Dipyrimidine–copper(II) dinitrate complexes showing magnetic interactions

Crystals of Cu^II(NO₃)₂(pm)₃ (1), and two crystalline forms of Cu^II(NO₃)₂(H₂O)₂(pm)₂, (2) and (3), showed ferromagnetic, antiferromagnetic and paramagnetic interactions at extremely low temperatures, respectively. Crystal structure analyses revealed that the complexes were catena-dinitrato[μ-pyrimidine-κN¹:κN³]-(pyrimidine-N¹)copper(II), [Cu(NO₃)₂(pm)₂]_n, catena-diaquadinitrato[μ-pyrimidine-κN¹:κN³]copper(II), [Cu(NO₃)₂(H₂O)₂(pm)]_n, and diaquadinitratodipyrimidinecopper(II), Cu(NO₃)₂(H₂O)₂(pm)₂ for (1), (2) and (3), respectively. In (1) the Cu atom is coordinated by the two nitrates and N atoms of the non-bridging pyrimidine and bridging pyrimidine to form a one-dimensional coordination polymer. The complex is a five-coordinated square pyramid and can be regarded as a pseudo-seven-coordinated complex, since other short non-bonding Cu...O contacts are observed. In the crystals of (2) the pyrimidine bridges the Cu atoms to form a one-dimensional coordination chain. On the other hand, complex (3) is not a coordination polymer. It is important to form a coordination polymer for the appearance of the magnetic interactions. Types of coordination of the bridging organic moieties should also play an important role in magnetic properties. Magnetic measurements of (1) and (2) show that they are good examples of uniform S = 1/2 ferro- and antiferromagnetic Heisenberg chains with exchange parameters 2J/kB = +1.8 and −36 K, respectively.

Computing details

Data collection: AFC Control Software (Rigaku, 1994) for (1a), (2); AFC Control Software Ver.5.3.1 (Rigaku, 1994) for (1b), (3). Cell refinement: AFC Control Software (Rigaku, 1994) for (1a), (2); AFC Control Software Ver.5.3.1 (Rigaku, 1994) for (1b), (3). For all compounds, data reduction: TEXSAN, (Molecular Science Corporation, 1992). Program(s) used to solve structure: SIR88 (Burla. et al. 1989) for (1a), (1b), (3); DIRDIF92 (Beurskens et al., 1992) for (2). Program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) for (1a), (2), (3); MOLLY5 (Hansen & Coppens, 1978) for (1b). For all compounds, molecular graphics: ORTEPII (Johnson, 1972); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

(1a) catena-dinitrato-[m-pyrimidine-N1:N3]-(pyrimidine-N1)-copper(II)

Crystal data

Cu(II)(NO3)2(C4H4N2)2	F(000) = 700
Mr = 347.74	Dx = 1.887 Mg m^−3
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 25 reflections
a = 9.991 (5) Å	θ = 14.8–17.5°
b = 8.531 (6) Å	µ = 1.83 mm^−1
c = 14.359 (5) Å	T = 295 K
V = 1223.9 (11) Å^3	Prism, blue
Z = 4	0.40 × 0.30 × 0.20 mm

Data collection

Rigaku AFC7R diffractometer	1394 reflections with I > 2σ(I)
Radiation source: Rigaku rotating anode	Rint = 0.000
Graphite monochromator	θmax = 27.5°, θmin = 2.4°
ω–2θ scans	h = 0→12
Absorption correction: ψ scan (north, et al., 1968) ?	k = 0→11
Tmin = 0.582, Tmax = 0.711	l = −18→0
1464 measured reflections	3 standard reflections every 150 reflections
1464 independent reflections	intensity decay: 0.2%

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	Riding
R[F^2 > 2σ(F^2)] = 0.029	Calculated w = 1/[σ^2(Fo^2) + (0.0619P)^2 + 0.1183P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.078	(Δ/σ)max < 0.001
S = 1.04	Δρmax = 0.70 e Å^−3
1464 reflections	Δρmin = −0.60 e Å^−3
199 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.0030 (12)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.011 (19)

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	0.62030 (3)	0.30440 (4)	0.49625 (5)	0.02450 (14)
O1	0.6662 (3)	0.1936 (3)	0.6140 (2)	0.0347 (6)
O2	0.8303 (4)	0.1010 (4)	0.6950 (2)	0.0468 (7)
O3	0.8665 (3)	0.1934 (3)	0.5568 (3)	0.0456 (8)
O4	0.5602 (3)	0.4150 (3)	0.38263 (18)	0.0334 (5)
O5	0.7612 (3)	0.3624 (4)	0.3352 (2)	0.0492 (7)
O6	0.6164 (3)	0.4613 (4)	0.2395 (2)	0.0507 (8)
N1	0.7926 (3)	0.1625 (3)	0.6224 (2)	0.0328 (6)
N2	0.6490 (3)	0.4132 (3)	0.3167 (2)	0.0307 (6)
N3	0.5773 (3)	0.0968 (3)	0.4323 (2)	0.0298 (6)
N4	0.6375 (4)	−0.1684 (4)	0.4031 (4)	0.0488 (10)
N5	0.7083 (2)	0.5032 (3)	0.5453 (2)	0.0272 (5)
N6	0.9050 (3)	0.6583 (3)	0.5491 (2)	0.0277 (5)
C1	0.6554 (4)	−0.0286 (4)	0.4433 (3)	0.0405 (9)
H1	0.7289	−0.0179	0.4825	0.052 (13)*
C2	0.5311 (4)	−0.1816 (4)	0.3480 (3)	0.0414 (9)
H2	0.5145	−0.2773	0.3192	0.060 (16)*
C3	0.4459 (4)	−0.0605 (5)	0.3323 (3)	0.0417 (8)
H3	0.3719	−0.0723	0.2936	0.07 (2)*
C4	0.4724 (4)	0.0815 (4)	0.3756 (3)	0.0354 (7)
H4	0.4164	0.1668	0.3651	0.037 (12)*
C5	0.8318 (3)	0.5389 (4)	0.5181 (2)	0.0275 (7)
H5	0.8705	0.4745	0.4733	0.034 (13)*
C6	0.8461 (4)	0.7534 (4)	0.6119 (3)	0.0319 (6)
H6	0.8938	0.8383	0.6353	0.050 (16)*
C7	0.7192 (4)	0.7284 (4)	0.6417 (3)	0.0398 (8)
H7	0.6785	0.7971	0.6833	0.055 (16)*
C8	0.6518 (4)	0.5982 (4)	0.6087 (3)	0.0357 (7)
H8	0.5663	0.5760	0.6307	0.030 (10)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0234 (2)	0.0197 (2)	0.0304 (2)	−0.00116 (10)	−0.00185 (17)	0.00080 (16)
O1	0.0331 (14)	0.0344 (14)	0.0367 (14)	−0.0001 (9)	−0.0035 (12)	0.0060 (9)
O2	0.0577 (18)	0.0414 (14)	0.0415 (15)	0.0159 (14)	−0.0132 (14)	0.0008 (12)
O3	0.0372 (16)	0.046 (2)	0.053 (2)	0.0022 (10)	0.0063 (13)	0.0034 (13)
O4	0.0346 (12)	0.0293 (12)	0.0362 (13)	0.0046 (9)	0.0002 (10)	0.0047 (10)
O5	0.0319 (13)	0.0605 (19)	0.0551 (18)	0.0065 (13)	−0.0014 (12)	−0.0125 (16)
O6	0.064 (2)	0.0551 (19)	0.0328 (15)	0.0023 (14)	−0.0015 (11)	0.0119 (15)
N1	0.0374 (15)	0.0244 (11)	0.0365 (15)	0.0048 (12)	−0.0058 (13)	−0.0023 (11)
N2	0.0374 (14)	0.0243 (14)	0.0305 (14)	−0.0016 (11)	0.0001 (12)	−0.0018 (11)
N3	0.0252 (13)	0.0245 (12)	0.0396 (15)	−0.0019 (11)	0.0006 (11)	−0.0008 (11)
N4	0.049 (2)	0.0265 (14)	0.070 (3)	0.0029 (14)	−0.0062 (18)	−0.0109 (18)
N5	0.0244 (11)	0.0228 (10)	0.0343 (12)	−0.0030 (10)	−0.0006 (11)	−0.0022 (11)
N6	0.0247 (11)	0.0222 (11)	0.0361 (15)	−0.0022 (11)	−0.0012 (12)	−0.0022 (12)
C1	0.0373 (16)	0.0283 (17)	0.056 (2)	0.0053 (14)	−0.0103 (18)	−0.0059 (16)
C2	0.043 (2)	0.0271 (16)	0.055 (2)	−0.0029 (14)	0.0058 (19)	−0.0110 (14)
C3	0.0411 (19)	0.0387 (19)	0.045 (2)	−0.0097 (15)	−0.0071 (16)	−0.0068 (16)
C4	0.0349 (17)	0.0286 (17)	0.0426 (18)	0.0002 (13)	−0.0074 (15)	−0.0005 (13)
C5	0.0230 (13)	0.0221 (13)	0.0375 (17)	−0.0025 (12)	0.0013 (11)	−0.0035 (11)
C6	0.0332 (14)	0.0230 (15)	0.0395 (17)	0.0006 (14)	−0.0008 (15)	−0.0049 (15)
C7	0.0363 (19)	0.0335 (15)	0.050 (2)	0.0023 (16)	0.0088 (15)	−0.0172 (16)
C8	0.0269 (13)	0.0346 (17)	0.046 (2)	−0.0031 (14)	0.0074 (15)	−0.0074 (17)

Geometric parameters (Å, º)

Cu1—O1	1.990 (3)	N5—C5	1.329 (4)
Cu1—O4	1.978 (3)	N5—C8	1.343 (5)
Cu1—N3	2.041 (3)	N6—C5	1.331 (4)
Cu1—N5	2.036 (3)	N6—C6	1.348 (5)
Cu1—N6^i	2.303 (3)	N6—Cu1^ii	2.303 (3)
O1—N1	1.296 (4)	C2—C3	1.358 (6)
O2—N1	1.227 (4)	C3—C4	1.387 (5)
O3—N1	1.225 (5)	C6—C7	1.356 (6)
O4—N2	1.297 (4)	C7—C8	1.384 (5)
O5—N2	1.231 (4)	C1—H1	0.9300
O6—N2	1.227 (5)	C2—H2	0.9300
Cu1—O3	2.776 (3)	C3—H3	0.9300
Cu1—O5	2.752 (4)	C4—H4	0.9300
N3—C1	1.334 (5)	C5—H5	0.9300
N3—C4	1.333 (5)	C6—H6	0.9300
N4—C1	1.337 (5)	C7—H7	0.9300
N4—C2	1.330 (6)	C8—H8	0.9300
O1—Cu1—O4	175.56 (12)	C5—N6—Cu1^ii	120.6 (2)
O1—Cu1—N3	91.08 (12)	C6—N6—Cu1^ii	123.0 (2)
O1—Cu1—N5	90.13 (12)	N3—C1—N4	125.9 (4)
O1—Cu1—N6^i	90.05 (12)	N3—C1—H1	117.0
O4—Cu1—N3	88.77 (12)	N4—C1—H1	117.0
O4—Cu1—N5	91.10 (11)	N4—C2—C3	122.4 (4)
O4—Cu1—N6^i	85.53 (11)	N4—C2—H2	118.8
N3—Cu1—N5	165.81 (11)	C3—C2—H2	118.8
N3—Cu1—N6^i	94.09 (12)	C2—C3—C4	118.1 (4)
N5—Cu1—N6^i	100.05 (11)	C2—C3—H3	121.0
Cu1—O1—N1	113.6 (2)	C4—C3—H3	121.0
Cu1—O4—N2	112.9 (2)	N3—C4—C3	120.6 (3)
O1—N1—O2	117.7 (3)	N3—C4—H4	119.7
O1—N1—O3	118.2 (3)	C3—C4—H4	119.7
O2—N1—O3	124.1 (3)	N5—C5—N6	126.0 (3)
O4—N2—O5	118.0 (3)	N5—C5—H5	117.0
O4—N2—O6	118.3 (3)	N6—C5—H5	117.0
O5—N2—O6	123.7 (4)	N6—C6—C7	121.7 (3)
Cu1—N3—C4	121.7 (2)	N6—C6—H6	119.2
Cu1—N3—C1	121.3 (3)	C7—C6—H6	119.2
C1—N3—C4	117.0 (3)	C6—C7—C8	118.2 (3)
C1—N4—C2	116.0 (4)	C6—C7—H7	120.9
Cu1—N5—C5	119.3 (2)	C8—C7—H7	120.9
Cu1—N5—C8	123.7 (2)	N5—C8—C7	120.8 (3)
C5—N5—C8	116.8 (3)	N5—C8—H8	119.6
C5—N6—C6	116.4 (3)	C7—C8—H8	119.6

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

(1b) catena-dinitrato-[m-pyrimidine-N1:N3]-(pyrimidine-N1)-copper(II)

Crystal data

Cu(II)(NO3)2(C4H4N2)2	F(000) = 700
Mr = 347.74	Dx = 1.926 Mg m^−3
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 25 reflections
a = 10.000 (2) Å	θ = 14.0–15.6°
b = 8.4519 (2) Å	µ = 1.87 mm^−1
c = 14.187 (2) Å	T = 100 K
V = 1199.1 (4) Å^3	Prism, blue
Z = 4	0.15 × 0.14 × 0.10 mm

Data collection

Rigaku AFC7R diffractometer	5759 reflections with > 3σ(F)
Radiation source: Rigaku rotating anode	Rint = 0.069
Graphite monochromator	θmax = 60.0°, θmin = 2.0°
ω–2θ scans	h = −24→24
Absorption correction: analytical (de Meulenaer, et al., 1965) ?	k = −20→0
Tmin = 0.749, Tmax = 0.801	l = 0→34
15315 measured reflections	3 standard reflections every 100 reflections
7876 independent reflections	intensity decay: 1.0%

Refinement

Refinement on F	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Not refined
wR(F^2) = 0.034	Calculated w = 1/[σ^2(Fo^2)]
S = 1.24	(Δ/σ)max = 0.001
5759 reflections	Δρmax = 1.34 e Å^−3
535 parameters	Δρmin = −1.44 e Å^−3
0 restraints	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.035 (9)

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. For 1 b, after the refinements with full-matrix least-squares methods using the program SHELXL97 (Sheldrick, 1997) [R = 0.0366 for 4958 reflections (I>2 s(I)), wR2 = 0.1012 for 7876 reflections with 197 parameters, flack parameter = 0.0350 (9), H atoms were treated riding model] and high-order refinements with sinq/l > 0.6, further refinements were carried out using the multipole expansion atomic scattering factors by the program MOLLY5 (Hansen et al., 1978).

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

	x	y	z	Uiso*/Ueq
Cu1	0.62021 (2)	0.30507 (2)	0.50000	0.00978 (5)
O1	0.6677 (2)	0.1927 (3)	0.61950 (14)	0.0147 (5)
O2	0.8333 (3)	0.1030 (3)	0.70201 (17)	0.0183 (7)
O3	0.8695 (2)	0.1947 (3)	0.56093 (18)	0.0194 (7)
O4	0.5599 (2)	0.4159 (2)	0.38476 (14)	0.0137 (5)
O5	0.7626 (2)	0.3629 (3)	0.33843 (18)	0.0184 (7)
O6	0.6185 (3)	0.4614 (3)	0.24014 (15)	0.0192 (7)
N1	0.7945 (2)	0.1633 (2)	0.62841 (14)	0.0134 (5)
N2	0.6503 (2)	0.4133 (2)	0.31875 (13)	0.0127 (5)
N3	0.57843 (19)	0.0963 (2)	0.43616 (14)	0.0125 (5)
N4	0.6411 (2)	−0.1709 (3)	0.40536 (19)	0.0181 (7)
N5	0.70849 (18)	0.5047 (2)	0.55017 (13)	0.0120 (5)
N6	0.90607 (18)	0.6592 (2)	0.55368 (13)	0.0120 (4)
C1	0.6583 (2)	−0.0308 (3)	0.44610 (16)	0.0158 (6)
C2	0.5317 (2)	−0.1875 (3)	0.35149 (17)	0.0169 (6)
C3	0.4431 (2)	−0.0633 (3)	0.33617 (15)	0.0155 (6)
C4	0.4709 (2)	0.0794 (2)	0.37983 (15)	0.0143 (6)
C5	0.83337 (18)	0.5391 (2)	0.52203 (13)	0.0123 (5)
C6	0.8490 (2)	0.7577 (2)	0.61613 (14)	0.0137 (5)
C7	0.7183 (2)	0.7352 (3)	0.64669 (16)	0.0161 (6)
C8	0.6512 (2)	0.6027 (2)	0.61287 (15)	0.0148 (6)
H1	0.7345	−0.0186	0.4855	0.022*
H2	0.5144	−0.2869	0.3230	0.024*
H3	0.3667	−0.0762	0.2973	0.020*
H4	0.4131	0.1671	0.3701	0.020*
H5	0.8727	0.4716	0.4762	0.013*
H6	0.8987	0.8445	0.6401	0.023*
H7	0.6770	0.8068	0.6889	0.038*
H8	0.5632	0.5818	0.6345	0.023*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.01062 (6)	0.00915 (5)	0.00958 (5)	−0.00036 (7)	−0.00062 (11)	0.00039 (12)
O1	0.0157 (6)	0.0156 (6)	0.0129 (5)	−0.0001 (6)	−0.0012 (5)	0.0029 (6)
O2	0.0229 (9)	0.0175 (7)	0.0148 (7)	0.0055 (7)	−0.0038 (7)	0.0016 (7)
O3	0.0163 (7)	0.0226 (8)	0.0194 (7)	0.0005 (8)	0.0024 (6)	0.0006 (8)
O4	0.0145 (6)	0.0147 (6)	0.0122 (5)	0.0012 (5)	0.0001 (5)	0.0017 (5)
O5	0.0143 (7)	0.0235 (8)	0.0176 (8)	0.0025 (7)	−0.0006 (6)	−0.0041 (8)
O6	0.0238 (9)	0.0219 (8)	0.0121 (6)	0.0006 (8)	0.0000 (7)	0.0038 (6)
N1	0.0158 (6)	0.0130 (5)	0.0116 (5)	0.0019 (5)	−0.0020 (5)	0.0000 (5)
N2	0.0157 (6)	0.0124 (5)	0.0102 (5)	−0.0001 (5)	0.0001 (5)	0.0000 (5)
N3	0.0133 (6)	0.0111 (5)	0.0132 (5)	0.0003 (5)	−0.0021 (5)	−0.0004 (5)
N4	0.0179 (7)	0.0126 (6)	0.0241 (9)	0.0022 (6)	−0.0021 (7)	−0.0036 (6)
N5	0.0120 (5)	0.0117 (5)	0.0125 (5)	−0.0015 (5)	0.0003 (5)	−0.0004 (5)
N6	0.0115 (5)	0.0113 (5)	0.0135 (5)	−0.0016 (5)	0.0004 (5)	−0.0016 (5)
C1	0.0155 (7)	0.0138 (6)	0.0184 (7)	0.0019 (6)	−0.0031 (6)	−0.0025 (6)
C2	0.0195 (7)	0.0126 (6)	0.0187 (7)	−0.0011 (6)	0.0004 (6)	−0.0035 (6)
C3	0.0172 (7)	0.0135 (6)	0.0160 (7)	−0.0027 (6)	−0.0026 (6)	−0.0024 (6)
C4	0.0158 (6)	0.0121 (6)	0.0151 (6)	−0.0006 (5)	−0.0026 (5)	−0.0007 (5)
C5	0.0122 (5)	0.0122 (5)	0.0125 (5)	−0.0016 (5)	0.0010 (4)	−0.0022 (5)
C6	0.0148 (6)	0.0115 (5)	0.0150 (6)	−0.0008 (5)	0.0000 (5)	−0.0030 (5)
C7	0.0156 (7)	0.0151 (6)	0.0177 (7)	0.0000 (6)	0.0036 (6)	−0.0054 (6)
C8	0.0137 (6)	0.0142 (6)	0.0168 (7)	−0.0013 (5)	0.0029 (5)	−0.0037 (6)

Geometric parameters (Å, º)

Cu1—O1	2.001 (2)	N5—C5	1.343 (3)
Cu1—O4	1.978 (2)	N5—C8	1.344 (3)
Cu1—N3	2.0268 (19)	N6—C5	1.327 (3)
Cu1—N5	2.0329 (18)	N6—C6	1.343 (3)
Cu1—N6^i	2.2928 (18)	N6—Cu1^ii	2.2928 (18)
O1—N1	1.298 (3)	C6—C7	1.389 (3)
O2—N1	1.225 (3)	C7—C8	1.391 (3)
O3—N1	1.245 (3)	Cu1—O3	2.799 (2)
O4—N2	1.302 (3)	Cu1—O5	2.742 (3)
O5—N2	1.233 (3)	C1—H1	0.950
O6—N2	1.229 (3)	C2—H2	0.948
N3—C1	1.346 (3)	C3—H3	0.948
N3—C4	1.347 (3)	C4—H4	0.950
N4—C1	1.329 (3)	C5—H5	0.950
N4—C2	1.342 (3)	C6—H6	0.949
C2—C3	1.390 (3)	C7—H7	0.947
C3—C4	1.384 (3)	C8—H8	0.948
O1—Cu1—O4	175.95 (9)	N3—C1—N4	126.0 (2)
O1—Cu1—N3	90.81 (9)	N4—C2—C3	122.0 (2)
O1—Cu1—N5	89.68 (8)	C2—C3—C4	117.4 (2)
O1—Cu1—N6^i	90.17 (8)	N3—C4—C3	121.2 (2)
O4—Cu1—N3	88.85 (8)	N5—C5—N6	125.05 (18)
O4—Cu1—N5	91.66 (8)	N6—C6—C7	121.36 (19)
O4—Cu1—N6^i	85.83 (8)	C6—C7—C8	117.2 (2)
N3—Cu1—N5	165.58 (8)	N5—C8—C7	121.2 (2)
N3—Cu1—N6^i	94.04 (7)	O1—Cu1—O3	50.83 (9)
N5—Cu1—N6^i	100.37 (7)	O3—Cu1—O5	81.67 (8)
Cu1—O1—N1	113.92 (17)	O4—Cu1—O5	51.92 (8)
Cu1—O4—N2	112.01 (15)	N3—C1—H1	116.8
O1—N1—O2	118.2 (2)	N4—C1—H1	117.2
O1—N1—O3	118.2 (2)	N4—C2—H2	118.9
O2—N1—O3	123.6 (2)	C3—C2—H2	119.1
O4—N2—O5	118.4 (2)	C2—C3—H3	121.2
O4—N2—O6	117.9 (2)	C4—C3—H3	121.5
O5—N2—O6	123.7 (3)	N3—C4—H4	119.3
Cu1—N3—C1	121.71 (16)	C3—C4—H4	119.5
Cu1—N3—C4	121.47 (15)	N5—C5—H5	117.3
C1—N3—C4	116.8 (2)	N6—C5—H5	117.7
C1—N4—C2	116.5 (2)	N6—C6—H6	119.5
Cu1—N5—C5	118.64 (14)	C7—C6—H6	119.1
Cu1—N5—C8	123.92 (15)	C6—C7—H7	121.4
C5—N5—C8	117.40 (18)	C8—C7—H7	121.5
C5—N6—C6	117.68 (18)	N5—C8—H8	119.7
C5—N6—Cu1^ii	120.00 (14)	C7—C8—H8	119.1
C6—N6—Cu1^ii	122.31 (14)

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

(2) catena-diaquadinitrato-[m-pyrimidine-N1:N1]-copper(II)

Crystal data

Cu(II)(C4H4N2)(H2O)2(NO3)2	F(000) = 612.00
Mr = 303.68	Dx = 2.072 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 12.408 (8) Å	θ = 12.6–16.7°
b = 11.511 (9) Å	µ = 2.29 mm^−1
c = 7.518 (9) Å	T = 294 K
β = 114.99 (5)°	Prismatic, light blue
V = 973.2 (15) Å^3	0.40 × 0.40 × 0.30 mm
Z = 4

Data collection

Rigaku AFC7R diffractometer	1076 reflections with I > 2σ(I)
Radiation source: Rigaku rotating anode	Rint = 0.060
Graphite monochromator	θmax = 27.5°, θmin = 2.5°
ω–2θ scans	h = 0→16
Absorption correction: ψ scan (North, Phillips & Mathews, 1968)	k = 0→14
Tmin = 0.323, Tmax = 0.544	l = −9→8
1162 measured reflections	3 standard reflections every 150 reflections
1113 independent reflections	intensity decay: 6.7%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.029	Refined
wR(F^2) = 0.082	Calculated w = 1/[σ^2(Fo^2) + (0.0538P)^2 + 0.857P] where P = (Fo^2 + 2Fc^2)/3
S = 1.15	(Δ/σ)max = 0.001
1113 reflections	Δρmax = 0.61 e Å^−3
97 parameters	Δρmin = −0.87 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.104 (4)

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	0.2500	0.2500	0.0000	0.0167 (2)
O1	0.30255 (14)	0.12893 (12)	0.2740 (2)	0.0314 (4)
O2	0.3659 (2)	0.26462 (14)	0.4942 (3)	0.0360 (5)
O3	0.36386 (14)	0.08531 (12)	0.58062 (19)	0.0296 (4)
O4	0.34933 (12)	0.13604 (12)	−0.0687 (2)	0.0230 (3)
N1	0.34458 (13)	0.16213 (14)	0.4501 (2)	0.0216 (4)
N2	0.39930 (12)	0.34724 (12)	0.1354 (2)	0.0181 (3)
C1	0.5000	0.2939 (2)	0.2500	0.0185 (5)
C2	0.40005 (15)	0.46374 (15)	0.1327 (3)	0.0221 (4)
C3	0.5000	0.5262 (2)	0.2500	0.0256 (6)
H1	0.5000	0.207 (5)	0.2500	0.050 (12)*
H2	0.331 (3)	0.502 (2)	0.053 (4)	0.032 (6)*
H3	0.5000	0.600 (3)	0.2500	0.021 (8)*
H41	0.354 (2)	0.068 (2)	−0.029 (4)	0.026 (6)*
H42	0.349 (3)	0.132 (3)	−0.172 (6)	0.054 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0145 (3)	0.0156 (3)	0.0177 (3)	−0.00128 (8)	0.00465 (16)	−0.00171 (8)
O1	0.0463 (9)	0.0278 (7)	0.0180 (6)	−0.0053 (6)	0.0116 (6)	−0.0017 (5)
O2	0.0496 (12)	0.0237 (8)	0.0392 (10)	−0.0115 (7)	0.0232 (9)	−0.0092 (6)
O3	0.0395 (8)	0.0277 (7)	0.0195 (6)	−0.0011 (6)	0.0105 (6)	0.0032 (5)
O4	0.0287 (7)	0.0213 (7)	0.0214 (7)	0.0007 (5)	0.0130 (5)	−0.0018 (5)
N1	0.0232 (7)	0.0226 (8)	0.0208 (7)	−0.0029 (6)	0.0112 (6)	−0.0012 (6)
N2	0.0165 (7)	0.0179 (7)	0.0181 (7)	0.0001 (5)	0.0055 (6)	−0.0002 (5)
C1	0.0185 (11)	0.0171 (12)	0.0184 (11)	0.000	0.0064 (9)	0.000
C2	0.0193 (8)	0.0189 (8)	0.0243 (9)	0.0023 (6)	0.0054 (7)	0.0021 (6)
C3	0.0239 (12)	0.0164 (12)	0.0303 (14)	0.000	0.0053 (11)	0.000

Geometric parameters (Å, º)

Cu1—O1^i	2.340 (2)	N2—C2	1.341 (2)
Cu1—O1	2.340 (2)	C1—N2^ii	1.331 (2)
Cu1—O4^i	2.0109 (16)	C2—C3	1.382 (2)
Cu1—O4	2.0109 (16)	C3—C2^ii	1.382 (2)
Cu1—N2^i	2.0315 (18)	O4—H41	0.83 (3)
Cu1—N2	2.0315 (18)	O4—H42	0.78 (4)
O1—N1	1.260 (2)	C1—H1	1.00 (5)
O2—N1	1.224 (2)	C2—H2	0.93 (3)
O3—N1	1.266 (2)	C3—H3	0.85 (4)
N2—C1	1.331 (2)
O1—Cu1—O1^i	180.0	O1—N1—O3	117.46 (17)
O1—Cu1—O4	82.22 (8)	O2—N1—O3	121.00 (18)
O1—Cu1—O4^i	97.78 (9)	C1—N2—C2	117.43 (16)
O1^i—Cu1—O4	97.78 (8)	Cu1—N2—C1	118.55 (14)
O1^i—Cu1—O4^i	82.22 (8)	Cu1—N2—C2	123.64 (12)
O1—Cu1—N2	91.78 (8)	N2—C1—N2^ii	125.0 (2)
O1—Cu1—N2^i	88.22 (8)	N2—C2—C3	121.41 (17)
O1^i—Cu1—N2^i	91.78 (8)	C2—C3—C2^ii	117.2 (2)
O1^i—Cu1—N2	88.22 (8)	Cu1—O4—H41	118.3 (18)
O4—Cu1—O4^i	180.0	Cu1—O4—H42	124 (2)
O4—Cu1—N2	87.71 (8)	H41—O4—H42	106 (3)
O4—Cu1—N2^i	92.29 (8)	N2^ii—C1—H1	117.49 (11)
O4^i—Cu1—N2^i	87.71 (8)	N2—C1—H1	117.49 (12)
O4^i—Cu1—N2	92.29 (8)	N2—C2—H2	118.6 (17)
N2—Cu1—N2^i	180.0	C3—C2—H2	120.0 (17)
Cu1—O1—N1	125.60 (13)	C2—C3—H3	121.38 (12)
O1—N1—O2	121.54 (17)	C2^ii—C3—H3	121.38 (12)

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

(3) diaquadinitratodipyrimidinecopper(II)

Crystal data

Cu(II)(C4H4N2)2(H2O)2(NO3)2	F(000) = 390.00
Mr = 383.78	Dx = 1.836 Mg m^−3
Monoclinic, P21/a	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yab	Cell parameters from 25 reflections
a = 7.1658 (12) Å	θ = 17.2–17.5°
b = 14.105 (2) Å	µ = 1.63 mm^−1
c = 7.5358 (14) Å	T = 296 K
β = 114.324 (12)°	Prism, blue
V = 694.1 (2) Å^3	0.30 × 0.20 × 0.20 mm
Z = 2

Data collection

Rigaku AFC7R diffractometer	1291 reflections with I > 2σ(I)
Radiation source: Rigaku rotating anode	Rint = 0.043
Graphite monochromator	θmax = 26.9°, θmin = 2.9°
ω–2θ scans	h = 0→9
Absorption correction: ψ scan (North, Phillips & Mathews, 1968)	k = 0→17
Tmin = 0.612, Tmax = 0.734	l = −9→8
1625 measured reflections	3 standard reflections every 150 reflections
1508 independent reflections	intensity decay: 3.0%

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)] = 0.052	Hydrogen site location: difference Fourier map
wR(F^2) = 0.148	Refined
S = 1.08	Calculated w = 1/[σ^2(Fo^2) + (0.1118P)^2 + 0.2222P] where P = (Fo^2 + 2Fc^2)/3
1508 reflections	(Δ/σ)max = 0.001
130 parameters	Δρmax = 1.54 e Å^−3
0 restraints	Δρmin = −1.32 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
Cu1	0.0000	0.5000	0.0000	0.0235 (2)
O1	−0.3227 (4)	0.4740 (3)	−0.2808 (4)	0.0488 (7)
O2	−0.5284 (4)	0.36486 (19)	−0.2676 (4)	0.0507 (7)
O3	−0.6024 (6)	0.51148 (19)	−0.2541 (6)	0.0503 (8)
O4	0.1498 (3)	0.42298 (16)	−0.1170 (3)	0.0303 (5)
N1	−0.4848 (4)	0.4501 (2)	−0.2672 (4)	0.0342 (6)
N2	−0.0342 (3)	0.38376 (17)	0.1397 (3)	0.0252 (5)
N3	−0.1220 (4)	0.22208 (18)	0.1213 (4)	0.0334 (6)
C1	−0.1084 (5)	0.3038 (2)	0.0413 (4)	0.0285 (6)
C2	0.0257 (4)	0.3821 (2)	0.3329 (4)	0.0303 (6)
C3	0.0176 (5)	0.2999 (2)	0.4285 (5)	0.0363 (7)
C4	−0.0557 (5)	0.2199 (2)	0.3147 (5)	0.0354 (7)
H1	−0.150 (5)	0.304 (2)	−0.087 (5)	0.021 (7)*
H2	0.059 (6)	0.437 (3)	0.385 (5)	0.028 (9)*
H3	0.048 (7)	0.305 (4)	0.549 (6)	0.043 (12)*
H4	−0.057 (6)	0.165 (3)	0.375 (6)	0.041 (10)*
H41	0.237 (7)	0.453 (4)	−0.142 (6)	0.053 (13)*
H42	0.220 (7)	0.383 (3)	−0.033 (6)	0.044 (11)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0268 (4)	0.0133 (3)	0.0344 (4)	0.00150 (14)	0.0165 (2)	0.00228 (15)
O1	0.0312 (13)	0.0715 (18)	0.0447 (14)	−0.0132 (13)	0.0164 (11)	0.0000 (14)
O2	0.0459 (14)	0.0349 (14)	0.0766 (19)	−0.0044 (11)	0.0305 (13)	−0.0097 (12)
O3	0.0582 (19)	0.0336 (14)	0.075 (2)	0.0030 (11)	0.0434 (18)	0.0040 (12)
O4	0.0324 (11)	0.0216 (10)	0.0421 (12)	0.0057 (9)	0.0205 (10)	0.0045 (9)
N1	0.0321 (13)	0.0389 (15)	0.0314 (12)	−0.0039 (11)	0.0129 (10)	−0.0034 (11)
N2	0.0264 (11)	0.0170 (11)	0.0343 (12)	−0.0010 (8)	0.0146 (9)	0.0014 (9)
N3	0.0391 (14)	0.0197 (12)	0.0424 (14)	−0.0051 (10)	0.0178 (11)	0.0002 (10)
C1	0.0302 (14)	0.0218 (14)	0.0328 (15)	−0.0033 (10)	0.0122 (11)	−0.0021 (11)
C2	0.0332 (15)	0.0234 (15)	0.0349 (15)	−0.0035 (11)	0.0144 (12)	−0.0045 (12)
C3	0.0408 (18)	0.0351 (17)	0.0334 (16)	−0.0019 (13)	0.0157 (13)	0.0046 (13)
C4	0.0381 (17)	0.0242 (15)	0.0458 (17)	−0.0010 (12)	0.0192 (14)	0.0079 (13)

Geometric parameters (Å, º)

Cu1—O1	2.435 (3)	N3—C1	1.323 (4)
Cu1—O4	1.973 (2)	N3—C4	1.334 (4)
Cu1—N2	2.017 (2)	C2—C3	1.378 (5)
Cu1—N2^i	2.017 (2)	C3—C4	1.384 (5)
Cu1—O1^i	2.435 (3)	C1—H1	0.89 (3)
Cu1—O4^i	1.973 (2)	C2—H2	0.86 (4)
O1—N1	1.254 (4)	C3—H3	0.85 (4)
O2—N1	1.242 (4)	C4—H4	0.90 (4)
O3—N1	1.240 (4)	O4—H41	0.84 (5)
N2—C1	1.335 (4)	O4—H42	0.84 (5)
N2—C2	1.338 (4)
O1—Cu1—O1^i	180.0	O1—N1—O3	120.1 (3)
O1—Cu1—O4	91.45 (10)	O2—N1—O3	119.8 (3)
O1—Cu1—N2	93.17 (10)	C1—N2—C2	117.8 (3)
O4—Cu1—N2	89.50 (9)	C1—N3—C4	117.3 (3)
O1^i—Cu1—O4	88.55 (10)	N3—C1—N2	124.8 (3)
O1—Cu1—O4^i	88.55 (10)	N2—C2—C3	121.4 (3)
O1^i—Cu1—N2	86.83 (10)	C2—C3—C4	116.7 (3)
O1—Cu1—N2^i	86.83 (10)	N3—C4—C3	122.1 (3)
O1^i—Cu1—O4^i	91.45 (10)	Cu1—O4—H41	115 (4)
O1^i—Cu1—N2^i	93.17 (10)	Cu1—O4—H42	108 (3)
O4^i—Cu1—O4	180.0	H41—O4—H42	103 (4)
O4^i—Cu1—N2^i	89.50 (9)	N3—C1—H1	116 (2)
O4—Cu1—N2^i	90.50 (9)	N2—C1—H1	119 (2)
O4^i—Cu1—N2	90.50 (9)	N2—C2—H2	113 (2)
N2^i—Cu1—N2	180.0	C3—C2—H2	126 (2)
Cu1—O1—N1	123.3 (2)	C2—C3—H3	116 (3)
Cu1—N2—C1	120.22 (19)	C4—C3—H3	127 (3)
Cu1—N2—C2	121.9 (2)	N3—C4—H4	120 (3)
O1—N1—O2	120.1 (3)	C3—C4—H4	118 (3)

Symmetry code: (i) −x, −y+1, −z.