni1—O2—C7	143.7 (5)
N1—Ni1—S1—C1	40.3 (5)	O1—Ni1—O2—C7	63.8 (4)
O1—Ni1—S1—C1	2.2 (3)	S1—Ni1—O2—C7	−18.3 (4)
O4—Ni1—N1—C5	−66.7 (5)	C8—S1—C1—C2	121.5 (6)
O3—Ni1—N1—C5	−160.0 (4)	Ni1—S1—C1—C2	25.5 (6)
O2—Ni1—N1—C5	19.0 (4)	C3—O1—C2—C1	−178.5 (6)
O1—Ni1—N1—C5	112.0 (4)	Ni1—O1—C2—C1	56.8 (7)
S1—Ni1—N1—C5	73.6 (6)	S1—C1—C2—O1	−53.0 (8)
O4—Ni1—N1—C4	172.2 (4)	C2—O1—C3—C4	−178.7 (6)
O3—Ni1—N1—C4	79.0 (5)	Ni1—O1—C3—C4	−50.7 (6)
O2—Ni1—N1—C4	−102.0 (4)	C5—N1—C4—C3	−132.8 (6)
O1—Ni1—N1—C4	−9.1 (4)	Ni1—N1—C4—C3	−16.2 (7)
S1—Ni1—N1—C4	−47.4 (6)	O1—C3—C4—N1	44.5 (8)
O4—Ni1—O1—C3	95 (7)	C4—N1—C5—C6	74.6 (7)
O3—Ni1—O1—C3	−64.4 (4)	Ni1—N1—C5—C6	−45.0 (7)
O2—Ni1—O1—C3	116.2 (4)	C7—O2—C6—C5	−170.8 (5)
N1—Ni1—O1—C3	33.8 (4)	Ni1—O2—C6—C5	−36.4 (7)
S1—Ni1—O1—C3	−159.8 (4)	N1—C5—C6—O2	55.4 (8)
O4—Ni1—O1—C2	−137 (7)	C6—O2—C7—C8	175.4 (5)
O3—Ni1—O1—C2	63.7 (4)	Ni1—O2—C7—C8	43.8 (6)
O2—Ni1—O1—C2	−115.8 (4)	O2—C7—C8—S1	−52.6 (7)
N1—Ni1—O1—C2	161.9 (4)	C1—S1—C8—C7	−64.2 (6)
S1—Ni1—O1—C2	−31.8 (4)	Ni1—S1—C8—C7	33.8 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O7	0.91	2.44	3.177 (9)	139
N1—H1···O8	0.91	2.56	3.180 (9)	126
O3—H31···O9	0.96	2.02	2.779 (8)	134
O3—H31···O8	0.96	2.65	3.244 (10)	121
O3—H32···O5^i	0.96	2.00	2.734 (7)	132
O3—H32···O7^i	0.96	2.40	3.347 (9)	171
O3—H32···N2^i	0.96	2.55	3.465 (8)	160
O4—H41···O6	0.96	1.99	2.763 (9)	136
O4—H41···O7	0.96	2.32	3.174 (10)	149
O4—H41···N2	0.96	2.49	3.380 (8)	154
O4—H42···O10^ii	0.96	2.14	2.704 (8)	116

Symmetry codes: (i) x−y+1, x, z−1/6; (ii) x+1, y, z.

(II) bis(nitrato)(1,4,7-trioxa-10-azacyclododecane)mercury(II)

Crystal data

[Hg(C8H17NO3)(NO3)2]	F(000) = 952
Mr = 499.84	Dx = 2.381 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.245 (3) Å	Cell parameters from 25 reflections
b = 11.927 (2) Å	θ = 10–14°
c = 14.272 (5) Å	µ = 11.09 mm^−1
β = 96.60 (2)°	T = 275 K
V = 1394.2 (7) Å^3	Prism, colourless
Z = 4	0.30 × 0.20 × 0.20 mm

Data collection

Enraf-Nonius CAD4 diffractometer	2082 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.024
Graphite monochromator	θmax = 25.0°, θmin = 2.2°
ω–2θ scans	h = 0→9
Absorption correction: ψ scan (North et al., 1968)	k = 0→14
Tmin = 0.055, Tmax = 0.109	l = −16→16
2623 measured reflections	3 standard reflections every 120 min
2444 independent reflections	intensity decay: <5%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.033	H-atom parameters constrained
wR(F^2) = 0.087	Calculated w = 1/[σ^2(Fo^2) + (0.0622P)^2 + 1.3329P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
2444 reflections	Δρmax = 1.46 e Å^−3
191 parameters	Δρmin = −3.30 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: Patterson	Extinction coefficient: 0.0018 (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
Hg1	0.07460 (3)	0.140753 (19)	0.310704 (17)	0.03087 (15)
N1	0.1946 (7)	0.2309 (5)	0.4327 (4)	0.0360 (13)
H1	0.2046	0.1810	0.4813	0.043*
O1	−0.0481 (6)	0.3365 (4)	0.3058 (3)	0.0365 (11)
O2	0.1265 (6)	0.2609 (4)	0.1614 (3)	0.0402 (11)
O3	0.3852 (6)	0.1594 (4)	0.2794 (4)	0.0408 (12)
C1	0.0879 (9)	0.3214 (7)	0.4604 (5)	0.0415 (17)
H1A	0.1454	0.3634	0.5121	0.050*
H1B	−0.0084	0.2886	0.4825	0.050*
C2	0.0362 (10)	0.4001 (6)	0.3802 (5)	0.0423 (17)
H2A	−0.0347	0.4580	0.4006	0.051*
H2B	0.1311	0.4359	0.3590	0.051*
C3	−0.0593 (9)	0.3885 (7)	0.2161 (6)	0.0436 (18)
H3A	−0.0837	0.4675	0.2230	0.052*
H3B	−0.1490	0.3552	0.1756	0.052*
C4	0.0939 (11)	0.3775 (6)	0.1700 (6)	0.0448 (19)
H4A	0.0802	0.4125	0.1083	0.054*
H4B	0.1839	0.4138	0.2080	0.054*
C5	0.2792 (10)	0.2355 (7)	0.1308 (6)	0.0487 (19)
H5A	0.3011	0.2885	0.0822	0.058*
H5B	0.2743	0.1612	0.1030	0.058*
C6	0.4172 (9)	0.2394 (7)	0.2095 (6)	0.048 (2)
H6A	0.5195	0.2219	0.1854	0.058*
H6B	0.4256	0.3139	0.2369	0.058*
C7	0.4575 (9)	0.1861 (7)	0.3726 (6)	0.050 (2)
H7A	0.5662	0.2156	0.3691	0.060*
H7B	0.4684	0.1178	0.4097	0.060*
C8	0.3621 (8)	0.2691 (6)	0.4215 (6)	0.0415 (17)
H8A	0.4195	0.2845	0.4834	0.050*
H8B	0.3556	0.3387	0.3861	0.050*
N2	−0.0985 (7)	0.0310 (5)	0.1530 (4)	0.0385 (13)
O4	0.0454 (6)	0.0177 (4)	0.1985 (4)	0.0425 (12)
O5	−0.1850 (7)	0.1050 (5)	0.1810 (4)	0.0574 (15)
O6	−0.1402 (8)	−0.0291 (6)	0.0863 (4)	0.0672 (18)
N3	−0.1663 (6)	0.0164 (5)	0.4295 (4)	0.0332 (13)
O7	−0.2714 (6)	−0.0165 (4)	0.4780 (4)	0.0458 (13)
O8	−0.1597 (6)	0.1178 (4)	0.4103 (4)	0.0463 (13)
O9	−0.0676 (7)	−0.0483 (5)	0.4004 (4)	0.0545 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Hg1	0.0312 (2)	0.0282 (2)	0.0330 (2)	−0.00259 (9)	0.00311 (11)	−0.00102 (10)
N1	0.043 (3)	0.040 (3)	0.024 (3)	−0.008 (3)	0.002 (2)	0.009 (2)
O1	0.039 (3)	0.031 (2)	0.038 (3)	0.000 (2)	−0.001 (2)	−0.004 (2)
O2	0.050 (3)	0.037 (3)	0.036 (3)	0.005 (2)	0.010 (2)	0.003 (2)
O3	0.032 (3)	0.033 (3)	0.058 (3)	0.005 (2)	0.008 (2)	0.005 (2)
C1	0.046 (4)	0.045 (4)	0.033 (4)	−0.006 (4)	0.008 (3)	−0.011 (3)
C2	0.052 (5)	0.029 (4)	0.045 (4)	0.004 (3)	0.001 (3)	−0.012 (3)
C3	0.047 (4)	0.038 (4)	0.043 (4)	0.009 (3)	−0.007 (3)	0.008 (3)
C4	0.065 (5)	0.032 (4)	0.037 (4)	0.006 (3)	0.005 (4)	0.010 (3)
C5	0.053 (5)	0.047 (4)	0.049 (4)	0.004 (4)	0.022 (4)	0.003 (4)
C6	0.042 (4)	0.044 (4)	0.062 (5)	0.003 (3)	0.024 (4)	0.014 (4)
C7	0.029 (4)	0.052 (5)	0.066 (5)	0.007 (3)	−0.003 (3)	0.014 (4)
C8	0.029 (4)	0.039 (4)	0.054 (4)	−0.001 (3)	−0.005 (3)	0.004 (3)
N2	0.038 (3)	0.038 (3)	0.039 (3)	0.000 (3)	0.001 (3)	0.002 (3)
O4	0.044 (3)	0.035 (3)	0.046 (3)	0.004 (2)	−0.007 (2)	−0.002 (2)
O5	0.047 (3)	0.057 (3)	0.067 (4)	0.013 (3)	0.003 (3)	−0.011 (3)
O6	0.060 (4)	0.075 (4)	0.062 (4)	−0.003 (3)	−0.010 (3)	−0.035 (3)
N3	0.026 (3)	0.041 (3)	0.030 (3)	0.002 (2)	−0.007 (2)	0.001 (3)
O7	0.044 (3)	0.046 (3)	0.047 (3)	−0.009 (2)	0.007 (2)	0.015 (2)
O8	0.040 (3)	0.040 (3)	0.059 (3)	0.001 (2)	0.006 (3)	0.018 (3)
O9	0.047 (3)	0.059 (4)	0.054 (3)	0.017 (3)	−0.008 (3)	−0.017 (3)

Geometric parameters (Å, º)

Hg1—O4	2.166 (5)	O2—C4	1.424 (8)
Hg1—N1	2.184 (5)	O3—C6	1.427 (9)
Hg1—O8	2.541 (5)	O3—C7	1.429 (10)
Hg1—O1	2.543 (5)	C1—C2	1.504 (11)
Hg1—O2	2.644 (5)	C3—C4	1.495 (11)
Hg1—O3	2.659 (5)	C5—C6	1.505 (11)
Hg1—O5	2.698 (6)	C7—C8	1.488 (11)
Hg1—O9	2.906 (6)	N2—O6	1.208 (8)
N1—C1	1.474 (9)	N2—O5	1.231 (8)
N1—C8	1.480 (8)	N2—O4	1.295 (7)
O1—C3	1.415 (9)	N3—O9	1.228 (7)
O1—C2	1.420 (8)	N3—O7	1.234 (7)
O2—C5	1.413 (9)	N3—O8	1.243 (7)
O4—Hg1—N1	157.7 (2)	C1—N1—Hg1	110.1 (4)
O4—Hg1—O8	108.29 (19)	C8—N1—Hg1	114.1 (4)
N1—Hg1—O8	84.87 (19)	C3—O1—C2	114.7 (6)
O4—Hg1—O1	126.29 (17)	C3—O1—Hg1	114.3 (4)
N1—Hg1—O1	73.28 (18)	C2—O1—Hg1	108.1 (4)
O8—Hg1—O1	77.79 (16)	C5—O2—C4	114.9 (6)
O4—Hg1—O2	77.63 (18)	C5—O2—Hg1	111.4 (4)
N1—Hg1—O2	105.99 (18)	C4—O2—Hg1	114.2 (4)
O8—Hg1—O2	135.48 (16)	C6—O3—C7	114.2 (6)
O1—Hg1—O2	65.19 (15)	C6—O3—Hg1	115.6 (4)
O4—Hg1—O3	87.69 (18)	C7—O3—Hg1	99.7 (4)
N1—Hg1—O3	74.71 (19)	N1—C1—C2	112.3 (6)
O8—Hg1—O3	155.73 (18)	O1—C2—C1	107.9 (6)
O1—Hg1—O3	107.86 (15)	O1—C3—C4	112.9 (6)
O2—Hg1—O3	64.61 (16)	O2—C4—C3	107.6 (6)
O4—Hg1—O5	51.21 (18)	O2—C5—C6	112.7 (6)
N1—Hg1—O5	151.11 (19)	O3—C6—C5	108.5 (6)
O8—Hg1—O5	76.85 (19)	O3—C7—C8	113.5 (6)
O1—Hg1—O5	81.04 (17)	N1—C8—C7	113.3 (6)
O2—Hg1—O5	73.85 (18)	O6—N2—O5	123.9 (7)
O3—Hg1—O5	126.98 (18)	O6—N2—O4	118.9 (6)
O4—Hg1—O9	77.50 (17)	O5—N2—O4	117.1 (6)
N1—Hg1—O9	101.51 (17)	N2—O4—Hg1	107.8 (4)
O8—Hg1—O9	45.49 (16)	N2—O5—Hg1	83.9 (4)
O1—Hg1—O9	123.06 (15)	O9—N3—O7	121.7 (6)
O2—Hg1—O9	152.46 (15)	O9—N3—O8	119.3 (6)
O3—Hg1—O9	125.73 (14)	O7—N3—O8	118.9 (6)
O5—Hg1—O9	81.42 (18)	N3—O8—Hg1	106.5 (4)
C1—N1—C8	113.3 (6)	N3—O9—Hg1	88.7 (4)
O4—Hg1—N1—C1	178.8 (5)	C8—N1—C1—C2	73.7 (7)
O8—Hg1—N1—C1	−53.6 (4)	Hg1—N1—C1—C2	−55.4 (7)
O1—Hg1—N1—C1	25.2 (4)	C3—O1—C2—C1	−160.8 (6)
O2—Hg1—N1—C1	82.4 (4)	Hg1—O1—C2—C1	−32.0 (7)
O3—Hg1—N1—C1	139.6 (5)	N1—C1—C2—O1	59.1 (8)
O5—Hg1—N1—C1	−3.1 (7)	C2—O1—C3—C4	79.6 (8)
O9—Hg1—N1—C1	−96.1 (4)	Hg1—O1—C3—C4	−46.1 (8)
O4—Hg1—N1—C8	50.0 (7)	C5—O2—C4—C3	−171.8 (6)
O8—Hg1—N1—C8	177.7 (5)	Hg1—O2—C4—C3	−41.3 (7)
O1—Hg1—N1—C8	−103.5 (5)	O1—C3—C4—O2	58.4 (9)
O2—Hg1—N1—C8	−46.4 (5)	C4—O2—C5—C6	81.5 (8)
O3—Hg1—N1—C8	10.9 (4)	Hg1—O2—C5—C6	−50.3 (7)
O5—Hg1—N1—C8	−131.8 (5)	C7—O3—C6—C5	−152.9 (6)
O9—Hg1—N1—C8	135.1 (4)	Hg1—O3—C6—C5	−38.0 (7)
O4—Hg1—O1—C3	−34.5 (5)	O2—C5—C6—O3	60.0 (9)
N1—Hg1—O1—C3	133.4 (5)	C6—O3—C7—C8	81.0 (8)
O8—Hg1—O1—C3	−138.3 (5)	Hg1—O3—C7—C8	−42.9 (7)
O2—Hg1—O1—C3	16.3 (4)	C1—N1—C8—C7	−166.5 (6)
O3—Hg1—O1—C3	66.1 (5)	Hg1—N1—C8—C7	−39.4 (7)
O5—Hg1—O1—C3	−59.9 (5)	O3—C7—C8—N1	60.0 (9)
O9—Hg1—O1—C3	−133.5 (4)	O6—N2—O4—Hg1	179.4 (6)
O4—Hg1—O1—C2	−163.5 (4)	O5—N2—O4—Hg1	−0.7 (7)
N1—Hg1—O1—C2	4.4 (4)	N1—Hg1—O4—N2	179.2 (5)
O8—Hg1—O1—C2	92.7 (4)	O8—Hg1—O4—N2	55.4 (4)
O2—Hg1—O1—C2	−112.7 (5)	O1—Hg1—O4—N2	−32.7 (5)
O3—Hg1—O1—C2	−62.9 (5)	O2—Hg1—O4—N2	−78.8 (4)
O5—Hg1—O1—C2	171.0 (5)	O3—Hg1—O4—N2	−143.3 (4)
O9—Hg1—O1—C2	97.4 (4)	O5—Hg1—O4—N2	0.3 (4)
O4—Hg1—O2—C5	−72.8 (5)	O9—Hg1—O4—N2	89.3 (4)
N1—Hg1—O2—C5	84.5 (5)	O6—N2—O5—Hg1	−179.6 (7)
O8—Hg1—O2—C5	−176.4 (4)	O4—N2—O5—Hg1	0.5 (5)
O1—Hg1—O2—C5	146.9 (5)	O4—Hg1—O5—N2	−0.4 (4)
O3—Hg1—O2—C5	20.5 (4)	N1—Hg1—O5—N2	−179.5 (4)
O5—Hg1—O2—C5	−125.6 (5)	O8—Hg1—O5—N2	−127.3 (4)
O9—Hg1—O2—C5	−98.7 (5)	O1—Hg1—O5—N2	153.2 (4)
O4—Hg1—O2—C4	155.0 (5)	O2—Hg1—O5—N2	86.6 (4)
N1—Hg1—O2—C4	−47.7 (5)	O3—Hg1—O5—N2	47.6 (5)
O8—Hg1—O2—C4	51.4 (6)	O9—Hg1—O5—N2	−81.2 (4)
O1—Hg1—O2—C4	14.8 (5)	O9—N3—O8—Hg1	0.4 (7)
O3—Hg1—O2—C4	−111.6 (5)	O7—N3—O8—Hg1	179.9 (4)
O5—Hg1—O2—C4	102.2 (5)	O4—Hg1—O8—N3	49.6 (4)
O9—Hg1—O2—C4	129.2 (5)	N1—Hg1—O8—N3	−111.9 (4)
O4—Hg1—O3—C6	87.9 (5)	O1—Hg1—O8—N3	174.1 (4)
N1—Hg1—O3—C6	−105.9 (5)	O2—Hg1—O8—N3	140.5 (4)
O8—Hg1—O3—C6	−139.6 (5)	O3—Hg1—O8—N3	−79.4 (6)
O1—Hg1—O3—C6	−39.6 (5)	O5—Hg1—O8—N3	90.6 (4)
O2—Hg1—O3—C6	10.5 (5)	O9—Hg1—O8—N3	−0.2 (3)
O5—Hg1—O3—C6	52.6 (5)	O7—N3—O9—Hg1	−179.8 (5)
O9—Hg1—O3—C6	160.7 (5)	O8—N3—O9—Hg1	−0.4 (6)
O4—Hg1—O3—C7	−149.1 (4)	O4—Hg1—O9—N3	−131.7 (4)
N1—Hg1—O3—C7	17.0 (4)	N1—Hg1—O9—N3	71.1 (4)
O8—Hg1—O3—C7	−16.7 (6)	O8—Hg1—O9—N3	0.2 (3)
O1—Hg1—O3—C7	83.3 (4)	O1—Hg1—O9—N3	−6.4 (4)
O2—Hg1—O3—C7	133.5 (4)	O2—Hg1—O9—N3	−105.9 (4)
O5—Hg1—O3—C7	175.5 (4)	O3—Hg1—O9—N3	150.4 (3)
O9—Hg1—O3—C7	−76.3 (4)	O5—Hg1—O9—N3	−79.7 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O7^i	0.91	2.10	2.895 (8)	145

Symmetry code: (i) −x, −y, −z+1.

(III) aqua(1,7-dioxa-4-thia-10-azacyclododecane)nitratocopper(II) nitrate

Crystal data

[Cu(NO3)(C8H19N3O)(H2O)](NO3)	Z = 2
Mr = 378.84	F(000) = 394
Triclinic, P1	Dx = 1.707 Mg m^−3
a = 8.6167 (9) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.3975 (8) Å	Cell parameters from 25 reflections
c = 10.118 (1) Å	θ = 10–14°
α = 95.627 (8)°	µ = 1.53 mm^−1
β = 112.107 (9)°	T = 295 K
γ = 99.509 (9)°	Prism, blue
V = 737.05 (12) Å^3	0.60 × 0.60 × 0.30 mm

Data collection

Enraf-Nonius CAD4 diffractometer	2392 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.025
Graphite monochromator	θmax = 25.0°, θmin = 2.2°
ω–2θ scans	h = 0→10
Absorption correction: ψ scan (North et al., 1968)	k = −11→11
Tmin = 0.401, Tmax = 0.632	l = −12→11
2774 measured reflections	3 standard reflections every 120 min
2586 independent reflections	intensity decay: <5%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.024	H-atom parameters constrained
wR(F^2) = 0.068	Calculated w = 1/[σ^2(Fo^2) + (0.0343P)^2 + 0.4836P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
2586 reflections	Δρmax = 0.36 e Å^−3
200 parameters	Δρmin = −0.27 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: Patterson	Extinction coefficient: 0.096 (3)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.21252 (3)	0.31381 (3)	0.28989 (3)	0.02718 (12)
N1	0.4259 (2)	0.3414 (2)	0.2459 (2)	0.0323 (4)
H1	0.4852	0.4361	0.2790	0.039*
N2	0.2809 (2)	0.13935 (19)	0.3690 (2)	0.0324 (4)
H2	0.3292	0.1633	0.4674	0.039*
N3	−0.0304 (2)	0.2185 (2)	0.2627 (2)	0.0358 (4)
H3	−0.0734	0.2846	0.3028	0.043*
O1	0.1719 (2)	0.51182 (16)	0.26897 (18)	0.0363 (4)
O2	0.0888 (2)	0.22036 (17)	0.04050 (17)	0.0363 (4)
H21	0.1158	0.5411	0.3073	0.044*
H22	0.2444	0.5720	0.2825	0.044*
C1	0.2013 (3)	0.3174 (3)	−0.0028 (3)	0.0417 (6)
H1A	0.1890	0.4175	0.0144	0.050*
H1B	0.1748	0.2892	−0.1051	0.050*
C2	0.3804 (3)	0.3044 (3)	0.0871 (3)	0.0414 (6)
H2A	0.3916	0.2050	0.0642	0.050*
H2B	0.4609	0.3695	0.0621	0.050*
C3	0.5307 (3)	0.2438 (3)	0.3283 (3)	0.0401 (5)
H3A	0.5948	0.2912	0.4286	0.048*
H3B	0.6118	0.2239	0.2874	0.048*
C4	0.4125 (3)	0.1017 (3)	0.3205 (3)	0.0409 (5)
H4A	0.3585	0.0481	0.2219	0.049*
H4B	0.4769	0.0408	0.3823	0.049*
C5	0.1237 (3)	0.0239 (2)	0.3266 (3)	0.0409 (5)
H5A	0.1456	−0.0504	0.3873	0.049*
H5B	0.0864	−0.0225	0.2265	0.049*
C6	−0.0126 (3)	0.0955 (3)	0.3451 (3)	0.0428 (6)
H6A	−0.1210	0.0246	0.3095	0.051*
H6B	0.0195	0.1322	0.4469	0.051*
C7	−0.1451 (3)	0.1706 (3)	0.1063 (3)	0.0458 (6)
H7A	−0.2583	0.1877	0.0903	0.055*
H7B	−0.1566	0.0662	0.0795	0.055*
C8	−0.0768 (3)	0.2509 (3)	0.0112 (3)	0.0429 (6)
H8A	−0.1519	0.2168	−0.0901	0.051*
H8B	−0.0677	0.3554	0.0342	0.051*
N4	0.1509 (2)	0.4333 (2)	0.6302 (2)	0.0361 (4)
O3	0.2037 (2)	0.5294 (2)	0.73981 (19)	0.0467 (4)
O4	−0.0026 (2)	0.3634 (2)	0.5789 (2)	0.0533 (5)
O5	0.2479 (2)	0.4077 (2)	0.56979 (19)	0.0444 (4)
N5	0.4988 (2)	0.2483 (2)	0.7541 (2)	0.0384 (5)
O6	0.5639 (2)	0.25468 (19)	0.66193 (18)	0.0443 (4)
O7	0.3773 (3)	0.1476 (2)	0.7311 (3)	0.0823 (8)
O8	0.5587 (3)	0.3456 (3)	0.8614 (2)	0.0633 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.02852 (17)	0.02262 (16)	0.03316 (17)	0.00233 (10)	0.01675 (11)	0.00476 (10)
N1	0.0321 (9)	0.0310 (9)	0.0381 (10)	0.0037 (8)	0.0198 (8)	0.0071 (8)
N2	0.0409 (10)	0.0270 (9)	0.0319 (9)	0.0043 (8)	0.0187 (8)	0.0056 (7)
N3	0.0340 (10)	0.0297 (9)	0.0456 (11)	0.0013 (8)	0.0223 (9)	−0.0021 (8)
O1	0.0398 (9)	0.0259 (8)	0.0523 (10)	0.0050 (6)	0.0295 (8)	0.0060 (7)
O2	0.0379 (8)	0.0367 (8)	0.0354 (8)	0.0090 (7)	0.0150 (7)	0.0076 (7)
C1	0.0535 (15)	0.0449 (14)	0.0315 (12)	0.0096 (11)	0.0214 (11)	0.0125 (10)
C2	0.0482 (14)	0.0482 (14)	0.0404 (13)	0.0101 (11)	0.0308 (11)	0.0119 (11)
C3	0.0328 (12)	0.0470 (14)	0.0459 (13)	0.0119 (10)	0.0194 (10)	0.0123 (11)
C4	0.0471 (14)	0.0360 (12)	0.0492 (14)	0.0181 (11)	0.0245 (11)	0.0137 (10)
C5	0.0526 (14)	0.0240 (11)	0.0495 (14)	0.0007 (10)	0.0272 (12)	0.0077 (10)
C6	0.0496 (14)	0.0318 (12)	0.0525 (14)	−0.0058 (10)	0.0332 (12)	0.0042 (10)
C7	0.0299 (12)	0.0427 (14)	0.0544 (15)	−0.0005 (10)	0.0121 (11)	−0.0049 (11)
C8	0.0371 (12)	0.0422 (13)	0.0395 (13)	0.0104 (10)	0.0056 (10)	−0.0006 (10)
N4	0.0359 (10)	0.0348 (10)	0.0412 (11)	0.0119 (8)	0.0174 (9)	0.0074 (8)
O3	0.0497 (10)	0.0459 (10)	0.0427 (10)	0.0072 (8)	0.0206 (8)	−0.0034 (8)
O4	0.0367 (9)	0.0516 (11)	0.0677 (12)	0.0017 (8)	0.0236 (9)	−0.0052 (9)
O5	0.0399 (9)	0.0496 (10)	0.0497 (10)	0.0144 (8)	0.0242 (8)	0.0014 (8)
N5	0.0342 (10)	0.0364 (11)	0.0494 (12)	0.0079 (8)	0.0205 (9)	0.0129 (9)
O6	0.0470 (10)	0.0474 (10)	0.0399 (9)	0.0017 (8)	0.0236 (8)	0.0034 (7)
O7	0.0667 (14)	0.0498 (12)	0.144 (2)	−0.0096 (11)	0.0681 (16)	0.0114 (13)
O8	0.0663 (13)	0.0763 (14)	0.0448 (11)	0.0028 (11)	0.0289 (10)	−0.0063 (10)

Geometric parameters (Å, º)

Cu1—O1	1.9663 (15)	O2—C8	1.428 (3)
Cu1—N2	1.9742 (18)	O2—C1	1.438 (3)
Cu1—N1	2.0312 (18)	C1—C2	1.501 (4)
Cu1—N3	2.0393 (18)	C3—C4	1.515 (3)
Cu1—O2	2.3465 (16)	C5—C6	1.506 (4)
Cu1—O5	2.7682 (17)	C7—C8	1.504 (4)
N1—C3	1.486 (3)	N4—O3	1.241 (3)
N1—C2	1.493 (3)	N4—O5	1.247 (2)
N2—C4	1.472 (3)	N4—O4	1.257 (3)
N2—C5	1.477 (3)	N5—O7	1.222 (3)
N3—C6	1.484 (3)	N5—O8	1.228 (3)
N3—C7	1.490 (3)	N5—O6	1.257 (3)
O1—Cu1—N2	163.92 (7)	C6—N3—C7	113.13 (19)
O1—Cu1—N1	96.37 (7)	C6—N3—Cu1	105.76 (14)
N2—Cu1—N1	86.73 (7)	C7—N3—Cu1	111.33 (14)
O1—Cu1—N3	96.54 (7)	C8—O2—C1	116.32 (19)
N2—Cu1—N3	86.40 (8)	C8—O2—Cu1	97.41 (13)
N1—Cu1—N3	156.15 (8)	C1—O2—Cu1	98.62 (13)
O1—Cu1—O2	95.29 (6)	O2—C1—C2	106.39 (19)
N2—Cu1—O2	100.79 (7)	N1—C2—C1	112.69 (19)
N1—Cu1—O2	79.83 (7)	N1—C3—C4	108.98 (19)
N3—Cu1—O2	79.07 (7)	N2—C4—C3	107.58 (19)
O1—Cu1—O5	81.64 (6)	N2—C5—C6	107.65 (18)
N2—Cu1—O5	83.03 (6)	N3—C6—C5	108.79 (18)
N1—Cu1—O5	118.63 (6)	N3—C7—C8	111.87 (19)
N3—Cu1—O5	83.11 (7)	O2—C8—C7	106.0 (2)
O2—Cu1—O5	161.46 (5)	O3—N4—O5	120.5 (2)
C3—N1—C2	111.98 (18)	O3—N4—O4	119.46 (19)
C3—N1—Cu1	105.46 (13)	O5—N4—O4	120.0 (2)
C2—N1—Cu1	111.26 (14)	N4—O5—Cu1	136.44 (14)
C4—N2—C5	115.95 (18)	O7—N5—O8	123.3 (2)
C4—N2—Cu1	108.32 (13)	O7—N5—O6	118.5 (2)
C5—N2—Cu1	107.86 (14)	O8—N5—O6	118.2 (2)
O1—Cu1—N1—C3	150.35 (14)	O5—Cu1—O2—C8	22.0 (2)
N2—Cu1—N1—C3	−13.81 (15)	O1—Cu1—O2—C1	60.69 (14)
N3—Cu1—N1—C3	−87.3 (2)	N2—Cu1—O2—C1	−119.50 (14)
O2—Cu1—N1—C3	−115.40 (15)	N1—Cu1—O2—C1	−34.85 (13)
O5—Cu1—N1—C3	66.42 (16)	N3—Cu1—O2—C1	156.35 (14)
O1—Cu1—N1—C2	−88.04 (15)	O5—Cu1—O2—C1	140.12 (18)
N2—Cu1—N1—C2	107.80 (16)	C8—O2—C1—C2	158.04 (19)
N3—Cu1—N1—C2	34.4 (3)	Cu1—O2—C1—C2	55.31 (19)
O2—Cu1—N1—C2	6.22 (14)	C3—N1—C2—C1	141.5 (2)
O5—Cu1—N1—C2	−171.96 (14)	Cu1—N1—C2—C1	23.7 (2)
O1—Cu1—N2—C4	−116.4 (2)	O2—C1—C2—N1	−58.0 (3)
N1—Cu1—N2—C4	−14.67 (15)	C2—N1—C3—C4	−81.9 (2)
N3—Cu1—N2—C4	142.48 (16)	Cu1—N1—C3—C4	39.2 (2)
O2—Cu1—N2—C4	64.33 (15)	C5—N2—C4—C3	161.1 (2)
O5—Cu1—N2—C4	−134.04 (15)	Cu1—N2—C4—C3	39.8 (2)
O1—Cu1—N2—C5	117.4 (2)	N1—C3—C4—N2	−53.5 (2)
N1—Cu1—N2—C5	−140.89 (15)	C4—N2—C5—C6	−163.2 (2)
N3—Cu1—N2—C5	16.26 (14)	Cu1—N2—C5—C6	−41.6 (2)
O2—Cu1—N2—C5	−61.89 (15)	C7—N3—C6—C5	83.6 (2)
O5—Cu1—N2—C5	99.74 (14)	Cu1—N3—C6—C5	−38.5 (2)
O1—Cu1—N3—C6	−151.71 (14)	N2—C5—C6—N3	54.1 (3)
N2—Cu1—N3—C6	12.42 (14)	C6—N3—C7—C8	−140.1 (2)
N1—Cu1—N3—C6	85.9 (2)	Cu1—N3—C7—C8	−21.2 (2)
O2—Cu1—N3—C6	114.14 (14)	C1—O2—C8—C7	−161.99 (19)
O5—Cu1—N3—C6	−70.99 (14)	Cu1—O2—C8—C7	−58.53 (18)
O1—Cu1—N3—C7	85.03 (16)	N3—C7—C8—O2	58.9 (2)
N2—Cu1—N3—C7	−110.84 (16)	O3—N4—O5—Cu1	−148.60 (17)
N1—Cu1—N3—C7	−37.3 (3)	O4—N4—O5—Cu1	30.2 (3)
O2—Cu1—N3—C7	−9.12 (15)	O1—Cu1—O5—N4	71.5 (2)
O5—Cu1—N3—C7	165.75 (16)	N2—Cu1—O5—N4	−113.4 (2)
O1—Cu1—O2—C8	−57.47 (14)	N1—Cu1—O5—N4	164.2 (2)
N2—Cu1—O2—C8	122.34 (14)	N3—Cu1—O5—N4	−26.2 (2)
N1—Cu1—O2—C8	−153.01 (14)	O2—Cu1—O5—N4	−10.2 (3)
N3—Cu1—O2—C8	38.19 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O5^i	0.91	2.36	3.153 (3)	145
N1—H1···O8^i	0.91	2.61	3.234 (3)	127
N2—H2···O6	0.91	2.19	2.994 (3)	147
N2—H2···O7	0.91	2.56	3.428 (4)	159
N2—H2···N5	0.91	2.68	3.582 (3)	174
N3—H3···O3^ii	0.91	2.22	3.000 (3)	143
N3—H3···O4	0.91	2.62	3.257 (3)	127
O1—H21···O4^ii	0.79	2.00	2.788 (2)	172
O1—H21···O3^ii	0.79	2.57	3.162 (2)	133
O1—H21···N4^ii	0.79	2.64	3.398 (2)	161
O1—H22···O6^i	0.73	1.98	2.709 (2)	174

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