Poly[bis-[μ(4)-N-(2-hydroxy-imino-propion-yl)-N'-(2-oxidoimino-propion-yl)propane-1,3-diaminato]dimethano-lcalciumdicopper(II)].

In the title compound, [CaCu(2)(C(9)H(13)N(4)O(4))(2)(CH(3)OH)(2)](n), the Ca(II) atom lies on an inversion center and is situated in a moderately distorted octa-hedral environment. The Cu(II) atom is in a distorted square-pyramidal geometry, defined by four N atoms belonging to the amide and oxime groups of the triply deprotonated residue of N,N'-bis-(2-hydroxy-imino-propano-yl)propane-1,3-diamine (H(4)pap) and one oxime O atom from a neighboring Hpap ligand at the apical site, forming a dimeric [Cu(2)(Hpap)(2)](2-) unit. Each dimeric unit connects four Ca atoms and each Ca atom links four [Cu(2)(Hpap)(2)](2-) units through Ca-O(amide) bonds, leading to a three-dimensional framework. The crystal structure involves intra- and inter-molecular O-H⋯O hydrogen bonds.

Related literature

For the coordination chemistry of tetra­dentate oxime-and-amide open-chain ligands, see: Duda et al. (1997 ▶); Fritsky et al. (1999 ▶). For oximes as efficient metal chelators, see: Gumienna-Kontecka et al. (2000 ▶); Onindo et al. (1995 ▶); Sliva et al. (1997a ▶,b ▶). For the use of oximes in stabilizing high oxidation states of metal ions, see: Fritsky et al. (1998 ▶, 2006 ▶). For related structures, see: Kanderal et al. (2005 ▶); Fritsky (1999 ▶); Fritsky et al. (2000 ▶); Mokhir et al. (2002 ▶); Moroz et al. (2008 ▶); Wörl et al. (2005 ▶).

Experimental

Crystal data

[CaCu2(C9H13N4O4)2(CH4O)2]

M = 713.71

Monoclinic,

a = 10.0554 (4) Å

b = 8.7794 (3) Å

c = 15.4465 (7) Å

β = 97.882 (2)°

V = 1350.74 (9) Å3

Z = 2

Mo Kα radiation

μ = 1.83 mm−1

T = 120 K

0.28 × 0.24 × 0.13 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.622, T max = 0.796

8392 measured reflections

3074 independent reflections

2573 reflections with I > 2σ(I)

R int = 0.035

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.079

S = 1.04

3074 reflections

192 parameters

H-atom parameters constrained

Δρmax = 1.11 e Å−3

Δρmin = −0.56 e Å−3

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809033467/hy2216sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809033467/hy2216Isup2.hkl

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

[CaCu2(C9H13N4O4)2(CH4O)2]	F(000) = 736
Mr = 713.71	Dx = 1.755 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3254 reflections
a = 10.0554 (4) Å	θ = 1.0–27.5°
b = 8.7794 (3) Å	µ = 1.83 mm−1
c = 15.4465 (7) Å	T = 120 K
β = 97.882 (2)°	Block, dark red
V = 1350.74 (9) Å3	0.28 × 0.24 × 0.13 mm
Z = 2

Nonius KappaCCD diffractometer	3074 independent reflections
Radiation source: fine-focus sealed tube	2573 reflections with I > 2σ(I)
horizontally mounted graphite crystal	Rint = 0.035
Detector resolution: 9 pixels mm-1	θmax = 27.5°, θmin = 2.6°
φ and ω scans with κ offset	h = −11→13
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −11→10
Tmin = 0.622, Tmax = 0.796	l = −20→19
8392 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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.079	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0351P)2 + 1.0009P] where P = (Fo2 + 2Fc2)/3
3074 reflections	(Δ/σ)max = 0.002
192 parameters	Δρmax = 1.11 e Å−3
0 restraints	Δρmin = −0.56 e Å−3

	x	y	z	Uiso*/Ueq
Cu1	0.07005 (3)	0.90813 (3)	0.122024 (17)	0.01389 (10)
Ca1	0.0000	1.0000	0.5000	0.01418 (14)
O1	−0.02176 (17)	1.23359 (18)	0.11376 (10)	0.0201 (4)
H1O	0.0287	1.2169	0.0643	0.030*
O2	0.11916 (16)	1.14306 (18)	−0.00651 (10)	0.0171 (3)
O3	−0.05881 (17)	0.92919 (19)	0.35557 (10)	0.0213 (4)
O4	0.38614 (16)	0.70750 (19)	0.04006 (11)	0.0210 (4)
O5	−0.21320 (16)	1.12267 (19)	0.48180 (11)	0.0219 (4)
H5O	−0.2529	1.2181	0.4868	0.033*
N1	−0.01214 (18)	1.0977 (2)	0.15866 (12)	0.0146 (4)
N2	0.01537 (19)	0.8358 (2)	0.23095 (12)	0.0173 (4)
N3	0.1956 (2)	0.7474 (2)	0.10597 (12)	0.0180 (4)
N4	0.15835 (18)	1.0068 (2)	0.03093 (12)	0.0144 (4)
C1	−0.1226 (3)	1.2240 (3)	0.27158 (17)	0.0288 (6)
H1A	−0.0570	1.3063	0.2843	0.043*
H1B	−0.1542	1.1913	0.3259	0.043*
H1C	−0.1989	1.2607	0.2305	0.043*
C2	−0.0587 (2)	1.0934 (3)	0.23219 (15)	0.0169 (5)
C3	−0.0343 (2)	0.9408 (3)	0.27836 (15)	0.0168 (5)
C4	0.0562 (3)	0.6895 (3)	0.27209 (15)	0.0225 (5)
H4A	−0.0109	0.6109	0.2505	0.027*
H4B	0.0575	0.6985	0.3361	0.027*
C5	0.1924 (3)	0.6394 (3)	0.25333 (17)	0.0294 (6)
H5A	0.2165	0.5452	0.2872	0.035*
H5B	0.2581	0.7185	0.2762	0.035*
C6	0.2103 (3)	0.6087 (3)	0.15904 (17)	0.0251 (5)
H6A	0.3006	0.5648	0.1570	0.030*
H6B	0.1429	0.5329	0.1340	0.030*
C7	0.2839 (2)	0.7824 (3)	0.05361 (14)	0.0163 (5)
C8	0.2556 (2)	0.9315 (3)	0.00510 (14)	0.0158 (4)
C9	0.3318 (2)	0.9800 (3)	−0.06579 (15)	0.0219 (5)
H9A	0.2709	1.0303	−0.1120	0.033*
H9B	0.3720	0.8905	−0.0899	0.033*
H9C	0.4028	1.0511	−0.0423	0.033*
C10	−0.3241 (2)	1.0385 (3)	0.43680 (17)	0.0251 (5)
H10A	−0.2903	0.9503	0.4076	0.038*
H10B	−0.3758	1.1041	0.3931	0.038*
H10C	−0.3821	1.0035	0.4789	0.038*

	U11	U22	U33	U12	U13	U23
Cu1	0.01633 (15)	0.01304 (15)	0.01304 (14)	0.00299 (10)	0.00462 (10)	0.00150 (10)
Ca1	0.0144 (3)	0.0150 (3)	0.0135 (3)	−0.0026 (2)	0.0032 (2)	−0.0004 (2)
O1	0.0261 (9)	0.0151 (8)	0.0197 (8)	0.0043 (7)	0.0050 (7)	0.0032 (7)
O2	0.0183 (8)	0.0135 (7)	0.0195 (8)	0.0018 (6)	0.0021 (6)	0.0054 (6)
O3	0.0271 (9)	0.0250 (9)	0.0130 (8)	−0.0030 (7)	0.0071 (7)	−0.0015 (7)
O4	0.0192 (8)	0.0214 (8)	0.0231 (8)	0.0078 (7)	0.0053 (7)	−0.0014 (7)
O5	0.0176 (9)	0.0183 (8)	0.0293 (9)	0.0011 (6)	0.0012 (7)	−0.0042 (7)
N1	0.0148 (9)	0.0136 (9)	0.0153 (9)	0.0007 (7)	0.0015 (7)	0.0017 (7)
N2	0.0221 (10)	0.0158 (9)	0.0146 (9)	0.0019 (8)	0.0053 (8)	0.0026 (8)
N3	0.0225 (10)	0.0155 (9)	0.0167 (9)	0.0049 (8)	0.0057 (8)	0.0039 (8)
N4	0.0139 (9)	0.0140 (9)	0.0148 (9)	0.0009 (7)	0.0003 (7)	0.0009 (7)
C1	0.0398 (16)	0.0247 (13)	0.0239 (13)	0.0110 (11)	0.0120 (11)	−0.0002 (11)
C2	0.0155 (11)	0.0186 (11)	0.0165 (11)	0.0013 (9)	0.0020 (9)	−0.0017 (9)
C3	0.0148 (11)	0.0200 (11)	0.0151 (10)	−0.0021 (9)	0.0007 (8)	0.0000 (9)
C4	0.0309 (14)	0.0201 (12)	0.0175 (11)	0.0041 (10)	0.0071 (10)	0.0046 (10)
C5	0.0306 (14)	0.0299 (14)	0.0277 (14)	0.0073 (11)	0.0043 (11)	0.0093 (12)
C6	0.0306 (14)	0.0202 (12)	0.0257 (13)	0.0113 (10)	0.0082 (11)	0.0045 (10)
C7	0.0169 (11)	0.0165 (11)	0.0146 (10)	0.0030 (9)	−0.0008 (8)	−0.0016 (9)
C8	0.0148 (11)	0.0186 (11)	0.0138 (10)	0.0004 (9)	0.0010 (8)	−0.0012 (9)
C9	0.0195 (12)	0.0265 (13)	0.0209 (12)	0.0005 (10)	0.0065 (9)	0.0019 (10)
C10	0.0199 (12)	0.0237 (12)	0.0304 (13)	−0.0006 (10)	−0.0007 (10)	−0.0041 (11)

Cu1—N1	1.9751 (18)	C1—C2	1.486 (3)
Cu1—N2	1.9469 (18)	C1—H1A	0.9800
Cu1—N3	1.9320 (19)	C1—H1B	0.9800
Cu1—N4	1.9650 (18)	C1—H1C	0.9800
Cu1—O2i	2.4646 (16)	C2—C3	1.522 (3)
Ca1—O3	2.3134 (16)	C4—C5	1.504 (4)
Ca1—O4ii	2.2818 (16)	C4—H4A	0.9900
Ca1—O5	2.3811 (16)	C4—H4B	0.9900
O1—N1	1.377 (2)	C5—C6	1.516 (4)
O1—H1O	0.9852	C5—H5A	0.9900
O2—N4	1.363 (2)	C5—H5B	0.9900
O3—C3	1.255 (3)	C6—H6A	0.9900
O4—C7	1.262 (3)	C6—H6B	0.9900
O5—C10	1.436 (3)	C7—C8	1.516 (3)
O5—H5O	0.9358	C8—C9	1.482 (3)
N1—C2	1.287 (3)	C9—H9A	0.9800
N2—C3	1.317 (3)	C9—H9B	0.9800
N2—C4	1.466 (3)	C9—H9C	0.9800
N3—C7	1.316 (3)	C10—H10A	0.9800
N3—C6	1.464 (3)	C10—H10B	0.9800
N4—C8	1.288 (3)	C10—H10C	0.9800
N3—Cu1—N2	98.02 (8)	H1B—C1—H1C	109.5
N3—Cu1—N4	82.10 (8)	N1—C2—C1	124.7 (2)
N2—Cu1—N4	166.31 (8)	N1—C2—C3	112.64 (19)
N3—Cu1—N1	163.47 (8)	C1—C2—C3	122.6 (2)
N2—Cu1—N1	81.29 (8)	O3—C3—N2	127.6 (2)
N4—Cu1—N1	94.69 (8)	O3—C3—C2	118.5 (2)
N3—Cu1—O2i	103.12 (7)	N2—C3—C2	113.87 (19)
N2—Cu1—O2i	106.54 (7)	N2—C4—C5	112.4 (2)
N4—Cu1—O2i	86.66 (6)	N2—C4—H4A	109.1
N1—Cu1—O2i	92.83 (7)	C5—C4—H4A	109.1
O4iii—Ca1—O4ii	180.00 (8)	N2—C4—H4B	109.1
O4iii—Ca1—O3iv	91.40 (6)	C5—C4—H4B	109.1
O4ii—Ca1—O3iv	88.60 (6)	H4A—C4—H4B	107.9
O4iii—Ca1—O3	88.60 (6)	C4—C5—C6	117.9 (2)
O4ii—Ca1—O3	91.40 (6)	C4—C5—H5A	107.8
O3iv—Ca1—O3	180.0	C6—C5—H5A	107.8
O4iii—Ca1—O5	85.18 (6)	C4—C5—H5B	107.8
O4ii—Ca1—O5	94.82 (6)	C6—C5—H5B	107.8
O3iv—Ca1—O5	95.69 (6)	H5A—C5—H5B	107.2
O3—Ca1—O5	84.31 (6)	N3—C6—C5	112.0 (2)
O4iii—Ca1—O5iv	94.82 (6)	N3—C6—H6A	109.2
O4ii—Ca1—O5iv	85.18 (6)	C5—C6—H6A	109.2
O3iv—Ca1—O5iv	84.31 (6)	N3—C6—H6B	109.2
O3—Ca1—O5iv	95.69 (6)	C5—C6—H6B	109.2
O5—Ca1—O5iv	180.0	H6A—C6—H6B	107.9
N1—O1—H1O	104.7	O4—C7—N3	127.8 (2)
C10—O5—H5O	100.9	O4—C7—C8	118.0 (2)
C2—N1—O1	117.47 (18)	N3—C7—C8	114.15 (19)
C2—N1—Cu1	116.42 (15)	N4—C8—C9	124.9 (2)
O1—N1—Cu1	126.09 (14)	N4—C8—C7	112.86 (19)
C3—N2—C4	118.48 (19)	C9—C8—C7	122.2 (2)
C3—N2—Cu1	115.18 (15)	C8—C9—H9A	109.5
C4—N2—Cu1	124.40 (15)	C8—C9—H9B	109.5
C7—N3—C6	120.9 (2)	H9A—C9—H9B	109.5
C7—N3—Cu1	114.57 (15)	C8—C9—H9C	109.5
C6—N3—Cu1	123.60 (15)	H9A—C9—H9C	109.5
C8—N4—O2	120.42 (18)	H9B—C9—H9C	109.5
C8—N4—Cu1	115.63 (15)	O5—C10—H10A	109.5
O2—N4—Cu1	123.91 (13)	O5—C10—H10B	109.5
C2—C1—H1A	109.5	H10A—C10—H10B	109.5
C2—C1—H1B	109.5	O5—C10—H10C	109.5
H1A—C1—H1B	109.5	H10A—C10—H10C	109.5
C2—C1—H1C	109.5	H10B—C10—H10C	109.5
H1A—C1—H1C	109.5
N3—Cu1—N1—C2	−87.3 (3)	N2—Cu1—N4—O2	−93.4 (3)
N2—Cu1—N1—C2	1.52 (17)	N1—Cu1—N4—O2	−21.15 (16)
N4—Cu1—N1—C2	−165.30 (17)	O2i—Cu1—N4—O2	71.42 (16)
O2i—Cu1—N1—C2	107.82 (17)	Cu1i—Cu1—N4—O2	50.60 (13)
Cu1i—Cu1—N1—C2	150.40 (17)	O1—N1—C2—C1	0.4 (3)
N3—Cu1—N1—O1	91.4 (3)	Cu1—N1—C2—C1	179.3 (2)
N2—Cu1—N1—O1	−179.78 (18)	O1—N1—C2—C3	−176.28 (17)
N4—Cu1—N1—O1	13.41 (17)	Cu1—N1—C2—C3	2.5 (2)
O2i—Cu1—N1—O1	−73.47 (17)	C4—N2—C3—O3	−4.2 (4)
Cu1i—Cu1—N1—O1	−30.90 (16)	Cu1—N2—C3—O3	−169.08 (19)
N3—Cu1—N2—C3	157.38 (17)	C4—N2—C3—C2	173.6 (2)
N4—Cu1—N2—C3	67.8 (4)	Cu1—N2—C3—C2	8.8 (2)
N1—Cu1—N2—C3	−5.93 (16)	N1—C2—C3—O3	170.6 (2)
O2i—Cu1—N2—C3	−96.30 (17)	C1—C2—C3—O3	−6.2 (3)
Cu1i—Cu1—N2—C3	−65.8 (2)	N1—C2—C3—N2	−7.4 (3)
N3—Cu1—N2—C4	−6.4 (2)	C1—C2—C3—N2	175.8 (2)
N4—Cu1—N2—C4	−96.0 (4)	C3—N2—C4—C5	−133.0 (2)
N1—Cu1—N2—C4	−169.8 (2)	Cu1—N2—C4—C5	30.3 (3)
O2i—Cu1—N2—C4	99.87 (19)	N2—C4—C5—C6	−62.6 (3)
Cu1i—Cu1—N2—C4	130.39 (16)	C7—N3—C6—C5	132.3 (2)
N2—Cu1—N3—C7	−159.43 (17)	Cu1—N3—C6—C5	−35.9 (3)
N4—Cu1—N3—C7	6.74 (16)	C4—C5—C6—N3	65.8 (3)
N1—Cu1—N3—C7	−73.0 (3)	Ca1v—O4—C7—N3	57.7 (5)
O2i—Cu1—N3—C7	91.42 (17)	Ca1v—O4—C7—C8	−122.4 (3)
Cu1i—Cu1—N3—C7	45.67 (17)	C6—N3—C7—O4	1.4 (4)
N2—Cu1—N3—C6	9.4 (2)	Cu1—N3—C7—O4	170.55 (19)
N4—Cu1—N3—C6	175.6 (2)	C6—N3—C7—C8	−178.6 (2)
N1—Cu1—N3—C6	95.8 (3)	Cu1—N3—C7—C8	−9.4 (2)
O2i—Cu1—N3—C6	−99.71 (19)	O2—N4—C8—C9	−0.9 (3)
Cu1i—Cu1—N3—C6	−145.46 (18)	Cu1—N4—C8—C9	176.75 (18)
N3—Cu1—N4—C8	−2.44 (16)	O2—N4—C8—C7	−179.45 (17)
N2—Cu1—N4—C8	89.0 (4)	Cu1—N4—C8—C7	−1.8 (2)
N1—Cu1—N4—C8	161.24 (16)	O4—C7—C8—N4	−172.59 (19)
O2i—Cu1—N4—C8	−106.19 (16)	N3—C7—C8—N4	7.3 (3)
Cu1i—Cu1—N4—C8	−127.01 (18)	O4—C7—C8—C9	8.9 (3)
N3—Cu1—N4—O2	175.17 (17)	N3—C7—C8—C9	−171.2 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O2	0.99	1.65	2.610 (2)	165
O5—H5O···O2vi	0.94	1.79	2.681 (2)	159

Table 1

Selected bond lengths (Å)

Cu1—N1	1.9751 (18)
Cu1—N2	1.9469 (18)
Cu1—N3	1.9320 (19)
Cu1—N4	1.9650 (18)
Cu1—O2i	2.4646 (16)
Ca1—O3	2.3134 (16)
Ca1—O4ii	2.2818 (16)
Ca1—O5	2.3811 (16)

Symmetry codes: (i) ; (ii) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯O2	0.99	1.65	2.610 (2)	165
O5—H5O⋯O2iii	0.94	1.79	2.681 (2)	159

Symmetry code: (iii) .