[μ-10,21-Dimethyl-3,6,14,17-tetra­aza­tricyclo­[17.3.1^8,12]tetra­cosa-1(23),8,10,12(24),19,21-hexa­ene-23,24-diolato-κ⁴N³,N⁶,O²³,O²⁴:κ⁴N¹⁴,N¹⁷,O²³,O²⁴]bis­(nitrato-κO)zinc(II)

The title compound, [Zn₂(NO₃)₂(C₂₂H₃₀N₄O₂)], is a centrosymmetric dinuclear zinc compound. Each Zn atom has a square-pyramidal geometry with N₂O₃ donors, being coordinated by two N atoms and two O atoms from the macrocyclic 10,21-dimethyl-3,6,14,17-tetra­azatricyclo­[17.3.1^8,12]tetra­cosa-1(23),8,10,12(24),19,21-hexa­ene-23,24-diolate ligand and one O atom from a nitrate anion. In the structure, two Zn atoms are linked by two phenolate O atoms to give a four-membered Zn₂O₂ ring.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.028
• wR factor = 0.080
• Data-to-parameter ratio = 17.0

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for         N3

Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 =          3
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Zn1    -   O2      ..       5.66 su
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O2
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Zn1
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety         C1
PLAT420_ALERT_2_C D-H Without Acceptor       N1     -   H1N    ...          ?

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT793_ALERT_1_G Check the Absolute Configuration of N1     = ...          S
PLAT793_ALERT_1_G Check the Absolute Configuration of N2     = ...          R
PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn1         (2)       2.01

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   7 ALERT level C = Check and explain
   5 ALERT level G = General alerts; check

   5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

---

S1. Comment

Dinuclear zinc(II) cores have attracted much interest as a result of their significance in biological systems (Dealwis et al., 1995; Burley et al., 1990; Roderick & Mathews, 1993). In addition, some synthetic dinuclear zinc(II) compounds are found to have functions in dephosphorylation (Bazzicalupi et al., 1997). To further widen the scope of application of such zinc compounds, there is a need to prepare new series of dinuclear zinc compounds. In this work, a new dinuclear zinc(II) compound has been synthesized, and its structure (I) is reported here.

As shown in Fig. 1, [Zn₂L(NO₃)₂] is a centrosymmetric dinuclear zinc compound. The coordination environment around zinc is a square-pyramid with two N atoms and two O atoms from L ligand occupying the basal positions and one O atom from NO₃^- anion occupying the apical position. In the crystal structure two zinc atoms are bridged by two phenolate O atoms to generate a four-membered Zn₂O₂ ring. The Zn—O and Zn—N distances are normal (Dutta et al., 2005).

Related literature

For related literature, see: Dealwis et al. (1995); Burley et al. (1990); Roderick & Mathews (1993); Dutta et al. (2005); Mandal & Nag (1986); Bazzicalupi et al. (1997).

S2. Experimental

The ligand C₂₂H₃₂N₄O₂ (H₂L) was prepared by the reported procedure (Mandal & Nag, 1986). A mixture of H₂L (0.10 g, 0.26 mmol) and Zn(NO₃)₂. 6H₂O (0.15 g, 0.52 mmol) in methanol (20 ml) was stirred for 10 min. The resulting solution was filtered. Colorless single crystals were obtained by slow evaporation of the filtrate at room temperature (yield 56%).

S3. Refinement

All H-atoms bound to carbon were refined using a riding model with d(C—H) = 0.93 Å, U_iso = 1.2U_eq (C) for aromatic and 0.96 Å, U_iso = 1.5U_eq (C) for CH₃ atoms. The imino H atoms were located in a difference Fourier map and refined isotropically with U_iso(H) = 1.5 U_eq(N).

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1990); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. A view of the molecule of (I). Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity.

[µ-10,21-Dimethyl-3,6,14,17-tetraazatricyclo[17.3.1^8,12]tetracosa- 1(23),8,10,12 (24),19,21-hexaene-23,24-diolato- κ⁴N³,N⁶,O²³,O²⁴:κ⁴N¹⁴,N¹⁷,O²³,O²⁴]bis(nitrato-κO)zinc(II)

Crystal data

[Zn2(NO3)2(C22H30N4O2)]	F(000) = 656
Mr = 637.26	Dx = 1.695 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybc	Cell parameters from 3000 reflections
a = 8.2190 (5) Å	θ = 2.4–28.4°
b = 14.1450 (8) Å	µ = 1.98 mm^−1
c = 11.0550 (6) Å	T = 293 K
β = 103.744 (9)°	Block, colorless
V = 1248.43 (12) Å^3	0.40 × 0.30 × 0.25 mm
Z = 2

Data collection

Bruker APEX CCD area-detector diffractometer	3027 independent reflections
Radiation source: fine-focus sealed tube	2524 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
ω scans	θmax = 28.4°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
Tmin = 0.495, Tmax = 0.609	k = −10→18
7558 measured reflections	l = −14→14

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.080	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0446P)^2 + 0.1778P] where P = (Fo^2 + 2Fc^2)/3
3027 reflections	(Δ/σ)max = 0.001
178 parameters	Δρmax = 0.40 e Å^−3
0 restraints	Δρmin = −0.29 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
Zn1	0.52604 (3)	0.398830 (14)	0.56583 (2)	0.03572 (9)
C1	1.0529 (3)	0.3634 (2)	0.1572 (3)	0.0680 (7)
H1A	1.1433	0.3280	0.2081	0.102*
H1B	1.0967	0.4190	0.1262	0.102*
H1C	0.9960	0.3251	0.0885	0.102*
C2	0.9306 (3)	0.39238 (14)	0.2345 (3)	0.0509 (6)
C3	0.9619 (3)	0.37071 (14)	0.3605 (2)	0.0478 (5)
H3	1.0562	0.3352	0.3964	0.057*
C4	0.8564 (3)	0.40063 (12)	0.4347 (2)	0.0419 (5)
C5	0.9026 (3)	0.38988 (14)	0.5739 (2)	0.0463 (5)
H5A	1.0041	0.3525	0.5969	0.056*
H5B	0.9277	0.4520	0.6108	0.056*
C6	0.8087 (3)	0.36047 (16)	0.7661 (2)	0.0487 (5)
H6A	0.8335	0.4267	0.7845	0.058*
H6B	0.9060	0.3237	0.8069	0.058*
C7	0.6586 (3)	0.33110 (16)	0.8152 (2)	0.0495 (5)
H7A	0.6401	0.2637	0.8027	0.059*
H7B	0.6816	0.3436	0.9039	0.059*
C8	0.7136 (2)	0.45295 (13)	0.3782 (2)	0.0402 (4)
C9	0.7880 (3)	0.44471 (16)	0.1820 (2)	0.0493 (5)
H9	0.7665	0.4604	0.0980	0.059*
C10	0.6769 (3)	0.47418 (14)	0.2512 (2)	0.0437 (5)
C11	0.5148 (3)	0.52395 (15)	0.1905 (2)	0.0483 (5)
H11A	0.5111	0.5339	0.1031	0.058*
H11B	0.4214	0.4835	0.1956	0.058*
N1	0.7725 (2)	0.34492 (11)	0.62923 (17)	0.0400 (4)
N2	0.5050 (2)	0.38322 (13)	0.75088 (18)	0.0435 (4)
N3	0.3579 (2)	0.22836 (14)	0.4825 (2)	0.0524 (5)
O1	0.61249 (19)	0.48312 (10)	0.44910 (15)	0.0504 (4)
O2	0.3842 (3)	0.30868 (13)	0.44489 (18)	0.0728 (5)
O3	0.2602 (3)	0.17463 (14)	0.4146 (2)	0.0801 (6)
O4	0.4378 (4)	0.20400 (16)	0.5846 (2)	0.1122 (9)
H1N	0.773 (7)	0.290 (3)	0.614 (5)	0.168*
H2N	0.414 (7)	0.353 (4)	0.749 (5)	0.168*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.03569 (14)	0.03053 (13)	0.04245 (15)	0.00473 (8)	0.01229 (10)	0.00441 (8)
C1	0.0588 (15)	0.0631 (15)	0.095 (2)	−0.0046 (12)	0.0434 (15)	−0.0265 (15)
C2	0.0465 (12)	0.0400 (11)	0.0748 (16)	−0.0088 (9)	0.0316 (11)	−0.0194 (10)
C3	0.0346 (10)	0.0321 (9)	0.0811 (16)	−0.0013 (8)	0.0227 (10)	−0.0089 (10)
C4	0.0371 (10)	0.0275 (9)	0.0650 (13)	−0.0025 (7)	0.0199 (9)	−0.0024 (8)
C5	0.0352 (10)	0.0368 (10)	0.0672 (14)	−0.0018 (8)	0.0129 (10)	0.0041 (9)
C6	0.0458 (11)	0.0436 (11)	0.0527 (12)	0.0066 (9)	0.0035 (9)	0.0043 (9)
C7	0.0573 (13)	0.0453 (11)	0.0444 (11)	0.0103 (9)	0.0092 (10)	0.0099 (9)
C8	0.0410 (10)	0.0279 (9)	0.0583 (12)	0.0013 (7)	0.0247 (9)	−0.0004 (8)
C9	0.0513 (12)	0.0462 (12)	0.0554 (13)	−0.0061 (9)	0.0226 (10)	−0.0136 (9)
C10	0.0442 (11)	0.0341 (10)	0.0565 (12)	−0.0024 (8)	0.0193 (9)	−0.0071 (8)
C11	0.0479 (12)	0.0478 (12)	0.0492 (12)	0.0017 (9)	0.0117 (9)	−0.0077 (9)
N1	0.0371 (8)	0.0299 (8)	0.0531 (10)	0.0014 (6)	0.0107 (7)	0.0034 (7)
N2	0.0460 (10)	0.0402 (9)	0.0450 (9)	0.0038 (7)	0.0124 (8)	0.0023 (7)
N3	0.0438 (10)	0.0504 (11)	0.0658 (13)	−0.0012 (8)	0.0185 (9)	−0.0124 (9)
O1	0.0557 (9)	0.0413 (8)	0.0654 (10)	0.0207 (6)	0.0365 (8)	0.0171 (7)
O2	0.0836 (13)	0.0563 (11)	0.0666 (11)	−0.0142 (9)	−0.0057 (10)	0.0032 (8)
O3	0.0671 (12)	0.0692 (12)	0.1050 (16)	−0.0187 (9)	0.0225 (11)	−0.0374 (11)
O4	0.144 (2)	0.0728 (14)	0.0964 (17)	−0.0331 (15)	−0.0171 (17)	0.0208 (13)

Geometric parameters (Å, º)

Zn1—O1^i	2.0057 (13)	C6—H6A	0.9700
Zn1—O1	2.0068 (14)	C6—H6B	0.9700
Zn1—O2	2.0079 (18)	C7—N2	1.489 (3)
Zn1—N2	2.1051 (19)	C7—H7A	0.9700
Zn1—N1	2.1216 (16)	C7—H7B	0.9700
C1—C2	1.523 (3)	C8—O1	1.340 (2)
C1—H1A	0.9600	C8—C10	1.397 (3)
C1—H1B	0.9600	C9—C10	1.388 (3)
C1—H1C	0.9600	C9—H9	0.9300
C2—C3	1.389 (4)	C10—C11	1.515 (3)
C2—C9	1.391 (3)	C11—N2^i	1.490 (3)
C3—C4	1.394 (3)	C11—H11A	0.9700
C3—H3	0.9300	C11—H11B	0.9700
C4—C8	1.402 (3)	N1—H1N	0.80 (5)
C4—C5	1.503 (3)	N2—C11^i	1.490 (3)
C5—N1	1.494 (3)	N2—H2N	0.86 (5)
C5—H5A	0.9700	N3—O4	1.213 (3)
C5—H5B	0.9700	N3—O3	1.224 (3)
C6—N1	1.488 (3)	N3—O2	1.246 (3)
C6—C7	1.519 (3)	O1—Zn1^i	2.0057 (13)
O1^i—Zn1—O1	74.53 (6)	C6—C7—H7A	109.4
O1^i—Zn1—O2	104.21 (8)	N2—C7—H7B	109.4
O1—Zn1—O2	100.80 (8)	C6—C7—H7B	109.4
O1^i—Zn1—N2	89.50 (6)	H7A—C7—H7B	108.0
O1—Zn1—N2	144.15 (7)	O1—C8—C10	120.25 (18)
O2—Zn1—N2	114.32 (8)	O1—C8—C4	118.52 (19)
O1^i—Zn1—N1	143.63 (7)	C10—C8—C4	121.23 (18)
O1—Zn1—N1	88.27 (6)	C10—C9—C2	121.9 (2)
O2—Zn1—N1	110.44 (8)	C10—C9—H9	119.0
N2—Zn1—N1	86.19 (7)	C2—C9—H9	119.0
C2—C1—H1A	109.5	C9—C10—C8	118.5 (2)
C2—C1—H1B	109.5	C9—C10—C11	121.3 (2)
H1A—C1—H1B	109.5	C8—C10—C11	120.12 (18)
C2—C1—H1C	109.5	N2^i—C11—C10	113.11 (18)
H1A—C1—H1C	109.5	N2^i—C11—H11A	109.0
H1B—C1—H1C	109.5	C10—C11—H11A	109.0
C3—C2—C9	118.26 (19)	N2^i—C11—H11B	109.0
C3—C2—C1	120.9 (2)	C10—C11—H11B	109.0
C9—C2—C1	120.8 (2)	H11A—C11—H11B	107.8
C2—C3—C4	122.0 (2)	C6—N1—C5	111.31 (17)
C2—C3—H3	119.0	C6—N1—Zn1	103.15 (12)
C4—C3—H3	119.0	C5—N1—Zn1	115.58 (12)
C3—C4—C8	118.1 (2)	C6—N1—H1N	111 (4)
C3—C4—C5	122.1 (2)	C5—N1—H1N	107 (4)
C8—C4—C5	119.36 (18)	Zn1—N1—H1N	110 (4)
N1—C5—C4	115.52 (18)	C7—N2—C11^i	113.39 (18)
N1—C5—H5A	108.4	C7—N2—Zn1	105.06 (13)
C4—C5—H5A	108.4	C11^i—N2—Zn1	111.88 (14)
N1—C5—H5B	108.4	C7—N2—H2N	113 (4)
C4—C5—H5B	108.4	C11^i—N2—H2N	105 (4)
H5A—C5—H5B	107.5	Zn1—N2—H2N	108 (3)
N1—C6—C7	109.84 (18)	O4—N3—O3	121.7 (2)
N1—C6—H6A	109.7	O4—N3—O2	118.1 (2)
C7—C6—H6A	109.7	O3—N3—O2	120.1 (2)
N1—C6—H6B	109.7	C8—O1—Zn1^i	129.47 (12)
C7—C6—H6B	109.7	C8—O1—Zn1	123.38 (12)
H6A—C6—H6B	108.2	Zn1^i—O1—Zn1	105.47 (6)
N2—C7—C6	111.27 (17)	N3—O2—Zn1	118.45 (15)
N2—C7—H7A	109.4
C9—C2—C3—C4	−0.7 (3)	O2—Zn1—N1—C5	104.10 (15)
C1—C2—C3—C4	176.62 (19)	N2—Zn1—N1—C5	−141.34 (15)
C2—C3—C4—C8	0.9 (3)	C6—C7—N2—C11^i	−86.8 (2)
C2—C3—C4—C5	−170.78 (18)	C6—C7—N2—Zn1	35.7 (2)
C3—C4—C5—N1	−129.7 (2)	O1^i—Zn1—N2—C7	−152.22 (14)
C8—C4—C5—N1	58.7 (2)	O1—Zn1—N2—C7	−90.10 (16)
N1—C6—C7—N2	−57.0 (2)	O2—Zn1—N2—C7	102.38 (15)
C3—C4—C8—O1	−179.12 (17)	N1—Zn1—N2—C7	−8.36 (14)
C5—C4—C8—O1	−7.2 (3)	O1^i—Zn1—N2—C11^i	−28.78 (14)
C3—C4—C8—C10	0.4 (3)	O1—Zn1—N2—C11^i	33.3 (2)
C5—C4—C8—C10	172.34 (17)	O2—Zn1—N2—C11^i	−134.18 (14)
C3—C2—C9—C10	−0.9 (3)	N1—Zn1—N2—C11^i	115.08 (15)
C1—C2—C9—C10	−178.2 (2)	C10—C8—O1—Zn1^i	−32.2 (3)
C2—C9—C10—C8	2.1 (3)	C4—C8—O1—Zn1^i	147.37 (15)
C2—C9—C10—C11	−174.79 (19)	C10—C8—O1—Zn1	130.89 (16)
O1—C8—C10—C9	177.62 (18)	C4—C8—O1—Zn1	−49.6 (2)
C4—C8—C10—C9	−1.9 (3)	O1^i—Zn1—O1—C8	−166.5 (2)
O1—C8—C10—C11	−5.4 (3)	O2—Zn1—O1—C8	−64.57 (18)
C4—C8—C10—C11	175.08 (18)	N2—Zn1—O1—C8	126.99 (17)
C9—C10—C11—N2^i	−125.4 (2)	N1—Zn1—O1—C8	45.92 (17)
C8—C10—C11—N2^i	57.7 (3)	O1^i—Zn1—O1—Zn1^i	0.0
C7—C6—N1—C5	169.00 (16)	O2—Zn1—O1—Zn1^i	101.92 (9)
C7—C6—N1—Zn1	44.46 (18)	N2—Zn1—O1—Zn1^i	−66.52 (14)
C4—C5—N1—C6	−164.74 (17)	N1—Zn1—O1—Zn1^i	−147.59 (8)
C4—C5—N1—Zn1	−47.5 (2)	O4—N3—O2—Zn1	−10.1 (3)
O1^i—Zn1—N1—C6	64.33 (16)	O3—N3—O2—Zn1	173.52 (17)
O1—Zn1—N1—C6	124.92 (13)	O1^i—Zn1—O2—N3	−128.41 (18)
O2—Zn1—N1—C6	−134.20 (13)	O1—Zn1—O2—N3	155.00 (18)
N2—Zn1—N1—C6	−19.64 (13)	N2—Zn1—O2—N3	−32.4 (2)
O1^i—Zn1—N1—C5	−57.37 (19)	N1—Zn1—O2—N3	62.8 (2)
O1—Zn1—N1—C5	3.22 (14)

Symmetry code: (i) −x+1, −y+1, −z+1.